JP2006346557A - Particle, its production method, toner and image forming method using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a particle having a resin coating layer formed on a surface of a resin fine particle by at least either a supercritical fluid or a subcritical fluid, being excellent in an electrostatic property and especially suitable for toner or the like, a production method of the particle, toner produced by a production method of the particle and an image forming method capable of attaining a higher image quality using the toner. <P>SOLUTION: The production method of the particle comprises at least a resin coating layer forming step for forming the resin coating layer containing an olefin copolymer having a cyclic structure on the surface of the resin fine particle by using at least either a supercritical fluid or a subcritical fluid, wherein the olefin copolymer has a glass transition temperature of 60 to 180°C and a number average molecular weight of 1,000 to 120,000. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a particle suitable as a toner used in electrophotography, electrostatic recording method, electrostatic printing method, and the like, a manufacturing method thereof, a toner, and an image forming method using the toner.

  In an image forming apparatus such as an electrophotographic apparatus, a process of forming an electrostatic latent image on a photosensitive member by charging and exposing the photosensitive member including a photosensitive material, and the electrostatic latent image is developed by a developer containing toner. A step of developing and forming a visible image, a step of transferring a visible image composed of a developer to a recording material such as paper, a step of fixing the transferred visible image to the recording material by means of heating or pressing, In addition, an image is formed on the recording body through a process of removing the developer remaining on the surface of the photoreceptor. Further, in an image forming apparatus using toner jet (toner flight recording), a recording material such as paper is charged through the opening of the aperture electrode by controlling the step of charging the toner and the electric field applied to the aperture electrode. The image is formed on the recording body through a step of forming a toner image on the recording material and a step of fixing the toner adhering to the recording material by means such as heating or pressurization.

  In such an image forming apparatus, toner and a developer containing toner are used as an image forming agent. The developer containing toner includes a one-component developer containing toner and a two-component developer containing toner and carrier. The toner is resin particles including a binder resin, a colorant, and, if necessary, a release agent, a charge control agent, a fluidity imparting agent, inorganic fine particles, and resin fine particles. As a typical toner production method, a melt kneading and pulverizing method and a polymerization method in a liquid solvent (including suspension polymerization method, emulsion aggregation method, dispersion polymerization method, etc.) are mainly used.

  Furthermore, in recent years, there has been a demand for a toner manufacturing method that improves energy saving and has less environmental impact. As such a toner production method, a particle production method using a RESS (Rapid Expansion of Supercritical Solution) method has attracted attention. In the RESS method, a substance that is soluble in the supercritical fluid is dissolved in the supercritical fluid, the supercritical fluid in which the substance is dissolved is rapidly expanded, and the solubility of the substance in the supercritical fluid is reduced, and the substance consists of the substance. Fine particles can be generated.

  For example, a binder resin component can be used as a method for producing a toner that can maintain the dispersibility while increasing the content of the colorant in the toner, achieve a desired image quality with a small amount of toner, and achieve energy saving. Is dissolved in a supercritical fluid or a subcritical fluid and mixed with a colorant component, and the solubility of the binder resin component in the supercritical fluid or subcritical fluid is lowered to reduce the binder resin. There has been proposed a toner manufacturing method in which components are precipitated in the form of particles while dispersing a colorant component inside a binder resin component (see Patent Document 1). Further, in Patent Document 1, a surface modifier component for mother toner particles having a binder resin component and a colorant component is dissolved in a supercritical fluid or a subcritical fluid, Mixing with the mother toner particles, decreasing the solubility of the surface modifier component in the supercritical fluid or subcritical fluid, and depositing the surface modifier component on the surface of the mother toner particles A method for producing toner is also disclosed. In the toner production method of Patent Document 1, the solubility of the binder resin component in the supercritical fluid or subcritical fluid is decreased by any of rapid expansion, poor solvent introduction, and surfactant introduction.

  However, as in Patent Document 1, when the solubility of the binder resin component in the supercritical fluid or subcritical fluid is reduced by any of the methods of rapid expansion, poor solvent introduction, and surfactant introduction, It is difficult to control the particle shape, particle size, and particle size distribution of the toner particles because the aggregation and coalescence between the deposited toner particles easily occur. There are problems that aggregates of toner particles having a particle size and toner having a wide particle size distribution are formed.

On the other hand, as a method for stably finely pulverizing a polymer solid raw material, particularly a powder coating material without adversely affecting the environment, the polymer solid raw material is converted into a supercritical phase using carbon dioxide and a polar organic solvent. A method for producing polymer fine particles which are dissolved and rapidly expanded has been proposed (see Patent Document 2).
According to Patent Document 2, since the polar organic solvent does not dissolve the finely divided polymer, there is a possibility that aggregation and coalescence of the polymer fine particles can be suppressed. Polar organic solvent remains on the surface. For this reason, it is necessary to dry the obtained polymer fine particles to remove the polar organic solvent from the polymer fine particles.

JP 2001-312098 A JP-A-8-113652

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, in the present invention, a resin coating layer having electrically excellent characteristics is formed on the surface of resin fine particles by at least one of a supercritical fluid and a subcritical fluid. It is an object of the present invention to provide suitable particles, a method for producing the particles, and a toner containing the particles and an image forming method capable of improving image quality using the toner.

Means for solving the problems are as follows. That is,
<1> including at least a resin coating layer forming step of forming a resin coating layer containing an olefin-based copolymer having a cyclic structure on the surface of resin fine particles using at least one of a supercritical fluid and a subcritical fluid;
It is a method for producing particles, wherein the olefin copolymer has a glass transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000.
<2> The resin coating layer has at least one of a supercritical fluid and a subcritical fluid, resin fine particles, a glass transition temperature of 60 to 180 ° C., and a number average molecular weight of 1,000 to 120,000. It is a manufacturing method of the particle | grains as described in said <1> formed by making the olefin type copolymer which has a structure contact.
<3> At least one of the supercritical fluid and the subcritical fluid can dissolve the olefin copolymer having a cyclic structure without dissolving the resin fine particles. It is a manufacturing method of the described particle.
<4> The resin coating layer is formed by depositing an olefin copolymer having a cyclic structure dissolved in at least one of a supercritical fluid and a subcritical fluid. It is the manufacturing method of the particle | grains in any one.
<5> The method for producing particles according to any one of <1> to <4>, wherein at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture.
<6> The method for producing particles according to any one of <1> to <5>, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.
<7> The method for producing particles according to any one of <1> to <6>, wherein at least one of the supercritical fluid and the subcritical fluid includes an entrainer.
<8> The method for producing particles according to <7>, wherein the content of the entrainer is 0.1 to 10% by mass.
<9> The method for producing particles according to any one of <7> to <8>, wherein the entrainer is a polar organic solvent.
<10> A particle produced by the method for producing a particle according to any one of <1> to <9>.
<11> A toner comprising the particles according to <10>.
<12> A toner-containing container filled with the toner according to <11>.
<13> An electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to <11> to form a visible image. It is a process cartridge characterized by having at least.
<14> 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 toner according to <11> And developing means for forming a visible image by development, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. The image forming apparatus.
<15> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to <11> to form a visible image. An image forming method comprising: a developing step for forming; a transferring step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.

