JP2009300733A - Method of manufacturing toner for electrostatic charge image development, toner, image forming apparatus, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing toner having cleaning performance facilitating cleaning without the existence of dust between character parts and without reducing fine line reproducibility, and to provide toner, an image forming apparatus using the toner, and a process cartridge thereof. <P>SOLUTION: In the method of manufacturing toner for electrostatic charge image development, where a toner composition including at least a resin, a colorant, and a releasing agent is dissolved or dispersed into an organic solvent, the dissolved substance or the dispersed substance is turned into an oil-phase dispersion liquid, the oil-phase dispersion liquid is dispersed into an aqueous medium with the existence of particulate dispersion agent, the obtained emulsified dispersion liquid is supplied to a continuous vacuum defoaming apparatus, and turned into a thin film by centrifugal force so that the toner base is obtained by removing the organic solvent while applying shear force to the emulsified dispersion liquid, the oil-phase dispersion liquid includes at least a layered inorganic mineral in which at least part of ions between the layers is modified with an organic ion, and a thixotropy value (TI value) of the oil-phase dispersion liquid is adjusted so as to be in a range of 1.3 to 5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc., and a toner obtained by the production method, an image forming apparatus, and It relates to a process cartridge.

  In an electrophotographic image forming apparatus, an electric charge is applied to the surface of a photoconductor by discharge, an electrostatic latent image is formed thereon by exposure, and then development is performed using toner having the same polarity as the latent image. The image is developed by an apparatus to form a visible image with toner on the photoreceptor, and then the visible image is transferred to a recording member such as paper conveyed by a transfer device, and the transferred visible image is transferred by a fixing device. It is fixed on the recording member. On the other hand, the toner remaining on the photoreceptor after the transfer is cleaned by the cleaning device for the next image formation.

  In recent years, there has been a demand for high-quality images with high reproducibility even for electrophotographic images. This is a strong demand not only for monochrome images but also for full-color images. In particular, in a full-color image, there are many halftone portions, and by increasing the reproduction accuracy, it is possible to increase the number of colors that can be reproduced with less graininess. Therefore, a toner having a reduced particle size and / or a spherical shape has been developed.

For example, Patent Documents 1 to 3 describe a method for producing a toner containing at least a binder resin and a colorant, in which toner base particles are dispersed in water or an aqueous solvent containing a dispersant to form a dispersion system. A step of causing the toner base particles to absorb the softener by introducing a mixed solution of the softener and water or an aqueous solvent that is soluble in the dispersion and an organic solvent that dissolves the softener. A method for producing a toner having a step of removing a softener from toner base particles is disclosed. Accordingly, the toner can be made spherical without being limited by the type of resin component contained in the toner and without impairing the particle size distribution of the toner base particles.
However, since the spherical toner disclosed in Patent Document 1 and the like is easy to roll on the photosensitive member, it often enters between the photosensitive member and the cleaning member, resulting in poor cleaning, and the toner during development and transfer. There is a problem that there is a lot of dust around the dots.

Further, for example, in Patent Documents 4 to 6, the electrostatic image developing toner is composed of toner particles containing a colorant and a binder resin, and the volume average particle diameter of the toner particles is 3 to 9 μm. A toner satisfying a predetermined particle size distribution is disclosed. Thereby, it is said that graininess and fog can be improved.
However, in the small particle size toner disclosed in Patent Document 4 and the like, when cleaning the toner having a small particle size from the photosensitive member, the toner easily enters the gap between the cleaning member and the photosensitive member, resulting in poor cleaning. Often. In addition, the toner having an irregular shape (uneven toner shape) works favorably for cleaning, but the toner behavior at the time of development and transfer becomes irregular for individual particles, and there are problems such as a decrease in fine line reproducibility. .

In Patent Document 7, toner particles obtained by salting out / fusion-bonding resin particles having a number average primary particle diameter of 10 to 500 nm to produce secondary particles and flattening the secondary particles are obtained. A flat toner having a flat shape is disclosed. As a result, a high-density image can be obtained even with a small amount of toner consumption, and a high-quality image with little unevenness and no toner scattering can be obtained.
However, if the toner shape is flattened, the powder flowability deteriorates, and it is difficult to arrange dense and uniform toner particles when forming the toner dots. Can not do. The same applies to the irregular toner.

  In Patent Document 8, a method called volumetric shrinkage called a polymer dissolution suspension method is studied. In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing an inorganic dispersant, and then the volatile solvent is removed. In that case, the volumetric shrinkage of the droplets occurs, and if a solid fine particle dispersant that does not dissolve in the aqueous medium is selected as the dispersant, amorphous particles can be obtained, but the solid content in the solvent is increased to increase productivity. When the amount is increased, the viscosity of the dispersed phase increases, and the resulting particles have a large particle size and a broad distribution. Conversely, when the molecular weight of the resin used is lowered and the viscosity of the dispersed phase is lowered, the fixability (particularly hot offset resistance) must be sacrificed.

  On the other hand, in Patent Document 9, the resin used in the polymer dissolution suspension method has a low molecular weight to lower the viscosity of the dispersed phase, to facilitate emulsification, and to improve the fixability by carrying out a polymerization reaction in the particles. However, the obtained particles had a wide particle size distribution, and the shape was not smooth and the shape was not controlled.

  On the other hand, in Patent Document 10, a toner material is dissolved or dispersed in an organic solvent, the dissolved or dispersed material is dispersed in an aqueous medium in which a fine particle dispersant is present, and the resulting emulsified dispersion is subjected to continuous vacuum defoaming. Introduced into the machine and thinned by centrifugal force in the thin-film dispersion region of the rotating body, the organic solvent is removed while applying a shearing force to the emulsified dispersion to obtain cleaning properties equivalent to those of the irregular toner. It has been studied to efficiently produce a toner that can be used. However, when the thixotropy value of the emulsified dispersion is low, the emulsion becomes spherical, and when the thixotropy value of the emulsified dispersion is high, the proportion of the irregular toner increases and fine powder increases.

JP 2002-148863 A JP-A-5-313416 JP-A-2-148046 Japanese Patent Laid-Open No. 61-22354 JP-A-6-250439 JP-A-9-068823 JP 2002-207317 A JP-A-7-152202 JP-A-11-149179 Japanese Patent No. 4030937

  The present invention has been made in view of the above problems, and its purpose is to provide a cleaning performance that is easy to clean, without dust between the character portions and the like, without reducing fine line reproducibility. It is an object of the present invention to provide a toner production method, a toner, an image forming apparatus using the toner, and a process cartridge.

