JP2007249088A - Developer, image forming apparatus, image forming method, and developer container - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a developer having stable electrification in repeated use. <P>SOLUTION: In the developer containing a toner matrix containing at least a coloring agent and a binder resin, and an external additive particulates added externally in the toner matrix, the external additive particulates contain at least a plurality of kinds of the external additive particulates. At least one of the plurality of the kinds of the external additive particulates is the external additive particulates subjected to surface treatment by an electrification control agent selected from a group consisting of a calixarene compound contained metal azo dye, salicylic acid metal salt, salicylic acid derivative metal salt, and boron complex, and adhesion strength of the external additive particulates subjected to surface treatment by the electrification control agent with the toner matrix is 60% or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a developer, an image forming apparatus, an image forming method, and a developer container.

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

  The toner contained in the developer includes a positively charged toner and a negatively charged toner depending on the electrostatic latent image and the process, and those that impart negative chargeability include a charge control agent such as a metal-containing azo dye, Inorganic powders, organic powders, carrier coating agents, and the like are known.

  For the purpose of improving the flow characteristics and charging characteristics of the toner, it has been proposed to mix and use toner particles and inorganic fine powders such as various metal oxides. It is called an external additive. Further, for the purpose of modifying the hydrophobicity, charging characteristics, etc. of the surface of the inorganic fine powder as required, a method of treating with a specific silane coupling agent, titanate coupling agent, silicone oil, organic acid, etc., a specific A method of coating a resin has also been proposed.

  As the inorganic fine powder, for example, silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, tin oxide and the like are known. In particular, silica particles in which silica or titanium oxide fine particles are reacted with organosilicon compounds such as dimethyldichlorosilane, hexamethyldisilazane, silicone oil, etc. to replace the silanol groups on the surface of the silica fine particles with organic groups are used to make them hydrophobic. .

  Of these, silicone oil is preferable as a hydrophobizing agent that exhibits sufficient hydrophobicity and exhibits excellent transferability due to its low surface energy when contained in the toner. In the techniques described in Patent Document 1 and Patent Document 2, the degree of hydrophobicity of silica treated with silicone oil is defined. Patent Document 3 and Patent Document 4 describe those in which the amount of silicone oil added and the carbon content in the additive are defined.

  In order to hydrophobize the inorganic fine particles that are the base material of the external additive and ensure the stability of the charging property of the developer under high humidity, the content of the silicone oil and the degree of hydrophobicity in the above-mentioned publications are used. It is not satisfactory.

  In addition, for the purpose of improving charging characteristics, various types of charge control agents and methods for incorporating them in toners have been studied. In Patent Document 5, Patent Document 6, Patent Document 7, and Patent Document 8, an attempt is made to impart chargeability to the toner by attaching a charge control agent to the toner particle surface, but the chargeability is not sufficient, and the toner is detached from the surface. It is easy, and its manufacturing method cannot provide the desired chargeability.

  In addition, a method of dry-processing the charge control agent on the toner surface using a Henschel mixer is also conceivable, but this also does not provide the intended chargeability, and the charge control agent is gradually released by the pressure of the toner regulating member. In addition, the floating charge control agent contaminates the developing roller and causes a charging failure.

Therefore, it is desired to provide a developer that is improved in chargeability and stable during durability.
Japanese Patent Publication No.7-3600 Japanese Patent No. 2568244 Japanese Patent Laid-Open No. 7-271087 JP-A-8-292598 JP 63-104064 A JP 05-119513 A JP 09-127720 A JP 11-327199 A

  An object of the present invention is to provide a developer, an image forming apparatus, an image forming method, and a developer container that can solve at least one of the problems of the prior art.

  A first aspect of the present invention is a developer comprising a toner base containing at least a colorant and a binder resin, and external additive fine particles added externally to the toner base, wherein the external additive fine particles are: A group comprising at least a plurality of types of external additive fine particles, wherein at least one of the plurality of types of external additive fine particles comprises a calixarene compound-containing metal azo dye, a salicylic acid metal salt, a metal salt of a salicylic acid derivative, and a boron complex. Externally added fine particles surface-treated with a charge control agent selected from the above, wherein the adhesion strength between the toner base and the externally added fine particles surface-treated with the charge control agent is 60% or more. Developer.

