JP6146184B2 - Toner, developer, developer container and image forming apparatus - Google Patents

Description

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

  Conventionally, inorganic particles having an average primary particle size of several nanometers to several tens of nanometers have been used as external additives for toner. Specifically, hydrophobized silica particles are used from the viewpoint of imparting chargeability, imparting fluidity, imparting hydrophobicity, etc., and the electrification property under temperature / humidity environmental conditions is used. From the viewpoint of maintaining and suppressing fluctuations in the retained charge amount, hydrophobized titanium oxide particles and the like are used.

  On the other hand, organic particles are also used as an external additive for toner.

  Patent Document 1 discloses a powder toner for image formation in which toner particles having a particle size dispersity of 1.2 or less are used as mother particles and polyimide fine particles are externally added to the mother particles.

  However, there are problems that heat-resistant storage stability is reduced, transfer defects and background stains occur.

  An object of one embodiment of the present invention is to provide a toner that is excellent in heat-resistant storage stability and can suppress generation of transfer failure and background contamination in view of the problems of the above-described conventional technology.

  According to one embodiment of the present invention, a toner includes base particles containing a binder resin and an external additive. The external additive includes polyimide particles, and the polyimide particles have a median diameter of 25 nm to 120 nm. .

  According to one embodiment of the present invention, it is possible to provide a toner that is excellent in heat-resistant storage stability and can suppress the occurrence of transfer failure and background contamination.

  Next, the form for implementing this invention is demonstrated.

  The toner has base particles including a binder resin and an external additive, and the external additive includes polyimide particles.

  The median diameter d50 of the polyimide particles is 12 to 120 nm, and preferably 25 to 80 nm. When the median diameter d50 of the polyimide particles is less than 12 nm, the heat-resistant storage stability of the toner is deteriorated, and when it exceeds 120 nm, transfer defects and background staining occur.

  The ratio of the volume average particle diameter Dv to the number average particle diameter Dn of the polyimide particles is usually 1.1 to 1.4, preferably 1.2 to 1.3.

  The particle size distribution of the polyimide particles can be measured by a laser diffraction / scattering method.

  Unlike inorganic particles, polyimide particles have high hydrophobicity and chargeability of the material itself, so that hydrophobic treatment for imparting hydrophobicity and adjusting chargeability can be omitted or simplified. As a result, performance changes due to external stress are less likely to occur, and changes in chargeability and hydrophobicity are less likely to occur. As a result, the effect can be maintained over a long period of time, and the toner can be provided with durability, environmental characteristics, and hydrophobicity.

  The polyimide particles can be synthesized by reacting tetracarboxylic anhydride and diisocyanate to synthesize a polyimide precursor and then imidizing the polyimide precursor.

  Although tetracarboxylic anhydride is not particularly limited, hexahydropyromellitic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (BTDA), 3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene Anhydride, 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′- Benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, naphthalene-1,2, 4,5-tetraca Aromatic tetracarboxylic acid anhydrides such as boronic acid dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride; butane -1, aliphatic tetracarboxylic anhydrides such as 1,2,3,4-tetracarboxylic dianhydride; alicyclic tetracarboxylic anhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride Thiophene-2,3,4,5-tetracarboxylic acid anhydride, heterocyclic tetracarboxylic acid anhydrides such as pyridine-2,3,5,6-tetracarboxylic acid anhydride, etc. You may use together. Of these, BTDA and pyromellitic dianhydride are preferable.

  The diisocyanate is not particularly limited, but 1,4-hexacyclodiisocyanate, 1,3-diisocyanatecyclohexane, m-xylene diisocyanate, hexamethylene diisocyanate, 1,3-bisisocyanate methylcyclohexane, 2,4-diisocyanate-1- Examples include methylcyclohexane, toluene-2,4-diisocyanate, methylenediphenyl diisocyanate, 1,3-diisocyanate-2-methylcyclohexane, methylenedicyclohexyl diisocyanate, isophorone diisocyanate, and the like. Among these, 1,4-hexacyclodiisocyanate, toluene-2,4-diisocyanate, and isophorone diisocyanate are preferable.

  The temperature at which tetracarboxylic anhydride and diisocyanate are reacted is usually about 0 to 130 ° C, and preferably 20 to 40 ° C.

  The reaction time of tetracarboxylic anhydride and diisocyanate is usually about 30 seconds to 120 minutes.

  The molar ratio of diisocyanate to tetracarboxylic anhydride when reacting tetracarboxylic anhydride with diisocyanate is usually 0.5 to 1.5, preferably 0.9 to 1.1.

  Tetracarboxylic anhydride and diisocyanate are preferably reacted in a solvent.

  Tetracarboxylic anhydride and diisocyanate can also be reacted in the presence of an amine catalyst. Thereby, a polyimide precursor can be efficiently synthesized.

  The amine catalyst is not particularly limited, but 1,4-diazabicyclo [2.2.2] octane, triethylamine, benzyldimethylamine, 2-dimethylaminomethylphenol, 2,4,6-tris-dimethylaminomethyl-3. -Isocyanate phenol etc. are mentioned, You may use 2 or more types together. Among these, 1,4-diazabicyclo [2.2.2] octane and triethylamine are preferable.

  It is preferable to react tetracarboxylic anhydride and diisocyanate while stirring with ultrasonic waves using a known ultrasonic device (for example, ultrasonic cleaner). Thereby, the fine and highly monodisperse polyimide particles can be synthesized.

  At this time, the median diameter of the polyimide particles can be controlled by the frequency of the ultrasonic waves.

  When the tetracarboxylic anhydride and the diisocyanate are reacted, it is preferable to mix a solution in which the tetracarboxylic anhydride is dissolved in the organic solvent and a solution in which the diisocyanate is dissolved in the organic solvent.

  The organic solvent is not particularly limited as long as the resulting polyimide precursor does not dissolve, but 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), acetic acid Examples thereof include ethyl, acetanilide, methanol, ethanol, isopropanol, toluene, xylene and the like, and two or more of them may be used in combination.

  In addition, it can adjust so that a polyimide precursor may not melt | dissolve by mixing the good solvent of a polyimide precursor, and the poor solvent of a polyimide precursor.

  The good solvent for the polyimide precursor is not particularly limited, but aprotic polarities such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), etc. A solvent etc. are mentioned.

  Although it does not specifically limit as a poor solvent of a polyimide precursor, Acetone, ethyl acetate, MEK, toluene, xylene, etc. are mentioned.

  The concentration of the tetracarboxylic anhydride solution is usually about 0.001 to 0.20 mol / L, preferably 0.01 to 0.10 mol / L.

  The concentration of the diisocyanate solution is usually about 0.001 to 0.20 mol / L, preferably 0.01 to 0.10 mol / L.

  The polyimide precursor can be recovered by solid-liquid separation using a known method such as a centrifugal separation method.

