JP2006349897A - Method for manufacturing toner for electrostatic image development, toner, image forming apparatus, and toner container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner which maintains sufficient charging property in a nonmagnetic one-component developing process and hardly causes image degradation such as ground stain due to use of long duration, and an image forming method. <P>SOLUTION: In a method for manufacturing the toner for electrostatic image development formed of at least a colorant, a release agent and a polyester not containing a vinyl polymerizable group as a binder resin, in a step of obtaining particles by dispersing or emulsifying, in an aqueous medium, an oily phase prepared by dissolving or dispersing the above colorant, release agent and polyester resin in an organic solvent whose Hansen solubility parameter becomes ≤19.5, a radical generator is made to coexist in the aqueous medium and/or the oily phase and particles are formed. An image forming apparatus using the toner is also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a toner for developing electrostatic charge, and an image forming apparatus using the toner produced thereby, and as an application field, the toner of the present invention can be used as it is as colored particles for electronic paper.

At present, copying machines, printers, and MFPs using electrophotography tend to replace monochrome printing with full color printing.
Among them, printers and MFPs used in SOHO or distributed in offices occupy a large number of shipments, but they are desired to be inexpensive and compact. In order to achieve such needs, a non-magnetic one-component development process that can be configured with a small number of parts is advantageous.
In the non-magnetic one-component development process, the toner regulating member in contact with the toner carrier gives a charge to the toner particles due to friction, and at the same time, the toner carrier and the latent image carrier face each other. In this method, the electrostatic latent image on the latent image carrier is developed and visualized as a toner image.
In non-magnetic one-component development, toner is imparted with a charge necessary for development by friction with the toner regulating member, so that the toner regulating member is applied to the toner carrier with a certain amount of pressure in order to uniformly impart sufficient charge. If the developing operation is performed continuously, the toner is cracked by the pressure of the toner regulating member, or the toner is fused or agglomerated and fixed to the surface of the carrier, and density unevenness is formed on the formed image. There was a problem that occurred.

In order to solve the problem, generally, a method of increasing the toner resin molecular weight and increasing the mechanical strength of the toner is employed. However, when trying to set a low toner fixing temperature from the viewpoint of reducing the environmental impact of copying machines, printers, and MFPs, it is necessary to lower the melting temperature of the toner resin, making it extremely difficult to balance with low-temperature fixing properties. It becomes.
Therefore, instead of keeping the resin molecular weight relatively low, a method of preventing the localization of the force applied to the toner particles by making the shape of the toner spherical or close to it can be considered.
For example, in a toner obtained by mixing, kneading, pulverizing, and classifying at least a resin and a pigment, there is a method of increasing the circularity of toner particles by heating to a temperature higher than the glass transition temperature of the resin after classification or in a classification process. However, it is not preferable from the viewpoints of complicated processes, fusion between toners, generation of bleeding such as wax components contained in the toner, and increase in energy consumed during production.

In recent years, polymerized toners produced by various production methods have been put on the market.
For example, in Patent Document 1, as a method for obtaining toner particles having a uniform shape, a particle size distribution and a sharp charge amount distribution, for example, resin particles obtained by an emulsion polymerization method and colorant particles are associated (aggregated and fused). A method of making it wear) is disclosed. In this method, a toner having a shape close to a sphere can be obtained. However, the pressure of the toner regulating member often causes cracking at the fusion interface of the resin particles, causing image deterioration.
Further, a method is known in which toner particles are prepared by suspension polymerization of a vinyl resin in the presence of a colorant or the like (Patent Document 2). In this method, a styrene-acrylic resin is generally used, but the styrene-acrylic resin is brittle especially when the molecular weight is small, and it is difficult to achieve both low temperature fixability.
On the other hand, a prepolymer composed of at least a modified polyester resin and a material containing a toner component are dissolved or dispersed in an organic solvent, and the solution or dispersion is subjected to a crosslinking reaction and / or elongation reaction in an aqueous medium. A method for obtaining a toner by removing a solvent from a dispersed liquid is known (Patent Document 3). According to this method, a toner having a nearly spherical shape mainly composed of polyester can be produced, and compatibility with low-temperature fixability can be achieved.
However, as the extension reaction of modified polyester, the reaction of isocyanate, amine, and alcohol is often used, and the urea bond and urethane bond derived from it inhibit the negative chargeability of the toner and cause image smearing due to poor charging. For this reason, a separate measure for imparting negative chargeability is required.

