JP2005301060A - Electrophotographic toner and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner having excellent durability and fixing property and causing less filming. <P>SOLUTION: The toner contains aggregated particles having blocks of resin particles. The blocks of the resin particles have a shape such that the resin particles are melted with one another or are in contact with one another via interfaces and the aggregated particles constitute a network structure. In the toner, a release agent is held in the gaps among the resin particles. The toner is prepared by a method including steps of: preparing the dispersion liquid of resin particles having a functional group and of release agent particles; compounding a network forming agent which reacts with the functional group to form a network among the resin particles into the above dispersion liquid; and spray drying the dispersion liquid. The particle diameter A of the resin particles and the particle diameter B of the release agent particles satisfy the relation of 0.13≤B/A≤0.31. The release agent particles of 1 to 3 parts by mass are added to resin particles of 100 parts by mass. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner used for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like and forming an image by thermal fixing.

  In general, a toner for forming an electrostatic image is obtained by melting and kneading a colorant or the like in a toner resin (binder resin) such as a polyester resin or a styrene / acrylic copolymer resin, followed by pulverization and classification. ing. However, since the toner obtained by this pulverization method has low sphericity, it has poor fluidity (smoothness) and inferior transferability as compared with toner having high sphericity (closer to a true sphere). Furthermore, in recent years, there has been a demand for higher image quality of printers, and there has been a movement to reduce the toner particles. However, in the pulverization method, there are problems of pulverization, classification, etc. Is difficult to obtain.

  In order to solve such problems, attempts have been made to produce a toner (polymerized toner) by a polymerization method. In general, a polymerized toner is obtained by emulsifying a monomer as a raw material of a resin by a method such as emulsion polymerization or suspension polymerization, polymerizing the emulsion in a state of emulsion to produce primary particles, and aggregating them by heating and drying. It is done. In this heating / drying process, the polymer particles are thermally fused and partially melted or the resin particles are thermally fused to each other. However, since this bond is weak, the toner is liable to disintegrate, so that there is a problem that the durability during use is poor and the stability during storage is lacking.

  For example, in Patent Document 1, primary particles of a polymer having an acidic polar group or a basic polar group are prepared by emulsion polymerization, and colorant particles and a charge control agent are added to the primary particles and heated. It is described that colored secondary particles are obtained and the secondary particles are further associated to obtain toner particles. It is described that at least a part of the contact portion between the secondary particles is film-formed and fused, and the associated particles do not collapse during storage, transportation, and developer production. However, when the toner composed of associated particles of the heat-bonded secondary particles contains a release agent, the release agent having a glass transition point lower than that of the resin melts and enters between the secondary particles. Since the bond strength between the secondary particles is weakened, the toner is easy to disintegrate and lacks durability during use.

  Patent Document 2 discloses a polymerized toner having a small particle diameter excellent in fixability. In this polymerized toner, a monomer composition containing a polymerizable monomer and a fixability improver is emulsified and polymerized to obtain a toner having a small particle diameter. In the production of this toner, it is described that a polymerized particle is prepared by adding a cross-linking agent in order to increase the strength of the polymerized particle, and this is associated. However, although the strength of the individual polymer particles is increased, the bond strength between the polymer particles is weak, and, as in Patent Document 1, the release agent melts and enters between the polymer particles. Is weakened. Therefore, it is easy to disintegrate, lacks durability at the time of use, and the fixing property also deteriorates.

Furthermore, Patent Document 3 discloses a toner having a capsule structure (core-shell structure) for the purpose of improving low-temperature fixability. In this method, first, a polymerizable composition containing a polymerizable monomer, a colorant and the like is subjected to suspension polymerization or emulsion polymerization, and this is agglomerated to obtain core particles, which are then separated around the core particles. The particles are agglomerated and dried as necessary to obtain toner particles having a capsule structure. Although this toner is excellent in low-temperature fixability, since the particles need to be combined only by the agglomeration force and the aggregation process must be performed twice, the durability during use is poor and the storage stability is low. There is a problem of lacking.
JP-A 63-186253 Japanese Patent Laid-Open No. 5-66611 Japanese Patent Laid-Open No. 11-7156

  As described above, the conventional polymerized toner has a problem that it is inferior in durability when it is excellent in low-temperature fixability. On the other hand, there is a problem in that the low-temperature fixability is lowered when durability is improved. Therefore, there is a demand for a toner that has excellent durability and low-temperature fixability. An object of the present invention is to provide a toner that is excellent in low-temperature fixability and also has durability.