  Regarding “at least plural types of external additive fine particles”, “multiple types” means external additive particles having different types of external additives, particle sizes, prescription amounts, ratios of plural types of external additives, surface treatment, and the like. Indicates that multiple types are included.

  A second aspect of the present invention is an image forming apparatus that forms an image using the developer according to the first aspect of the present invention.

  A third aspect of the present invention is an image forming method characterized in that an image is formed using the developer according to the first aspect of the present invention.

  A fourth aspect of the present invention is a developer container filled with the developer according to the first aspect of the present invention.

  According to the present invention, it is possible to provide a developer, an image forming apparatus, an image forming method, and a developer container that can solve at least one of the problems of the prior art.

  Next, embodiments of the present invention will be described with reference to the drawings.

  First, the following configurations (1) to (20) are provided as embodiments of the present invention.

  (1) In a developer containing a toner base containing at least a colorant (colorant), a release material and a binder resin, and external additive fine particles added externally to the toner base, the external additive fine particles are: It contains at least a plurality of types of external additive fine particles, at least one of which is surface-treated with a charge control agent selected from a calixarene compound-containing metal azo dye, a salicylic acid metal salt, a metal salt of a salicylic acid derivative, and a boron complex. A developer characterized in that the adhesion strength with externally added fine particles which are additive fine particles and surface-treated with the charge control agent is 60% or more.

  (2) The electrostatic image developing toner according to (1), wherein the binder resin is a polyester resin having a glass transition temperature of 40 ° C. or higher. The glass transition temperature of the polyester resin having a glass transition temperature of 40 ° C. or higher is preferably 75 ° C. or lower. When the glass transition temperature exceeds 75 ° C., it is difficult to ensure low temperature fixing performance.

  (3) The electrostatic image developing toner according to (1) or (2), wherein the binder resin described above contains a polyester resin extended by urethane or / and a urea bond.

  (4) In any one of (1) to (3), the polyester resin described above contains a polyester resin component formed by a reaction between a modified polyester resin having an isocyanate group at the terminal and amines. The toner for developing an electrostatic image according to the description.

  (5) The electrostatic charge image development according to any one of (1) to (4), wherein the toner has a circularity of 0.95 or more and less than 0.99 and a volume average particle diameter of 4 to 8 microns. Toner.

  (6) The toner for developing an electrostatic charge image according to any one of (1) to (5), wherein the toner described above is obtained by removing an organic solvent after forming particles in an aqueous medium.

  (7) The toner according to any one of (1) to (6), wherein the toner described above is obtained by subjecting the toner to a washing treatment with a washing aqueous medium after forming particles in the aqueous medium and then drying the toner. Toner for developing electrostatic images.

  (8) The mold release material described above contains one or more selected from paraffins, synthetic esters, polyolefins, carnauba wax, or rice wax, (1) to (7) The toner for developing an electrostatic image according to any one of the above.

  (9) The toner for developing an electrostatic charge image according to any one of (1) to (8), wherein the toner described above contains a charge control agent.

  (10) The electrostatic image developing toner according to any one of (1) to (9), wherein the toner described above is a non-magnetic one-component developing toner.

  (11) An image forming apparatus using the non-magnetic one-component developing toner described in (10).

  (12) The image forming apparatus according to (11), wherein the image forming apparatus is an apparatus for forming a multicolor image.

  (13) The image forming apparatus according to (11) or (12), wherein the image forming apparatus includes an endless intermediate transfer unit.

  (14) The image forming apparatus according to any one of (11) to (13), wherein the image forming apparatus does not include a blade as a residual toner cleaning unit in the photoreceptor or / and the intermediate transfer unit.

  (15) The image forming apparatus according to any one of (11) to (14), wherein the image forming apparatus includes a blade cleaning unit.

  (16) The image forming apparatus according to any one of (11) to (15), wherein the image forming apparatus includes a fixing unit using a roller provided with a heating device.

  (17) The image forming apparatus according to any one of (11) to (16), wherein the image forming apparatus includes a fixing unit using a belt provided with a heating device.

  (18) The image forming apparatus according to any one of (11) to (17), wherein the image forming apparatus includes an oilless fixing unit that does not require oil application to a fixing member.