  The polyimide precursor can be imidized by a carbon dioxide removal reaction. In other words, the polyimide precursor is a substance capable of generating polyimide by carbon dioxide removal. For example, a polyimide precursor can be synthesized by reacting hexahydropyromellitic anhydride as tetracarboxylic acid anhydride and trans-1,4-hexacyclodiisocyanate as diisocyanate.

  When mixing the base particles and the external additive, a mixer can be used, but it is preferable to adjust the internal temperature by providing a jacket or the like.

  In order to change the history of the load applied to the external additive, the external additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Moreover, after applying a strong load, a weak load may be applied and vice versa.

  Although it does not specifically limit as a mixer, A V-type mixer, a rocking mixer, a Laedige mixer, a Nauter mixer, a Henschel mixer, etc. are mentioned.

  The content of polyimide particles in the toner is usually 2 to 10% by mass. When the content of the polyimide particles in the toner is less than 2% by mass, the storage stability of the toner and performance maintenance in the environment are not sufficient, and the toner particles may be fused together. Deterioration or degradation of image quality called background contamination may occur.

  As the external additive, inorganic particles can be used in combination with polyimide particles. Thereby, the fluidity, developability, and chargeability of the toner can be improved.

  The inorganic particles are not particularly limited, but include titanium oxide particles, silicon oxide (silica) particles, alumina particles, barium titanate particles, magnesium titanate particles, calcium titanate particles, strontium titanate particles, zinc oxide particles, tin oxide. Examples include particles, fatty acid metal salt particles such as zinc stearate particles and calcium stearate particles, layered double hydroxide particles such as hydrotalcite particles, and the like. Of these, hydrophobically-treated titanium oxide particles and hydrophobically-treated silica particles are preferable.

  Specific examples of the titanium oxide particles that have been subjected to hydrophobic treatment include rutile-type titanium oxide that has been subjected to hydrophobic treatment with isobutyl.

  Specific examples of the silica particles that have been hydrophobically treated include hydrophobic silica that has been treated with hexamethyldisilazane.

  The binder resin is not particularly limited, but is a homopolymer of styrene such as polystyrene, poly (p-chlorostyrene), polyvinyltoluene and the like, a styrene-p-chlorostyrene copolymer, and a styrene-propylene copolymer. Polymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, styrene-isopropylene Copolymer, styrene copolymer such as styrene-maleic acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polyester, polyurethane, epoxy resin, polyvinyl butyral , Polyacrylic acid, rosin, modified rosin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic petroleum resin, and the like. Among these, amorphous polyester is preferable, urea-modified polyester is more preferable, a combination of urea-modified polyester and amorphous polyester, and a combination of urea-modified polyester, amorphous polyester, and crystalline polyester are also preferable.

  The non-crystalline polyester is a so-called unmodified polyester (non-modified polyester) that does not contain other than an ester bond (including only an ester bond) as a bonding unit.

  A non-crystalline polyester can be combined with a urea-modified polyester and a crystalline polyester to form a binder resin. For example, amorphous polyester and urea-modified polyester can be used as a binder resin.

  The combined use of urea-modified polyester and non-crystalline polyester improves low-temperature fixability and gloss when used in a full-color device, and is preferable to using urea-modified polyester alone.

  It is preferable in terms of low-temperature fixability and hot offset resistance that the urea-modified polyester and the amorphous polyester are at least partially compatible. For this reason, it is preferable that the polyester component constituting the urea-modified polyester is similar to the component constituting the amorphous polyester.

  The peak molecular weight of the amorphous polyester is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When the peak molecular weight of the amorphous polyester is less than 1000, the heat-resistant storage stability of the toner may be lowered, and when it exceeds 30000, the low-temperature fixability of the toner may be lowered.

  The weight average molecular weight of the amorphous polyester is usually 2000 to 90000.

  The glass transition point of the amorphous polyester is usually 40 to 80 ° C.

  The hydroxyl value of the amorphous polyester is usually 5 mgKOH / g or more, preferably 10 to 120 mgKOH / g, more preferably 20 to 80 mgKOH / g. When the hydroxyl value of the amorphous polyester is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability of the toner.

  The acid value of the amorphous polyester is usually 1 to 30 mgKOH / g, and preferably 5 to 20 mgKOH / g. When the acid value of the non-crystalline polyester is less than 1 mgKOH / g, the toner may be difficult to be negatively charged. When the acid value exceeds 30 mgKOH / g, the image deteriorates under high temperature and high humidity and low temperature and low humidity. Sometimes.

  The urea-modified polyester includes an ester bond and a urea bond as a bond unit. The urea-modified polyester can be synthesized by reacting a compound having an amino group with a polyester prepolymer having an isocyanate group.

  For example, if the binder resin contains a urea-modified polyester produced by reacting an isocyanate group-containing polyester prepolymer with an isocyanate group as a binder resin precursor, the minimum fixing temperature and the hot offset occurrence temperature Can be widened and the mold release width can be improved. Further, by coexisting urea-modified polyester as the binder resin, the heat resistant storage stability of the toner tends to be good even when the glass transition point of the binder resin is low.

  The polyester prepolymer having an isocyanate group can be synthesized by reacting a polyester having a hydroxyl group with a polyisocyanate.

  The polyester having a hydroxyl group can be synthesized by polycondensation of a polyol and a polycarboxylic acid.

  The divalent polyol is not particularly limited, but alkylene glycol (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol), alkylene Ether glycol (for example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol), alicyclic diol (for example, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A), bisphenol (For example, 4,4′-dihydroxybiphenyls such as bisphenol A, bisphenol F, bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, (3-fluoro-4-hydroxyphenyl) 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), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3 Bis (hydroxyphenyl) alkanes such as hexafluoropropane, bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether, alkylene oxides of the above alicyclic diols (for example, ethylene Oxides, propylene oxides, butylene oxides) adducts, the above bisphenols Examples include adducts such as ethylene oxide, propylene oxide, butylene oxide, and the like, which may be used in combination of two or more, among them, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols. Preferably, an alkylene oxide adduct of bisphenols, an alkylene oxide adduct of bisphenols and an alkylene glycol having 2 to 12 carbon atoms are more preferred.

  Although it does not specifically limit as a polyol more than trivalence (for example, glycerin, a trimethylol ethane, a trimethylol propane, pentaerythritol, sorbitol), a trihydric or more phenols (for example, Trisphenol PA, phenol novolac, cresol novolac), alkylene oxide adducts of the above trivalent or higher polyphenols, and the like, and two or more of them may be used in combination.

  Examples of the divalent polycarboxylic acid include alkylene dicarboxylic acid (for example, succinic acid, adipic acid, sebacic acid), alkenylene dicarboxylic acid (for example, maleic acid, fumaric acid), and aromatic dicarboxylic acid (for example, 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 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) and the like, and two or more of them may be used in combination. Among these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

  Examples of the trivalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid), and two or more kinds may be used in combination.