  According to the method for producing particles of the present invention, a resin coating layer is formed by forming a resin coating layer containing an olefin copolymer having a cyclic structure on the surface of resin fine particles using at least one of a supercritical fluid and a subcritical fluid. The glass transition temperature of the said olefin type copolymer is 60-180 degreeC, and a number average molecular weight is 1,000-120,000. According to the method for producing particles of the present invention, the resin coating layer covering the surface of the resin fine particles has a cyclic structure having a transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000. Therefore, it is possible to easily and efficiently produce particles having excellent electrical characteristics.

  Since the particles of the present invention are produced by the method for producing particles of the present invention, they have a resin coating layer having electrically excellent characteristics, and are particularly suitable as a toner.

  Since the toner of the present invention contains particles produced by the method for producing particles of the present invention, it is excellent in charging performance and surface properties.

  Since the developer of the present invention contains the toner of the present invention, when an image is formed by electrophotography using the developer, a high quality image with excellent charging performance and high image density can be obtained. It is done.

  Since the toner-containing container of the present invention contains the toner of the present invention, when an image is formed by electrophotography using the toner stored in the toner-containing container, the charging performance is excellent and the high image A high quality image with high density and sharpness can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. As a result, it can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that a high quality image with high image density and high sharpness can be obtained with excellent charging performance and the like.

  The image forming apparatus of the present invention includes 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 the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus of the present invention, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, it is possible to obtain a high-quality image with excellent charging performance and a high image density and high sharpness.

  The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image is developed using the toner of the present invention to be visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming method of the present invention, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, it is possible to obtain a high-quality image with excellent charging performance and a high image density and high sharpness.

  According to the present invention, conventional problems can be solved, and a resin coating layer having electrically excellent characteristics is formed on the surface of resin fine particles by at least one of a supercritical fluid and a subcritical fluid. Therefore, it is possible to provide particles having excellent chargeability, particularly suitable as a toner, a method for producing the particles, and a toner containing the particles and an image forming method capable of improving the image quality using the toner.

(Particles and particle production method)
The method for producing particles of the present invention includes at least a resin coating layer forming step, a resin fine particle production step, and further other steps appropriately selected as necessary.
The particles of the present invention are obtained by the method for producing the particles of the present invention.
Hereinafter, the details of the particles of the present invention will be clarified through the description of the method for producing particles of the present invention.

<Manufacturing process of resin fine particles>
The process for producing the resin fine particles is a process for producing the resin fine particles. In the present invention, the “resin fine particles” may include not only the resin fine particles themselves but also resin fine particles including a colorant, a charge control agent, a release agent, and the like.

The resin fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include resin fine particles obtained by a pulverization method or a polymerization method. There is no restriction | limiting in particular as this polymerization method, According to the objective, it can select suitably, For example, a suspension method, an emulsification method, a dispersion method etc. are mentioned.
The toner may be produced by a microencapsulation method (spray drying method, coacervation method, etc.), etc., in addition to the pulverization method and polymerization method.
As the resin fine particles, those appropriately synthesized may be used, or commercially available products may be used.

  The pulverization method is, for example, a method for producing the resin fine particles by melting and kneading a material containing at least a binder resin, and then pulverizing and classifying the material. In the case of the pulverization method, the shape may be controlled by applying a mechanical impact force to the obtained resin fine particles for the purpose of increasing the average circularity of the resin fine particles. In this case, the mechanical impact force can be applied to the resin fine particles using, for example, a device such as a hybridizer or mechanofusion.

As the resin fine particles by the polymerization method, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, Etc. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Also formed with polystyrene, methacrylic acid ester, acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polycondensation resin such as silicone resin, benzoguanamine, nylon, thermosetting resin, etc. The obtained resin fine particles have a sharp particle size distribution and are suitable. Among these, the resin fine particles obtained by dispersion polymerization are preferable because of their sharper particle sizes. Further, if the toner is imparted with low-temperature fixability, resin fine particles made of a polyester resin or a polyol resin can be selected. That is, the resin can be selected in accordance with the design of the targeted resin fine particles.

Here, the dispersion polymerization method will be specifically described.
First, a polymer compound dispersant that dissolves in the hydrophilic organic liquid is added to the hydrophilic organic liquid, and the polymer is dissolved in the hydrophilic liquid, but the resulting polymer is swollen by the hydrophilic liquid. Or hardly dissolve. One or more vinyl monomers are added to this to form particles. 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 as that used to produce the seed particles, or may be another monomer, but the polymer must not be dissolved in the hydrophilic organic liquid. The polymer dispersion obtained by such a method can be used as it is in the subsequent resin coating layer forming step, which contributes to the simplification of the manufacturing process.

As the hydrophilic organic liquid, a liquid that dissolves the vinyl monomer to be used and does not dissolve the obtained resin fine particles (polymer particles) is used. Examples of the liquid include methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, 3-pentanol and octyl alcohol. , Benzyl alcohol, cyclohexanol, furfuryl alcohol, alcohols such as ethylene glycol, glycerin, diethylene glycol, methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether And ether alcohols such as ether That. These organic liquids can be used singly or as a mixture of two or more. In addition, by using together with the above-mentioned alcohols and ether alcohols in organic liquids other than alcohols and ether alcohols, various SPs can be used under conditions that do not make the polymer particles soluble in organic liquids. By changing the value and changing the polymerization conditions, it is possible to suppress the size of the generated particles, the coalescence of the particles, and the generation of new particles.
Examples of the organic liquid include hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, and xylene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, and tetrabromoethane; ethyl ether, dimethyl Ethers such as glycol, trioxane and tetrahydrofuran; acetals such as methylal and diethyl acetal; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexa; esters such as butyl formate, butyl acetate, ethyl propionate and cellosolve acetate Acids such as formic acid, acetic acid and propionic acid; sulfur and nitrogen-containing organic compounds such as nitropropene, nitrobenzene and dimethylamine; and water.
State in which SO ₄ ²⁻ , NO ₂ ⁻ , PO ₄ ³⁻ , Cl ⁻ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , and other inorganic ions are present in the solvent mainly composed of the hydrophilic organic liquid. The polymerization may be carried out at In addition, the average particle size, particle size distribution, drying conditions, and the like of the polymer particles can be adjusted by changing the type and composition of the mixed solvent at the start of polymerization, during polymerization, and at the end of polymerization.