(19) A toner container filled with the electrostatic image developing toner according to any one of (1) to (9).
(20) A toner container filled with the nonmagnetic one-component developing toner according to (10).

  Next, embodiments of the present invention will be described in more detail.

  The toner of the present invention will be described below with specific examples.

  The toner manufacturing method includes, for example, a prepolymer composed of at least a modified polyester resin in an organic solvent, a solution suspension method published in Journal of the Imaging Society of Japan, Vol. 43, No. 1 (2004), and a toner component. It is intended for a novel polymerization method in which a toner is obtained by dissolving or dispersing a material, subjecting the solution or dispersion to a crosslinking reaction and / or elongation reaction in an aqueous medium, and removing the solvent from the obtained dispersion. 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 component and / or a radical generator are dissolved or dispersed in an organic solvent, The solvent is removed by emulsifying or dispersing dissolved or dispersed materials (called oil phases) in an aqueous medium in the presence of a radical generator. It is a manufacturing method such as get over. Hereinafter, this production method will be described.

I. Oil phase material <1-1 polyester resin>
The binder resin of the present invention uses a polyester resin that does not contain a vinyl polymerizable group, and the polyester is a so-called modified polyester obtained from an unmodified polyester obtained from a polycarboxylic acid and a polyol and a polyester prepolymer having an isocyanate group. Known polyester resins such as polyester can be used, or a single type or a combination of two or more types may be used.

<Outline of I-2 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 product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be 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.

<About I-2-1 polyol>
Examples of the polyol (1) include 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, Ethylene 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, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, and the like; bis (3-fluoro-4-hydroxypheny ) 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 (also known as: tetrafluorobisphenol A), bis (hydroxy) such as 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Phenyl) 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, etc.) Adducts; alkylene oxides of the above bisphenols (ethylene 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, polyhydric aliphatic alcohols having 3 to 8 or more valences (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or more phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric 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>
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (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′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic 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, polycarboxylic acids having 3 or more valences include 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.

<Ratio of I-2-3 polyol and polycarboxylic acid>
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

<I-2-4 polyisocyanate>
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

<Ratio of I-2-5 isocyanate group and hydroxyl group>
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.

<Number of isocyanate groups in I-2-6 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 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.

<I-2-7 crosslinker and extender>
In the present invention, amines can be used as a crosslinking agent and / or an 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, tetracosafluorododecylenediamine) Etc.).

  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 the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

  Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

<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).

<Ratio of I-2-9 amino group and isocyanate group>
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.

<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, the low-temperature fixability and the glossiness when used in a full-color apparatus 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 with each other 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 of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 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.

<Molecular weight of I-3-1 unmodified polyester>
The peak molecular weight of (C) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. 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 0.5 to 40, preferably 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 Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, 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, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon 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.

<Making master batch of I-4-1 colorant>
The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, 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-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

<I-4-2 Master batch creation method>
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. 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 colorant is mixed and kneaded with resin and 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 solution (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>
Further, 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 wax properties and applications 2nd edition” supervised by Kenzo Fusegawa, etc. 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 such as montan wax, ozokerite and ceresin Include fatty acid amide synthetic wax, such as an object-based wax and stearic acid amide.

Of these, polyolefins, paraffins, synthetic esters, carnauba wax, and rice wax are preferable, and these 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 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 that it does not 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 and 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.

<Organic solvent of I-6 oil phase>
In the toner according to the present invention, a toner composition comprising at least a polyester and a colorant as a binder resin is dissolved or dispersed in an organic solvent, and the dissolved or dispersed material is inorganicly dispersed in an aqueous medium in which a radical generator is present. It can be obtained by emulsifying or dispersing in the presence of an agent or resin fine particles, and then removing the solvent. The polyester as the binder resin does not contain a vinyl polymerizable group.

  An organic solvent for dissolving or dispersing a toner composition composed of a polyester resin and a colorant has a Hansen solubility parameter of 19.5 or less described in Volume 2, Section VII of “POLYMER HANDBOOK” 4th Edition, WILEY-INTERSCIENCE, for example. Is preferred. Further, it is particularly preferable that the boiling point is less than 150 ° C. from the viewpoint of easy removal of the solvent later. 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 media>
Next, as an aqueous medium to be used, water alone may be used, but 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 20000 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 radical generator>
As the radical generator of the present invention, those known as so-called polymerization initiators can be used, and examples thereof include those described in Volume 1, Section II of “POLYMER HANDBOOK” 4th Edition, WILEY-INTERSCIENCE. 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 this.