  In order to solve the above problems, the invention according to claim 1 is to dissolve or disperse a toner composition containing at least a resin, a colorant and a release agent in an organic solvent, and to disperse the dissolved or dispersed product in an oil phase. Dispersing the oil phase dispersion in an aqueous medium in the presence of a fine particle dispersant, supplying the resulting emulsified dispersion to a continuous vacuum deaerator, and forming a thin film by centrifugal force A method for producing a toner for developing an electrostatic charge image by removing an organic solvent while applying a shearing force to the emulsified dispersion, and using the toner as a toner base, wherein the oil phase dispersion contains at least part of ions between layers as organic ions. And a thixotropic value (TI value) of the oil phase dispersion is adjusted to 1.3 to 5.

  According to a second aspect of the present invention, in the method for producing a toner for developing an electrostatic charge image according to the first aspect, the oil phase dispersion is a polyester prepolymer in which the resin has an isocyanate group, and the modified layered inorganic The resin is added to a liquid obtained by dissolving or dispersing a mineral, the colorant, and the release agent in an organic solvent, and the mixture is mixed and stirred.

  The invention according to claim 3 is the method for producing a toner for developing an electrostatic charge image according to claim 1 or 2, wherein the oil phase dispersion includes a masterbatch containing the modified layered inorganic mineral, the colorant, A colorant / release agent dispersion in which the release agent is dispersed in an organic solvent is mixed and stirred to obtain a dispersion (M) containing a modified layered inorganic mineral / colorant / release agent, and then the dispersion The resin is prepared by adding the resin to (M) and mixing and stirring.

  A fourth aspect of the present invention is an electrostatic charge image developing toner obtained by the method for producing an electrostatic charge image developing toner according to any one of the first to third aspects, wherein the volume average particle size is 3 to 8 μm. The electrostatic charge image developing toner has an average circularity of 0.94 to 0.97.

  According to a fifth aspect of the present invention, there is provided an electrostatic charge image forming step for forming an electrostatic charge image on at least a photosensitive member, and developing the electrostatic charge image formed on the photosensitive member with a toner into a visible image. A developing step, a transferring step for transferring the visible image formed on the photoconductor onto the recording member, a fixing step for fixing the visible image transferred on the recording member, and a surface remaining on the surface of the photoconductor An image forming method including a cleaning step having a cleaning blade for cleaning toner to be used, wherein the toner according to claim 4 is used as the toner.

  According to a sixth aspect of the present invention, there is provided a photosensitive member that forms at least an electrostatic charge image, a developing unit that develops the electrostatic charge image formed on the surface of the photosensitive member with a toner into a visible image, and the photosensitive member. A transfer unit that transfers the visible image formed on the recording member; a fixing unit that fixes the visible image transferred on the recording member; and a cleaning blade that cleans residual toner on the surface of the photoreceptor. An image forming apparatus comprising: a cleaning unit, wherein the toner for developing an electrostatic charge image according to claim 4 is used as the toner.

  The invention according to claim 7 is a process cartridge that integrally supports at least one member selected from a photosensitive member and a developing unit, a charging unit, and a cleaning unit, and is detachable from an image forming apparatus main body. The developing means holds toner, and the toner is a process cartridge which is the electrostatic image developing toner according to claim 4.

  According to the present invention, it is possible to provide a method for producing a toner having no cleaning between the character portions and the like, without reducing the fine line reproducibility and having a cleaning performance that can be easily cleaned.

Hereinafter, the present invention will be described in detail.
The present invention relates to an aqueous medium in which a toner composition containing at least a resin and a colorant is dissolved or dispersed in an organic solvent, the solution or dispersion is used as an oil phase dispersion, and the oil phase dispersion is used as a fine particle dispersant. The resulting emulsion dispersion is supplied to a continuous vacuum defoamer and thinned by a centrifugal force to remove the organic solvent while applying a shearing force to the emulsion dispersion to form a toner base. A method for producing a toner for developing an electrostatic charge image, wherein the oil phase dispersion contains a layered inorganic mineral in which at least some of the ions between layers are modified with organic ions, and the thixotropy of the oil phase dispersion By adjusting the value (TI value) to 1.3 to 5, the developability, transferability, and cleaning properties of the toner are remarkably improved, and the dust between the character portions and the fine line reproducibility are not deteriorated. Moreover, it is easy to clean In which to obtain a toner having a Ningu performance.

  Examples of the resin include modified polyester resins such as polyester prepolymer (A) having an isocyanate group. Examples of the prepolymer (A) include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyisocyanate (3) reacted with a polyester having active hydrogen. Examples of the group having active hydrogen in the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferable.

If necessary, the resin may be reacted with a crosslinking agent and / or an extender in an aqueous medium. As the crosslinking agent and / or extender, amines (B) can be preferably used.
The toner of the present invention preferably contains, as a toner binder, a urea-modified polyester (i) that can be obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B).
The modified polyester refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. For example, a polyester end is reacted with something other than an ester bond, specifically, a functional group such as an acid group or an isocyanate group that reacts with a hydroxyl group is introduced at the end and further reacted with an active hydrogen compound to deform the end. Point to something.

  Examples of the polyol (1) include a diol (1-1) and a trihydric or higher polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) and the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat resistant storage stability and low temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1 to B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diamines). Cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted by using an extension terminator. Examples of the extension terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 2/1 to 1/2, preferably 1.5 / 1 to 1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  In the present invention, the urea-modified polyester (i) is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. At this time, the peak molecular weight is 1,000 to 10,000, and if it is less than 1,000, the extension reaction is difficult and the elasticity of the toner is small, and as a result, the hot offset resistance is deteriorated. On the other hand, if it exceeds 10,000, the problem of production becomes high in terms of deterioration of fixability, particle formation and pulverization. The number average molecular weight of the urea-modified polyester is not particularly limited when using the unmodified polyester (ii) described later, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of urea-modified polyester (i) alone, the number average molecular weight is usually 20,000 or less, preferably 1,000 to 10,000, more preferably 2,000 to 8,000. If it exceeds 20,000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.

  The toner of the present invention can contain not only the polyester (i) modified with a urea bond, but also the polyester (ii) not modified with the polyester (i) as a toner binder component. By using polyester (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to single use. Examples of polyester (ii) include polycondensates of polyol (1) and polycarboxylic acid (2) similar to the polyester component of polyester (i), and preferred ones are also the same as polyester (i). The polyester (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, such as a urethane bond. It is preferable that polyester (i) and polyester (ii) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component of polyester (i) and polyester (ii) preferably have similar compositions. When the polyester (ii) is contained, the weight ratio of the polyester (i) to the polyester (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25 /. 75, particularly preferably 7/93 to 20/80. When the weight ratio of the polyester (i) is less than 5 wt%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The peak molecular weight of the polyester (ii) is usually 1,000 to 10,000, preferably 2,000 to 8,000, and more preferably 2,000 to 5,000. If it is less than 1,000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of the polyester (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of polyester (ii) is 1-5, preferably 2-4. Since a high acid value wax is used as the release agent, the low acid value binder is easily matched with the two-component toner because the low acid value binder leads to charging and high volume resistance.

  In the toner of the present invention, the glass transition point (Tg) of the toner binder is 40 to 70 ° C., preferably 55 to 65 ° C. When the glass transition point is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and when the glass transition point exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.

