JP2005077776A - Method for producing electrostatic charge image developing toner, and the toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having a uniform particle diameter and narrow distribution of the particle size, the toner which efficiently suppresses the quantity of a decomposed product of a reaction initiator or a residual solvent, which has no odor, and which has superior reproducibility of thin lines and cleaning performance, and to provide a method for producing the toner and an image forming apparatus which uses the obtained toner. <P>SOLUTION: The method for producing an electrostatic charge image developing toner includes at least processes of dissolving or dispersing a toner composition, comprising at least resin and a colorant in an organic solvent; emulsifying and dispersing the dissolved product or dispersed product in an aqueous medium, in the presence of a particulate dispersant; and removing the organic solvents from the emulsified dispersion liquid in a sealed tank. In the process of removing the organic solvent, the surface area of the emulsified dispersion liquid, in contact with the gas phase, is larger than the horizontal cross-sectional area of the tank. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, a manufacturing method thereof, and an image forming apparatus. More specifically, the present invention relates to an electrophotographic toner used in a copying machine, a laser printer, a normal test fax, and the like using a direct or indirect electrophotographic developing system, a manufacturing method thereof, and an image forming apparatus.

Toner for electrostatic image development that has been widely used in electrophotography has been obtained by melting and uniformly dispersing a colorant, a charge control agent, an anti-offset agent, etc. in a thermoplastic resin. It has been manufactured by crushing and classifying products.
According to such a pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material.
For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle.
Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented.
In the suspension polymerization method, generally, a monomer composition in which a polymerizable monomer, a colorant, a charge control agent, an offset preventing agent, a polymerization initiator and the like are uniformly dissolved or dispersed contains a dispersion stabilizer. Put into water or an aqueous dispersion medium mainly composed of water, disperse using a mixing device having high shearing force, granulate the monomer composition as fine droplets, then polymerize and color polymer Particles (that is, polymerized toner) are formed.
In the suspension polymerization method, since a colorant and the like are dispersed in a low-viscosity liquid monomer, sufficient uniform dispersibility is ensured as compared with a pulverization method in which these compounding agents are added to a resin. Further, in the suspension polymerization method, a polymer toner having a very sharp particle size distribution can be obtained in a high yield. This polymerized toner is spherical and has a uniform surface and exhibits good development characteristics.
Development of a spherical toner having a small particle diameter is actively carried out by a polymerization method or an emulsion dispersion method.
In the polymerization method, there is no problem in reducing the particle size or spheroidizing, but the main component of the binder resin is limited to vinyl polymer capable of radical polymerization, and polyester resin or epoxy suitable for color toner and low-temperature fixing. Resin toner particles cannot be produced by suspension polymerization.
Further, the polymerization method has a problem that it is difficult to reduce volatile organic compounds composed of unreacted monomers, and improvement is desired.
On the other hand, as a method for producing a toner by an emulsification dispersion method, a method has been proposed in which a mixture of a binder resin and a colorant is mixed with an aqueous medium and emulsified to obtain toner particles (see, for example, Patent Documents 1 and 2).
This method, like the polymerization method, can easily cope with the reduction in the particle size and spheroidization of the toner, and compared with the polymerization method, a wider range of binder resin types can be selected, and volatile organic compounds can be selected. It has the advantage that it can easily reduce the concentration of colorants and the like, and it is easy to arbitrarily change the concentration of the colorant from a low concentration to a high concentration. It is what you have.

Polymerized toner contains residual monomers and low volatile matter, and as a result, there are problems such as strong odor and filming on the photoconductor. As a solution, the amount of residual monomer is reduced. A method for suppressing odor has been proposed.
For example, dehydrated carbon black is added to a polymerizable monomer, and this is heated and polymerized to prepare a prepolymer having a conversion rate of 40% or less, and then the prepolymer is suspended in an aqueous solution containing a radical polymerization initiator. In addition, there is a method of suspension polymerization until the residual polymerizable monomer is 0.5% or less (for example, see Patent Document 3).
However, this method requires a process for preparing a prepolymer, and the process is complicated.

Further, after polymerization, heating is performed at a temperature equal to or higher than the glass transition point of the obtained resin, and 5 to 50% by weight of water is distilled off with respect to the amount of water at the end of the polymerization, whereby the residual monomer in the resin is 200 ppm or less. A method has been proposed (see, for example, Patent Document 4).
However, this method has a drawback that the polymer particles tend to aggregate during dehydration.

  On the other hand, the spheroidized toner has good development / transfer characteristics, but has a drawback of poor cleaning properties. In development and transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not pose a problem, but photographic images with high image area ratio such as photographic images, and untransferred image formation due to poor paper feed, etc. The generated toner may be generated as untransferred toner on the photoconductor, and if accumulated, image smearing occurs. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited.