  The polymer compound dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid Acids such as fumaric acid, maleic acid or maleic anhydride; acrylic monomers; vinyl alcohol or ethers of vinyl alcohol; esters of vinyl alcohol and compounds containing a carboxyl group; acrylamide, methacrylamide, di Acetone acrylamide, or methylol compounds thereof; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; compounds having heterocycles; homopolymers of various monomers such as; or copolymers thereof; polyoxyethylene resins , Celluloses, and the like.

  The polymer compound dispersant is appropriately selected depending on the hydrophilic organic liquid to be used, the target polymer particle seed and the seed particle manufacturing or the growth particle manufacturing. In view of sterically preventing the polymer particles, those having high affinity and adsorbability to the polymer particle surface and high affinity and solubility to the hydrophilic organic liquid are selected. Further, in order to enhance the repulsion between particles in a three-dimensional manner, a molecular chain having a certain length, particularly a molecular weight of 10,000 or more is preferable. However, when the molecular weight is too high, the liquid viscosity is remarkably increased, the operability and the stirrability are deteriorated, and the precipitation probability of the produced polymer on the particle surface is varied, so care must be taken. In addition, it is effective for stabilization to allow the monomer of the polymer compound dispersant mentioned above to coexist with the monomer constituting the intended polymer particle.

  In general, the amount of the polymer compound dispersant used in the production of seed particles varies depending on the type of monomer for forming the polymer particles, but is 0.1 to 10% by mass with respect to the hydrophilic organic liquid. Preferably, 1-5 mass% is more preferable. When the concentration of the polymer compound dispersant is low, the produced polymer particles have a relatively large diameter, and when the concentration is high, small particles are obtained. Is less effective in reducing the diameter.

  In addition, the use of inorganic compound fine powders and surfactants in combination with these polymer compound dispersants can further improve the stabilization of the produced polymer particles and the improvement of the particle size distribution. Polymerization may be carried out in the presence of these materials in a vinyl monomer solution or a seed particle dispersion added for the purpose of preventing coalescence of particles. Initially generated particles are stabilized by a distributed polymer dispersant that is equilibrated in the hydrophilic organic liquid and on the polymer particle surface, but significant amounts of unreacted vinyl monomer are present in the hydrophilic organic liquid. In some cases, it will be somewhat swollen and sticky and will agglomerate over the steric repulsion of the polymeric dispersion stabilizer.

  Furthermore, when the amount of monomers is extremely large with respect to the hydrophilic organic liquid, it does not precipitate unless the polymerization that completely dissolves the produced polymer proceeds to some extent. The state of precipitation in this case takes the form of forming a highly sticky lump. Therefore, the amount of the monomer with respect to the hydrophilic organic liquid when producing the fine resin particles is not particularly limited, and is somewhat different depending on the kind of the hydrophilic organic liquid, but is preferably 100% by mass or less, and more preferably 50% by mass or less.

As the polymerization initiator, a normal radical initiator soluble in the solvent to be used is used. Examples of the polymerization initiator include azo polymerization initiators such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile); lauryl peroxide, benzoylperoxide Peroxide-based polymerization initiators such as oxide, tert-butyl peroctoate, potassium persulfate, etc., or a system in which sodium thiosulfate, amine, etc. are used in combination therewith are used.
As for the addition amount of the said polymerization initiator, 0.1-10 mass parts is preferable with respect to 100 mass parts of vinyl monomers. Polymerization is performed by completely dissolving the polymer dispersant in the hydrophilic organic liquid, and then adding one or more vinyl monomers, a polymerization initiator, etc., and stirring at a speed that makes the flow in the reaction vessel uniform. However, it is carried out by heating to a temperature corresponding to the dispersion rate of the polymerization initiator used. In addition, since the temperature at the initial stage of polymerization has a large influence on the particle size to be generated, it is preferable to increase the temperature to the polymerization temperature after adding the monomer and dissolve the polymerization initiator in a small amount of solvent.

  In the polymerization, it is preferable that oxygen in the reaction vessel is sufficiently expelled with an inert gas such as nitrogen gas or argon gas. If the oxygen purge is insufficient, fine particles may be easily generated.

  In order to perform the polymerization in a high polymerization rate region, a polymerization time of 5 to 40 hours is preferable. The polymerization rate can be increased by stopping the polymerization in a desired particle size and particle size distribution state, sequentially adding a polymerization initiator, or performing a reaction under high pressure.

Alternatively, the polymerization may be carried out in the presence of a compound having a large chain transfer constant for the purpose of adjusting the average molecular weight of the resin fine particles. Examples of the compound having a large chain transfer constant include a low molecular compound having a mercapto group, carbon tetrachloride, carbon tetrabromide, and the like.
There is no restriction | limiting in particular as a weight average molecular weight of the said resin fine particle, According to the objective, it can select suitably, For example, 1,000 or more are preferable, 2,000-10,000,000 are more preferable, 3, 000 to 1,000,000 is more preferable. When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said resin fine particle, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
The volume average particle diameter of the resin fine particles is preferably 3 to 12 μm, and more preferably 4 to 8 μm.

  The resin fine particles preferably contain a colorant, a charge control agent, a release agent, and other components, particularly when used as toner base particles.

  The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide And a simple substance of phosphorus or a compound thereof, a simple substance of tungsten or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. Among these, salicylic acid metal salts and metal salts of salicylic acid derivatives are preferred. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as said metal, According to the objective, it can select suitably, For example, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, cal Examples thereof include polymer compounds having a functional group such as a boxyl group and a quaternary ammonium salt.