Therefore, for example, a method of preparing a toner by dispersing a less colored charge control agent such as zinc salicylate can be considered, but it is difficult to uniformly disperse the toner, resulting in non-uniform chargeability of the toner, and scattering of toner and dirt. Occurs.
In addition, a method of dry-processing the charge control agent on the toner surface using a Henschel mixer or the like is also conceivable, but the charge control agent is gradually released by the pressure of the toner regulating member, and the floating charge control agent contaminates the developing roller and the like. Cause charging failure.
In other words, the properties required for a toner suitable for a non-magnetic one-component development process are: 1. It has sufficient strength and shape to withstand the pressure of the toner regulating member, and 2. The charged part is relatively near the surface. Two things are important: being uniformly present and not spent.
JP 2002-148858 A JP-A-2-168271 Japanese Patent No. 3571703 "POLYMER HANDBOOK" 4th Edition, WILEY-INTERSCIENCE Volume 2, Section VII "POLYMER HANDBOOK" 4th Edition, WILEY-INTERSCIENCE Volume 1, Section II

  It is an object of the present invention to provide a method for uniformly producing a toner that imparts chargeability maintaining characteristics and has little image deterioration. It is another object of the present invention to provide a toner and an image forming apparatus that maintain a sufficient chargeability in a non-magnetic one-component development process, and that cause less image deterioration such as a background stain due to use durability.

As a result of intensive studies, the present inventors have made the following invention.
(1) In a method for producing a toner formed from a polyester resin that does not contain a vinyl polymerizable group as at least a colorant, a release agent, and a binder resin, the Hansen solubility parameter is 19 for the colorant, the release agent, and the polyester resin. In the process of obtaining particles by dispersing or emulsifying an oil phase dissolved or dispersed in an organic solvent of 5 or less in an aqueous medium, particles are formed by coexisting a radical generator in the aqueous medium or / and the oil phase. And a method of producing a toner for developing an electrostatic charge image.
(2) The above aqueous medium is water or / and a water-soluble organic solvent, an organic solvent having a Hansen solubility parameter of 19.5 or less, a surfactant, a viscosity modifier, an emulsification / dispersion stabilized fine particle, a pH adjuster, or an inorganic 2. The method for producing a toner for developing an electrostatic charge image according to claim 1, comprising a combination selected from salts.
(3) In the above (1) or (2), the circularity of the toner obtained by the above method is 0.95 or more and less than 0.99 and the volume average particle diameter is 4.5 μm or more and less than 8 μm. It is a manufacturing method of the toner for electrostatic image development of description. Here, when the circularity of the toner is less than 0.95, the fluidity is lowered. The volume average particle size is preferably less than 8 μm in order to suppress the graininess of the image depending on the particle size of the toner, and is preferably 4.5 μm or more from the viewpoint of cleaning properties and influence on the human body as dust.
(4) The production of the electrostatic image developing toner according to any one of (1) to (3), wherein the toner is obtained by removing an organic solvent after forming particles in an aqueous medium. Method.

(5) The toner according to any one of (1) to (4), wherein the toner is obtained by subjecting the toner to a washing treatment with a washing aqueous medium after particle formation in an aqueous medium and then a drying treatment. A method for producing a toner for developing an electrostatic image.
(6) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (5), wherein the binder resin is a polyester resin having a glass transition temperature of 40 ° C. or higher. . This is because the glass transition temperature is preferably 40 ° C. or higher in view of the storage stability of the toner and the environment inside the image forming apparatus.
(7) The production of the toner for developing an electrostatic charge image according to any one of (1) to (6), wherein the binder resin contains a polyester resin extended by urethane or / and a urea bond. Method.
(8) The toner for developing an electrostatic charge image according to (7), wherein the polyester resin contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at the terminal and an amine. Production method.
(9) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (6), wherein the binder resin includes a polyester resin in which the polyester resin is not modified. .

(10) The binder resin includes a modified polyester resin and an unmodified polyester resin, and the weight ratio of the modified polyester resin to the unmodified polyester resin (modified polyester resin / unmodified polyester resin) is 0/100. 80/20 (excluding 0), The method for producing a toner for developing an electrostatic charge image according to the above (8) to (9).
(11) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (10), wherein the toner contains a wax as a release agent.
(12) The toner described above, wherein the toner contains 4 to 30% by weight of one or more selected from paraffins, synthetic esters, polyolefins, carnauba wax, or rice wax as a release agent. The method for producing a toner for developing an electrostatic charge image according to (11).
(13) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (12), wherein the toner contains a charge control agent.
(14) A toner for nonmagnetic one-component development, wherein the toner prepared by the method according to any one of (1) to (13) is used in a nonmagnetic one-component development process.
(15) An image forming apparatus using the nonmagnetic one-component developing toner described in (14).

(16) The image forming apparatus according to (15), wherein the image forming apparatus is an apparatus for forming a multicolor image.
(17) The image forming apparatus as described in (15) or (16) above, wherein the image forming apparatus has an endless intermediate transfer means.
(18) The image forming apparatus according to any one of (14) to (17), wherein the image forming apparatus does not include a blade as a residual toner cleaning unit in the photosensitive member and / or the intermediate transfer unit.
(19) The image forming apparatus according to any one of (15) to (17), wherein the image forming apparatus includes a blade cleaning unit.
(20) The image forming apparatus according to any one of (15) to (19), wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device.
(21) The image forming apparatus according to any one of (15) to (19), wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device.
(22) The image forming apparatus according to any one of (15) to (21), wherein the image forming apparatus includes an oilless fixing unit that does not require oil application to a fixing member.
(23) A toner container filled with the electrostatic image developing toner according to any one of (3) to (13).
(24) A toner container filled with the nonmagnetic one-component developing toner according to (14).