Furthermore, a construction method involving volume shrinkage called a polymer dissolution suspension method has been studied (see, for example, Patent Document 5).
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 a dispersant, and then the volatile solvent is removed. At that time, when the volumetric contraction of the droplets occurs and 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 in order to increase productivity. Is increased, the viscosity of the dispersed phase increases, and the resulting particles have a large particle size and a broad distribution.
On the other hand, 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.
As a solution to this problem, a method has been proposed in which the resin used in the polymer dissolution suspension method has a low molecular weight to reduce the viscosity of the dispersed phase, facilitate emulsification, and improve the fixability by carrying out a polymerization reaction in the particles. (For example, see Patent Document 6).
However, the particles obtained by this method have a wide particle size distribution, and the shape is not smooth, and the shape is not controlled.

JP-A-5-66600 JP-A-8-21655 JP-A-60-243664 JP-A 64-70765 JP-A-7-152202 JP-A-11-149179

  The present invention has been made in view of the above problems, and its purpose is to efficiently suppress the amount of decomposition product of the reaction initiator, residual solvent, etc., no odor, and excellent fine line reproducibility, It is another object of the present invention to provide a toner having a cleaning performance, a uniform particle size and a narrow particle size distribution, a method for producing the same, and an image forming apparatus using the obtained toner.

The above-described problem is solved by (1) “a step of dissolving / dispersing a toner composition comprising at least a resin and a colorant in an organic solvent, and the dissolved or dispersed material in an aqueous medium containing a fine particle dispersant. The emulsified dispersion step has at least a step of removing the organic solvent in the closed tank of the obtained emulsified dispersion, and the vapor phase contact surface area of the emulsified dispersion during the organic solvent removal step is greater than the horizontal cross-sectional area of the tank. And (2) “the ratio A1 / A2 of the gas phase contact surface area (A1) of the emulsified dispersion to the horizontal cross-sectional area (A2) of the tank is 1”. 2. The method for producing a toner for developing an electrostatic charge image according to the above item (1), characterized in that it is 2 or more, and (3) “The environment under which the organic solvent is removed is 101.3 kPa (atmospheric pressure)” Supply low and inert gas The method for producing a toner for developing an electrostatic charge image according to the above item (1) or (2) ”, (4)“ The glass in which the organic solvent is removed under the environment where the organic solvent is removed. The method for producing a toner for developing an electrostatic charge image according to any one of items (1) to (3), wherein the temperature is lower than a transition temperature. The production of a toner for developing an electrostatic charge image according to any one of (1) to (4) above, wherein the gas phase contact surface area of the emulsified dispersion is increased by bubbling an inert gas. Method ”, (6)“ Method for producing electrostatic image developing toner according to item (5) above, wherein inert gas supplied from below tank is nitrogen ”, (7)“ Tank ” The inert gas supplied from below is nitrogen and its per minute The supply amount is 1 to 30 vol% with respect to the amount of the emulsified dispersion in the tank. The method for producing a toner for developing an electrostatic charge image according to (6) above, wherein the tank is an “8” tank. The method according to any one of (1) to (4), wherein the emulsion dispersion liquid is dropped / sprayed into fine particles from above to increase the gas phase contact surface area of the emulsion dispersion liquid. Item (8), wherein the average particle size of the emulsion dispersion dripped / sprayed from above the tank is 0.1 to 2 mm. (10) "Flow rate per minute of emulsion dispersion dripped / sprayed from above the tank is 0.5 to 20 vol% of the amount of emulsion dispersion in the tank" The electrostatic image according to item (9), characterized in that Image toner manufacturing method ”, (11)“ A plurality of rotating disks are installed therein, and a solvent removal tank is installed so that at least a part of the rotating disks is immersed in the emulsified dispersion. (1) to (4), wherein the electrostatic charge image developing toner manufacturing apparatus is used and the plurality of rotating disks are rotated to increase the gas phase contact surface area of the emulsified dispersion. The method for producing a toner for developing an electrostatic charge image according to any one of the items).
In addition, the above-described problem is used in the method for producing a toner for developing an electrostatic charge image according to any one of (12) and (1) to (4) of the present invention, and a plurality of rotating disks are provided therein. Is installed so that at least a part of the plurality of rotating disks is immersed in the emulsified dispersion, and the rotating disk is rotated to increase the gas phase contact surface area of the emulsified dispersion. (13) “Desolvation tank according to item (12), characterized in that the surface of the rotating disk has irregularities” (14) “The solvent removal tank according to the item (12), wherein the rotating disk is composed of a porous structure”, (15) “the rotating disk is a honeycomb structure Desolubilization according to item (12), characterized in that It is resolved by the tank ".
In addition, the above-mentioned problem is solved. (16) Production of a toner for developing an electrostatic charge image, comprising the solvent removal tank according to any one of (12) to (15). Solved by "device".
Further, the above-mentioned problem is a toner for developing an electrostatic charge image obtained by the production method according to any one of (17) and “(1) to (11)” of the present invention, which is measured by gas chromatography. And (18) “volume average particle diameter (Dv) is 3 to 10 μm, wherein the residual solvent amount in the toner is 500 ppm or less”, and the flow equation of the toner particles The toner for developing an electrostatic charge image according to item (17), wherein the average circularity by a particle image analyzer is 0.92 to 0.96, (19) “Volume average particle diameter (Dv ) Divided by the number average particle diameter (Dn) (Dv / Dn) is 1.05 to 1.25, wherein the electrostatic charge according to item (17) or (18) This is solved by “image developing toner”.
Further, the above-described problems are solved by (20) “photosensitive member for forming a latent image, developing device for developing the latent image formed on the surface of the photosensitive member, and recording member for developing the developed toner image on the photosensitive member. A toner according to any one of Items (17) to (19), comprising: a transfer device that transfers the toner to a surface; and a cleaning device that includes a cleaning blade that cleans the toner on the surface of the photoreceptor. An image forming apparatus characterized by using “
In addition, the above-described problems are solved by (21) “Container in which toner according to any one of (17) to (19)” is stored.