  The addition amount of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 to 5 parts by mass, and 1 to 3 parts by mass with respect to 100 parts by mass of the resin fine particles. More preferred. When the addition amount is less than 0.5 parts by mass, the charging characteristics of the toner may be deteriorated. When the addition amount exceeds 5 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is increased. , And the electrostatic attraction force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
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 individually by 1 type and may use 2 or more types together.
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 the natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax.
Examples of the petroleum waxes include paraffin wax and microcrystalline wax.
Examples of the higher fatty acid include stearic acid, palmitic acid, myristic acid, and the like.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. If the melting point exceeds 160 ° C., it may easily cause a cold offset when fixing at a low temperature. May occur.

  There is no restriction | limiting in particular in the addition amount of the said mold release agent, Although it can select suitably according to the objective, 1-20 mass parts is preferable with respect to 100 mass parts of said resin fine particles, and 3-15 mass parts is more preferable. .

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, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, 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, Oh Lured, Quinacridone 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, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said dye, According to the objective, it can select suitably, For example, C.I. I. SOLVENT YELLOW (6, 9, 17, 31, 35, 100, 102, 103, 105), C.I. I. SOLVENT 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. SOLVENT BLUE (22,63,78,83-86,191,194,195,104), C.I. I. SOLVEN GREEN (24, 25), C.I. I. SOLVEN BROWN (3, 9) and the like.
Moreover, there is no restriction | limiting in particular as a commercially available dye, According to the objective, it can select suitably, For example, Hodogaya Chemical Co., Ltd. Aizen SOT dye 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; Sudan dye Yellow manufactured by BASF -146, 150, Orange-220, Red-290, 380, 460, Blue-670; Dialresin Yellow-3G, F, H2G, HG, HC, HL, Orange-HS, G, Red-GG manufactured by Mitsubishi Kasei. , S, HS, A, K, H5B, Violet-D, Blue-J, G, N, K, P, H3G, 4G, Green-C, Bro n-A: Oil color YElow-3G, GG-S, # 105, Orange-PS, PR, # 201, Scarlet- # 308, Red-5B, Brown-GR, # 416, Green-, manufactured by Orient Chemical Co., Ltd. BG, # 502, Blue-BOS, IIN, Black-HBB, # 803, EB, EX; Sumiplast Blue GP, OR, Red FB, 3B, Yellow FL7G, GC manufactured by Sumitomo Chemical; Nippon Kayaku Co., Ltd. Kayalon Polyester Black EX-SF300, Kaya Set Red-B, Blue A-2R, and the like can be used.

  There is no restriction | limiting in particular in the addition amount of the said coloring agent, Although it can select suitably according to a coloring degree, 1-50 mass parts is preferable with respect to 100 mass parts of said resin fine particles.

The fluidity improver, which is the other component, means a material that can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent Silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like.
The cleaning property improver is added to the resin fine particles in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, for example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples include polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

  The resin particles may contain additives such as the charge control agent, the release agent, and the colorant. The resin particles and the various additives may be mixed and then kneaded, and a resin coating layer forming step described later. And a method using any one of a supercritical fluid and a subcritical fluid, and the like, and a method of kneading after mixing resin particles and various additives is particularly preferable.

  In the method of kneading after mixing the resin particles and various additives, specifically, the resin particles and a known additive or resin are mixed by a mixer such as a Henschel mixer, and then a batch type two-roll, Banbury. Mixer, continuous twin screw extruder (for example, KTK type twin screw extruder (manufactured by Kobe Steel), TEM type twin screw extruder (manufactured by Toshiba Machine), TEX type twin screw extruder (Nippon Steel Works) Manufactured), PCM type twin screw extruder (Ikegai Iron Works Co., Ltd.), KEX type twin screw extruder (Kurimoto Iron Works Co., Ltd.)), continuous type single screw kneader (for example, Ko Nida (made by Buss)), etc. The components may be incorporated into the resin particles by kneading the constituent materials using a thermal kneading machine, etc., and in some cases, forming into pellets or sheets with various injection machines and cooling. it can. If necessary, the resin is coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier using a swirl stream or classification using the Coanda effect It can also be classified to a predetermined particle size by a machine.

<Resin coating layer forming step>
The resin coating layer forming step is a step of forming a resin coating layer containing an olefin-based copolymer having a cyclic structure on the surface of the resin fine particles using at least one of a supercritical fluid and a subcritical fluid. .

The glass transition temperature (Tg) of the olefin copolymer having a cyclic structure is 60 to 180 ° C, and more preferably 60 to 120 ° C.
The number average molecular weight (Mn) of the olefin copolymer having a cyclic structure is 1,000 to 120,000, more preferably 2,000 to 50,000.
If the glass transition temperature and the number average molecular weight of the olefin copolymer having a cyclic structure are out of the above ranges, it may be impossible to form a resin coating layer having excellent chargeability on the resin fine particles.

The olefin copolymer having a cyclic structure is not particularly limited as long as it has a glass transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000. It can be selected as appropriate according to the conditions.
In addition, as the olefin copolymer having the cyclic structure, an appropriately synthesized one may be used, or a commercially available product may be used. Examples of the commercially available products include Topas AG-09 (manufactured by Ticona).

  The resin coating layer has at least one of a supercritical fluid and a subcritical fluid, resin fine particles, a cyclic structure having a glass transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000. It is preferably formed by contacting with an olefin copolymer.

-Supercritical fluid and subcritical fluid-
The supercritical fluid has intermediate properties between gas and liquid, has properties such as fast mass transfer and heat transfer, low viscosity, and changes its temperature and pressure to change its density and dielectric constant. In other words, it means a fluid whose solubility parameter, free volume, etc. can be continuously changed greatly. Furthermore, since the supercritical fluid has an extremely small interfacial tension as compared with an organic solvent, even a small undulation (surface) can follow and be wet with the supercritical fluid.
The supercritical fluid exists as a non-condensable high-density fluid in a temperature and pressure range that exceeds the limit (critical point) where gas and liquid can coexist, does not cause condensation even when compressed, and exceeds the critical temperature. And, as long as it is a fluid in a state equal to or higher than the critical pressure, there is no particular limitation and can be appropriately selected according to the purpose, but those having a low critical temperature and critical pressure are preferable, and the subcritical fluid is As long as it exists as a high-pressure liquid in the temperature and pressure region near the critical point, there is no particular limitation, and it can be appropriately selected according to the purpose.

Examples of the supercritical fluid or subcritical fluid include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol, ethane, propane, 2,3-dimethylbutane, benzene, chlorotrifluoromethane, and dimethyl ether. Are preferable. Among these, carbon dioxide can easily create a supercritical state with a critical pressure of 7.3 MPa and a critical temperature of 31 ° C., and is nonflammable, inert, easy to handle, and non-aqueous. This is particularly preferable because the surface can be hydrophobized.
The supercritical fluid or the subcritical fluid may be used alone or as a mixture of two or more.