The (1) will be described. In the development process, it is necessary to use a toner that maintains sufficient chargeability and has little image deterioration such as scumming due to use durability. Conventionally, it has been supported by adding CCA. There were problems such as poor uniformity. Although the action of the radical generator is not necessarily clear, for example, as one of the actions of the radical generator, a functional group that can be a negatively charged site can be easily introduced into the toner base surface by using the radical generator, and It can be estimated that the strength of the surface resin can be increased, and a toner having improved toner strength and negative chargeability can be provided.
The above (2) to (13) are toners having a particle diameter and circularity controlled within a more preferable range, which is a characteristic of particle production by a polymerization method, and can achieve higher image quality than conventional pulverized toners. Toner can be provided.
With regard to the above (14) to (24), it is possible to secure an area relating to an image forming method necessary for cleanerless and oilless fixing with a non-magnetic one-component toner.

The toner of the present invention will be described below with specific examples.
Examples of the toner production method include a dissolution suspension method described in Journal of the Imaging Society of Japan, Vol. 43, No. 1 (2004), a prepolymer comprising at least a modified polyester resin in an organic solvent, and a toner composition. Intended for a novel polymerization method in which a toner is obtained by dissolving or dispersing a contained material, subjecting the dissolved or dispersed material to a crosslinking reaction and / or elongation reaction in an aqueous medium, and removing the solvent from the obtained dispersion liquid. Preferably, at least a polyester resin (which may include a prepolymer made of a modified polyester resin) as a binder resin, and a material including a toner composition and / or a radical generator are dissolved or dispersed in an organic solvent, By emulsifying or dispersing the solution or dispersion (these are called oil phases) in an aqueous medium in the presence of a radical generator, and removing the solvent. It is a manufacturing method such as obtaining a toner.

Hereinafter, this production method will be described.
I. Oil phase material I-1. Polyester resin Although the polyester resin which does not contain a vinyl polymerizable group is used for the binder resin of the present invention, the polyester resin includes an unmodified polyester resin obtained from a polycarboxylic acid and a polyol, and a polyester prepolymer having an isocyanate group. Known polyester resins such as so-called modified polyester resins can be used, and these may be used alone or in combination of two or more.
I-2. Summary of Modified Polyester Resin In the present invention, a polyester prepolymer having an isocyanate group can be used as the modified polyester resin. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2), and a polyester having an active hydrogen group further reacted with a polyisocyanate (3). Is mentioned. Examples of the active hydrogen group possessed by 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 preferred.

I-2-1. About Polyol Polyol (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) 4,4′-dihydroxybiphenyls such as F, bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, and the like; bis (3-fluoro-4-hydro Loxyphenyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 , 5-difluoro-4-hydroxyphenyl) propane (alias: tetrafluorobisphenol A), bis such as 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (Hydroxyphenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide) Adducts; alkylene oxides of the above bisphenols (eth Emissions oxide, propylene oxide, and the like butylene oxide, etc.) adducts.
Among them, 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. In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trivalent or higher polyphenols. In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

I-2-2. Polycarboxylic acid Polycarboxylic acid (2) 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, naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid 5-trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) Hexafluoropropane, 2,2'-bis (trifluoromethyl ) -4,4′-biphenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyl Dicarboxylic acid, hexafluoroisopropylidene diphthalic anhydride, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polyvalent polycarboxylic acids having 3 or more valences are aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1). In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

I-2-3. Ratio of polyol and polycarboxylic acid The ratio of polyol (1) and polycarboxylic acid (2) is usually 2/1 to 1 as the equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. / 1, preferably 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
I-2-4. Polyisocyanate Polyisocyanate (3) includes aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; phenols, oximes, polyisocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

I-2-5. Ratio of isocyanate group to hydroxyl group The ratio of the polyisocyanate (3) is usually 5/1 to 1/1 as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1, preferably 4/1 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.

I-2-6. Number of isocyanate groups in the prepolymer 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 average 1.8 to 2.5. 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.
I-2-7. Crosslinking agent and extender In the present invention, amines can be used as the crosslinker and / or extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.); alicyclic diamines ( 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc .; and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododeci Range amine).
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine, diethanolamine, 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 B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 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.

I-2-8. Terminator 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).
I-2-9. Ratio of amino group and isocyanate group The ratio of amines (B) is equivalent to the equivalent ratio of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups to amino groups [NHx] in amines (B) [ NCO] / [NHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, and 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.