  In the toner production method of the present invention, it is possible to efficiently produce a toner having high cleaning properties, suppressing the generation of odor, and having high reproducibility of fine lines.

Hereinafter, the present invention will be described in more detail.
The toner production method of the present invention comprises a step of dissolving or dispersing a toner composition comprising at least a resin and a colorant in an organic solvent, and a step of emulsifying and dispersing the dissolved or dispersed material in an aqueous medium in which a fine particle dispersant is present. And a step of removing the organic solvent from the obtained emulsified dispersion in a closed tank, wherein the surface area of the gas phase contact of the emulsified dispersion is larger than the horizontal cross-sectional area of the tank in the organic solvent removing step. To do.

Examples of the resin used in the production of the toner of the present invention include a modified polyester resin capable of reacting with an extender and / or a crosslinking agent, for example, a 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.
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. Means things.

  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 the 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) to 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, caprolactams, etc. 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 an 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% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, 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% by weight, 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 modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

  As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, 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. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds. 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 modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (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 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.
When [NCO] / [NHx] is greater than 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 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 hardly occurs, and the elasticity of the toner is small. 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 the unmodified polyester (ii) described later is used, 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). Polyester (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, 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 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 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

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.
If the glass transition point is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if the glass transition point exceeds 70 ° C., the low-temperature fixability becomes insufficient.
In the dry toner of the present invention, by coexisting with a urea-modified polyester resin, the heat-resistant storage stability tends to be good even when the glass transition point is low, as compared with known polyester-based toners.

  As the colorant of the toner of the present invention, 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 iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Physe Red Parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R , Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thio Indigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , 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, 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 wt%, preferably 3 to 10 wt%, based on 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 master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, 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, urethane, urea modified polyester, epoxy resin, epoxy polyol resin, polyurethane, Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. These can be used alone or in combination.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under high shearing force to obtain a master batch.
At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing 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.

In addition, the toner of the present invention may contain a wax together with a binder and a colorant.
Known waxes can be used, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sasol wax, etc.); carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone).
Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
The melting point of the wax used in the toner of the present invention is usually 40 to 160 ° C., preferably 50 to 120 ° C., more preferably 60 to 90 ° C.
A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature.
Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.
The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

In view of removal later, the organic solvent is preferably volatile with a boiling point of less than 150 ° 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 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.
The prepolymer (A) and other toner composition (hereinafter referred to as toner raw material), a colorant masterbatch, a release agent, an unmodified polyester resin, etc. are dissolved or dispersed in an organic solvent in advance. Then, the solution or dispersion is added and dispersed in an aqueous medium.

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

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

  As the inorganic fine particle dispersant hardly soluble in water, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used.

  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 (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) Micropearl (Sekisui Fine Chemical)).

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 acetic acid Vinyl, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetacrylamide or their methylol compounds, acid chlorides such as acrylic chloride, methacrylic chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene Alkylamine, 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.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  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) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), 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 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts.