  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 The (t-butylperoxy) triazine peroxide polymerization initiator or a peroxide, such as and the like polymeric initiator having a 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 an inorganic dispersant or resin fine particles.

  As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

<II-4 resin fine particles>
In addition, 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. Two or more of these resins may be used in combination. 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.

<Description of II-4-1 vinyl resin>
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. 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 alpha monoolefins, 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 acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-C24) ester, such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic 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-methyl styrene sulfonic acid 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) acrylamido-2-methylpropanesulfonic acid, 3 -(Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) mono (meth) acrylate sulfuric acid Ester [poly (n = 5-15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate,
(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl phosphate monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) 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 monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl 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 monomer:
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-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.

  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 cation 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 monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl 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-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, Vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxyacrylate, 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, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) ) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (2 Each alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraaryl. Roxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) ac Lilate, lauryl alcohol ethylene oxide 30-mole 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, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxy Ethyl ether, 3,4-dihumanro-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 element-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-octafluoro Pentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyl (Meth) acrylate, trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate, 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) 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 Tylate, vinyl perfluoroheptanoate, vinyl perfluorononanoate, vinyl perfluorooctanoate and the like.

<II-4-2 Vinyl Copolymer>
Examples of the vinyl monomer copolymer include a polymer obtained by copolymerizing any of the above-mentioned monomers (1) to (10) with 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- ( A meth) acrylic acid copolymer, a styrene- (meth) acrylic acid, a divinylbenzene copolymer, a 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).

<Monomer ratio of II-4-3 vinyl resin>
Since the resin forms 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 between 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 preferable that it is 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 Dispersion method of resin fine particles in water>
The method for 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.

<Particle size of II-4-5 resin fine particles>
The particle size of the resin fine particles is usually smaller than the particle size of the toner, and from the viewpoint of particle size uniformity, the value of the particle size ratio [volume average particle size of resin fine particles] / [volume average particle size of toner] is A range of 0.001 to 0.3 is preferable. 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 in order to emulsify and disperse the oily 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 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 Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-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 Such as 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, Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, 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 may remain on the surface of the toner particles, but 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 currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or 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. 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. Surface treatment As a means for surface-treating the charge control agent on the surface of the external additive fine particles, the charge control agent was dissolved in THF or ethanol to prepare a 1 to 20% solution. After stirring and mixing with the externally added fine particles, the solvent was removed using an evaporator and dried to obtain treated externally added fine particles. Next, the treated product was crushed using a mortar and sieved with a 105 μm mesh sieve to obtain surface-treated fine particles.

VIII. Charge control agents All 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. (Including 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 phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical 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.

<Amount of VIII-1 charge control agent>
The amount of the charge control agent is preferably 0.1 to 5% with respect to 100 parts by weight of the toner solid content, more preferably 0.3 to 3%, and 0.1% to 20% is preferable, and more preferably 0.3 to 10%.

IX. Immobilization treatment As a means for immobilizing the external additive fine particles on the surface of the toner particles, either a dry type or a wet type may be used. For example, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a cosmos system, a crypt. Surface reformer using high-speed air impact method such as Ron System (Kawasaki Heavy Industries), Inomizer System (Hosokawa Micron), Mechano Fusion System (Hosokawa Micron), Mechano Mill (Okada Seiko), etc. Surface reformer using dry mechanochemical method, surface reformer applying hot-air reforming method such as surfing system, Dispercoat (Nisshin Flour Mills), Coat Mizer (Freund Sangyo) High-speed rotation with a surface modification device, Q-type mixer, Henschel mixer, etc. An inversion type mixing mixer may be used, and these can be used in appropriate combination. Moreover, you may flow the temperature-controlled warm water (a jacket cooling part etc.) to these, and may promote a fixed degree.

X. External addition treatment Composite particles obtained by mixing with the obtained toner powder after drying together with external additive fine particles or immobilizing and fusing on the surface by applying mechanical impact force to the mixed powder It is possible to prevent the detachment of the foreign particles from the surface. 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.

XI. External additive <X-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 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 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, silica 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.