I-3. Unmodified Polyester In the present invention, it is important not only to use the modified polyester (A) alone, but also to contain the unmodified polyester (C) as a toner binder component together with the (A). By using (C) in combination, low-temperature fixability and glossiness when used in a full-color device are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (C). (C) 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 (A) and (C) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio [(A) / (C)] of (A) and (C) is usually 0/100 to 80/20 (excluding 0), preferably 5/95 to 75/25, more preferably 10/90 to 25/75, still more preferably 12/88 to 25/75, and particularly preferably 12/88 to 22/78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

I-3-1. The molecular weight of the unmodified polyester (C) is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (C) 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 (C) is usually from 0.5 to 40, preferably from 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

I-4. Colorant As the colorant 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 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 Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R , Para red, phissa red, paracro Luort Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin 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, pyra Ron 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 Gree 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% by weight, preferably 3 to 10% by weight, based on the toner.

I-4-1. Making Colorant Masterbatch The colorant used in the present invention can also be used as a masterbatch 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, 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, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein 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 resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

I-4-2. Masterbatch preparation method The masterbatch can be obtained by mixing and kneading a resin for a masterbatch and a colorant under high shearing force and kneading. At this time, an organic solvent can be used 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 shear dispersion device such as a three-roll mill is preferably used. In addition, it can be prepared and used as a dispersion / dissolution liquid (wet master) of an organic solvent for oil phase in order to enhance the dispersion / solubility in the solvent during the preparation of the oil phase.

I-5. Wax The toner according to the present invention may contain a wax together with a toner binder and a colorant. As the wax, known ones described in “Revised Properties and Applications of the Second Edition of Wax” by Ken Segawa, Seiko Shobo Co., Ltd. can be used. For example, polyolefins such as polyethylene wax and polypropylene wax; paraffin wax, sax Paraffins such as sol wax; trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid , Synthetic esters such as distearyl maleate and octadecyl stearate; natural plant waxes such as carnauba wax, rice wax and candelilla wax; natural minerals such as montan wax, ozokerite and ceresin And fatty acid amide synthetic waxes such as physical waxes and stearic acid amides. Of these, polyolefins, paraffins, synthetic esters, carnauba wax and rice wax are preferable, and they can be used alone or in combination of two or more.
In the present invention, the wax content in the toner can be 2 to 30% by weight, preferably 4 to 15% by weight, based on 100% by weight of the resin component. If the amount of the wax relative to the total amount of toner is less than 4%, the wax exudes on the surface of the fixing member at the time of fixing so as not to stick to the fixing member. The hot offset margin may be lost. On the other hand, if it exceeds 15%, the wax melts at a low temperature, so it is easily affected by thermal energy and mechanical energy. For example, when a low-melting wax is used, for example, when a toner for two-component development is used, the carrier in the developing section When the toner is agitated, the wax is detached from the toner surface and adheres to the toner regulating member or the photosensitive member to generate image noise. Noise may be generated.
Further, the endothermic peak at the time of temperature rise measured by a differential scanning calorimeter (DSC) of the wax can fix the toner at a low temperature of 65 to 115 ° C., but if the melting point is less than 65 ° C., the fluidity becomes poor. When the temperature is higher than 115 ° C., the fixability tends to deteriorate.

I-6. Oil phase organic solvent The toner according to the present invention is obtained by dissolving or dispersing a toner composition comprising at least a polyester as a binder resin and a colorant in an organic solvent, and the dissolved or dispersed aqueous system containing a radical generator. It can be obtained by emulsifying or dispersing in a medium in the presence of an inorganic dispersant or resin fine particles, and then removing the solvent. The polyester as the binder resin does not contain a vinyl polymerizable group.
The organic solvent that dissolves or disperses the toner composition comprising the polyester resin and the colorant is preferably, for example, a Hansen solubility parameter described in Non-Patent Document 1 of 19.5 or less, and further has a boiling point of less than 150 ° C. It is particularly preferable that it is easy to remove the solvent later. When the Hansen solubility parameter is greater than 19.5, the affinity with water increases and the solubility in the aqueous phase increases, which is disadvantageous for stabilization of the interface. On the other hand, the affinity of the toner constituting material, such as resin or wax, is reduced, resulting in problems in particle production. Examples of such organic solvents include hexane, cyclohexane, toluene, xylene, benzene, carbon tetrachloride, 1,1-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, chloroform, methyl acetate, ethyl acetate, butyl acetate. , Methyl ethyl ketone, tetrahydrofuran and the like can be used alone or in combination of two or more.

II. Materials for aqueous media
II-1. Aqueous medium Next, the aqueous medium to be used may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. Furthermore, an organic solvent having a Hansen solubility parameter of 19.5 or less used in the oil phase may be mixed, and preferably the addition amount in the vicinity of the saturation amount with respect to water increases the emulsification or dispersion stability of the oil phase. it can. The amount of the aqueous medium used relative to 100 parts by weight of the toner composition is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. 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 2000 parts by weight, it is not economical. The radical generator added to the aqueous phase is not particularly limited as long as it is dispersed or dissolved in water, and may be a single or a combination of two or more, or a combination of an oxidizing agent and a reducing agent utilizing a redox reaction. . The addition amount is adjusted by the radical generator type and granulation temperature with respect to the toner solid content, but is 0.1 to 20 wt%, preferably 0.5 to 10%.