The elongation 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), but 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 toner production method of the present invention, the toner surface shape can be controlled in the step of solvent removal from the dispersion (reaction solution) after the elongation and / or crosslinking reaction.
In order to remove the organic solvent from the obtained emulsified dispersion (reaction liquid), when removing the emulsified dispersion in a sealed tank (also referred to as a “desolvent tank”), the surface of the toner is removed according to the solvent removal conditions. Thus, toner particles having a concavo-convex shape can be obtained.
This is considered that when the solvent contained in the oil phase evaporates, unbalanced volume shrinkage occurred in the relatively hard and elastic oil phase.
In the present invention, the solvent removal is carried out by making the vapor phase contact surface area of the emulsified dispersion placed in the tank larger than the horizontal cross-sectional area of the tank. At this time, the gas phase contact surface area (A1) of the emulsified dispersion is used. ) And the horizontal sectional area (A2) of the tank, the ratio A1 / A2 is 1.2 or more, preferably 1.2 or more and less than 4.0, more preferably 1.2 or more and less than 2.5.

When A1 / A2 is 1.2 or less, the solvent removal rate from the emulsified dispersion is lowered, the productivity is lowered, and the solvent removal time is increased, so that volume shrinkage hardly occurs and the sphere is formed.
On the other hand, although the solvent removal rate is higher at 4.0 or more, an atomizer for increasing A1 / A2, for example, a deterioration in total productivity due to an increase in the amount of inert gas, or a droplet size reduction, This is not preferable because the particle size distribution is disturbed by excessive shearing force at the atomizing nozzle.
The adjustment of A1 / A2 is performed by bubbling an inert gas into the emulsified dispersion from below the tank containing the emulsified dispersion to change the gas phase contact surface area, as will be described later.

The solvent removal processing environment is 101.3 kPa (atmospheric pressure) or less, an inert gas is supplied, and the solvent removal temperature is set to be equal to or lower than the glass transition point of the toner constituting material so that the solvent removal time can be controlled quickly. preferable.
Lowering the boiling point of the solvent under reduced pressure is preferable because the solvent removal rate can be increased and the solvent removal temperature can be lowered, and the spheroidization of the particles can be easily prevented.

In the step of removing the solvent from the emulsified dispersion, a method of setting the ratio A1 / A2 between the gas phase contact surface area (A1) of the emulsified dispersion and the horizontal cross-sectional area (A2) of the tank to 1.2 or more is emulsified dispersion. There is a method of increasing the gas phase contact surface area by bubbling an inert gas into the emulsified dispersion from the lower side of the tank containing the gas.
Inert gases include argon, helium, nitrogen, neon, etc., but it is generally desirable to use nitrogen for profitability and handling.
In addition, the supply amount of the inert gas is preferably 1 to 30% by volume with respect to the amount of the emulsified dispersion in the tank. If it is 1% or less, it is difficult to make A1 / A2 1.2 or more, and if it is 30% or more, the flow state in the tank becomes unstable.
FIG. 1 is a conceptual diagram showing a method of bubbling an inert gas from below the tank.
Inert gas is introduced from the supply port (105) into the emulsified dispersion (107) in the solvent removal tank (101), and bubbles (106) are generated.

As another method for increasing the gas phase contact surface area of the emulsified dispersion, there is a method in which the emulsified dispersion in the tank is dropped / sprayed in the form of fine particles from above the tank.
It is desirable that the emulsion dispersion to be dropped / sprayed has an average particle size of 0.1 to 2.0 mm. In order to set the average particle size of the emulsified dispersion liquid to 0.1 mm or less, a high-pressure type nozzle or a high scissor type administrer is required. If it is 2.0 mm or more, the effect of the present invention cannot be obtained efficiently.
The flow rate per minute is preferably 0.5 to 20 vol% of the amount of the emulsified dispersion in the tank. If the flow rate per minute is 0.5 vol% or less, it is difficult to make A1 / A2 1.2 or more, and if it is 20 vol% or more, it is inefficient in terms of energy.

FIG. 2 is a conceptual diagram showing this dripping / spraying method.
The solvent removal tank (101) contains an emulsified dispersion (107), and the pressure is reduced by a vacuum pump (103). From the bottom of the solvent removal tank, the emulsified dispersion is sent to the top of the tank by a pump (201) and dropped / sprayed onto the fine particles from the supply port (202) into the tank.

FIG. 3 is a conceptual diagram showing a method of increasing the gas phase contact surface area of the emulsified dispersion by rotating a rotating body having a plurality of rotating disks inside the tank.
In the tank, there is a rotating body (301) having a plurality of rotating disks (302), and a part of the rotating disk (302) is immersed in the emulsified dispersion.
In order to increase the surface area of the emulsified dispersion, the surface of the rotating disk preferably has a concavo-convex shape, and is preferably composed of a porous or honeycomb structure.