  The present invention relates to a toner containing aggregate particles having resin particle lumps, wherein the resin particle lumps have a shape in which the resin particles melt or contact each other, and the aggregate particles Provides a toner having a network structure and having a release agent held in a gap between the resin particles.

  In a preferred embodiment, the network structure is formed by a network forming agent.

  In a preferred embodiment, the network forming agent is a crosslinker.

  The present invention is also a method for producing the toner, comprising: preparing a dispersion of resin particles having a functional group and a release agent particle; and reacting with the functional group to form a network between the resin particles. A step of blending a network forming agent into the dispersion; and a step of spray drying the dispersion; and the particle size A of the resin particles and the particle size B of the release agent particles are 0.13. ≦ B / A ≦ 0.31 is satisfied, and a method in which 1 to 3 parts by mass of the release agent particles are added to 100 parts by mass of the resin particles is provided.

  The toner of the present invention is a toner composed of aggregated particles, but is an aggregate in which resin particles constituting the toner are bonded to each other on the surface thereof, and a resin in which some resin particles are bonded to each other on the surface thereof. A particle aggregate or a resin particle aggregate in which several resin particles are melted together (hereinafter, these resin particle aggregates are referred to as resin particle aggregates). The agglomerated particles have a network structure and a release agent is held in the gap. Since the resin particles are bonded only on the surface in this way, the release agent is held between the resin particles, and even if the release agent enters the resin particles, the resin melting characteristics are changed. Without increasing the bonding strength between the resin particles. Therefore, the durability can be improved while maintaining the toner fixing property. Therefore, a toner having excellent low-temperature fixability and excellent durability is provided.

  In the toner of the present invention, aggregate particles composed of aggregates of resin particles have a network structure (that is, aggregates of resin particles are connected by a network). A release agent is held in the gap between the resin particles. FIG. 1 shows a partial structure of the toner of the present invention. In FIG. 1, the toner 1 has a single resin particle 11, three resin particles melted together to form a single resin particle mass 12, two resin particles contacted, and a boundary surface 17. Resin mass lump 13 and 4 resin particles that are bonded together are fused together to form a lump resin particle lump 14 and 3 resin particles that are in contact with each other and have a boundary surface 17 to form a lump. The resin particle mass 15 and the like are cross-linked or bonded to each other, and the resin particle mass has a boundary surface 17 to form a network 16. A release agent 18 is held in the gap between the resin particles. As described above, the “aggregate particle composed of an aggregate of resin particles” includes an aggregate formed by melting the resin particles (the resin particle masses 12 and 14 in FIG. 1), and the resin particle is a boundary. An aggregate (13, 15 resin particle masses in FIG. 1) in contact (preferably bonded) while leaving the surface 17 is included, and a release agent 18 is held in the gap.

  Since all of the resin particle masses 12 to 15 are generated from a single resin particle 11, first, (i) resin particles and (ii) which are materials used in the present invention will be manufactured. And (iii) a network forming agent and (iv) a release agent, and then (v) a method for producing the toner of the present invention.

(I) Resin Particles In the toner of the present invention, the resin particles, the aggregates, and the resin particles and the aggregates (hereinafter, these may be collectively referred to as “interparticles”) are in contact with each other at the interface. A network structure is formed between the particles, and the network formation between the particles is performed using the functional groups present in the resin particles and the aggregate of the resin particles. Therefore, the resin particles are prepared so as to have a functional group.

  Examples of functional groups that may be present in the resin particles include carboxyl groups, hydroxyl groups, epoxy groups, sulfonic acid groups, nitrogen-containing functional groups (for example, ammonium groups, amino groups, amide groups, etc.), acid anhydrides, and the like. Group, N-alkoxymethyl group, N-methylol group and the like, but are not limited thereto. Preferred are a carboxyl group, a hydroxyl group, an epoxy group, a sulfonic acid group, a functional group containing nitrogen, and an acid anhydride group, and more preferred are a carboxyl group, a hydroxyl group, and an epoxy group. The type of functional group in the resin particle may be one type or two or more types. Examples of the resin having the functional group include, but are not limited to, the following resins.