(Coloring agent)
As the colorant of the toner of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow oxidation Iron, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sae Red, parachlor Rutonitroaniline 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, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolo Red, Polyazo Red, Chrome Vermillion, 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, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Ki, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used.
The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

  The colorant can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Len-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be used alone or in combination. .

  The master batch can be obtained by mixing and kneading the resin for the master batch and the colorant under high shearing force and kneading. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

(Release agent)
As the release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface, thereby fixing. Effective against high temperature offset without applying a release agent such as oil to the roller. Examples of such a wax component include the following.
Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The release agent can be melt-kneaded together with the master batch and the binder resin, and of course, it may be added when dissolved and dispersed in the organic solvent.
The content of the release agent in the toner is usually 1 to 20 wt%, preferably 3 to 15 wt% with respect to the toner. When the content is less than 1 wt%, the effect of adding a release agent is hardly exhibited. When the content exceeds 20 wt%, the fluidity of the toner may be lowered.

(Charge control agent)
In the present invention, a charge control agent may be contained as necessary.
As the charge control agent, 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, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like.
Specifically, Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid chromium, zinc, Metals such as iron, zirconium, and aluminum, or their metal compound complexes / complexes, phenol-based condensate E-89 (above, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP- 415 (made by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst), LRA-901, LR, which is a boron complex 47 (manufactured by Japan Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  The toner production method of the present invention comprises dissolving or dispersing the above-mentioned resin, preferably the above-described polyester prepolymer (A) having an isocyanate group, and a toner composition containing a colorant, a release agent and the like in an organic solvent, The solution or dispersion is used as an oil phase dispersion, and the oil phase dispersion is dispersed and emulsified in an aqueous medium containing a fine particle dispersant. In the present invention, the modified layered inorganic material is added to the oil phase dispersion. In the case where the thixotropy value of the oil phase dispersion is within a specific range by including a mineral, the oil phase dispersion is emulsified, and the organic solvent is removed while applying a shearing force to the obtained emulsion dispersion. It has been found that the developability, transferability and cleaning property of the toner are remarkably improved. That is, the thixotropy value of the oil phase dispersion containing the modified layered inorganic mineral is preferably 1.3 to 5, and if it is less than 1.3, it becomes a true spherical toner and has poor cleaning properties. If it exceeds 5, the proportion of the irregular shaped toner increases, the fine powder increases, dust is confirmed in the developability and transferability, and the cleaning property is inferior.

  In the present invention, the thixotropy value (TI value) is obtained by measuring 6 rpm viscosity and 60 rpm viscosity at 25 ° C. of an oil phase dispersion having a solid content of 50% using a B-type viscometer, and expressed as 6 rpm viscosity / 60 rpm viscosity. Is done. That is, the polyester prepolymer (A) having an isocyanate group, a colorant, a release agent, or the modified layered inorganic mineral is dissolved or dispersed in an organic solvent to obtain an oil phase having a solid content of 50% by mass. The viscosity of the oil phase is adjusted so that the ratio A / B between the viscosity A of 6 rpm and the viscosity B of 60 rpm measured by a B-type viscometer is in the range of 1.3 to 5.

(Modified layered inorganic mineral)
As described above, the method for producing a toner of the present invention contains a layered inorganic mineral as a toner composition in order to obtain a preferable toner shape with good cleaning properties.
Layered inorganic minerals have a structure in which inorganic mineral layers with a thickness of several nanometers are stacked almost in parallel by weak forces such as van der Waals force and electrostatic force, and swell or cleave by coordinating or absorbing the solvent between the layers. It means an inorganic mineral that exhibits the properties of

  The layered inorganic mineral is preferably a modified layered inorganic mineral obtained by modifying at least part of ions between layers with organic ions. Here, “modify” means introducing organic ions into ions existing between the layers, and broadly means intercalation.

  As the layered inorganic mineral, for example, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, kanemite, etc. are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, if the layered inorganic mineral is used in a toner that is dispersed and granulated in an aqueous medium without modification, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. It becomes highly hydrophilic, easily deformed during granulation, dispersed and refined, and exhibits a sufficient charge adjustment function. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.1 wt% to 5.0 wt%.

The modified layered inorganic mineral is preferably one having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of the said layered inorganic mineral for a trivalent metal. However, since the hydrophilicity is high when the metal anion is introduced, a layered inorganic mineral in which at least a part of the metal anion is modified with an organic anion is preferable.
Examples of the organic ion modifier in the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like. Among these, quaternary alkyl ammonium salts are particularly preferable. Examples of the quaternary alkyl ammonium include trimethyl stearyl ammonium, dimethyl stearyl benzyl ammonium, dimethyl octadecyl ammonium, oleyl bis (2-hydroxyethyl) methyl ammonium, and the like.

  Examples of the organic ion modifier include branched, unbranched, or cyclic alkyl (1 to 44 carbon atoms), alkenyl (1 to 22 carbon atoms), alkoxy (8 to 32 carbon atoms), hydroxyalkyl (2 to 22 carbon atoms). , Sulfates having ethylene oxide, propylene oxide, and the like; sulfonates, carboxylates, and phosphates. Among these, carboxylic acids having an ethylene oxide skeleton are particularly preferable.

  The layered inorganic mineral partially modified with organic ions is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, or a mixture thereof. It is done. Among these, organically modified montmorillonite or bentonite is particularly preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

  Commercially available layered inorganic minerals partially modified with organic cations include, for example, Bentone 3, Bentone 38, Bentone 38V (both manufactured by Leox); Thixogel VP (manufactured by United catalyst); Kraton 34, Kraton 40, Quatium 18 bentonite such as Clayton XL (both manufactured by Southern Clay); Bentone 27 (manufactured by Leox); Thixogel LG (manufactured by United catalyst); Clayton AF, Clayton APA (both manufactured by Southern Clay) Stearalkonium bentonite; quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (both manufactured by Southern Clay Co.). Among these, Clayton AF and Clayton APA are particularly preferable.

  Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable.

_{R 1 (OR 2) n OSO} 3 M ··· formula (1)
In the general formula (1), R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element. Examples of the organic anion represented by the following general formula (1) include Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

By using the modified layered inorganic mineral, since it has an appropriate hydrophobicity, it tends to be present at the interface of the droplets, and the modified layered inorganic mineral is unevenly distributed on the toner surface and can exhibit charging properties. The volume average particle diameter (dispersion diameter) of the modified layered inorganic mineral is preferably 0.1 μm to 0.5 μm. When the volume average particle size exceeds 0.5 μm, the toner shape tends to be spherical, and the effect on cleaning properties and toner charging performance may be reduced.
The volume average particle diameter of the modified layered inorganic mineral can be measured using, for example, a laser Doppler particle size distribution measuring apparatus. The content of the modified layered inorganic mineral in the toner is preferably 0.1% by mass to 5.0% by mass, and more preferably 0.3% by mass to 3.0% by mass. When the content is less than 0.1% by mass, the toner shape tends to be spherical, and the effect on the cleaning property and the toner charging performance may be reduced. When the content exceeds 5.0% by mass, the fixing performance is improved. May get worse.