  In place of polycarboxylic acid, polycarboxylic acid anhydride, lower alkyl ester (for example, methyl ester, ethyl ester, isopropyl ester) or the like may be used.

  The molar ratio [OH] / [COOH] of the polyol hydroxyl group to the carboxyl group of the polycarboxylic acid when synthesizing the polyester having a hydroxyl group is usually 1 to 2, preferably 1 to 1.5, More preferably, it is 1.02-1.3.

  The peak molecular weight of the polyester having a hydroxyl group is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When the peak molecular weight of the polyester having a hydroxyl group is less than 1000, the heat-resistant storage stability of the toner may be lowered, and when it exceeds 30000, the low-temperature fixability of the toner may be lowered.

  Although it does not specifically limit as polyisocyanate, Aliphatic polyisocyanate (for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate), alicyclic polyisocyanate (for example, isophorone diisocyanate, cyclohexyl methane) Diisocyanate), aromatic diisocyanate (for example, tolylene diisocyanate, diphenylmethane diisocyanate), araliphatic diisocyanate (for example, α, α, α ′, α′-tetramethylxylylene diisocyanate), isocyanurates, and the like. Two or more species may be used in combination.

  Instead of polyisocyanate, a compound in which the isocyanate group of polyisocyanate is blocked with a phenol derivative, oxime, caprolactam or the like may be used.

  The molar ratio [NCO] / [OH] of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester prepolymer having a hydroxyl group in the synthesis of the polyester prepolymer having an isocyanate group is usually 1 to 5, 4 is preferable, and 1.5 to 2.5 is more preferable. When [NCO] / [OH] is less than 1, the offset resistance of the toner may be lowered, and when it exceeds 5, the low-temperature fixability of the toner may be lowered.

  The content of the component derived from polyisocyanate in the polyester prepolymer having an isocyanate group is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and 2 to 20% by mass. More preferably. When the content of the polyisocyanate-derived constituent component in the polyester prepolymer having an isocyanate group is less than 0.5% by mass, the offset resistance of the toner may be reduced, and when it exceeds 40% by mass, Low temperature fixability may be reduced.

  The number of isocyanate groups contained in the polyester prepolymer is usually 1 or more, preferably 1.5 to 3, and more preferably 1.8 to 2.5. If the number of isocyanate groups in the polyester prepolymer is less than 1, the offset resistance of the toner may be lowered.

  The compound having an amino group is not particularly limited, and examples thereof include diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, and amino acid.

  Examples of the diamine include aromatic diamines (for example, phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine), and alicyclic diamines (for example, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc.), aliphatic diamines (eg, ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluoride) Decylene diamine) and the like.

  Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetraamine.

  Examples of amino alcohols include ethanolamine and hydroxyethylaniline.

  Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan.

  Examples of amino acids include aminopropionic acid and aminocaproic acid.

  In place of the compound having an amino group, a compound such as ketimine or oxazoline in which the amino group is blocked with a ketone (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone) may be used.

  When the polyester prepolymer having an isocyanate group and the compound having an amino group are reacted, the molar ratio [NCO] / [NHx] of the isocyanate group of the polyester prepolymer to the amino group of the compound having an amino group is usually 0.5. To ˜2, preferably 2/3 to 1.5, and more preferably 5/6 to 1.2. When [NCO] / [NHx] is less than 0.5 or more than 2, the hot offset resistance of the toner may be lowered.

  The time for reacting the polyester prepolymer having an isocyanate group and the compound having an amino group is usually 1 minute to 40 hours, and preferably 1 to 24 hours.

  The temperature at which the polyester prepolymer having an isocyanate group and the compound having an amino group are reacted is usually 0 to 150 ° C, and preferably 20 to 98 ° C.

  In addition, when making the polyester prepolymer which has an isocyanate group, and the compound which has an amino group react, a well-known catalyst can be used as needed.

  When the polyester prepolymer having an isocyanate group is reacted with the compound having an amino group, a terminator can be used as necessary. Thereby, the molecular weight of the urea-modified polyester can be adjusted.

  Although it does not specifically limit as a terminator, For example, a monoamine (for example, diethylamine, dibutylamine, butylamine, laurylamine) etc. are mentioned.

  In place of monoamine, ketimine in which the amino group of monoamine is blocked may be used.

  Crystalline polyester can be synthesized by the reaction of an alcohol component and an acid component, and has a melting point.

  The alcohol component is not particularly limited, but is a saturated aliphatic diol having 2 to 12 carbon atoms (for example, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decane). Diol, 1,12-dodecanediol) or derivatives thereof.

  Although it does not specifically limit as an acid component, The C2-C12 dicarboxylic acid which has a carbon-carbon double bond, C2-C12 saturated dicarboxylic acid (For example, a fumaric acid, 1, 4- butane dicarboxylic acid). Acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid) or derivatives thereof.

  By using crystalline polyester as the binder resin, it is possible to suppress contamination of the carrier and the charging member due to the release agent present on the surface of the base particle while maintaining the releasability at the time of fixing.

  The content of the crystalline polyester in the base particles is usually 1 to 30% by mass. If the content of the crystalline polyester in the base particles is less than 1% by mass, the low-temperature fixability of the toner may be reduced. If the content exceeds 30% by mass, the image quality is deteriorated due to contamination of the photoreceptor and other members. Or the fluidity of the developer may decrease, or the image density may decrease.

  The base particles may further contain a colorant, a release agent, a charge control agent and the like.

  The colorant is not particularly limited as long as it is a dye or a pigment, but 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, bengara, red lead, lead vermilion, cadmium red, cadmium mercurial red, antimon vermilion, permanent red 4R, para red, phise red, p-chloro -O-nitroani 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, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, poly Zored, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyani N, Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon, etc., may be used in combination.

  The content of the colorant in the base particles is usually 1 to 15% by mass, and preferably 3 to 10% by mass.

  The colorant may be used as a master batch combined with a resin.

  The resin is not particularly limited, but is a homopolymer of styrene or a substituted product thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy. Resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, etc. You may use together.

  Although it does not specifically limit as a mold release agent, The wax which has a carbonyl group, polyolefin wax, a long chain hydrocarbon, etc. are mentioned, You may use 2 or more types together. Among these, a wax having a carbonyl group is preferable.

  Examples of the wax having a carbonyl group include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones. Of these, polyalkanoic acid esters are particularly preferred.

  Examples of polyalkanoic acid esters include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distea. Rate and the like.

  Examples of polyalkanol esters include tristearyl trimellitic acid and distearyl maleate.

  Examples of the polyalkanoic acid amide include dibehenyl amide.

  Examples of the polyalkylamide include trimellitic acid tristearylamide.

  Examples of dialkyl ketones include distearyl ketone.

  Examples of the polyolefin wax include polyethylene wax and polypropylene wax.

  Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  The melting point of the release agent is usually 45 to 120 ° C. When the melting point of the release agent is less than 45 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 120 ° C., the low-temperature fixability of the toner may be lowered.

  The melt viscosity at a temperature 20 ° C. higher than the melting point of the release agent is usually 5 to 1000 cps, and preferably 10 to 100 cps. If the melt viscosity at a temperature 20 ° C. higher than the melting point of the release agent is less than 5 cps, the releasability of the toner may be lowered, and if it exceeds 1000 cps, the hot offset resistance and the low-temperature fixability of the toner are lowered. There are things to do.

  The content of the release agent in the base particles is usually 1 to 40% by mass, and preferably 3 to 30% by mass. When the content of the release agent in the base particles exceeds 40% by mass, the fluidity of the toner may be lowered.

  As the charge control agent, a positive or negative charge control agent can be used according to the positive / negative of the charge charged on the photoconductor.

  Although it does not specifically limit as a negative charge control agent, The resin or compound which has an electron-donating group, an azo dye, a metal complex of an organic acid, etc. are mentioned, You may use 2 or more types together.

  Commercially available negative charge control agents include Bontron S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E- 82, E-84, E-86, E-88, A, 1-A, 2-A, 3-A (above, manufactured by Orient Chemical Industries), Kaya Charge N-1, N-2, Kaya Set Black T-2, 004 (above, Nippon Kayaku Co., Ltd.), Eisenspiron Black T-37, T-77, T-95, TRH, TNS-2 (above, Hodogaya Chemical Co., Ltd.), FCA-1001 -N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.) and the like.

  Although it does not specifically limit as a positive charge control agent, Cationic compounds, such as basic compounds, such as a nigrosine dye, a quaternary ammonium salt, the metal salt of a higher fatty acid, etc., You may use 2 or more types together.

  Commercially available products of positive charge control agents include Bontron N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N- 13, P-51, P-52, AFP-B (above, manufactured by Orient Chemical Industry Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Industry Co., Ltd.), Copy Blue PR, Copy Charge PX-VP-435, NX-VP-434 (manufactured by Hoechst), FCA201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301 ( As mentioned above, Fujikura Kasei Co., Ltd.), PLZ1001, 2001, 6001, 7001 (above, Shikoku Kasei Kogyo Co., Ltd.) etc. are mentioned.

  The mass ratio of the charge control agent to the binder resin is usually 0.05 to 1.0%. If the mass ratio of the charge control agent to the binder resin is less than 0.05%, the charge rise and charge amount may be insufficient. If it exceeds 1.0%, the chargeability of the toner is too high. As a result, the electrostatic attractive force with the developing roller increases, and the fluidity of the developer may decrease or the image density may decrease.

  The volume average particle size of the base particles is usually 3.0 to 6.0 μm.

  The ratio of the volume average particle size to the number average particle size of the base particles is usually 1.05 to 1.25.

  Although it does not specifically limit as a manufacturing method of a base particle, The method etc. which disperse | distribute a pulverization method and an oil phase in an aqueous phase are mentioned. Among them, a method of dispersing the oil phase in the aqueous phase is preferable because base particles having a spherical shape and a controlled particle size distribution can be obtained.

  In the case of producing base particles by a pulverization method, first, components constituting the base particles are mixed and then melt kneaded using a melt kneader to obtain a kneaded product.

  The melt kneader is not particularly limited, and examples thereof include a uniaxial and biaxial continuous kneader, and a batch kneader using a roll mill.

  Commercially available melt kneaders include KTK type twin screw extruder (Kobe Steel Co., Ltd.), TEM type extruder (Toshiba Machine Co., Ltd.), twin screw extruder (casey Kay company), PCM type twin screw extrusion. Machine (Ikegai Iron Works Co., Ltd.), Conyder (Bus Co., Ltd.), etc.

  Next, the kneaded product is pulverized to obtain a pulverized product.

  When the kneaded product is pulverized, it is preferable that the kneaded product is coarsely pulverized and then finely pulverized.

  The pulverization method of the kneaded product is not particularly limited, but the method of pulverizing the kneaded product against a collision plate in a jet stream, the method of pulverizing the kneaded product in a jet stream, and mechanical rotation Examples thereof include a method of pulverizing the kneaded material in a narrow gap between the rotor and the stator.

  Further, the pulverized product is classified to adjust the particle size of the pulverized product.

  When classifying the pulverized product, it is preferable to first remove fine particles by a cyclone, a decanter, a centrifugal separator or the like, and then remove coarse particles and aggregated particles using a sieve of 250 mesh or more.

  In the case of producing base particles by dispersing an oil phase in an aqueous phase, an oil phase in which a toner composition containing a binder resin and / or a precursor of the binder resin is dissolved or dispersed in an organic solvent is used. It is preferable to remove the organic solvent after dispersion in the aqueous phase.

  The boiling point of the organic solvent is usually 100 ° C. or lower. This facilitates removal.

  The organic solvent is not particularly limited, but toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples thereof include ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone, and two or more kinds may be used in combination. Of these, ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable.

  The toner composition may be dissolved or dispersed at the same time, but each component may be dissolved or dispersed alone.

  The organic solvents used when dissolving or dispersing each component alone may be different, but are preferably the same.

  The content of the binder resin and / or the precursor of the binder resin in the oil phase is usually 40 to 80% by mass. When the content of the binder resin and / or the precursor of the binder resin in the oil phase is less than 40% by mass, the toner production amount may be reduced. When the content exceeds 80% by mass, the binder resin and In some cases, it becomes difficult to dissolve or disperse the precursor of the binder resin, and the viscosity may increase.

  When mixing a non-crystalline polyester and / or a crystalline polyester and a polyester prepolymer having an isocyanate group, a single solution or dispersion may be prepared, or a solution or dispersion may be prepared separately. However, considering the respective solubility and viscosity, it is preferable to prepare separate solutions or dispersions.

  The compound having an amino group may be mixed in the oil phase before the oil phase is dispersed in the aqueous phase, or may be added in an aqueous medium.

  The colorant may be dissolved or dispersed in an organic solvent, or may be dissolved or dispersed in a solution or dispersion of an amorphous polyester and / or a crystalline polyester. When the colorant is dispersed in an organic solvent, a dispersion aid, an amorphous polyester and / or a crystalline polyester may be added as necessary, or a master batch may be used.

  When the release agent is dispersed in an organic solvent in which the release agent is not dissolved, the organic solvent and the release agent may be mixed and then dispersed using a disperser such as a bead mill. Further, after mixing the organic solvent and the release agent, heating to the melting point of the release agent, cooling with stirring, and then dispersing using a dispersing machine such as a bead mill may shorten the dispersion time. Further, a dispersion aid, amorphous polyester and / or crystalline polyester may be added.