  Examples of the resin having a carboxyl group include (meth) acrylic acid polymers such as poly (meth) acrylic acid, methyl methacrylate- (meth) acrylic acid copolymer, and acrylic acid-polyvinyl alcohol copolymer; methyl Examples thereof include vinyl ether-maleic acid copolymers; styrene polymers such as styrene-maleic acid copolymers and styrene- (meth) acrylic acid copolymers.

  Examples of the resin having a hydroxyl group include polyalkylene oxides such as polyethylene oxide and ethylene oxide-propylene oxide copolymers; vinyl alcohol polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers; ether groups and the like. Vinyl ester polymers such as polyoxyalkylene-vinyl acetate copolymers; copolymers containing hydroxy-containing (meth) acrylates; (meth) acrylic acid-polyvinyl alcohol copolymers; ethylene-maleic anhydride copolymers; And vinyl acetate-methyl acrylate copolymer. In the following description, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid, and (meth) acrylate is a generic term for acrylate and methacrylate.

  Examples of the resin containing an epoxy group include polyglycidyl (meth) acrylate, glycidyl (meth) acrylate- (meth) acrylate copolymer, styrene-glycidyl (meth) acrylate copolymer, styrene- (meth) acrylic acid-glycidyl. (Meth) acrylate copolymer etc. are mentioned.

  Examples of the resin having a sulfonic acid group include styrene polymers such as polystyrene sulfonic acid and polyvinyl sulfonic acid.

  Examples of resins having functional groups containing nitrogen include quaternary ammonium salts such as polyvinylbenzyltrimethylammonium chloride and polydiallyldimethylammonium chloride, polydimethylaminoethyl (meth) acrylate, polyvinylpyridine, polyvinylimidazole, polyethyleneimine, and polyamide polyamine. , Poly (meth) acrylamide, polydiacetone (meth) acrylamide, polyvinylpyrrolidone and the like.

  Examples of the resin containing an acid anhydride group include alkyl vinyl ether-maleic anhydride copolymers such as methyl vinyl ether-maleic anhydride copolymer; ethylene-maleic anhydride copolymer: vinyl acetate-maleic anhydride copolymer. Styrene-maleic anhydride copolymer; (meth) acrylate-maleic anhydride copolymer.

  Examples of the resin having an N-alkoxymethyl group or an N-methylol group include N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl (meth) acrylamide.

  Furthermore, you may use polyester, a polyurethane, an epoxy resin, etc. which have the said functional group.

By the way, when aiming at low-temperature fixability, the flow softening point (Tf _1/2 ) of the resin used for the toner is preferably low, and from the viewpoint of storage stability, the glass transition temperature (Tg) is preferably high. The flow softening point (Tf _1/2 ) of the toner particles is preferably low. Tf _1/2 is, for example, preferably 85 to 150 ° C, more preferably 90 to 130 ° C, and further preferably 100 to 120 ° C. The glass transition temperature (Tg) of the toner particles is preferably 40 to 150 ° C, and more preferably 50 to 90 ° C.

  From the viewpoint that the flow softening point and glass transition temperature of the resin can be easily adjusted, it is preferable that (meth) acrylic acid and (meth) acrylate-based resins are the main components, and poly (meth) acrylic acid, (meth) Acrylic acid- (meth) acrylate copolymer, styrene-functional (meth) acrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene- (meth) acrylic acid- (meth) acrylate copolymer A coalescence or the like is preferably used. These resins may be used alone or in combination of two or more.

(Ii) Monomers for producing resin particles (ii-1) Types of monomers In the production of resins having the above functional groups, monomers having functional groups and functional groups are not present. Any of the monomers can be used. In order to prepare the resin particles used in the present invention, at least one monomer having a functional group is included.