  In the present invention, the organic solvent is preferably volatile with a boiling point of less than 150 ° C. from the viewpoint of easy removal, in view of removal later. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.

  In the present invention, a urea-modified polyester (UMPE) can be obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion composed of a modified polyester such as urea-modified polyester or a prepolymer (A) in an aqueous medium, the dispersion is made of a modified polyester or prepolymer (A) such as a urea-modified polyester in an aqueous medium. Examples thereof include a method in which the composition of the toner raw material is added and dispersed by shearing force.

As described in the preparation of the oil phase, the prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), such as a colorant, a release agent, and a modified layered inorganic mineral, It can be dissolved or dispersed in a solvent, and the dissolved or dispersed material can be added and dispersed in an aqueous medium. However, the oil phase dispersion can satisfactorily disperse the modified layered inorganic mineral, release agent, and colorant. Therefore, it is preferable to produce by the following method.
That is, first, a master batch is prepared by stirring and mixing water, a modified layered inorganic mineral, a resin, for example, a low molecular polyester, and a master batch solution is prepared by further adding the low molecular polyester and a solvent to the master batch. . Separately, a dispersion in which a colorant and a release agent are dispersed in an organic solvent is prepared, and the master batch solution, the dispersion containing the pigment and the release agent are mixed and stirred, and a modified layered shape is formed. A dispersion liquid (M) containing an inorganic mineral, a pigment, a release agent, and a low molecular weight polyester is used, and the dispersion liquid (M) is reacted with the prepolymer (A) or the prepolymer (A) and the prepolymer (A). A compound having an active hydroxyl group such as diamine is added and mixed and stirred to prepare an oil phase dispersion.

  As the aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

  A method for dispersing in an aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. A high-speed shearing method is preferable in order to make the particle diameter of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2,000 parts by mass, preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner composition containing a polyester such as urea-modified polyester or prepolymer (A). If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size cannot be obtained. If it exceeds 2,000 parts by mass, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Various dispersants are used to emulsify and disperse the oily phase in which the toner composition is dispersed in a liquid containing water. In the present invention, a fine particle dispersant such as an inorganic fine particle dispersant or a polymer fine particle dispersant is used, but in addition to this, a surfactant or the like may be used in combination.

  Tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as inorganic fine particle dispersants that are hardly soluble in water.

  Further, the same effect as that of the inorganic dispersant was confirmed for the fine particle polymer. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm (PB-200H (manufactured by Kao), SGP (manufactured by Soken)), Technopolymer SB (manufactured by Sekisui Plastics Co., Ltd.) SGP-3G (manufactured by Soken), Micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.)) and the like.

  In addition, as a dispersant that can be used in combination with the above inorganic dispersant and fine particle polymer, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetacrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene Lenalkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl ester, etc. Celluloses such as polyoxyethylene, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like can be used.

  As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acid and metal salt thereof, perfluoroalkyl (C7 to C13) carboxylic acid and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl ) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Etc.

  As a trade name, Surflon S-111, S-112, S-113 (above, Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (above, made by Sumitomo 3M), Unidyne DS-101, DS-102 (above, Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (above, Dainippon Ink Co., Ltd.) ), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footent F-100, F150 (above, manufactured by Neos) ) And the like.

  Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzaza. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , MegaFuck F-150, F-824 (manufactured by Dainippon Ink & Co., Ltd.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

  Furthermore, in order to lower the viscosity of the dispersion medium containing the toner composition, a solvent in which a polyester such as urea-modified polyester or prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. The usage-amount of the solvent with respect to 100 mass parts of prepolymers (A) is 0-300 mass parts normally, Preferably it is 0-100 mass parts, More preferably, it is 25-70 mass parts.

  The extension and / or cross-linking reaction time is selected, for example, depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), and is usually 10 minutes to 40 hours, preferably 2 to 24 hours. It's time. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In the present invention, shape control is performed in the step of solvent removal from the dispersion (reaction liquid) after the elongation and / or crosslinking reaction.

  In order to remove the organic solvent from the resulting emulsified dispersion (reactant), as a batch processing method, the entire system is gradually heated in a laminar stirring state, and strong stirring (pruning force) in a certain temperature range. There is a method of obtaining irregularly shaped toner particles by removing the solvent while applying a continuous shear force and a continuous shearing force using a centrifugal force such as a stirring thin film type and a centrifugal thin film type and solvent removal as a continuous type. For example, there is a method capable of obtaining irregularly shaped toner particles using an apparatus capable of performing such processing. In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable from the viewpoint of chargeability of the toner that the dispersant is washed and removed after the extension and / or crosslinking reaction.

  Depending on the solvent removal conditions, the surface shape (unevenness) of the toner can be appropriately adjusted. In order to adjust the indentation to an appropriate diameter, it is necessary to set solvent removal conditions in addition to the dispersant. As the conditions, the oil phase solid content of the liquid emulsified and dispersed in the aqueous medium is 5 to 5. The solvent removal temperature is preferably 10 to 50 ° C., and the solvent removal time is preferably within 30 minutes as the residence time when the toner is removed. Since the solvent contained in the oil phase evaporates in a short time, it is considered that the oil phase is relatively hard at a low temperature and an unbalanced volume shrinkage occurs in the elastic oil phase. When the oil phase solid content is more than 50% by mass, the evaporation solvent is small and the conditions for volume shrinkage are reduced, and when it is less than 5% by mass, the productivity is remarkably reduced. As the time increases, the volume shrinkage is less likely to occur, so the shape becomes spherical. However, the above conditions are not absolute conditions, and it is necessary to balance temperature and solvent removal time.

  As a batch processing method, a step of stirring the dispersion liquid in a stirring tank having no baffle plate or wall surface inside is provided, and after stirring the liquid with a strong stirring force (shearing force), There is a method of removing the solvent at 50 ° C. The toner shape can be controlled by liquid agitation before the solvent removal. The emulsified liquid that has been emulsified and dispersed in an aqueous medium and further subjected to extension and / or cross-linking reaction is stirred with a strong stirring force of 30 to 50 ° C. in a stirring tank having no baffle plates or protrusions before desolvation to form a toner. After confirming the above, the solvent is removed at a solvent removal temperature of 10 to 50 ° C. At this time, in order to arbitrarily change and control the evaporation rate, it is preferable to lower the processing environment to less than 101.3 kPa (atmospheric pressure) and supply an inert gas. Since this condition is not an absolute condition, it is necessary to select the condition as appropriate. However, after stretching and / or cross-linking reaction after emulsification and dispersion, an indefinite shape is created by applying shear with a strong stirring force in a stirring tank. . This is presumed that ethyl acetate or the like contained in the granulation changed from spherical to indeterminate due to a stronger stirring force by lowering the viscosity of the emulsion.