  As the aqueous phase, water can be used, but a solvent miscible with water and water can be used in combination.

  Solvents miscible with water are not particularly limited, but alcohols (eg, methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (eg, methyl cellosolve), lower ketones (eg, acetone, methyl ethyl ketone), etc. Is mentioned.

  The mass ratio of the aqueous phase to the toner composition is usually from 0.5 to 20, and preferably from 1 to 10. When the mass ratio of the aqueous phase to the toner composition is less than 0.5, the dispersion state of the toner composition may be lowered, and when it exceeds 20, the economy may not be economical.

  The aqueous phase is preferably dispersed with an inorganic dispersant or resin particles. Thereby, the particle size distribution of the toner composition is narrowed and can be stably dispersed.

  The inorganic dispersant is not particularly limited, and examples thereof include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite, and two or more kinds may be used in combination.

  The resin particles are not particularly limited as long as they can be dispersed in an aqueous phase, but vinyl resin particles, polyurethane particles, epoxy resin particles, polyester particles, polyamide particles, polyimide particles, silicon resin particles, phenols. Resin particles, melamine resin particles, urea resin particles, aniline resin particles, ionomer resin particles, polycarbonate particles and the like may be mentioned, and two or more kinds may be used in combination. Among these, vinyl resin particles, polyurethane particles, epoxy resin particles, and polyester particles are preferable because fine spherical resin particles are easily obtained.

  The aqueous phase may further contain a surfactant.

  Surfactants include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type cationics such as imidazoline. Surfactant, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactant such as benzethonium chloride, fatty acid amide derivative, Amphoterics such as nonionic surfactants such as polyhydric alcohol derivatives, alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine Surface active agents. Among these, a surfactant having a fluoroalkyl group is preferable because the amount added can be very small.

  Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms and a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6 to C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid and Its 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) perfluorooctane Sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. .

  Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and aliphatic 4 such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt. Examples include quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.

  The aqueous phase may further contain a polymeric protective colloid.

  Polymeric protective colloids include acids (eg, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride) and hydroxyl groups (Meth) acrylic monomers (for example, β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate, γ-hydroxypropyl (meth) acrylate, 3-chloro (meth) acrylate -2-hydroxypropyl, diethylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, N-methylol (meth) acrylamide), vinyl alcohol and alcohol ethers (eg, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether) ), Vinyl alcohol carbo Acid esters (for example, vinyl acetate, vinyl propionate, vinyl butyrate), (meth) acrylamide, diacetone acrylamide or methylolated products thereof, acid chlorides (for example, acrylic acid chloride, methacrylic acid chloride), nitrogen atom or its Homopolymers or copolymers such as compounds having a heterocyclic ring (for example, vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine), polyoxyalkylenes (for example, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine) , Polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene Ren stearyl phenyl ester, polyoxyethylene nonyl phenyl ester), celluloses (such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose) and the like.

  In addition, when using a compound that can be dissolved in acid or alkali such as tricalcium phosphate as the inorganic dispersant, by dissolving tricalcium phosphate with an acid such as hydrochloric acid, and then washing with water, Tricalcium phosphate can be removed. In addition, it can be removed by enzymatic degradation.

  When an inorganic dispersant is used, it can be used in a state where the inorganic dispersant remains on the surface of the base particle, but it is preferable to remove the inorganic dispersant by washing from the charged surface of the toner.

  The disperser used when dispersing the oil phase in the aqueous phase is not particularly limited, but a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, an ultrasonic disperser, etc. Is mentioned. Especially, in order to make the average particle diameter of a dispersion 2-20 micrometers, a high-speed shearing-type disperser is preferable.

  The rotational speed of the high-speed shearing disperser is usually 1000 to 30000 rpm, and preferably 5000 to 20000 rpm.

  In the case of a batch method, the time for dispersing using a high-speed shearing disperser is usually 0.1 to 5 minutes.

  The temperature for dispersion using a high-speed shearing disperser is usually 0 to 150 ° C. (under pressure), and preferably 20 to 80 ° C.

  The method for removing the organic solvent is not particularly limited, but there are a method for evaporating the organic solvent by gradually raising the temperature under normal pressure or reduced pressure, a method for removing the organic solvent by spraying in a dry atmosphere, and the like. Can be mentioned.

  Although it does not specifically limit as dry atmosphere, Although the gas in which air, nitrogen, a carbon dioxide gas, combustion gas, etc. are heated is mentioned, The airflow heated to the temperature beyond the boiling point of an organic solvent is generally used.

  At this time, the processing time can be shortened by using a spray dryer, a belt dryer, a rotary kiln or the like.

  The base particles formed by removing the organic solvent are usually washed and then dried. That is, after solid-liquid separation with a centrifuge, filter press, etc., the cake is re-dispersed in ion-exchanged water at room temperature to about 40 ° C., and if necessary, the pH is adjusted with acid or alkali and then solid-liquid again. Repeat the separation process several times. Thereby, after removing impurities, surfactants, etc., they are dried by an air flow dryer, a circulation dryer, a vacuum dryer, a vibration fluidized dryer or the like. At this time, fine particles may be removed by centrifugation or the like, and after drying, a desired particle size distribution can be obtained using a known classifier as necessary.

  The developer is not particularly limited, and examples thereof include a one-component developer composed of toner and a two-component developer composed of toner and carrier. Among these, when used in a high-speed printer capable of improving the information processing speed, a two-component developer is preferable in terms of life.

  The mass ratio of the toner to the carrier in the two-component developer is usually 0.01 to 0.10.

  The carrier preferably has a core material, and a protective layer is preferably formed on the core material.

  Although it does not specifically limit as a material which comprises a core material, 50-90emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-Mg) type material, etc. are mentioned, 2 or more types combined use May be. Among them, a highly magnetized material such as iron (100 emu / g or more), magnetite (75 to 120 emu / g) is preferable in terms of image density. In addition, it is possible to weaken the hitting of the toner that is in a spiked state to the photosensitive member, and it is advantageous in improving the image quality. From the viewpoint of improving the image quality, a copper-zinc (Cu—Zn) system (30 to 80 emu / g) or the like. The weakly magnetized material is preferred.

  The weight average particle diameter of the core material is usually 10 to 200 μm, and preferably 40 to 100 μm. When the weight average particle diameter of the core material is less than 10 μm, carrier scattering may occur, and when it exceeds 150 μm, toner scattering may occur.

  The protective layer contains a binder resin.

  The binder resin is not particularly limited, but amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, Fluoropolymers such as polyhexafluoropropylene, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers A terpolymer, a silicone resin, etc. are mentioned, You may use 2 or more types together.

  Examples of amino resins include urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins.

  Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral.

  Examples of polystyrene resins include polystyrene and styrene-acrylic copolymers.

  Examples of the halogenated olefin resin include polyvinyl chloride.

  Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

  The protective layer may further contain conductive powder.