  For example, the following monomers are exemplified: (meth) acrylic acid, crotonic acid, maleic acid, maleic acid half ester, itaconic acid, itaconic acid half ester, fumaric acid, fumaric acid half ester and the like. Mer: hydroxyl group-containing monomer such as ethylene oxide, propylene oxide, vinyl alcohol monomer, vinyl acetate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate (has a hydroxyl group by reaction) Monomers containing epoxy groups such as glycidyl (meth) acrylate and allyl glycidyl ether; monomers containing sulfonic acid groups such as styrenesulfonic acid and vinylsulfonic acid; vinylbenzyltrimethylammonium chloride; Diallyl dime Monomers containing nitrogen-containing functional groups such as ruammonium chloride, dimethylaminoethyl (meth) acrylate, vinylpyridine, vinylimidazole, ethyleneimine, (meth) acrylamide, diacetone (meth) acrylamide, vinylpyrrolidone; maleic anhydride Acid anhydride-containing monomers such as itaconic anhydride and fumaric anhydride; N-methylol group-containing monomers such as N-methylol (meth) acrylamide; N-methoxymethyl (meth) acrylamide, N-ethoxymethyl ( N-alkoxymethyl group-containing monomers such as (meth) acrylamide; styrene monomers (styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, etc.), vinylanisole, vinylnaphthalene, divinylbenzene, etc. Aromatic vinyl Monomers, olefins such as ethylene, butadiene, isoprene and chloroprene; alkyl (meth) acrylates such as (meth) acrylate and methyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl caproate and vinyl propionate; (Meth) acrylonitrile; vinyl ketones such as methyl vinyl ketone; vinyl ethers such as methyl vinyl ether; crotonaldehyde; allyl alcohol; allyl esters such as allyl acetate: etc.

  A monomer having a functional group is selected from these monomers and other known monomers, a polymer of the monomer having a functional group (homopolymer), a monomer having a functional group Or a copolymer of a monomer having a functional group and a monomer having no functional group can be prepared. When the monomer is referred to as a functional group, it does not include a polymerizable reactive group used for forming a resin such as an α, β-ethylenically unsaturated group.

  In addition, 0.1-10 mass parts is preferable with respect to 100 mass parts of monomers which do not have a functional group, and the monomer which has a functional group has 0.5-5 mass parts between suitable polymer particles. This is preferable in terms of giving a binding force of.

  As described above, since a styrene-containing resin mainly composed of a (meth) acrylic acid and a (meth) acrylate-based resin is suitable, a monomer (( (Meth) acrylate monomer, (meth) acrylic acid monomer, and styrene monomer) will be described in more detail. In addition, when it says acrylic acid, the inorganic salt (For example, metal salts, such as ammonium salt or sodium salt, potassium salt) shall also be included. Similarly, other acids (such as maleic acid) include these inorganic salts.

(Ii-2) (meth) acrylate monomers (meth) acrylate monomers include alkyl (meth) acrylates; (meth) acrylates having hydroxyl groups; (meth) acrylates having amino groups; glycidyl groups (Meth) acrylates having a polyfunctional (meth) acrylate and the like.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl ( Examples include meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, and the like.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxypropyl (meth) acrylate.

  Examples of the (meth) acrylate having an amino group include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

  Examples of the (meth) acrylate having a glycidyl group include glycidyl (meth) acrylate.

  Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate.

  In addition, cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate, aryl (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, aralkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, etc. are also used. it can.

(Ii-3) (Meth) acrylic acid monomers (Meth) acrylic monomers include (meth) acrylic acid, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) Acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, t-butyl (meth) acrylic acid, pentyl (meth) acrylic acid, hexyl (meth) acrylic acid, octyl (Meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid, decyl (meth) acrylic acid, dodecyl (meth) acrylic acid, stearyl (meth) acrylic acid and the like.

  Moreover, 2-hydroxypropyl (meth) acrylic acid, dimethylaminoethyl (meth) acrylic acid, diethylaminoethyl (meth) acrylic acid, glycidyl (meth) acrylic acid, ethylene glycol di (meth) acrylic acid, trimethylolpropane tri ( In addition to the carboxylic acid, a monomer that can provide a functional group (for example, a hydroxyl group) different from the carboxylic acid in the resin particles is used, such as (meth) acrylic acid.

(Ii-4) Styrene monomer Examples of the styrene monomer include styrene, α-methylstyrene, vinyltoluene, and the like. Styrene is preferably used. Styrene sulfonic acid and vinyl sulfonic acid may be used.