  The critical temperature and critical pressure of the supercritical fluid are not particularly limited and may be appropriately selected depending on the intended purpose. However, the critical temperature is preferably −273 to 300 ° C., more preferably 0 to 200 ° C. preferable. Moreover, as said critical pressure, 5-100 MPa is preferable and 10-50 MPa is more preferable.

In the present invention, the resin coating layer can be formed by positively utilizing the properties of the supercritical fluid or the subcritical fluid.
It is preferable that at least one of the supercritical fluid and the subcritical fluid can dissolve the olefin copolymer having a cyclic structure as the resin coating layer forming material without dissolving the resin fine particles.
The resin coating layer may be formed by precipitating an olefin copolymer having a cyclic structure as a resin coating layer forming material dissolved in at least one of a supercritical fluid and a subcritical fluid. preferable.
The resin coating layer is formed by controlling the solubility (controlled by temperature and pressure) of the olefin copolymer having a cyclic structure as a solute in the supercritical fluid, and forming a uniform resin coating layer on the surface of the resin fine particles. (Precipitation) can be performed. Specifically, after dissolving or finely dispersing the olefin copolymer having a cyclic structure under the condition that the resin fine particles are not dissolved, the olefin copolymer having a cyclic structure is deposited on the surface of the resin fine particles by reducing the pressure. To form a uniform resin coating layer.
In addition, since the supercritical fluid can be easily separated from the target product and can be recovered and reused, an epoch-making production method with a low environmental load that does not use a solvent can be realized.

  In addition to the supercritical fluid and the subcritical fluid, other fluids can be used in combination. The other fluid is preferably one that can easily control the solubility of the olefin copolymer having a cyclic structure as the resin coating layer forming material. Specifically, methane, ethane, propane, ethylene, and the like are preferable.

  In addition to the supercritical fluid and the subcritical fluid, an entrainer (azeotropic agent) may be added. By adding the entrainer, the resin coating layer can be formed more easily. There is no restriction | limiting in particular as said entrainer, Although it can select suitably according to the objective, A polar organic solvent is preferable. Examples of the polar organic solvent include methanol, ethanol, propanol, butanol, hexane, toluene, ethyl acetate, chloroform, dichloromethane, ammonia, melamine, urea, thioethylene glycol, and the like. Among these, cleaning and removal aids such as chloroform are particularly preferable from the viewpoint of high resin solubility. By adding the chloroform, the precipitation effect on the surface of the resin fine particles of the olefin copolymer having a cyclic structure as the resin coating layer forming material is increased. The supercritical fluid or subcritical fluid is preferably selected from the types that can dissolve the materials forming the various resin coating layers without dissolving the resin fine particles. In particular, a lower alcohol solvent exhibiting poor solvent properties at normal temperature and normal pressure is suitable for resin fine particles.

Examples of the entrainer include those in which the resin fine particles used do not dissolve, or those that cause slight swelling. Specifically, the difference between the solubility parameter [SP value] and the [SP value] of the resin fine particles used is 1. 0.0 or more is preferable, and 2.0 or more is more preferable. For example, for styrene-acrylic resins, use alcohols such as methanol, ethanol, and n-propanol with high [SP value], or n-hexane, n-heptane, etc. with low [SP value]. Is preferred. Of course, when the difference in [SP value] is large, wetting with respect to the resin fine particles is deteriorated, and good dispersion of the resin fine particles cannot be obtained. Therefore, the optimum [SP value] difference is preferably 2 to 5.
Moreover, 0.1-10 mass% is preferable and, as for content of the entrainer in the mixed fluid of at least any one of the said supercritical fluid and a subcritical fluid, and an entrainer, 0.5-5 mass% is more preferable. When the content is less than 0.1% by mass, it may be difficult to obtain the effect as an entrainer. When the content exceeds 10% by mass, the properties of the entrainer as a liquid become too strong, and supercritical or May make it difficult to obtain a subcritical state.

  The addition amount of the olefin-based copolymer having a cyclic structure as the resin coating layer forming material is not particularly limited and can be appropriately selected depending on the purpose, but is 1 to 300 with respect to 100 parts by mass of the resin fine particles. A mass part is preferable and 10-200 mass parts is more preferable.

The method for forming the resin coating layer is not particularly limited as long as at least one of the supercritical fluid and the subcritical fluid is brought into contact with the resin fine particles, and can be appropriately selected according to the purpose.
Here, the apparatus used for forming the resin coating layer is not particularly limited and may be appropriately selected depending on the purpose. For example, a pressure vessel for performing resin coating layer forming treatment on the resin fine particles And a pressurizing pump for supplying the supercritical fluid. As a treatment method using the apparatus, first, the resin fine particles are charged into the pressure vessel, the supercritical fluid is supplied into the pressure vessel by a pressure pump, and the supercritical fluid is brought into contact with the resin particles. The olefin copolymer having a cyclic structure as a resin coating layer forming material is deposited on the surface of the resin fine particles, and the supercritical containing the olefin copolymer having a cyclic structure as the resin coating layer forming material is prepared. Drain the fluid. When the supercritical fluid is returned to room temperature and normal pressure, the supercritical fluid becomes a gas, so that removal of the solvent is not necessary, and wastewater generated by cleaning the surface of the resin fine particles, which has been conventionally required, is generated. It becomes unnecessary and the burden on the environment is reduced.

The temperature at which the resin coating layer is formed is not particularly limited as long as it is equal to or higher than the critical temperature of the supercritical fluid or subcritical fluid to be used, and can be appropriately selected according to the purpose. The upper limit of the temperature is preferably lower than the melting point of the substance forming the resin fine particles, and more preferably a temperature at which aggregation such as adhesion between the resin fine particles does not occur. The lower limit of the critical temperature is preferably a temperature at which the other fluid that can be added to the supercritical fluid can exist as a gas.
Specifically, the temperature at which the resin coating layer is formed is preferably 0 to 100 ° C, and more preferably 20 to 80 ° C. When the temperature exceeds 60 ° C., resin fine particles may be dissolved.

  The pressure for forming the resin coating layer is not particularly limited as long as it is equal to or higher than the critical pressure of the supercritical fluid or the subcritical fluid to be used, and can be appropriately selected according to the purpose. 60 MPa is preferred.