The toner obtained by the production method of the present invention preferably has a residual solvent amount in the toner of 500 ppm or less as measured by gas chromatography. If it is 500 ppm or more, the odor at the time of fixing becomes strong, and further, the residual solvent gradually moves to the toner surface during storage, and this also has the problem that the charging characteristics change.
The residual solvent is measured by adding 2 parts by weight of 2-propanol to 1 part by weight of the toner to be measured, dispersing it with ultrasound for 30 minutes, and then storing it in a refrigerator (5 ° C.) for 1 day or longer. The solvent is extracted, the supernatant liquid is analyzed by gas chromatography (GC-14A, SHIMADZU), and the solvent concentration and the residual monomer are quantified to determine the solvent concentration.

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, if 20% or more of toner of 2 μm or less is present, the amount of toner having a small particle size that is difficult to be developed on the surface of the magnetic carrier or the developing roller increases. Insufficient reverse charge toner increases, background stains occur, and 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 1.05 to 1.25.
When the particle size distribution is sharpened, the toner charge amount distribution becomes uniform, and the background fog can be reduced.
When Dv / Dn exceeds 1.25, it becomes difficult to obtain a high-quality image because the toner charge amount distribution becomes wide.
The particle diameter of the toner is measured using a Coulter Counter Multisizer (manufactured by Coulter), and an aperture having a measurement hole size of 50 μm is selected and used according to the particle diameter of the toner to be measured. Measure the particle size of 000 particles and calculate the average value.

The toner in the present invention preferably has a specific shape and shape distribution, and the toner having an average circularity of 0.92 or less and an irregular shape that is too far from the spherical shape exhibits satisfactory transferability. There is a tendency that high-quality images without dust are difficult to obtain.
In addition, as a shape measuring method, a suspension containing particles is passed through an imaging unit detection zone on a flat plate, and a particle image is optically detected and analyzed using a CCD camera. Is appropriate.
The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particles. A toner having an average circularity of 0.94 to 0.96 is appropriate. It was found that the method is effective for forming a high-definition image having a density reproducibility.
More preferably, particles having an average circularity of 0.945 to 0.955 and a circularity of less than 0.94 are 10% or less.
Further, when the average circularity is 0.96 or more, in a system employing blade cleaning or the like, a cleaning failure occurs on the photosensitive member or the transfer belt, causing stain on the image.
For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not pose a problem, but images with a high image area ratio such as photographic images, and untransferred images due to poor paper feed, etc. The formed toner may be generated as a transfer residual toner on the photoconductor, and if it is accumulated, image smearing occurs.
In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.).
As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been previously removed, and further measurement is performed. Add about 0.1-0.5g of sample.
The suspension in which the sample is dispersed is obtained by performing a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes and measuring the shape and distribution of the toner with the above apparatus with a dispersion concentration of 3000 to 10,000 / μl. .

The toner of the present invention may contain a charge control agent as necessary.
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin, and particularly preferably in the range of 0.2 to 5 parts by weight.
When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density Cause a decline.

As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used.
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 weight of the toner, and particularly preferably 0.01 to 2.0% by weight.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester, acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Examples thereof include polymer particles made of a resin.

Such a fluidizing agent performs surface treatment to increase hydrophobicity, and can prevent deterioration of fluidity 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. .