  In preparing the resin particles, one or more monomers are selected so as to include at least a monomer having a functional group. For example, when a styrene-acrylate copolymer is desired, since the styrene-alkyl acrylate copolymer does not have a functional group in the resin particle, styrene sulfonic acid is used instead of styrene, or alkyl acrylate A functional group is introduced into the resin particles by a method such as using glycidyl acrylate instead of. Alternatively, in addition to styrene and alkyl acrylate, a resin particle obtained by combining the (meth) acrylic acid monomer of (ii-3) or the monomer having the functional group exemplified in (ii-1) above Manufacturing.

(Iii) Network forming agent In this invention, a network forming agent means the substance which produces the coupling | bonding between particle | grains. The network forming agent includes a cross-linking agent that cross-links between functional groups present in each resin particle, or a reactive monomer, a reactive polymer, a polymerizing agent, a polymerization agent that bonds functional groups in each resin particle to each other. Auxiliaries, polymerization initiators and the like are included.

  The network forming agent used in the present invention is water-soluble, easily dispersible in water, or soluble in a trace amount of water-soluble solvent from the viewpoint of crosslinking between particles or bonding between particle surfaces in an emulsion state. It preferably has a property of being solubilized with a surfactant.

(Iii-1) Crosslinking agent The crosslinking agent is not particularly limited as long as it is a compound capable of reacting with a functional group present in resin particles or aggregate particles to form a crosslink between the particles. A crosslinking agent can be used individually or in combination of 2 or more types.

  (Iii-1-1) When the functional group is a carboxyl group, as the crosslinking agent, a compound having an epoxy group or an isocyanate group, a metal compound, or the like is preferably used.

  As the compound having an epoxy group, a compound having two or more epoxy groups, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, Glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, 1,3-3,4-diepoxybutane and the like are used.

  As the compound having an isocyanate group, a polyisocyanate compound such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, a prepolymer having an isocyanate group (hydroxyl-containing polyester, hydroxyl-containing polyether, etc.) And a polymer having an isocyanate group at the terminal) obtained by reacting the above-mentioned polyisocyanate with an excessive amount of the polyol.

  The metal compound is preferably a water-soluble metal compound having a valence of 2 or more, and a halide of a metal such as boron, aluminum, iron, copper, zinc, tin, titanium, nickel, magnesium, vanadium, chromium, zirconium, etc. And salts (carbonates, nitrates, sulfates, etc.), oxides, hydroxides and the like. In particular, boric acid, borax, aluminum chloride, aluminum sulfate, ammonium zirconium carbonate, zirconium chloride, iron alum and the like are preferable.

  (Iii-1-2) When the functional group is a hydroxyl group, the crosslinking agent includes a compound having a carboxyl group or an acid anhydride group, a compound having an aldehyde group, a compound having an epoxy group, a nitrogen-containing compound, and an acrylamide moiety. , Compounds having an isocyanate group, metal compounds, and the like. Especially, the compound (especially polyhydric carboxylic acid or its acid anhydride) which has a carboxyl group or an acid anhydride group, and a metal compound are preferable.

  Examples of the polyvalent carboxylic acid include aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, aromatic polycarboxylic acid, oxypolycarboxylic acid, and heterocyclic polycarboxylic acid.

  As aliphatic polycarboxylic acid, C2-10 aliphatic saturated polycarboxylic acid (for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.), Alternatively, C4-6 aliphatic unsaturated polycarboxylic acids (fumaric acid, maleic acid, maleic anhydride, citraconic acid, mesaconic acid, itaconic acid, etc.) and the like can be mentioned.

  Examples of the alicyclic polycarboxylic acid include C8-10 alicyclic polycarboxylic acids (for example, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, etc.).

  Examples of the aromatic polycarboxylic acid include C8-12 aromatic polycarboxylic acids or acid anhydrides thereof (for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.). .

  Examples of the oxypolycarboxylic acid include C3-6 oxypolyvalent carboxylic acids (eg, tartronic acid, malic acid, tartaric acid, citric acid, etc.).

  The heterocyclic polyvalent carboxylic acid is a polyvalent carboxylic acid having at least one heteroatom selected from nitrogen, oxygen and sulfur atoms (for example, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyridinetetracarboxylic acid, tropic acid, etc.) Etc. As the polyvalent carboxylic acid in the heterocyclic polyvalent carboxylic acid, an aliphatic, alicyclic or aromatic polycarboxylic acid (particularly a C3-10 polycarboxylic acid) is preferably used.