II-2. As the radical generator of the present invention, those known as so-called polymerization initiators can be used, and examples include those described in Non-Patent Document 2. The radical generator can be added to the oil phase or / and the water phase. When adding to the oil phase, it is preferable to use an oil-soluble polymerization initiator. When adding to the water phase, a water-soluble polymerization initiator is added. It is preferable to do.
Examples of the oil-soluble polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carboxyl). Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo- or diazo-based polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate , Cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,4- t-butylperoxycyclohexyl) propane, tris- (t Examples thereof include peroxide polymerization initiators such as -butylperoxy) triazine and polymer initiators having a peroxide in the side chain.
On the other hand, water-soluble polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, 2,2′-azobis (2-methylpropionamidine dihydrochloride), 2,2′-azobis [N- (2- Carboxyethyl) -2-methylpropionamidine], 4,4′-azobis (4-cyanovaleric acid) azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide, and the like.

II-3. Inorganic Dispersant The dissolved or dispersed toner composition is dispersed in the aqueous medium in the presence of the inorganic dispersant or resin fine particles. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. The use of a dispersant is preferable in that the particle size distribution becomes sharp and the dispersion is stable.
II-4. Resin fine particles It is preferable to add resin fine particles to the toner according to the present invention. As the resin forming the resin fine particles, any resin that can form an aqueous dispersion can be used, and it may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

II-4-1. Description of Vinyl Resin Vinyl resin is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbons: Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins, etc .; alkadienes Such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene. Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene and indene.
Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.
(2) Carboxyl group-containing vinyl monomers and salts thereof: C3-C30 unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides and monoalkyl (C1-C24) esters thereof such as (meth) Acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester Carboxyl group-containing vinyl monomers such as cinnamic acid.

(3) Sulfone group-containing vinyl monomers, vinyl sulfate monoesters and their salts: Alkene sulfonic acids having 2 to 14 carbon atoms, such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene Sulfonic acid; and alkyl derivatives thereof having 2 to 24 carbon atoms such as α-methylstyrene sulfonic acid, etc .; sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2- Hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2 -Hydroxypropanesulfonic acid, 2- (meth) Acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, alkyl (3 to 18 carbon atoms) allylsulfosuccinic acid, poly (n = 2 to 30) oxyalkylene (ethylene, propylene, (Butylene: single, random, or block) Mono (meth) acrylate sulfate [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, etc.

(4) Phosphoric acid group-containing vinyl monomers and salts thereof: (meth) acryloyloxyalkyl phosphoric acid monoesters, such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxy Alkyl (having 1 to 24 carbon atoms) phosphonic acids such as 2-acryloyloxyethylphosphonic acid; and salts thereof.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.
(5) Hydroxyl group-containing vinyl monomers: hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, black Tyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomers: amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl ( (Meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinyl Pyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and Luo salts, and the like.
Amide group-containing vinyl monomers; (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, cinnamon Acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like. Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
Quaternary ammonium cationic group-containing vinyl monomers: tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine Monomer quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate). Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomers: glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylethylene oxide and the like.
(8) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones: vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl -4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl ( (Meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dode Syl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight chain, branched chain having 2 to 8 carbon atoms) Or an alicyclic group), a dialkyl maleate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), poly (meth) allyloxy Alkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol ( Molecular weight 300) Mono (meth) acrylate, Polypropylene glycol (Molecular weight 500) Acrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) acrylate, lauryl alcohol ethylene oxide 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.]. Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl Ether, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene. Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone; vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(9) Other vinyl monomers: isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
(10) Fluorine atom-containing vinyl monomer: 4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, Perfluorocyclohexylmethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H-hexafluorobutyl (meth) Acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecaf Orodecyl (meth) acrylate, trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate, 2- (N-butylperfluorooctanesulfonamido) ethyl (meta ) Acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate, and the corresponding compounds derived from α-fluoroacrylic acid, bis-hexafluoroisopropyl itaconate, bis-hexafluoroisopropyl maleate, bis -Perfluorooctyl itaconate, bis-perfluorooctyl maleate, bis-trifluoroethyl itaconate and bis-trifluoroethyl maleate, vinyl heptafluorobut Tylates, vinyl perfluoroheptanoate, vinyl perfluorononanoate and vinyl perfluorooctanoate.