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

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 weight of the toner with respect to 100 parts by weight 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, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, 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.
Further, the toner of the present invention is stored in a conventionally known toner container such as a plastic bottle type, a stirring spring built-in type inside, and a process cartridge, and the container is used by being mounted on an image forming apparatus.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited only to these examples. In the following examples, parts and% are based on weight unless otherwise specified.
Example 1
(Synthesis of unmodified polyester)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 690 parts of bisphenol A ethylene oxide 2-mole adduct and 256 parts of terephthalic acid were placed at normal pressure at 230 ° C. for 8 hours, and then at a reduced pressure of 10-15 mmHg. After 5 hours of reaction, the mixture was cooled to 160 ° C., 18 parts of phthalic anhydride was added thereto and reacted for 2 hours to obtain unmodified [Polyester (B)].
(Prepolymer synthesis)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg, cooled to 160 ° C., and 32 parts of phthalic anhydride was added thereto. Reacted for hours. Next, the mixture was cooled to 80 ° C. and reacted with 230 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate group-containing [prepolymer (A)].
(Synthesis of ketimine)
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound (1)].
(Manufacture of toner)
14.3 parts of the above [Prepolymer (A)], 55 parts of [Polyester (B)] and 78.6 parts of ethyl acetate are placed in a tank and dissolved by stirring. 10 parts of melting point 83 ° C.) and 4 parts of copper phthalocyanine blue pigment were added, stirred at 12,000 rpm for 15 minutes with a TK homomixer at 60 ° C., and dispersed at 20 ° C. for 60 minutes with a bead mill. This is designated as [toner material solution (1)].
Next, 306 parts of ion-exchanged water, 265 parts of a 10% tricalcium phosphate suspension, and 0.2 part of sodium dodecylbenzenesulfonate were placed in a tank and dissolved uniformly.
Next, while stirring at 12,000 rpm with a TK homomixer, 2.7 parts of the above [toner material solution (1)] and [ketimine compound (1)] were added to cause a urea reaction. When the particle size was large while observing the particle size and particle size distribution with an optical microscope, the stirring speed was increased to 14,000 rpm, and the operation was further continued for 5 minutes.
The solvent removal process was performed by the following method.
The emulsified dispersion obtained in the previous step is transferred to a desolvation tank with a thermometer, and nitrogen gas becomes 1.0 vol% per minute with respect to the dispersion at 45 ° C. and atmospheric pressure (101.3 kPa). Thus, the solvent was supplied / bubbled into the emulsified dispersion from the bottom of the solvent removal tank, and the solvent was removed for 20 hours.
The ratio A1 / A2 between the gas phase contact surface area (A1) of the emulsified dispersion and the horizontal cross-sectional area (A2) of the solvent removal tank was determined from the average bubble diameter and residence time.
Thereafter, the resultant was filtered, washed, and dried to obtain toner base particles of Example 1.

Example 2
The toner base particles of Example 2 were obtained in the same manner as in Example 1 except that the pressure in the solvent removal step was changed to 50 kPa, and the nitrogen gas supply amount from the bottom of the solvent removal tank was changed to 5.0 vol% per minute. It was.

Example 3
The toner base particles of Example 3 were obtained in the same manner as in Example 1 except that the nitrogen supply amount from below the solvent removal tank in the solvent removal step was changed to 35.0 vol%.

Example 4
An emulsified dispersion was produced in the same manner as in Example 1.
The solvent removal process was performed by the following method.
The emulsified dispersion obtained in the previous step is transferred to a desolvation tank equipped with a thermometer, and the emulsified dispersion is sent from the bottom of the desolvation tank to the top of the desolvation tank under a reduced pressure of 45 ° C. and 50 kPa. The solvent was dropped / sprayed into the solvent removal tank so that the permeate flow rate was 2.0 vol% of the emulsified dispersion in the tank, and the solvent was removed for 20 hours.
A1 / A2 was determined from the drop average particle diameter of 0.6 mm and the gas phase average residence time of 0.5 sec.
Thereafter, filtration, washing, and drying were performed to obtain toner base particles of Example 4.

Example 5
In the solvent removal step of Example 4, the toner base particles of Example 5 were prepared in the same manner except that the flow rate per minute of the emulsified dispersion dropped / sprayed into the solvent removal tank was changed to 23.0 vol%. Obtained.
The solvent removal time at this time was 12 hours, and A1 / A2 was determined from the drop average particle size of 2.0 mm and the vapor phase average residence time of 0.4 sec.

Example 6
An emulsified dispersion was produced in the same manner as in Example 1.
The solvent removal process was performed by the following method.
The emulsified dispersion obtained in the previous step is transferred to a rotator having five rotating disks and a solvent removal tank with a thermometer, and the peripheral speed of the rotator is reduced to 10 m / min under reduced pressure at 45 ° C. and 50 kPa for 20 hours. Solvent was performed.
A1 / A2 at this time was 1.26.
Thereafter, filtration, washing, and drying were performed to obtain toner base particles of Example 6.

Comparative Example 1
An emulsified dispersion was produced in the same manner as in Example 1.
The solvent removal process was performed by the following method.
The emulsified dispersion obtained in the previous step was transferred to a solvent removal tank equipped with a thermometer, and the solvent was removed at 45 ° C. and atmospheric pressure (101.3 kPa) for 20 hours. Thereafter, filtration, washing, and drying were performed to obtain toner base particles of Comparative Example 1.

Comparative Example 2
An emulsified dispersion was produced in the same manner as in Example 1.
The solvent removal process was performed by the following method. The emulsified dispersion obtained in the previous step is transferred to a tank equipped with a stirring blade and a thermometer, and stirred for 20 hours at 45 ° C. under atmospheric pressure (101.3 kPa) at a stirring blade outer peripheral speed of 8 m / s. Solvent removal was performed. Thereafter, filtration, washing, and drying were performed to obtain toner base particles of Comparative Example 2.