  As a more preferable method, there is a continuous method using a continuous vacuum deaerator (trade name: Bubble Buster, manufactured and sold by Ashizawa Co., Ltd.). Since this machine is capable of decompressing a centrifugal thin film while continuously supplying slurry into a rotating ball, the effect of the present invention is further enhanced in that a uniform shearing force can be applied to all particles. Is possible. The conditions in this case are that the processing environment is made lower than 101.3 kPa (atmospheric pressure) to arbitrarily change and control the evaporation rate, an inert gas is supplied, and the emulsified dispersion is made into a thin film state using a rotating body. To do. The treatment environment is preferably 1 to 40 kPa, and the inert gas includes argon, helium, nitrogen, neon, etc., but it is generally desirable to use nitrogen for profitability and handling from the handling amount.

  Moreover, about the supply amount of an inert gas, it is 0.1 to 70% by volume% with respect to an emulsion dispersion liquid, Preferably it is 1 to 50%. The peripheral speed of the rotator for turning the emulsified dispersion into a thin film is 10 to 60 m / sec, preferably 20 to 50 m / sec.

The processing method when this apparatus is used will be described in more detail with reference to FIG.
FIG. 1 shows a conceptual diagram of a continuous vacuum deaerator. The fixed decompression vessel 201 is decompressed and adjusted to a predetermined pressure by a vacuum pump 203, and the rotating ball 202 rotates so that the outer peripheral end portion has a predetermined peripheral speed. The dispersion before shape control is supplied by itself from the supply port 204 into the rotating ball 202 due to a pressure difference. At this time, it is assumed that nitrogen gas is supplied from the nitrogen gas supply port 206 into the dispersion, and bubbles of nitrogen gas are mixed in the dispersion.

  Thereafter, the dispersion containing nitrogen gas becomes a thin film along the inner wall 210 of the rotating ball due to centrifugal force and moves to the outer peripheral portion. At this time, the dispersion is subjected to a strong shearing force and at the same time immediately becomes a thin film under reduced pressure. The solvent will evaporate. Furthermore, since nitrogen gas is mixed in the dispersion in advance, the solvent can be removed more efficiently. The processing liquid moved to the outer periphery of the rotating ball 202 has a fixed shape because the solvent removal is completed. Further, the processing liquid is discharged from the discharge port 205 by centrifugal force.

  An example of use of the present invention using a continuous vacuum deaerator is shown in FIG. There are a method used as a one-pass continuous process as shown in (a) and a method using a batch continuous method as shown in (b). By giving the heat amount necessary for evaporation to the treatment liquid in advance, it is possible to efficiently remove the solvent, and it is preferable to adjust the temperature of the treatment liquid.

(Volume average particle diameter of toner)
The toner of the present invention produced as described above preferably has a volume average particle diameter of 3 to 8 μm.
The smaller the volume average particle diameter Dv of the toner, the better the fine line reproducibility can be improved. However, since the cleaning property decreases as the particle size decreases, it is preferably at least 3 μm. In particular, when the toner of 2 μm or less is present in an amount of 20% by mass or more, the toner having a small particle diameter that is difficult to be developed on the surface of the magnetic carrier or the developing roller increases. Becomes insufficient, the amount of reversely chargeable toner increases, background stains occur, and the image quality deteriorates.

  The particle size distribution represented by the ratio (Dv / Dn) of the volume average particle size Dv to the number average particle size Dn is preferably in the range of 1.00 to 1.20. By sharpening the particle size distribution, the toner charge amount distribution becomes uniform and background fogging can be reduced. When Dv / Dn exceeds 1.20, the charge amount distribution of the toner becomes wide, and it becomes difficult to obtain a high-quality image. The particle size of the toner up to this point is 50, using a Coulter counter multisizer (manufactured by Coulter Co., Ltd.) and selecting an aperture having a measurement hole size of 50 μm corresponding to the particle size of the toner to be measured. This was done by measuring the average particle size of 000 particles.

(Average circularity)
The toner of the present invention preferably has an average circularity of 0.94 to 0.97. If the average circularity is less than 0.94, the image uniformity during development is deteriorated, or the toner transfer efficiency from the electrophotographic photosensitive member to the intermediate transfer member or from the intermediate transfer member to the transfer material is lowered, and uniform transfer cannot be obtained. If it exceeds 0.97, the untransferred toner tends to rub through the cleaning blade, and as a result, there is a risk of promoting the occurrence of defective cleaning.

(Measurement of average circularity)
In the present invention, a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) is used to measure ultrafine toner, and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10) is used. And analyzed.
Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 ml beaker, and each toner 0.1 to 0.5 g was added and stirred with a micropartel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl.
In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. The amount of toner added varies depending on the particle size, and it is small for small particle sizes and needs to be increased for large particle sizes. When the toner particle size is 3 to 8 μm, the toner amount is 0.1 to 0.3. By adding 5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

(External additive)
In the toner of the present invention, inorganic fine particles can be preferably used as an external additive for assisting fluidity, developability and chargeability. In particular, hydrophobic silica and / or hydrophobic titanium oxide are preferable. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass.

  Specific examples of other inorganic fine particles include, for example, alumina, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  The toner of the present invention can be used as a two-component developer. In this case, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is preferably 1 to 10 parts by mass of the toner with respect to 100 parts by mass of the carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene resins , Copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl fluoride Fluoro such as terpolymers of isopropylidene and a non-fluorinated monomer, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner or non-magnetic toner that does not use a carrier.

(Image forming method)
Next, an image forming method using the toner of the present invention will be described.
The image forming method of the present invention has at least an electrostatic charge image forming step, a developing step, a transfer step and a fixing step, and a cleaning step, and other steps appropriately selected as necessary, for example, a static elimination step, a recycling step, You may have a control process etc. further.

  The electrostatic charge image forming step is a step of forming an electrostatic charge image on the photoreceptor. The electrostatic charge image can be formed, for example, by charging the surface of the photosensitive member uniformly by applying a voltage using a charging device and then performing imagewise exposure using an exposure device. it can.

  The material, shape, structure, size and the like of the photoreceptor are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Amorphous silicon photoreceptors are preferable in terms of long life. .

The charging device is not particularly limited and can be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, Examples thereof include a non-contact charger using corona discharge such as corotron and scorotron. The charging device is preferably arranged in contact or non-contact with the photoreceptor, and charges the surface of the photoreceptor by applying a DC voltage and an AC voltage in a superimposed manner.
The charging device is a charging roller that is disposed in close proximity to the photoconductor via a gap tape, and charges the surface of the photoconductor by applying a DC voltage and an AC voltage superimposed on the charging roller. Those that do are preferred.

  The exposure apparatus is not particularly limited as long as it can image-wise expose the surface of the photoreceptor charged by the charging apparatus, and can be appropriately selected according to the purpose. Examples thereof include a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of a photoreceptor.