  The conductive powder is not particularly limited, and examples thereof include metal powder, carbon black, titanium oxide powder, tin oxide powder, and zinc oxide powder.

  The average particle size of the conductive powder is usually 1 μm or less. When the average particle size of the conductive powder exceeds 1 μm, it may be difficult to control the electric resistance.

  The protective layer can be formed by applying a coating solution in which a binder resin is dissolved in a solvent to the surface of the core, then drying and baking.

  A method for applying the coating solution is not particularly limited, and examples thereof include a dipping method, a spray method, and a brush coating method.

  Although it does not specifically limit as a solvent, Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, butyl acetate, etc. are mentioned.

  The baking method is not particularly limited and may be either an external heating method or an internal heating method, but a method using a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, The method to use etc. are mentioned.

  The content of the protective layer in the carrier is usually 0.01 to 5.0% by mass. When the content of the protective layer in the carrier is less than 0.01% by mass, the protective layer may not be formed uniformly on the surface of the core material. When the content exceeds 5.0% by mass, the protective layer is It may become too thick and granulation of carriers may occur.

  The developer can be applied to various electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

  Since the developer container contains the developer, an image can be formed by electrophotography using the developer.

  The image forming apparatus includes a photoconductor, a charging device, an exposure device, a developing device, a transfer device, and a fixing device, and may further include a static elimination device, a cleaning device, a recycling device, a control device, and the like.

  The image forming apparatus integrally supports a photoconductor on which an electrostatic latent image is formed and a developing device that develops the electrostatic latent image formed on the photoconductor using a developer. A process cartridge that is detachable from the main body may be provided.

  Note that the process cartridge may be integrally supported by other means.

  In the developing device, the developer can be used in a state of being accommodated in the developer accommodating container.

  The electrostatic latent image can be formed by applying a voltage to the surface of the photoconductor using a charging device to uniformly charge it, and then exposing it imagewise using an exposure device. .

  The shape of the photoreceptor is preferably a drum shape.

  The photoreceptor is not particularly limited, and examples thereof include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, an amorphous silicon photoreceptor is preferable in terms of long life.

  Examples of the charging device include, but are not limited to, contact chargers including conductive or semiconductive rolls, brushes, films, rubber blades, and non-contact chargers using corona discharge such as corotron and scorotron. .

  The charging device is arranged in contact or non-contact with the photoreceptor, and it is preferable to charge the surface of the photoreceptor by applying a DC voltage and an AC voltage in a superimposed manner.

  The charging device is preferably a charging roller that is disposed in a non-contact proximity to the photoreceptor via a gap tape.

  The exposure apparatus is not particularly limited as long as the surface of the charged photoconductor can be exposed imagewise, and examples thereof include a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. .

  Note that an optical backside exposure apparatus that performs imagewise exposure from the back side of the photoreceptor may be used.

  The developing device is not particularly limited as long as it can develop an electrostatic latent image using a developer. However, the developer is accommodated and the developer is brought into contact or non-contact with the electrostatic latent image. Examples thereof include a developing device having a developer carrier that can be applied. Among these, a developing device that is detachably provided with a developer container is preferable.

  The developing device may be either a single-color developing device or a multi-color developing device, and usually has a stirrer for charging the developer by frictional stirring and a rotatable magnet roller.

  For example, in a developing device using a two-component developer, toner and a carrier are mixed, and the toner is charged by friction at that time, and is held on the surface of a rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the photoreceptor. Note that an alternating electric field is preferably applied when the toner is moved to the surface of the photoreceptor.

  The transfer device preferably includes a primary transfer device that forms a composite toner image by transferring a toner image of two or more colors onto an intermediate transfer member, and a secondary transfer device that transfers the composite toner image onto an image support. . The transfer device (primary transfer device, secondary transfer device) preferably has a transfer device for transferring the toner image formed on the photoreceptor.

  The transfer device is not particularly limited, and examples thereof include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The primary transfer device may be single or plural.

  Although it does not specifically limit as an intermediate transfer body, A transfer belt etc. are mentioned.

  The image support is not particularly limited, but a known recording medium can be used.

  The fixing device is preferably heat-pressed and fixed using a fixing member.

  The fixing member is not particularly limited, and examples thereof include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.

  The temperature for heating using the fixing member is usually 80 to 200 ° C.

  The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body via the film, and the toner image is transferred between the film and the pressure member. It is preferable to fix by heating and pressing through an image support.

  A known optical fixing device may be used together with the fixing device or instead of the fixing device.

  The neutralization device is not particularly limited as long as it can apply a neutralization bias to the photoreceptor, and includes a neutralization lamp.

  The cleaning device is not particularly limited as long as it can remove the toner remaining on the photosensitive member, but a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, etc. Be mentioned.

  The recycling device is not particularly limited as long as the toner removed by the cleaning device can be recycled by the developing device.

  The control device is not particularly limited as long as the operation of each device can be controlled, and examples thereof include a sequencer and a computer.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to an Example. Parts and% are based on mass.

<Preparation of base particles>
(Synthesis of vinyl resin dispersion 1)
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries) of ethylene oxide adduct of methacrylic acid, 83 parts of styrene, 83 of methacrylic acid Parts, 110 parts of butyl acrylate and 1 part of ammonium persulfate were added, followed by stirring at 400 rpm for 15 minutes. Next, the temperature was raised to 75 ° C. and reacted for 5 hours, and then 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain a dispersion 1 of vinyl resin. Using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by HORIBA), the weight average particle diameter of the vinyl resin dispersion 1 was measured to be 105 nm. Further, when a part of the vinyl resin dispersion 1 was dried to isolate the resin component, the resin component had a glass transition point of 59 ° C. and a weight average molecular weight of 1.5 × 10 ⁵ .

(Preparation of aqueous phase 1)
990 parts of water, 83 parts of a vinyl resin dispersion, 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, eleminol MON-7 (manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed, and the aqueous phase 1 was mixed. Obtained.

(Synthesis of amorphous polyester 1)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of an ethylene oxide 2-mole adduct of bisphenol A, 529 parts of a propylene oxide 3-mole adduct of bisphenol A, 208 parts of terephthalic acid, 46 parts of adipic acid, and After adding 2 parts of dibutyltin oxide, the mixture was reacted at 230 ° C. for 8 hours. Next, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was added and reacted at 180 ° C. for 2 hours to obtain amorphous polyester 1. Amorphous polyester 1 had a number average molecular weight of 2500, a weight average molecular weight of 6700, a glass transition point of 43 ° C., and an acid value of 25 mgKOH / g.

(Synthesis of polyester prepolymer 1)
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and the polyester which has a hydroxyl group was obtained. The polyester having a hydroxyl group had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition point of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.