<XI-2 polymer fine particles>
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

<Surface treatment of XI-3 external additive>
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

XII. 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.

XIII. Base Charge Control Agent The toner base of the present invention may contain a charge control agent as necessary.

<Amount of XIII-1 charge control agent>
The content of the charge control agent in the toner base is uniquely determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These can be melt-kneaded together with the masterbatch and the resin, or may be added when dissolved and dispersed in an organic solvent.

  The toner was analyzed and evaluated as follows.

<Particle size (Coulter)>
Next, a method for measuring the particle size distribution of toner particles will be described.

  Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include 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 an aqueous electrolytic solution. Here, the electrolytic solution is prepared by preparing an about 1% NaCl aqueous solution using primary sodium chloride, and 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 electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measuring device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and 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 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

<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 an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. 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. .

<Molecular weight>
The molecular weights of the polyester resin and vinyl copolymer resin used were measured under the following conditions by normal GPC (gel permeation chromatography).

・ Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-M x 3
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 0.35 ml / min ・ Sample: 0.01 ml injection of a sample having a concentration of 0.05 to 0.6% A molecular weight calibration curve prepared by a monodisperse polystyrene standard sample from the molecular weight distribution of the toner resin measured under the above conditions Was used to calculate the weight average molecular weight Mw. As the monodisperse polystyrene standard sample, 10 samples in the range of 5.8 × 100 to 7.5 × 1000000 were used.

<Glass transition point>
For measuring the glass transition point of the polyester resin or vinyl copolymer resin to be used, for example, using a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.) After heating at 150 ° C. for 10 minutes, let stand at 150 ° C. for 10 minutes, cool the sample to room temperature, leave it for 10 minutes, and again heat to 150 ° C. at a heating rate of 10 ° C./min. The height of the baseline above the glass transition point can be obtained from a curved portion corresponding to ½.

<Adhesion strength>
Wet 4 g of toner in 40 g of 0.2% aqueous solution of polyoxyethyl phenyl ether, and use ultrasonic homogenizer US-1200T (manufactured by Nippon Seiki Co., Ltd .; specification frequency: 15 kHz) to transmit ultrasonic energy to the main unit. The residual ratio of the first and second inorganic fine particles after adjusting the value of the ammeter indicating the value to indicate 60 μA (50 w) and applying for 5 minutes is calculated by fluorescent X-ray, and is defined as the adhesion strength.

<Evaluation of charge amount>
The toner (developer) subjected to the external addition treatment was continuously printed in a N / N environment (23 ° C., 45%) with a predetermined print pattern having a B / W ratio of 6% using Ricoh ipsio CX2500. After continuous printing of 50 and 2000 sheets in N / N environment (after endurance), the toner on the developing roller during blank pattern printing is sucked and the amount of charge is measured with an electrometer. After 50 and 2000 sheets The charge amount of was evaluated.

○: The absolute value of the charge amount difference is in the range of 15 to 25 μC / g. Δ: The absolute value of the charge amount difference is in the range of 10 μC / g to 15 μC / g. X: The absolute value of the charge amount difference is 10 μC / g or less < Filming evaluation>
The toner (developer) subjected to the external addition treatment was continuously printed in a N / N environment (23 ° C., 45%) with a predetermined print pattern having a B / W ratio of 6% using Ricoh ipsio CX2500. After continuous printing (after endurance) in an N / N environment, the photosensitive member and the intermediate transfer belt were visually observed and evaluated. Judgment criteria are as follows.

○: There was no filming on the photosensitive member and the intermediate transfer member, and there was no problem at all;
Δ: Filming was observed on one of the photosensitive member and the intermediate transfer member, but it was not visible on the copied image, and there was no practical problem;
X: Filming occurred on the photoreceptor and / or the intermediate transfer member, which could be confirmed on the image, and there was a problem in practical use.

  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 into 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.

<Synthesis of prepolymer>
In a reaction vessel equipped with a condenser, 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, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg 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 tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of master batch>
Carbon black (Regal 400R manufactured by Cabot Corporation): 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)>
In a container in which a stir bar and a thermometer are set, 378 parts of [Low molecular weight polyester 1], 127 parts of paraffin wax, 127 parts of WAX dispersant described in JP-A-2004-246305, and 947 parts of ethyl acetate are charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged 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 Koki Kogyo Co., Ltd.) at 5,000 rpm for 1 minute, add 1200 parts of [aqueous phase 1] and using TK homomixer for 15 minutes at 13,000 rpm. By mixing, [Emulsified slurry 1] was obtained.