Comparative Example 3
A dry pulverized toner was manufactured using a polyester resin synthesized from a bisphenoldiol type and a polycarboxylic acid.
Polyester resin (number average molecular weight Mn = 6,000, weight average molecular weight Mw = 50,000, glass transition point Tg = 61 ° C.) 86 parts, rice wax (acid value 0.5) 10 parts, copper phthalocyanine blue pigment (Toyo (Made by Ink Co., Ltd.) 4 parts of the mixture was thoroughly stirred and mixed in a Henschel mixer, heated and melted at a temperature of 80 to 110 ° C. for about 40 minutes with a roll mill, cooled to room temperature, and then the resulting kneaded product was pulverized and classified. Thus, toner base particles of Comparative Example 3 were obtained.

To 100 parts of the obtained toner base particles, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide were mixed with a Henschel mixer. The obtained toner physical property values are shown in Table 2.
A developer composed of 5% by weight of toner subjected to external additive treatment and 95% by weight of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 μm can be prepared, and 45 sheets of A4 size paper can be printed per minute. Evaluation was made using the Ricoh imagio Neo 450 according to the following criteria, and the results are shown in Table 3.

(Evaluation methods)
(A) Method for Measuring Residual Solvent in Toner The amount of residual solvent in the toner is measured by the following measurement method.
After adding 2 parts by weight of 2-propanol to 1 part by weight of the toner to be measured and dispersing with ultrasonic waves for 30 minutes, it was stored in a refrigerator (5 ° C.) for 1 day or longer to extract the solvent in the toner. The supernatant was analyzed by gas chromatography (GC-14A, SHIMADZU), and the solvent concentration was measured by quantifying the solvent and residual monomer in the toner.
Measurement conditions at the time of such analysis are as follows.
Device: Shimadzu GC-14A
Column: CBP20-M 50-0.25
Detector: FID
Injection volume: 1-5 μl
Carrier gas: He 2.5 kg / cm ²
Hydrogen flow rate: 0.6 kg / cm ²
Air flow rate: 0.5 kg / cm ²
Chart speed: 5mm / min
Sensitivity: Range101 × Atten20
Column temperature: 40 ° C
Injection Temp: 150 ° C

(B) Measuring method of toner odor Evaluation of odor is performed by 30 panelists at the start of image printing and during the continuous running of 100,000 sheets in an environment of 20 ° C. and 60% in a sealed room of a container 50 m ³ .
Evaluation items are scored based on overall scales based on odor intensity, comfort / discomfort, odor problem level as office equipment, etc.
Rank A: Level that is not a problem as office equipment. Almost everyone feels uncomfortable.
Rank B: A level at which people feel uncomfortable between Ranks A and B.
Rank C: A level at which almost everyone feels uncomfortable and causes problems as office equipment.

(C) Image quality (fine line reproducibility)
The reproducibility of fine lines having 5 pairs of black and white lines on 1 mm on the image chart was visually determined by enlarging the reproducibility on the photoreceptor after development with a lens.

(D) Cleaning property The transfer residual toner on the photosensitive member that has passed through the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and measured with a Macbeth reflection densitometer RD514. The evaluation was evaluated as ○ (good) when the difference was 0.01 or less, and Δ (good) when the difference from the blank was 0.02 or less.

From Example 1 and Comparative Example 1, the effect of promoting solvent removal by bubbling of inert gas in the solvent removal process was confirmed.
The toner of Comparative Example 1 has a true spherical shape, poor cleaning properties, and residual solvent was also confirmed.
Further, since the toner of Comparative Example 2 was agitated by the agitating blade during the solvent removal treatment, excessive shear was applied to the toner particles, and the shape deteriorated.

The toners obtained in Examples 1, 2, 4, and 6 had high fine line reproducibility and low toner odor, but the solvent was removed by the same method of bubbling nitrogen as in Examples 1 and 2. In the toner of Example 3, since the supply amount of nitrogen was too large, the solvent removal rate from the particles was large, the shape and particle size distribution were deteriorated, and the fine line reproducibility was inferior.
The toner of Example 5 also had the same result as Example 3 because the flow rate of the emulsified dispersion was too large. The toner of Comparative Example 3 has an indefinite shape, which is excellent in cleaning properties but remarkably inferior in fine line reproducibility.