  After putting 410 parts of polyester having a hydroxyl group, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate in a reaction vessel set with a cooling pipe, a stirrer and a nitrogen introduction pipe, the polyester prepolymer 1 was reacted at 100 ° C. for 5 hours. Obtained. Polyester prepolymer 1 had a free isocyanate group content of 1.53%.

(Synthesis of ketimine 1)
After 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were placed in a reaction vessel equipped with a stirrer and a thermometer, the reaction was carried out at 50 ° C. for 5 hours to obtain ketimine 1. Ketimine 1 had an amine value of 418 mgKOH / g.

(Preparation of master batch 1)
After mixing 35 parts of water, 40 parts of phthalocyanine pigment FG7351 (manufactured by Toyo Ink) and 60 parts of non-crystalline polyester RS801 (manufactured by Sanyo Chemical Co., Ltd.) using a Henschel mixer (manufactured by Mitsui Mining) And kneaded at 150 ° C. for 30 minutes. Next, after rolling and cooling, a master batch 1 was obtained by pulverization using a pulverizer.

(Preparation of oil phase 1)
After placing 378 parts of amorphous polyester 1, 110 parts of carnauba wax, 22 parts of salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.) and 947 parts of ethyl acetate in a container equipped with a stirring bar and a thermometer, The temperature was raised to 80 ° C. and held for 5 hours. Next, after cooling to 30 ° C. in 1 hour, 500 parts of master batch 1 and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a raw material mixture.

  Using a bead mill, Ultra Visco Mill (manufactured by Imex), the feeding speed was 1 kg / h, the peripheral speed of the disk was 6 m / s, and 80% by volume of zirconia beads having a diameter of 0.5 mm were filled. Under the conditions, 1324 parts of the raw material mixture was dispersed. Next, 1324 parts of a 65% ethyl acetate solution of non-crystalline polyester 1 was added, followed by one pass under the above conditions to obtain a pigment dispersion. The pigment dispersion had a solid content concentration (measurement conditions: 130 ° C., 30 minutes and 50%.

  648 parts of pigment dispersion, 154 parts of polyester prepolymer 1 and 6.6 parts of ketimine 1 were mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain oil phase 1. .

(Emulsification)
After adding 1200 parts of the water phase 1 to the oil phase 1, it was mixed for 20 minutes at 13000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain an emulsified slurry 1.

(Shape control)
After adding 3.15 parts of cellogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.) little by little while stirring 75.6 parts of ion-exchanged water at 2000 rpm using a TK homomixer (manufactured by Koki Kogyo Co., Ltd.) And stirred at 20 ° C. for 30 minutes. Next, 43.3 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries) was added, and the mixture was stirred at 20 ° C. for 5 minutes. Further, 2000 parts of the emulsified slurry 1 was added and then mixed for 1 hour at 2000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to obtain a shape control slurry 1.

(Solvent removal)
The shape control 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, the mixture was aged at 45 ° C. for 4 hours to obtain a dispersion slurry 1.

(Washing, drying)
100 parts of dispersion slurry 1 was filtered under reduced pressure. 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by filtration. 100 parts of a 10% aqueous sodium hydroxide solution was added to the obtained filter cake, and the mixture was mixed at 12,000 rpm for 30 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by filtration under reduced pressure. 100 parts of 10% hydrochloric acid was added to the obtained filter cake, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), followed by filtration. 300 parts of ion-exchanged water was added to the obtained filter cake, and after mixing for 10 minutes at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), the operation of filtering was repeated twice.

  The obtained filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and then sieved with a mesh having an opening of 75 μm to obtain base particles. The base particles had a volume average particle size of 5.6 μm.

<Synthesis of polyimide particles A>
A solution prepared by dissolving 2.24 g (0.01 mol) of hexahydropyromellitic anhydride in 90 mL of acetone, a solution prepared by dissolving 1.66 g (0.01 mol) of 1,4-hexacyclodiisocyanate in 90 mL of acetone, A solution prepared by dissolving 0.4 g of 1,4-diazabicyclo [2.2.2] octane in 20 mL of acetone was mixed at 25 ° C. and then stirred for 1 hour at a frequency of 35 kHz using an ultrasonic cleaner. Next, after stirring for about 12 hours using a stir bar to precipitate a polyimide precursor, the polyimide precursor was recovered using a centrifuge. Furthermore, after washing | cleaning with acetone, operation which collect | recovers using a centrifuge was repeated, and the polyimide precursor was refine | purified. Next, about 3.0 g of the polyimide precursor is dispersed in 500 mL of n-dodecane and refluxed at 210 ° C. for 6 hours to generate polyimide particles A. Then, the polyimide particles A are collected using a centrifuge. did. Furthermore, after washing | cleaning with acetone, operation which collect | recovers using a centrifuge was repeated, and the polyimide particle A was refine | purified. When polyimide particle A was measured using a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by HORIBA), d50 was 120 nm and Dv / Dn was 1.3.

<Synthesis of polyimide particles B>
A polyimide particle B was obtained in the same manner as the polyimide particle A, except that the mixture was stirred for 1 hour at a frequency of 40 kHz using an ultrasonic cleaner. The polyimide particles B were measured using a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by HORIBA). As a result, d50 was 108 nm and Dv / Dn was 1.2.

<Synthesis of polyimide particles C>
Polyimide particles C were obtained in the same manner as polyimide particles A, except that the mixture was stirred for 1.5 hours at a frequency of 45 kHz using an ultrasonic cleaner. The polyimide particles C were measured using a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by HORIBA). As a result, d50 was 80 nm and Dv / Dn was 1.2.

<Synthesis of polyimide particles D>
A polyimide particle D was obtained in the same manner as the polyimide particle A except that it was stirred for 2 hours at a frequency of 65 kHz using an ultrasonic cleaner. The polyimide particles D were measured using a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by HORIBA). As a result, d50 was 23 nm and Dv / Dn was 1.4.

<Synthesis of polyimide particles E>
A polyimide particle E was obtained in the same manner as the polyimide particle A, except that it was stirred for 4 hours at a frequency of 65 kHz using an ultrasonic cleaner. The polyimide particles E were measured using a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by HORIBA). As a result, d50 was 18 nm and Dv / Dn was 1.6.

<Synthesis of polyimide particles F>
A polyimide particle F was obtained in the same manner as the polyimide particle A, except that it was stirred for 0.5 hour at a frequency of 35 kHz using an ultrasonic cleaner. The polyimide particles F were measured using a laser diffraction / scattering particle size distribution analyzer LA-750 (manufactured by HORIBA). As a result, d50 was 15 nm and Dv / Dn was 1.3.

  Table 1 shows the characteristics of the polyimide particles.