II-4-2. Vinyl-based copolymer Examples of the copolymer of vinyl-based monomers include polymers obtained by copolymerizing any of the above monomers (1) to (10) in two or more in an arbitrary ratio. For example, styrene- (meth) acrylic acid ester copolymer, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer Styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid, divinylbenzene copolymer, styrene-styrenesulfonic acid- (meth) acrylic acid ester copolymer, and the like. When introducing fluorine into the resin fine particles, copolymerization is carried out at an arbitrary ratio with the number of one or more of the arbitrary monomers of the above (10).

II-4-3. Monomer ratio of vinyl-based resin In order to form resin fine particles in the aqueous dispersion, it is necessary that the resin is not completely dissolved in water at least under the conditions for forming the aqueous dispersion. Therefore, when the vinyl resin is a copolymer, the ratio of the hydrophobic monomer and the hydrophilic monomer constituting the vinyl resin depends on the type of monomer selected, but generally the hydrophobic monomer is 10% or more. It is preferably 30% or more. When the ratio of the hydrophobic monomer is 10% or less, the vinyl resin becomes water-soluble and the particle size uniformity of the toner is impaired. Here, the hydrophilic monomer means a monomer that dissolves in water at an arbitrary ratio, and the hydrophobic monomer means another monomer (a monomer that is basically not miscible with water).

II-4-4. Method of Dispersing Resin Fine Particles in Aqueous Method The method of making the resin into an aqueous dispersion of resin fine particles is not particularly limited, and examples thereof include the following (a) to (h). (A) In the case of a vinyl resin, a method of directly producing an aqueous dispersion of resin fine particles by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material . (B) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, A method of producing an aqueous dispersion of resin fine particles by heating and then adding a curing agent to cure. (C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid) may be liquefied by heating. .) A method in which a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.

(D) A resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) can be used as a mechanical rotary type or jet type resin. A method in which resin fine particles are obtained by pulverization using a fine pulverizer and then classification, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method in which resin fine particles are obtained by spraying in the form of a mist and then dispersed in water in the presence of an appropriate dispersant.
(F) A solvent is added to a resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. The resin fine particles are precipitated by cooling the resin solution previously dissolved in a solvent by heating, and then the solvent is removed to obtain resin fine particles, which are then dispersed in water in the presence of a suitable dispersant. Method.
(G) A resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method of dispersing in an aqueous medium in the presence of an appropriate dispersant and removing the solvent by heating or decompression.
(H) In a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. A method of phase inversion emulsification by adding water after dissolving an appropriate emulsifier.

II-4-5. Particle size of resin fine particles The particle size of resin fine particles is usually smaller than the particle size of toner, and from the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of resin fine particles] / [volume average particle size of toner] The value of [diameter] is preferably in the range of 0.001 to 0.3. If the particle size ratio is larger than 0.3, the resin fine particles are not efficiently adsorbed on the surface of the toner, so that the particle size distribution of the obtained toner tends to be wide. Further, the volume average particle diameter of the resin fine particles can be appropriately adjusted within the range of the particle diameter ratio so as to be a particle diameter suitable for obtaining a toner having a desired particle diameter. For example, when it is desired to obtain a toner having a volume average particle diameter of 5 μm, it is preferably 0.0025 to 1.5 μm, particularly preferably in the range of 0.005 to 1.0 μm, and preferably when a toner of 10 μm is obtained. Is 0.005 to 3.0 μm, particularly preferably 0.05 to 2.0 μm. The volume average particle size is measured with a laser Doppler particle size distribution measuring device (UPA-150; manufactured by Nikkiso), a laser particle size distribution measuring device (LA-920; manufactured by Horiba Seisakusho) or Multisizer II (manufactured by Coulter). it can.

II-5. Surfactant Further, a surfactant or the like can be used as necessary to emulsify and disperse the oil phase containing the toner composition in the aqueous medium. 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. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms, and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

II-6. Protective colloid Further, the dispersed droplets may be stabilized by a polymer-based 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, or esters of compounds containing vinyl alcohol and carboxyl groups For example, vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene Homopolymers or copolymers such as those having a nitrogen atom such as imine or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, polyethylene Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used. 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 then 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. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

III. Dispersion / Emulsification Method The dispersion / emulsification method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 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 20 to 90 ° C. Higher temperatures are preferred in that the dispersion of the toner composition containing the polyester resin has a low viscosity and is easily dispersed. In order to promote the generation of radicals from the radical generator, it is preferable to appropriately heat in reference to, for example, the thermal decomposition half-life temperature, and the temperature can be selected in the range of 20 to 90 ° C. Moreover, it can heat-process suitably after a solvent removal (after-mentioned) process after dispersion | distribution.