<Desolvent>
[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].

<Washing->Drying>
[Dispersion Slurry 1] After filtering 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.

<Surface treatment ⇒ External addition>
(1) Sample 1 was prepared by subjecting 10 parts of S-34 to 100 parts of silica NAX50.

  (2) 100 parts of [toner base 1] and 1 part of sample were mixed with a Henschel mixer, and 0.5 part of silica TG-811 and 1 part of NX90 were mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds). By mixing, developer A of the present invention was obtained.

  The evaluation results are shown in Table 2. The evaluation results of Examples and Comparative Examples are summarized.

  In Examples 2 to 7 and Comparative Examples 1 to 4, the type and amount of externally added fine particles and the type of organic compound having charge controllability in the immobilization of Example 1 were changed as shown in Table 1, and external additives were added. The same procedure as in Example 1 was performed except that the treatment was changed as shown in Table 2.

以上、本発明の実施の形態及び実施例を具体的に説明してきたが、本発明は、これらの実施の形態及び実施例に限定されるものではなく、これら本発明の実施の形態及び実施例を、本発明の主旨及び範囲を逸脱することなく、変更又は変形することができる。

Although the embodiments and examples of the present invention have been specifically described above, the present invention is not limited to these embodiments and examples, and these embodiments and examples of the present invention are not limited thereto. Can be changed or modified without departing from the spirit and scope of the present invention.

  The present invention can be applied to a toner for developing an electrostatic image. Further, the toner of the present invention can be used as it is for colored particles for electronic paper.

Claims (20)

In a developer containing a toner base containing at least a colorant and a binder resin, and external additive fine particles added externally to the toner base,
The external additive fine particles include at least a plurality of types of external additive fine particles,
At least one of the plural types of external additive fine particles is surface-treated with a charge control agent selected from the group consisting of calixarene compound metal-containing azo dyes, salicylic acid metal salts, metal salts of salicylic acid derivatives, and boron complexes. Externally added fine particles,
A developer characterized in that the adhesion strength between the toner base and the externally added fine particles surface-treated with the charge control agent is 60% or more.   The developer according to claim 1, wherein the binder resin is a polyester resin having a glass transition temperature of 40 ° C. or higher and 75 ° C. or lower.   The developer according to claim 1, wherein the binder resin contains a polyester resin stretched by urethane and / or urea bonds.   The developer according to any one of claims 1 to 3, 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.   5. The circularity of the developer is 0.95 or more and less than 0.99, and the volume average particle diameter of the developer is 4 microns or more and less than 8 microns. The developer described in 1.   The developer according to claim 1, wherein the developer is obtained by removing the organic solvent after forming the particles in an aqueous medium.   The developer according to any one of claims 1 to 6, wherein the developer is obtained by carrying out a washing treatment with an aqueous medium for washing after particle formation in an aqueous medium, and then performing a drying treatment. Further including a release agent,
The release agent contains one or more compounds selected from paraffins, synthetic esters, polyolefins, carnauba wax, or rice wax. The developer described in 1.   The developer according to claim 1, comprising a charge control agent.   The developer according to claim 1, wherein the developer is a non-magnetic one-component developing toner.   An image forming apparatus that forms an image using the developer according to claim 1.   The image forming apparatus according to claim 11, wherein the image forming apparatus forms a multicolor image.   The image forming apparatus according to claim 11, further comprising an endless intermediate transfer unit.   The image forming apparatus according to claim 11, wherein the photosensitive member and / or the intermediate transfer unit includes a residual toner cleaning unit that does not include a blade.   The image forming apparatus according to claim 11, further comprising a blade cleaning unit.   The image forming apparatus according to claim 11, further comprising a fixing unit using a roller provided with a heating device.   The image forming apparatus according to claim 11, further comprising a fixing unit using a belt provided with a heating device.   18. The image forming apparatus according to claim 11, further comprising an oilless fixing unit that does not require oil application to the fixing member.   An image forming method comprising forming an image using the developer according to claim 1.   A developer container filled with the developer according to claim 1.