Here, a method for forming a resin coating layer made of an olefin polymer having a cyclic structure on the surface of resin fine particles using a resin coating layer forming apparatus will be described. In the resin coating layer forming apparatus shown in FIG. 1, a reaction vessel 9 having a volume of 1000 cm ³ was used. In FIG. 1, 2 is an entrainer tank, 4 is a pressure pump, 6 is a temperature sensor, 113 is an injection nozzle, and 114 is a pressure sensor.
Carbon dioxide (CO ₂ ) was used as a gas for the supercritical fluid. An olefin polymer having a cyclic structure as a resin coating layer forming material was charged into the reaction vessel 9, and resin fine particles as resin fine particles were charged.

Next, carbon dioxide gas was supplied from the gas cylinder 1, pressurized by the pressurizing pump 3, and introduced into the reaction vessel 9 through the valve 7. At this time, the valve 5 is closed, and carbon dioxide gas is not introduced into the ejection container 112 side. Here, the pressure reducing valve 8 for discharging and ejecting remains closed, and the pressure in the reaction vessel 9 rises due to the introduction of high-pressure carbon dioxide. In addition, the temperature inside the reaction vessel 9 was adjusted to 320 K with the heater 117.
When the pressure in the reaction vessel 9 is 7.3 MPa or more, the reaction vessel 9 is in a supercritical state. Moreover, each valve | bulb 5 and 7 was adjusted, the pressure in reaction container 9 was set to 20 Mpa, and it set to the state in which the olefin polymer which has a cyclic structure in reaction container 9 was dissolved. In this state, the valves 5 and 7 were closed, the dissolved state in the reaction vessel 9 was maintained for 120 minutes, and the supercritical fluid was sufficiently diffused and circulated. Thereafter, the valve 6 was opened, the pressure in the reaction vessel was adjusted to 10 MPa, and maintained for 60 minutes. Thereafter, carbon dioxide gas was introduced again from the high-pressure pump side, and introduction of carbon dioxide was continued while maintaining the pressure in the reaction vessel at 10 MPa. At this time, the supercritical fluid carbon dioxide contained in the mixed solution and the olefin polymer having a cyclic structure dissolved in the supercritical carbon dioxide are recovered by a recovery mechanism (not shown) and further illustrated. No separation device separates the carbon dioxide and the olefin copolymer having a cyclic structure from each other and reuses them.

  By continuing the introduction of supercritical carbon dioxide, the dissolved olefin-based polymer having a cyclic structure in the reaction vessel 9 is all discharged out of the vessel, and the reaction vessel 9 has an olefin having a deposited cyclic structure. Only resin fine particles and supercritical carbon dioxide fluid having a resin-based copolymer in the resin coating layer. Thereafter, the valve is opened, the supercritical carbon dioxide fluid is vaporized, and resin fine particles having a dried olefin copolymer having a cyclic structure in the resin coating layer can be produced.

(particle)
Through the above steps, the particles of the present invention can be obtained by forming a resin coating layer on the surface of the resin fine particles using at least one of the supercritical fluid and the subcritical fluid.
The particles use an olefin copolymer having a cyclic structure having a glass transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000 as a resin coating layer material. Since it has a resin coating layer with excellent characteristics, for example, a rear projection screen for viewing a display film, a magnetic recording medium, a spacer for liquid crystal display, a light diffusing agent for various lighting devices, a column filler, a carrier for a diagnostic agent, etc. , Seed particles (monodisperse particles) when producing resin particles for use in drug delivery systems, bioreactors, etc .; adhesives; alternative materials for metals or ceramics; electrophotography, electrostatic recording, electrostatic printing, etc. And resin particles used for the image forming particles used in the above.
The particles can be used as they are, or, if necessary, a treatment for modifying the surface by mixing with an additive, a treatment for fixing the additive, in the presence of a supercritical fluid or a subcritical fluid. It is also possible to add treatments such as immersion, extraction, and coating with the additive.

(toner)
The toner of the present invention contains particles produced by the method for producing particles of the present invention, and further contains other components as necessary.

  The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. The image density, the average circularity, the volume average particle size, the volume average particle are as follows. It is preferable to have a ratio of the diameter to the number average particle diameter (volume average particle diameter / number average particle diameter).

The image density is preferably 1.90 or more, more preferably 2.00 or more, and particularly preferably 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). preferable.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is, for example, imagio Neo 450 (manufactured by Ricoh Co., Ltd.), and the amount of developer attached to copy paper (TYPE6000 <70W>; manufactured by Ricoh Co., Ltd.) is 1.00 ± 0.05 mg / cm ^2. The solid roller image was formed at a fixing roller surface temperature of 160 ± 2 ° C., and the image density at any six locations in the solid image obtained was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Light). It can be measured by measuring and calculating the average value.

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 transfer belt, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. As a result, the accumulated toner may become a transfer residual toner on the photoconductor, which may cause background smearing of the image, or may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured, for example, by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).

There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3-8 micrometers is preferable.
When the volume average particle size is less than 3 μm, in the 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 a member such as a blade are likely to occur because the toner is thinned, and if it exceeds 8 μm, the resolution is high and the resolution is high. It becomes difficult to obtain an image having 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 volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25.
When the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) exceeds 1.25, the two-component developer causes the surface of the carrier to be agitated for a long period of time 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, 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 variation in the toner particle size may increase. is there.

  The volume average particle size and the ratio of the volume average particle size to the number average particle size (volume average particle size / number average particle size) 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, the toner diameter in the developer is little changed even if the toner balance for a long time is performed, and it is good even for long-term stirring in the developing device. And stable developability can be obtained.

-Career-
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized 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 core material has a volume average particle size of preferably 10 to 150 μm, and more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. 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 resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. 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 application method include an immersion method, a spray method, and a brush coating 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, cersol 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 mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, 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 mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner of the present invention, it is possible to stably form a high-quality image with excellent charging performance during image formation.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for a container, a process cartridge, an image forming apparatus, and an image forming method.

(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 toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(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. At least a 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. 2, the process cartridge includes a photosensitive member 101, includes a charging unit 102, a developing unit 104, and a cleaning unit 107, and further includes other members as necessary. Become. Reference numeral 103 denotes exposure means.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used.
An arbitrary charging member is used as the charging means 102.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably detachably provided in the electrophotographic apparatus of the present invention described later.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
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.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape thereof is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. . Among these, amorphous silicon or the like is preferable in terms of long life.