IV. Elongation reaction When the polyester prepolymer is converted into a urea-modified polyester in the present invention, an amine and a sulfonating agent may be mixed in the oil phase and then reacted with the prepolymer before dispersing the toner composition in the aqueous medium. Then, after dispersing the toner composition in the aqueous medium, amines may be added to cause a reaction from the particle interface. In the latter case, urea-modified polyester is preferentially produced on the surface of the toner particles to be produced, and a concentration gradient can be provided inside the particles. The time required for the polyaddition reaction is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer and the added amines, and is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

V. Desolvation In order to remove the organic solvent from the obtained emulsified dispersion, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained with a short processing time such as spray dryer, belt dryer, rotary kiln.
VI. Wet classification When the toner particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are carried out while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution. In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferably performed in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be wet. Further, it is preferable to remove the used dispersant as much as possible from the obtained dispersion, but it is preferable to carry out it simultaneously with the classification operation described above.

VII. External additive treatment The resulting dried toner powder is mixed with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. By applying, it is possible to immobilize and fuse on the surface, and to prevent dissociation of the different particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries Ltd.), automatic mortar, etc.

VIII. External additive
VIII-1. Inorganic fine particles 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 nm to 2 nm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used 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.
VIII-2. Polymer fine particles Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylate copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, polycondensation system such as silicone, benzoguanamine, nylon, heat Examples thereof include polymer particles made of a curable resin.

VIII-3. Surface Treatment of External Additives Such fluidizing agents 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 a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
IX. Cleaning aid As a cleaning improver for removing the developer after transfer remaining on the photoreceptor or primary transfer medium, for example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, for example, polymethyl methacrylate fine particles, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as polystyrene 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.

X. Charge Control Agent The toner of the present invention may contain a charge control agent as necessary. Any known charge control agent can be used, for example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based 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.

X-1. Amount of charge control agent In the present invention, the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as required, and the toner production method including the dispersion method. Although it is not limited to this, Preferably it is used in 0.1-10 weight part with respect to 100 weight part of binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These can be melt-kneaded together with the masterbatch and the resin, or may be added when dissolved and dispersed in an organic solvent. Furthermore, external addition may be performed using a Henschel mixer or the like.

  The invention described in claim 1 can provide a toner manufacturing method that suppresses wax and toner from adhering to the regulating blade and improves negative chargeability, and has low image deterioration such as development unevenness and background stain due to use durability. Can be provided. The inventions according to claims 2 to 13 use SPR dimples and spherical toners having the function and effect of the invention according to claim 1, and are therefore controlled within a more preferable range which is a characteristic of particle production by a polymerization method. Since a toner having a particle diameter and a circularity is used, it is possible to provide a toner capable of improving the image quality as compared with a conventional pulverized toner. The invention described in claims 14 to 24 can provide configurations such as cleanerless and oilless fixing useful for downsizing and cost reduction of an image forming method using a non-magnetic one-component toner, and downsizing and cost reduction. Is possible.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. “Parts” means all parts by mass.
Example 1
Synthesis of low molecular weight polyester:
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 45 parts of trimellitic anhydride to the reaction vessel, and add 2 parts at 180 ° C. under normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.
Prepolymer synthesis:
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 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, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.

Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.
Master batch synthesis:
Carbon black (Cabot Co., Ltd. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 Acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, Water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].
Preparation of pigment / WAX dispersion (oil phase):
378 parts of [low molecular weight polyester 1], 223 parts of carnauba wax, and 947 parts of ethyl acetate were charged into a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1]. [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. It was adjusted by adding ethyl acetate so that the solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

Preparation of aqueous medium:
953 parts of water, 88 parts of a 25 wt% aqueous dispersion of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), 48.48% of sodium dodecyl diphenyl ether disulfonate. 90 parts of 5% aqueous solution (Eleminol MON-7: manufactured by Sanyo Chemical Industries), 113 parts of ethyl acetate, and 11.2 parts of potassium persulfate as a radical generator were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].
Emulsification process:
[Pigment / WAX Dispersion 1] 976 parts and 6.0 parts of isophoronediamine as amines were put in a container and mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika). After adding 137 parts and mixing with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, add 1200 parts of [aqueous phase 1] and using TK homomixer at 13,000 rpm for 20 minutes. By mixing, [Emulsified slurry 1] was obtained.

Solvent removal:
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 60 ° C. for 10 hours to obtain [Dispersion slurry 1].
Wash and dry:
[Dispersion Slurry 1] After 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered. (2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less. (3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes. (4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1]. [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 1]. The volume average particle diameter (Dv) was 5.6 μm, the number average particle diameter (Dp) was 5.0 μm, Dv / Dp was 1.12 and the average circularity was 0.97. Subsequently, 100 parts of the base toner was mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain Developer A of the present invention.