It is a conceptual diagram which shows the method of bubbling an inert gas from the tank bottom used for the solvent removal process of this invention. It is a conceptual diagram which shows the method of dripping / spraying an emulsified dispersion liquid from the tank upper direction used for the solvent removal process of this invention. It is a conceptual diagram which shows the method of rotating the rotary body which has a some rotating disk in a tank used for the solvent removal process of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 101 Solvent removal tank 102 Nitrogen supply port 103 Vacuum pump 104 Heat exchanger 105 Inert gas supply port 106 Inert gas bubble 107 Emulsified dispersion 201 Pump 202 Emulsified dispersion supply port 301 Rotating body 302 Rotating disk

Claims (21)

A step of dissolving / dispersing a toner composition comprising at least a resin and a colorant in an organic solvent, a step of emulsifying and dispersing the solution or dispersion in an aqueous medium containing a fine particle dispersant, and an emulsified dispersion obtained At least a step of removing the organic solvent in the closed tank, and the surface area of the gas phase contact of the emulsified dispersion is larger than the horizontal sectional area of the tank during the organic solvent removal step. A method for producing a developing toner. 2. The electrostatic charge image developing toner according to claim 1, wherein the ratio A1 / A2 of the gas phase contact surface area (A1) of the emulsified dispersion and the horizontal cross-sectional area (A2) of the tank is 1.2 or more. Production method. The method for producing a toner for developing an electrostatic charge image according to claim 1 or 2, wherein an environment for removing the organic solvent is lower than 101.3 kPa (atmospheric pressure) and an inert gas is supplied. 4. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the environment for removing the organic solvent is carried out at a temperature lower than the glass transition temperature of the toner constituting material. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the gas phase contact surface area of the emulsified dispersion is increased by bubbling an inert gas from below the tank. 6. The method for producing a toner for developing an electrostatic charge image according to claim 5, wherein the inert gas supplied from below the tank is nitrogen. The inert gas supplied from below the tank is nitrogen, and the supply amount per minute is 1 to 30 vol% with respect to the amount of the emulsified dispersion in the tank. A method for producing a toner for developing a charge image. 5. The electrostatic charge image developing device according to claim 1, wherein a vapor phase contact surface area of the emulsified dispersion is increased by dropping / spraying the emulsified dispersion in the form of fine particles from above the tank. Toner manufacturing method. 9. The method for producing a toner for developing an electrostatic charge image according to claim 8, wherein the average particle diameter of the emulsified dispersion dropped / sprayed from above the tank is 0.1 to 2 mm. 10. The electrostatic charge image developing according to claim 9, wherein the flow rate per minute of the emulsion dispersion dropped / sprayed from above the tank is 0.5 to 20 vol% of the amount of the emulsion dispersion in the tank. Toner manufacturing method. Using an electrostatic charge image developing toner production apparatus comprising a plurality of rotating disks installed therein and a solvent removal tank installed so that at least a part of the plurality of rotating disks is immersed in an emulsified dispersion. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the gas phase contact surface area of the emulsified dispersion is increased by rotating the plurality of rotating disks. A solvent removal tank used in the method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein a plurality of rotating disks are installed therein, and at least a part of the plurality of rotating disks. Is removed so as to be immersed in the emulsified dispersion, and the rotating disk is rotated to increase the gas phase contact surface area of the emulsified dispersion. The solvent removal tank according to claim 12, wherein the surface of the rotating disk has an uneven shape. The solvent removal tank according to claim 12, wherein the rotating disk is composed of a porous structure. The solvent removal tank according to claim 12, wherein the rotating disk is formed of a honeycomb-like structure. An apparatus for producing a toner for developing an electrostatic charge image, comprising the solvent removal tank according to any one of claims 12 to 15. An electrostatic charge image developing toner obtained by the production method according to claim 1, wherein the residual solvent amount in the toner is 500 ppm or less as measured by gas chromatography. Toner for image development. The static average particle size according to claim 17, wherein the volume average particle diameter (Dv) is 3 to 10 µm, and the average circularity of the toner particles by a flow type particle image analyzer is 0.92 to 0.96. Toner for charge image development. The electrostatic charge image according to claim 17 or 18, wherein a value (Dv / Dn) obtained by dividing the volume average particle diameter (Dv) by the number average particle diameter (Dn) is 1.05 to 1.25. Development toner. A photosensitive member that forms a latent image; a developing device that develops the latent image formed on the surface of the photosensitive member; a transfer device that transfers a toner image developed on the photosensitive member to a recording member; and a toner on the surface of the photosensitive member. 20. An image forming apparatus comprising a cleaning device provided with a cleaning blade for cleaning, wherein the toner according to claim 17 is used. A container in which the toner according to claim 17 is stored.

Images