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 surface side of the electrostatic latent image carrier may be adopted.

-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 means is not particularly limited as long as it can be developed using, for example, the toner or 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 developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  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 latent electrostatic image bearing member (photoconductor) of the visible image 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, 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 80 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 neutralizing means is not particularly limited and may be appropriately selected from known neutralizers as long as it can apply a neutralizing bias to the latent electrostatic image bearing member. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic 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 electrophotographic color toner removed in 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.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 3 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and an exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is formed between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 4 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 4, the same components as those in FIG. 3 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 of the present invention will be described with reference to FIG. A tandem image forming apparatus 120 shown in FIG. 5 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15, and 16 and can be rotated clockwise in FIG. 5. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 120, a sheet reversing device 28 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 22 and the fixing device 25. Yes.

  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 the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (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 means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 6), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the upper surface, a photoconductor cleaning device 63, and a static eliminator 64. And cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 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. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 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 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, 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 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, since the toner of the present invention having excellent charging performance and the like is used, a high-quality image can be obtained efficiently.

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

Example 1
-Preparation of fine polymer particle solution-
64 parts by mass of ester wax is added to a monomer mixture composed of 108 parts by mass of styrene, 39 parts by mass of n-butyl acrylate, and 9.6 parts by mass of methacrylic acid. A body solution was prepared.
Subsequently, a surface activity obtained by dissolving 7.0 parts by mass of sodium dodecylbenzenesulfonate in 2400 parts by mass of ion-exchanged water in a 3.0 L separable flask equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing unit. The agent solution (aqueous medium) was charged, and the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 360 rpm under a nitrogen stream. The monomer solution (80 ° C.) is mixed and dispersed in the surfactant solution (80 ° C.) contained in a separable flask by a mechanical disperser having a circulation path, and has a uniform dispersed particle size. A dispersion of emulsified particles (oil droplets) was prepared. An initiator solution in which 0.8 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to the obtained dispersion, and this system was heated and stirred at 80 ° C. for 3 hours. Polymerization (first stage polymerization) was carried out to prepare [finely divided polymer particle solution 1].
Next, an initiator solution in which 7.7 parts by mass of potassium persulfate is dissolved in 240 parts by mass of ion-exchanged water is added to the obtained [fine particle polymerization particle solution 1], and after sufficiently stirring, at 80 ° C, A monomer mixed solution consisting of 380 parts by mass of styrene, 137.5 parts by mass of n-butyl acrylate, 36 parts by mass of methacrylic acid, and 14.5 parts by mass of t-dodecyl mercaptan was added dropwise over 2 hours. After completion of the dropwise addition, polymerization (second stage polymerization) was performed by heating and stirring for 60 minutes, followed by cooling to 40 ° C. to prepare [finely divided polymer particle solution 2].

-Preparation of colorant dispersion-
9.6 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water, and 20 parts by mass of carbon black (trade name: # 25B, manufactured by Mitsubishi Chemical Corporation) was gradually added to the dissolved solution. Then, a [colorant dispersion] was prepared by dispersing using a homomixer that can be mixed with a high shearing force (made by Tokki Kako Co., Ltd., TK type).

-Formation of associated particles-
[Fine particle solution 2] 1200 parts by mass, 2000 parts by mass of ion-exchanged water, and the above-mentioned [colorant dispersion] are 4 L of 5 L equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device. The mixture was placed in a neck flask and stirred.
After adjusting the liquid temperature to 30 ° C., 5N aqueous sodium hydroxide solution was added to the solution to adjust the pH to 10.0. Next, an aqueous solution in which 52.5 parts by mass of magnesium chloride hexahydrate was dissolved in 72 parts by mass of ion-exchanged water was added over 10 minutes with stirring at 30 ° C. After standing for 5 minutes, the temperature increase was started, and the system was heated to 90 ° C. over 10 minutes (temperature increase rate = 10 ° C./min). In this state, the particle size of the associated particles was measured with “Coulter Counter TA-II”. When the volume average particle size reached 6.0 μm, 115 parts by mass of sodium chloride was dissolved in 700 parts by mass of ion-exchanged water. The aqueous solution was added to stop particle growth. Further, the fusion was continued by stirring for 6 hours while maintaining the liquid temperature at 90 ° C. ± 2 ° C. Then, it cooled to 30 degreeC on 6 degree-C / min conditions. While stirring the resulting aqueous dispersion of associated particles, the pH of the system is adjusted to 4 or lower with sulfuric acid, and acid washing (25 ° C., 10 minutes) is performed. Water is separated by filtration, and then ion-exchanged water 500 is newly added. A part by mass was added to reslurry and washed with water. Thereafter, again, dehydration and water washing were repeated several times, and the solid content was separated by filtration, followed by drying at 45 ° C. for 24 hours with a dryer to obtain [polymer particles (toner) 1]. [Polymer particles (toner) 1] had a volume average particle diameter (Dv) of 6.0 μm and Dv / Dn of 1.23.

-Resin coating layer forming process-
As a method for forming the resin coating layer on the surface of the resin particles, the apparatus shown in FIG. 1 was used. As the reaction vessel 9, one having a volume of 1000 cm ³ was used. In this example, carbon dioxide (CO ₂ ) was used as the gas used as the supercritical fluid. Reaction of 5 g of “Topas AG-09” manufactured by Ticona, which is an olefin polymer having a cyclic structure as a resin coating layer material, having a glass transition temperature (Tg) of 67 ° C. and a number average molecular weight (Mn) of 4,600 Into the container 9, 300g of [Polymer particles (toner) 1] obtained in the colored polymer particle production step was charged as resin particles.
Next, carbon dioxide gas was supplied from the gas cylinder 1, pressurized by the pressurizing pump 3, and introduced into the reaction vessel 9 through the valve 7. At this time, the valve 15 is closed, and carbon dioxide gas is not introduced into the ejection container 112 side. Here, the pressure reducing valve 8 for discharging and ejecting remains closed, and the pressure in the reaction vessel 9 rises due to the introduction of high-pressure carbon dioxide. In addition, the temperature inside the reaction vessel 9 was adjusted to 320 K with the heater 117.
When the pressure in the reaction vessel 9 is 7.3 MPa or more, the reaction vessel 9 is in a supercritical state. Moreover, each valve | bulb 5 and 7 was adjusted, the pressure in reaction container 9 was set to 20 Mpa, and it set to the state in which the olefin polymer which has a cyclic structure in reaction container 9 was dissolved. In this state, the valves 5 and 7 were closed, the dissolved state in the reaction vessel 9 was maintained for 120 minutes, and the supercritical fluid was sufficiently diffused and circulated. Thereafter, the valve 6 was opened, the pressure in the reaction vessel was adjusted to 10 MPa, and maintained for 60 minutes. Thereafter, carbon dioxide gas was introduced again from the high-pressure pump side, and introduction of carbon dioxide was continued while maintaining the pressure in the reaction vessel at 10 MPa. At this time, the supercritical fluid carbon dioxide contained in the mixed solution and the olefin polymer having a cyclic structure dissolved in the supercritical carbon dioxide are recovered by a recovery mechanism (not shown) and further illustrated. No separation device separates the carbon dioxide and the olefin copolymer having a cyclic structure from each other and reuses them.