Particle size (Coulter):
Next, a method for measuring the particle size distribution of toner particles will be described.
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below. First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of the measurement sample is further added as a solid content. The electrolyte in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 · １００A aperture as the aperture. Then, the volume distribution and the number distribution are calculated. From the obtained distribution, the weight average particle diameter (Dv) and the number average particle diameter (Dp) of the toner can be obtained. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

Average circularity:
As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. 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 particle. This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. 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 removed in advance, 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 dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

Evaluation of adhesion on development regulating blade:
The externally added toner (developer) was placed in a black toner cartridge of Epson LP-1500C, and the fixation on the development regulating blade at the initial stage (50 sheets) and after 800 sheets of blank paper was visually observed.
Evaluation level: ○ No sticking, ΔSlightly sticking but no development unevenness, x
The toner (developer) subjected to the external addition treatment in the same manner as described above is put in a black toner cartridge of LP-1500C manufactured by Epson Corporation, and the toner (background stain) on the photosensitive member at the initial stage (50 sheets) and after 800 sheets of white paper is passed. The density when the tape was peeled off and affixed to white paper was visually observed.
Evaluation level: ○ No dirt at all, △ Slightly soiled but not worried, ×

The results of adhesion evaluation and background contamination evaluation on the development regulating blade are summarized in Table 1 (Evaluation results of Examples and Comparative Examples). Examples 2 to 8 were carried out in the same manner as in Example 1 except that the type and amount of the radical generator and the aging temperature in the preparation of the aqueous medium of Example 1 were changed as shown in Table 1. In Examples 9 and 10, the prepolymer of Example 1 was replaced with a considerable amount of low molecular weight polyester, and the types and amounts of radical generators in the adjustment of the oil phase and the aqueous medium, and the aging temperature were changed as shown in Table 1. Except for this, the same procedure as in Example 1 was performed.
Comparative Examples 1 and 2 were performed in the same manner except that no radical generator was added to Examples 1 and 9. The evaluation results are also summarized in Table 1.

Claims (24)

In a toner production method comprising at least a colorant, a release agent and a polyester resin not containing a vinyl polymerizable group as a binder resin, the Hansen solubility parameter of the colorant, the release agent and the polyester resin is 19.5 or less. In the step of obtaining particles by dispersing or emulsifying an oil phase dissolved or dispersed in an organic solvent, a particle is formed by coexisting a radical generator in the aqueous medium or / and the oil phase. A method for producing a toner for developing an electrostatic charge image. The aqueous medium is selected from water or / and a water-soluble organic solvent, an organic solvent having a Hansen solubility parameter of 19.5 or less, a surfactant, a viscosity modifier, an emulsification / dispersion stabilized fine particle, a pH adjuster, or an inorganic salt. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner comprises: 3. The electrostatic charge image developing device according to claim 1, wherein the toner obtained by the above method has a circularity of 0.95 or more and less than 0.99 and a volume average particle diameter of 4.5 μm or more and less than 8 μm. Toner manufacturing method. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the toner is obtained by removing an organic solvent after forming particles in an aqueous medium. 5. The toner for developing an electrostatic charge image according to claim 1, wherein the toner is obtained by subjecting the aqueous medium to washing with a washing aqueous medium after forming particles and then drying the toner. Manufacturing method. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the binder resin is a polyester resin having a glass transition temperature of 40 ° C. or higher. 7. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the binder resin contains a polyester resin stretched by urethane or / and a urea bond. 8. The method for producing a toner for developing an electrostatic charge image according to claim 7, wherein the polyester resin contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6, wherein the binder resin contains a polyester resin in which the polyester resin is not modified. The binder resin includes a modified polyester resin and an unmodified polyester resin, and the weight ratio of the modified polyester resin to the unmodified polyester resin (modified polyester resin / unmodified polyester resin) is 0/100 to 80 / 10. The method for producing a toner for developing an electrostatic charge image according to claim 8, wherein the toner is 20 (excluding 0). The method for producing a toner for developing an electrostatic image according to claim 1, wherein the toner contains a wax as a release agent. 12. The toner according to claim 11, wherein the toner contains 4 to 30% by weight of one or more selected from paraffins, synthetic esters, polyolefins, carnauba wax, or rice wax as a release agent. A method for producing the toner for developing an electrostatic image according to claim 1. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the toner contains a charge control agent. 14. A toner for non-magnetic one-component development, wherein the toner produced by the method according to claim 1 is used in a non-magnetic one-component development process. 15. An image forming apparatus using the non-magnetic one-component developing toner according to claim 14. The image forming apparatus according to claim 15, wherein the image forming apparatus forms a multicolor image. The image forming apparatus according to claim 15 or 16, wherein the image forming apparatus includes an endless intermediate transfer unit. 18. The image forming apparatus according to claim 15, wherein the image forming apparatus does not include a blade as a residual toner cleaning unit in the photosensitive member and / or the intermediate transfer unit. The image forming apparatus according to claim 15, wherein the image forming apparatus includes a blade cleaning unit. The image forming apparatus according to claim 15, wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device. The image forming apparatus according to claim 15, wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device. The image forming apparatus according to any one of claims 15 to 21, wherein the image forming apparatus includes an oilless fixing unit that does not require oil application to a fixing member. A toner container filled with the electrostatic image developing toner produced by the method according to claim 3. A toner container filled with the non-magnetic one-component developing toner according to claim 14.