  The developing step is a step of forming a visible image by developing the electrostatic image with the toner of the present invention using a developing device.

  The developing device is not particularly limited as long as it can be developed using the toner of the present invention, and can be appropriately selected from known ones. For example, the developing device contains a developer composed of the toner of the present invention, Examples include those having at least a developer-carrying body capable of bringing a developer into contact or non-contact with an electrostatic charge image, and preferably including a developer-containing container in a detachable manner. The developing device may be either a single-color developing device or a multi-color developing device, and examples thereof include a stirrer that charges a developer by frictional stirring and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by an electric attractive force. As a result, the electrostatic charge image is developed with toner, and a visible image is formed on the surface of the photoreceptor. Note that an alternating electric field is preferably applied when the toner is moved to the surface of the photoreceptor.

  The transfer process is a process in which a visible image is transferred to a transfer target using a transfer device. After the primary transfer of the visible image onto the intermediate transfer member using the intermediate transfer member, the visible image is transferred to the transfer target. A mode in which secondary transfer is performed on a transfer body is preferred. In addition, a primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer member using two or more colors, preferably full color toner, as the toner, and the composite transfer image on the transfer target An embodiment having a secondary transfer step of transferring is preferable. The visible image can be transferred by charging the photoconductor using, for example, a transfer charger.

  The transfer device preferably has a primary transfer device that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer device that transfers the composite transfer image onto a transfer target. The transfer device (primary transfer device, secondary transfer device) preferably has at least a transfer device that peels and charges the visible image formed on the photosensitive member toward the transfer target. There may be one transfer device or two or more transfer devices. 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 intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. Examples thereof include a transfer belt.

  The transfer target 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 transfer target using a fixing device, and may be fixed for each color toner each time it is transferred to the transfer target. The toners may be fixed simultaneously at the same time in a state where the toners are laminated.

  The fixing device is not particularly limited and may be appropriately selected according to the purpose. However, a fixing device that is heat-pressed and fixed using a known fixing member is preferable. The fixing member is preferably in the form of a roller or a belt, and examples thereof include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt. At this time, it is preferable that heating temperature is 80-200 degreeC normally.

  In the present invention, the fixing device includes a heating body having a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. It is possible to use means for heating and press-fixing the material to be transferred on which the received image is formed.

  Depending on the purpose, for example, a known optical fixing device may be used together with the fixing device or instead of the fixing device.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the photoconductor using a neutralization device.

  The neutralization device is not particularly limited, and may be any one as long as it can apply a neutralization bias to the photosensitive member, and can be appropriately selected from known neutralization devices. Examples thereof include a neutralization lamp.

  The cleaning step is a step of removing toner remaining on the photoreceptor using a cleaning device.

  The cleaning device is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller A cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. are mentioned.

  The recycling process is a process in which the toner removed in the cleaning process is recycled to the developing device using a recycling apparatus.

  There is no restriction | limiting in particular in a recycling apparatus, For example, a well-known conveyance means etc. are mentioned.

  A control process is a process of controlling each process using a control device.

  The control device is not particularly limited as long as the movement of each step can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

(Image forming device)
Next, the image forming apparatus of the present invention will be described with reference to FIG. 3 includes a photosensitive member 10, a charging device 20, an exposure device 30, a developing device 40, an intermediate transfer member 50, a cleaning device 60 having a cleaning blade, a charge eliminating device 70, a transfer device. A device 80 is provided. Note that a charging roller is used as the charging device 20, a static elimination lamp as the static elimination device 70, and a transfer roller as the transfer device 80.

The intermediate transfer member 50 is an endless belt, and is designed to be stretched by three support rollers 51 arranged on the inner side thereof so as to be movable in the arrow direction. A part of the three support rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof. Further, a transfer device 80 capable of applying a secondary transfer bias for transferring a visible image (secondary transfer) to the transfer target 95 is disposed opposite to the transfer device 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer body 50 and the transfer body 95.
Note that transfer paper is used as the transfer target 95.

  The developing device 40 includes a developing belt 41 as a developer carrier, 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. ing. The developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K, and the developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The developing unit 45M includes a developer accommodating portion 42M, a developer supply roller 43M, and a developing roller 44M. The developing unit 45C includes a developer accommodating portion 42C, the developer supplying roller 43C, and the developing roller 44C. Yes. 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 this image forming apparatus, after the charging device 20 uniformly charges the photoconductor 10, the exposure device 30 exposes the photoconductor 10 imagewise to form an electrostatic image. Next, the developing device 40 supplies the developer to develop the electrostatic charge image formed on the photoconductor 10 to form a visible image.
The visible image is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the support roller 51 and further transferred (secondary transfer) onto the transfer body 95. As a result, a transfer image is formed on the transfer target 95. The toner remaining on the photoconductor 10 is removed by the cleaning device 60, and the charge of the photoconductor 10 is removed by the charge eliminating lamp 70.

Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 4 has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan around the photosensitive member 10, instead of the developing device 40 in the image forming apparatus shown in FIG. The developing unit 45C has the same configuration as that of the image forming apparatus shown in FIG.
In FIG. 4, the same components as those of the image forming apparatus shown in FIG. The same applies to FIGS. 5 and 6 described later.

  Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 5 is a tandem type color image forming apparatus. The image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying 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 rotate clockwise in FIG. 4. A cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. On the intermediate transfer member 50 stretched by the support roller 14 and the support roller 15, four image forming units 18 of yellow, cyan, magenta, and black are arranged opposite to each other along the conveying direction. A means 120 is arranged. An exposure device 21 is disposed in the vicinity of the image forming unit 120. The secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the image forming unit 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 support rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are mutually connected. It is possible to touch. 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. A reversing device 28 for reversing the recording paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25 in order to form images on both sides of the recording paper.

  Next, formation of a full color image (color copy) using the image forming unit 120 will be described. First, an original 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 original document is set on the contact glass 32 of the scanner 300. Close.

  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. When this happens, the scanner 300 is immediately 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 a mirror in the second traveling body 34. Further, the image is received by the reading sensor 36 through the imaging lens 35, and the original is read to obtain image information of black, yellow, magenta and cyan. Next, each image information is transmitted to each image forming unit 18 in the image forming means 120, and a visible image of each color of black, yellow, magenta and cyan is formed.