  By continuing the introduction of supercritical carbon dioxide, the dissolved olefin-based polymer having a cyclic structure in the reaction vessel 9 is all discharged out of the vessel, and the reaction vessel 9 has an olefin having a deposited cyclic structure. It becomes only the resin particle which has a system copolymer in a resin coating layer, and a supercritical carbon dioxide fluid. Thereafter, the valve 6 was opened, the supercritical carbon dioxide fluid was vaporized, and resin particles having a dried olefin copolymer having a cyclic structure in the resin coating layer were obtained.

(Comparative Example 1)
In Example 1, Comparative Toner 1 was produced in the same manner as Example 1 except that the resin coating layer forming step was not performed.

-Production of developer-
Next, 100 parts by mass of the obtained toner 1 and comparative toner 1 are each 0.8 parts by mass of silica having a volume-average particle diameter of 12 nm (trade name “NA50H” manufactured by Nippon Aerosil Co., Ltd.) subjected to a hydrophobic treatment. And a surface treatment was performed using a Henschel mixer to prepare a developer.

  Next, the obtained developers of Example 1 and Comparative Example 1 were subjected to image density, charge amount, and comprehensive evaluation as follows. The results are shown in Table 1.

<Image density>
About each developer of Example 1 and Comparative Example 1 obtained, a non-magnetic one-component development system laser printer (manufactured by Kyocera Mita, DP-560) was used to copy paper (TYPE6000 <70W>, manufactured by Ricoh Co., Ltd.). ) Was formed as a solid image having an adhesion amount of each developer of 1.00 ± 0.05 mg / cm ² . The solid image was repeatedly formed on 8000 copy sheets. The image density of the obtained solid image was visually observed for the initial stage and after the endurance of 8000 sheets, and evaluated based on the following criteria.
Note that the higher the image density obtained, the higher the density image can be formed. This evaluation corresponds to an embodiment of the toner container, the process cartridge, and the image forming method of the present invention.
〔Evaluation criteria〕
◯: There was no change in the image density and high image quality was obtained at the initial stage and after the endurance of 8000 sheets.
Δ: The image density was slightly lowered and the image quality was lowered after the endurance of 8000 sheets.
X: After enduring 8000 sheets, the image density was remarkably lowered and the image quality was greatly lowered.

<Charge amount>
6 g of each developer was weighed, charged into a metal cylinder that could be sealed, and blown to obtain the charge amount. The developer concentration was adjusted to 4.5 to 5.5% by mass.

<Comprehensive evaluation>
From the evaluation results of the above characteristics, a comprehensive judgment was made and the following criteria were used.
○: Good ×: Bad (unusable)

From the results of Table 1, Example 1 using a toner containing resin fine particles in which a resin coating layer is formed with a supercritical fluid is superior in charging performance and has a high image density as compared with the developer of Comparative Example 1. It was confirmed.

  The method for producing particles of the present invention has a small environmental load. Further, the particles of the present invention produced by the method are excellent in charging performance and the like, and are particularly preferably used as a toner, and are preferably used for high quality image formation. The developer of the present invention using the toner of the present invention, the toner-containing container, the image forming method, and the first stage process cartridge are suitably used for high quality image formation.

FIG. 1 is a schematic view showing an example of an apparatus used in the resin coating layer forming step of the present invention. FIG. 2 is a schematic explanatory view showing an example of the process cartridge of the present invention. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. 6 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

1 Gas cylinder 3 Pressure pump 5, 7, 8 Valve 9 Reaction vessel 10 Photoconductor (photosensitive drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharger lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming apparatus 101 photoconductor 102 charging means 103 exposure 104 Developing means 105 Transfer body 106 Transfer means 107 Cleaning means 120 Tandem type developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heating source 126 Clean Ngurora 127 Temperature sensor 130 platen 142 paper feed roller 143 paper bank 144 sheet cassette 145 separating roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)

Claims (12)

Including at least a resin coating layer forming step of forming a resin coating layer containing an olefin-based copolymer having a cyclic structure on the surface of the resin fine particles using at least one of a supercritical fluid and a subcritical fluid;
The method for producing particles, wherein the olefin copolymer has a glass transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000.   The resin coating layer has at least one of a supercritical fluid and a subcritical fluid, resin fine particles, and a cyclic structure having a glass transition temperature of 60 to 180 ° C. and a number average molecular weight of 1,000 to 120,000. The method for producing particles according to claim 1, wherein the particles are formed by contacting with an olefin copolymer.   The method for producing particles according to any one of claims 1 to 2, wherein at least one of the supercritical fluid and the subcritical fluid is capable of dissolving the olefin copolymer having a cyclic structure without dissolving the resin fine particles. .   The particles according to any one of claims 1 to 3, wherein the resin coating layer is formed by precipitating an olefin copolymer having a cyclic structure dissolved in at least one of a supercritical fluid and a subcritical fluid. Manufacturing method.   The method for producing particles according to any one of claims 1 to 4, wherein at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture.   The method for producing particles according to any one of claims 1 to 5, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.   The method for producing particles according to any one of claims 1 to 6, wherein at least one of the supercritical fluid and the subcritical fluid includes an entrainer.   The method for producing particles according to claim 7, wherein the content of the entrainer is 0.1 to 10% by mass.   The method for producing particles according to claim 7, wherein the entrainer is a polar organic solvent.   A particle produced by the method for producing a particle according to claim 1.   A toner comprising the particles according to claim 10. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and a developing step of developing the electrostatic latent image using the toner according to claim 11 to form a visible image. And an image forming method comprising: a transfer step of transferring the visible image onto a recording medium; and a fixing step of fixing the transfer image transferred onto the recording medium.