＜実施例１＞
母体粒子１００部及び平均粒径が１５ｎｍのイソブチルによる疎水性処理されているルチル型酸化チタンＭＴ−１５０ＡＩ（ＴＡＩＣＡ社製）０．７５部を、ヘンシェルミキサーを用いて、攪拌翼の周速を３５ｍ／ｓとして、混合した後、３部のポリイミド粒子Ａを加え、上記の条件で混合し、トナーを得た。

<Example 1>
100 parts of base particles and 0.75 parts of rutile titanium oxide MT-150AI (manufactured by TAICA), which has been hydrophobically treated with isobutyl having an average particle diameter of 15 nm, are mixed with a Henschel mixer and the peripheral speed of the stirring blade is set to 35 m. After mixing, 3 parts of polyimide particles A were added and mixed under the above conditions to obtain a toner.

<Example 2>
A toner was obtained in the same manner as in Example 1 except that polyimide particle B was used instead of polyimide particle A, polyimide particle B was added, and the peripheral speed of the stirring blade was changed to 55 m / s.

<Example 3>
A toner was obtained in the same manner as in Example 2 except that the polyimide particles C were used in place of the polyimide particles B.

<Example 4>
A toner was obtained in the same manner as in Example 2 except that the polyimide particles D were used in place of the polyimide particles B.

<Comparative Example 1>
A toner was obtained in the same manner as in Example 1 except that the polyimide particles E were used in place of the polyimide particles A.

<Comparative example 2>
A toner was obtained in the same manner as in Example 2 except that the polyimide particles F were used in place of the polyimide particles B.

<Creation of carrier>
200 parts of a silicone resin solution (manufactured by Shin-Etsu Chemical Co., Ltd.) and 3 parts of carbon black (manufactured by Cabot) were dispersed in toluene to obtain a coating solution.

  Using a fluidized bed spray device Agromaster AGM-PJ (manufactured by Hosokawa Micron Co., Ltd.), 2500 parts of ferrite core material (manufactured by Toda Kogyo Co., Ltd.) is applied, and then fired at 300 ° C. for 2 hours using an electric furnace Got a career. The carrier had an average particle size of 36 μm.

<Production of developer>
Using a tumbler mixer T10B (manufactured by Shinmaru Enterprises), 7 parts of toner and 93 parts of carrier were mixed to obtain a developer.

  Next, transfer failure / background stain, graininess / sharpness and low-temperature fixability were evaluated using a developer, and heat resistant storage stability was evaluated using a toner.

<Transfer defects and background stains>
After passing 5000 sheets using an image forming apparatus imagioColor 2800 (manufactured by Ricoh Co., Ltd.), a solid black image was passed through and the transfer failure was visually evaluated.

  After passing 5000 sheets using an image forming apparatus imagioColor 2800 (manufactured by Ricoh Co., Ltd.), the sheet was stopped during the development of the blank image. Next, after transferring the developer on the photoreceptor with a scotch tape (manufactured by Sumitomo 3M), the difference from the image density of the untransferred tape is measured using a spectrodensitometer (manufactured by X-Rite). The soil was evaluated. A case where the difference from the image density of the untransferred tape was less than 0.30 was judged good, and a case where the difference was 0.30 or more was judged bad.

  When the transfer failure and the background stain were combined, the case where it was good was judged as ◯, the case where it was not good, but acceptable, Δ, and the case where it was bad was judged as ×.

<Granularity and sharpness>
Using a digital full-color copying machine imagioColor 2800 (manufactured by Ricoh), a photographic image was output in a single color, and the graininess and sharpness were visually evaluated. Judgment is given as ◎ if it is the same as offset printing, ◯ if it is slightly worse than offset printing, △ if it is much worse than offset printing, and × if it is about the conventional electrophotographic image did.

<Low temperature fixability>
Copying machine MF2200 (manufactured by Ricoh Co.) using a Teflon (registered trademark) roller as the fixing roller. Type 6200 paper (manufactured by Ricoh Company) is set in a machine with a modified fixing unit, and the fixing temperature is changed to lower the fixing minimum temperature The low-temperature fixability was evaluated. At this time, the linear speed of paper feed was set to 120 to 150 mm / s, the surface pressure was set to 1.2 kgf / cm ² , and the nip width was set to 3 mm. In addition, the case where the fixing lower limit temperature is less than 140 ° C. is ◎, the case where it is 140 ° C. or more and less than 150 ° C. is ◯, the case where it is 150 ° C. or more and less than 160 ° C. The case of 170 ° C. or higher was determined as x.

<Heat resistant storage stability>
The toner was stored in an environment of 50 ° C. for 8 hours and then sieved with 42 mesh for 2 minutes to determine the residual ratio of the toner on the 42 mesh, and the heat resistant storage stability was evaluated. When the residual ratio of the toner on 42 mesh is 30% or more, ×, when 20% or more and less than 30%, Δ when it is 10% or more and less than 20%, and when it is less than 10% As judged.

表２から、実施例１〜４のトナーは、転写不良・地汚れ、粒状性・鮮鋭性、低温定着性及び耐熱保存性が優れることがわかる。

From Table 2, it can be seen that the toners of Examples 1 to 4 are excellent in transfer failure / background stain, graininess / sharpness, low-temperature fixability, and heat-resistant storage stability.

  On the other hand, since the toner of Comparative Example 1 has a d50 of the polyimide particle E of 18 nm, the heat resistant storage stability is lowered.

  In the toner of Comparative Example 2, since the d50 of the polyimide particles F is 150 nm, the transfer defect, background stain, graininess, and sharpness are deteriorated.

JP-A-11-237760

Claims (9)

Having base particles containing a binder resin and external additives,
The external additive includes polyimide particles,
The toner according to claim 1, wherein the polyimide particles have a median diameter of 25 nm to 120 nm.   The toner according to claim 1, wherein the polyimide particles are synthesized by synthesizing a polyimide precursor by reacting tetracarboxylic anhydride and diisocyanate, and then imidizing the polyimide precursor. .   The toner according to claim 1, wherein the content of the polyimide particles is 2% by mass or more and 10% by mass or less.   The base particles are obtained by dispersing an oil phase in which a composition containing a binder resin and / or a precursor of the binder resin is dissolved or dispersed in an organic solvent in an aqueous phase, and then removing the organic solvent. The toner according to claim 1, wherein the toner is formed as described above.   The toner according to claim 4, wherein the binder resin includes at least one selected from the group consisting of non-crystalline polyester, urea-modified polyester, and crystalline polyester.   The toner according to claim 4, wherein the binder resin precursor includes a compound having an amino group or a blocked amino group and a polyester prepolymer having an isocyanate group.   A developer comprising the toner according to claim 1.   A developer storage container in which the developer according to claim 7 is stored. Charging means for charging the photoreceptor;
Exposure means for exposing the charged photoreceptor to form an electrostatic latent image;
Developing means for developing the electrostatic latent image formed on the photoreceptor using the developer according to claim 7 to form a toner image;
Transfer means for transferring a toner image formed on the photoreceptor to an image support;
An image forming apparatus comprising fixing means for fixing the toner image transferred to the image support.