  As shown in FIG. 6, the image forming unit 18 includes a photoconductor 10, a charging device (not indicated) for uniformly charging the photoconductor 10, and an exposure device 21, based on each image information. A developing device that develops an electrostatic charge image formed by exposing the photoconductor 10 to each other using each toner (black toner, yellow toner, magenta toner, and cyan toner) to form a visible image using each toner. (No code), a transfer charger (no code) for transferring a visible image onto the intermediate transfer member 50, a cleaning device (no code), and a charge eliminating device (no code) are provided, based on each image information Thus, a visible image of each color can be formed. Next, the visible images of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is rotated and moved by the support rollers 14, 15 and 16, and the visible images of the respective colors are superimposed to form a composite transfer image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper 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 to stop. Alternatively, the paper feed roller 142 is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual paper 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 recording paper. Then, the registration roller 49 is rotated in synchronization with the composite transfer image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the secondary transfer device. By transferring the composite transfer image onto the recording paper (secondary transfer) by 22, a color image is formed on the recording paper. The toner remaining on the intermediate transfer member 50 is removed by the cleaning device 17.

  The recording paper on which the color image is formed is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the composite transfer image is heated and pressed and fixed on the recording paper. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the paper discharge tray 57. Alternatively, it is switched by the switching claw 55 and reversed by the reversing device 28 and led to the transfer position again. After an image is formed also on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

(Process cartridge)
The process cartridge of the present invention includes an electrostatic charge image carrier on which an electrostatic charge image is formed, and a developing device that develops the electrostatic image formed on the electrostatic charge image carrier using the toner of the present invention. It is integrally supported and is detachable from the image forming apparatus main body. It should be noted that the process cartridge of the present invention may further support other means appropriately selected as needed.

  FIG. 7 shows an example of the process cartridge of the present invention. The process cartridge includes a photosensitive member 101 and includes a charging device 102, an exposure device 103, a developing device 104, a transfer device 106, and a cleaning device 107. These members can be the same as those used in the image forming apparatus described later.

  Examples of the present invention are shown below. Below, a part shows a mass part.

(Measuring method)
-Isocyanate group content The isocyanate group content was measured using the method defined in JIS K1603.

-Acid value According to the method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
The acid value is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator
(Metler Toledo)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No
(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and obtain the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

-Hydroxyl value 0.5 g of a sample is precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent is correctly added thereto. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Furthermore, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JISK0070-1966).

-Molecular weight The molecular weight of resin is measured by GPC (gel permeation chromatography) as follows. Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
In addition, when measuring the molecular weight of the prepolymer having an isocyanate group, a sample in which the isocyanate group was sealed was prepared by adding 3-fold equivalent of dibutylamine to the isocyanate group, and used for GPC measurement. .

・ Glass transition temperature Tg
The glass transition point is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.
A method for measuring Tg will be outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and left for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

[Example 1]
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, cooled to room temperature, left for 10 minutes, and again heated to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at ° C / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

(Production of resin fine particle dispersion)
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [resin fine particle dispersion] was obtained.
The volume average particle size of the [resin fine particle dispersion] measured with LA-920 (Horiba, Ltd., laser diffraction particle size distribution analyzer) was 105 nm. A part of [resin fine particle dispersion] was dried to isolate the resin content. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

(Manufacture of low molecular weight polyester)
229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propion oxide 3-mole adduct, 208 parts of terephthalic acid, 46 parts of isophthalic acid, and dibutyl 2 parts of tin oxide was added and reacted at 230 ° C. for 5 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Molecular polyester] was synthesized. The obtained [low molecular weight polyester] had a weight-average molecular weight (Mw) of THF-soluble content of 5,200, a glass transition temperature (Tg) of 45 ° C., and an acid value of 20 mgKOH / g.

(Prepolymer production)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added, and atmospheric pressure nitrogen was added. Under an air stream, the condensation reaction was performed at 210 ° C. for 8 hours. Next, the reaction was continued for 5 hours while dehydrating under a reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., and reacted with 1402 parts of ethyl acetate and 170 parts of isophorone diisocyanate for 2 hours to obtain [Prepolymer]. The weight average molecular weight of the obtained [prepolymer] was 5,000.

(Manufacture of master batch)
1200 parts of water, 349 parts of CRAYTONE APA (modified layered inorganic mineral) manufactured by SCP, and 1400 parts of the above [low molecular weight polyester] were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded with a two-roller at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch].

(Adjustment of toner material oil dispersion)
133.6 parts of [low molecular polyester], 10 parts of [masterbatch] and 80 parts of ethyl acetate were placed in a beaker and dissolved by stirring to obtain [masterbatch solution]. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 98.6 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. To the dispersion, 2.9 parts of isophoronediamine and 23.4 parts of [prepolymer] were added and stirred for 5 minutes at 12000 rpm using a TK homomixer. [Oil phase dispersion] Got. The TI value of the [oil phase dispersion] at this time was 1.6.

(Manufacture of toner)
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion] and 0.5 part of sodium dodecylbenzenesulfonate were added, and the above-mentioned aqueous dispersion was added to this aqueous dispersion while stirring at 12000 rpm with a TK homomixer. [Oil Phase Dispersion] 405.1 parts were added and reacted while stirring for 30 minutes to obtain [Emulsion Dispersion].

  The shape control and the solvent removal step were performed by the following method. The emulsified dispersion obtained in the previous step was continuously supplied to a continuous vacuum defoaming machine BB600 (trade name: Bubble Buster, manufactured and sold by Ashizawa Corporation). At this time, the peripheral speed of the outer peripheral end of the bucket of the rotating ball for forming the thin film is 8 m / sec, the pressure in the bucket is 30 kPa, and the supply amount of nitrogen gas is 10 vol% with respect to the dispersion. It was. Thereafter, the resultant was filtered, washed, and dried to obtain toner base particles of Example 1.

[Example 2]
[Oil phase dispersion] was produced in the same manner as in Example 1, except that 10 parts of [Masterbatch] were changed to 14 parts and 80 parts of ethyl acetate were changed to 84 parts. The TI value of the [oil phase dispersion] at this time was 3.8. Thereafter, toner base particles of Example 2 were obtained by the same treatment method as in Example 1.

Example 3
In Example 2, the same method as in Example 2 except that the peripheral speed 8 m / sec at the bucket outer peripheral edge was changed to 65 m / sec, and the nitrogen gas supply amount was changed from 10% by volume to 2% by volume with respect to the dispersion. Thus, toner base particles of Example 3 were obtained.

Example 4
In Example 1, toner base particles of Example 4 were obtained in the same manner as in Example 1 except that the peripheral speed at the outer peripheral edge of the bucket was changed to 40 m / sec.

[Comparative Example 1]
[Oil Phase Dispersion] was produced in the same manner as in Example 1, except that 10 parts of [Masterbatch] were changed to 0 part and 80 parts of ethyl acetate were changed to 70 parts, respectively. The TI value of the [oil phase dispersion] at this time was 1.2. Thereafter, toner base particles of Comparative Example 1 were obtained by the same treatment method as in Example 1.

[Comparative Example 2]
In Example 1, [Oil Phase Dispersion] was produced in the same manner except that [Masterbatch] was changed to 10 parts and 16 parts of ethyl acetate to 86 parts, respectively. The TI value of the [oil phase dispersion] at this time was 5.1. Thereafter, toner base particles of Comparative Example 2 were obtained by the same treatment method as in Example 1.

(Evaluation)
5 parts of these toners are mixed with 95 parts of a 100-250 mesh ferrite carrier coated with a silicone resin by a ball mill to form a two-component developer, and developed with an image forming apparatus (Imagio Neo 452, manufactured by Ricoh). Property, transfer property and cleaning property were evaluated.
Table 1 shows the presence or absence of the modified layered inorganic mineral in the oil phase dispersion and the TI value of the oil phase dispersion in the above Examples and Comparative Examples, and Table 2 shows the evaluation results of the toner.

(Measurement of toner particle diameter, number% of particle diameter of 2 μm or less and circularity)
The particle size (Dv (μm) of the obtained toner was measured using a Coulter Counter Multisizer (manufactured by Coulter Inc.). The number% and the circularity of the toner particle size of 2 μm or less were measured by a flow type particle image analyzer FPIA. -2000 (manufactured by Sysmex Corporation).

(Evaluation methods for developability, transferability, and cleaning properties)
For each item, an image was formed using an image chart, and the following evaluation was performed.
Among the developability, fine line reproducibility is the reproducibility of fine lines with 5 pairs of black and white lines in 1 mm on the image chart, and the reproducibility on the photoconductor after development is enlarged with a lens. Judged. Of the developability, Chile visually determined the presence or absence of toner on the fine white line.

  Of the transferability, the transfer rate was evaluated by measuring the amount of toner on the recording member (45 kg paper) and the amount of toner on the photoreceptor by forming a solid black image under the same conditions with the developer and the image forming apparatus. After confirming the developing dust, the transfer dust was transferred to the recording member under the same conditions, and the presence or absence of toner on the thin white line of the unfixed image before fixing was visually determined.

  The cleaning property was judged by whether or not the toner remained on the photoconductor when a halftone solid image was formed on the photoconductor and blade cleaning was performed without transferring the toner on the photoconductor to the recording member.

  In Table 2, the symbol “◯” indicates that there is no problem in practical use, “Δ” indicates that there is no problem in practical use although it is somewhat inferior, and “×” indicates that there is a problem in practical use.

  From these results, the toners of Examples 1 to 4 have no practical problems in developability (thin line reproducibility and dust), transferability (transfer rate and dust), and cleaning properties (presence of residual toner). I confirmed that there was. On the other hand, the toner of Comparative Example 1 has a spherical shape and has no practical problem in developability and transferability, but has poor cleaning properties. In addition, the toner of Comparative Example 2 has a lot of fine powder, dust was confirmed in developability and transferability, and cleaning properties were inferior.

FIG. 3 is a conceptual diagram of a continuous vacuum deaerator used in a toner base shape control step. It is a flowchart of the usage example of a continuous type vacuum deaerator. (A) is a one-pass continuous processing example, and (b) is a batch continuous processing example. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus in which a toner of the present invention is used. It is a schematic block diagram which shows the other example of the image forming apparatus in which the toner of this invention is used. 1 is a schematic configuration diagram illustrating an example of a tandem type image forming apparatus in which a toner of the present invention is used. FIG. 6 is a partially enlarged view of the tandem type image forming apparatus of FIG. 5. FIG. 3 is a schematic configuration diagram illustrating an example of a process cartridge in which the toner of the present invention is used.

Explanation of symbols

(About FIGS. 1-2)
201 Fixed decompression vessel 202 Rotating ball 203 Vacuum pump 204 Dispersion supply port 205 Discharge port 206 Nitrogen gas supply port 210 Thin film dispersion region 220 Nitrogen gas bubbles in the dispersion 300 Continuous vacuum deaerator 400 Tank (FIGS. 3 to 7) about)
10 Photoconductor (Photoconductor 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 roller 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 Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating 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 device 101 photoconductor 102 charging means (charging device) )
103 Exposure (exposure equipment)
104 Developing means (developing device)
105 Recording medium 106 Transfer means (transfer device)
DESCRIPTION OF SYMBOLS 107 Cleaning means 120 Tandem type developing device 130 Document base 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document transport Equipment (ADF)

Claims (7)

  An aqueous medium in which a toner composition containing at least a resin, a colorant and a release agent is dissolved or dispersed in an organic solvent, the dissolved or dispersed material is used as an oil phase dispersion, and the oil phase dispersion is present in a fine particle dispersant. The resulting emulsion dispersion is supplied to a continuous vacuum defoamer and thinned by a centrifugal force to remove the organic solvent while applying a shearing force to the emulsion dispersion to form a toner base. The oil phase dispersion contains a layered inorganic mineral in which at least some of the ions between layers are modified with organic ions, and the thixotropy value (TI value) of the oil phase dispersion Is adjusted to 1.3 to 5, a method for producing a toner for developing an electrostatic charge image.   The oil phase dispersion is a polyester prepolymer in which the resin has an isocyanate group, and the modified layered inorganic mineral, the colorant, and the release agent are dissolved or dispersed in an organic solvent. 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner is prepared by adding a resin and mixing and stirring.   The oil phase dispersion is obtained by mixing and stirring a masterbatch containing the modified layered inorganic mineral and a colorant / release agent dispersion obtained by dispersing the colorant and the release agent in an organic solvent. The dispersion liquid (M) containing a colorant / release agent is prepared, and then the resin is added to the dispersion liquid (M) and mixed and stirred to prepare the dispersion liquid (M). A method for producing a toner for developing an electrostatic image.   An electrostatic image developing toner obtained by the method for producing an electrostatic image developing toner according to any one of claims 1 to 3, wherein the volume average particle diameter is in the range of 3 to 8 µm, and the average circularity is An electrostatic charge image developing toner having a viscosity of 0.94 to 0.97.   An electrostatic charge image forming step of forming at least an electrostatic charge image on the photosensitive member; a developing step of developing the electrostatic charge image formed on the photosensitive member with toner to form a visible image; A transfer step for transferring the formed visible image onto the recording member; a fixing step for fixing the visible image transferred onto the recording member; and a cleaning blade for cleaning the toner remaining on the surface of the photoreceptor. An image forming method including a cleaning step, wherein the toner according to claim 4 is used as the toner.   A photosensitive member that forms at least an electrostatic charge image; a developing unit that develops the electrostatic charge image formed on the surface of the photosensitive member with toner to form a visible image; and a visible image formed on the photosensitive member. Image forming apparatus comprising: transfer means for transferring to a recording member; fixing means for fixing a visible image transferred onto the recording member; and a cleaning means having a cleaning blade for cleaning residual toner on the surface of the photoreceptor. An image forming apparatus using the electrostatic image developing toner according to claim 4 as the toner.   A process cartridge that integrally supports at least one unit selected from a photosensitive member, a developing unit, a charging unit, and a cleaning unit, and is detachable from the main body of the image forming apparatus, wherein the developing unit holds toner, The process cartridge according to claim 4, wherein the toner is an electrostatic image developing toner according to claim 4.

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