  A salt or partial salt of a polyvalent carboxylic acid is also preferably used. Examples of the polyvalent carboxylates include inorganic salts such as ammonium salts and alkali metal salts (potassium salts, sodium salts, etc.) and organic salts such as tertiary amines. As the polyvalent carboxylic acid, maleic acid or its acid anhydride (maleic anhydride) is particularly preferable.

  As the compound having an aldehyde group, a compound having a plurality of aldehyde groups, for example, glyoxal, malonaldehyde, glutaraldehyde, terephthalaldehyde, dialdehyde starch, acrolein copolymer acrylic resin and the like are used.

  Examples of nitrogen-containing compounds include C1-4 alkoxymelamines such as methoxymethylmelamine, methylol group-containing compounds such as N-methylolmelamine and N-methylolurea, guanamines such as acetoguanamine and benzoguanamine, melamine-formalin resin, urea -Formalin resin or the like is used.

  Examples of the compound having an acrylamide group include methylene-bis (meth) acrylamide, N, N′-dimethylol-methylene-bisacrylamide, 1,1-bisacrylamide-ethane and the like.

  The compound and metal compound having an epoxy group or an isocyanate group are as described in (iii-1-1) “When the functional group is a carboxyl group”.

  (Iii-1-3) When the functional group is a functional group other than a carboxyl group and a hydroxyl group, a crosslinking agent having a functional group capable of reacting with the functional group may be selected in consideration of the above explanation. For example, when the functional group is an amide group, a dihydroxy compound may be used.

(Iii-2) Network forming agents other than crosslinking agents Examples of network forming agents other than crosslinking agents include reactive monomers, reactive polymers, polymerization agents, polymerization aids, polymerization initiators and the like as described above. It is done. The reactive monomer and the reactive polymer react with a functional group in the resin particle to form a network between the resin particles.

(Iii-2-1) Reactive monomer The reactive monomer which is a network forming agent refers to a polymerizable monomer. The reactive monomer includes a monomer having a group capable of reacting with a functional group present in the resin particle (functional group-containing reactive monomer) and a functional group present in the resin particle. Any monomer that does not (functional group-free reactive monomer) is used. In order to prepare the toner of the present invention, at least one functional group-containing reactive monomer is used. The functional group-free reactive monomer is used in combination with a functional group-containing reactive monomer. As the functional group-containing reactive monomer, various monomers described in the above “(ii) Monomer for producing resin particles” can be used. For example, when the functional group of the resin particle is a carboxyl group, a monomer having an epoxy group (for example, glycidyl (meth) acrylate) is used. When the functional group of the resin particle is an epoxy group, a monomer having a carboxyl group (for example, methacrylic acid) is used. The functional group-free reactive monomer includes (a) a monomer having no functional group (for example, styrene, (meth) acrylate, olefin, etc.), and (b) a functional group present in the resin particle. Monomers having functional groups that do not react are included. The monomer corresponding to (b) is based on the functional group of the functional group-containing reactive monomer, referring to the descriptions in (iii-1-1) and (iii-1-2) above. Those skilled in the art can easily select.

(Iii-2-2) Reactive polymer A reactive polymer is a polymer that itself can be polymerized, and a polymer having a group capable of reacting with a functional group present in a resin particle (functional Both a group-containing reactive polymer) and a polymer that does not react with a functional group present in the resin particles (non-functional group-containing reactive polymer) are used. Here, the functional group of the reactive polymer does not include a polymerizable reactive group such as an α, β-ethylenically unsaturated group. In order to prepare the toner of the present invention, at least one functional group-containing reactive polymer is used. The functional group-free reactive polymer is used in combination with the functional group-containing reactive polymer. The functional group-containing reactive polymer refers to a homopolymer or copolymer obtained using a reactive monomer having at least a functional group. The functional group-free reactive polymer includes (a) a monomer having no functional group (for example, styrene, (meth) acrylate, olefin, etc.), and (b) a functional group present in the resin particle. And a homopolymer of each of the monomers having a functional group that does not, and a copolymer of the monomer (a) and the monomer (b). The monomer corresponding to (b) is based on the functional group of the functional group-containing reactive polymer, referring to the description of (iii-1-1) and (iii-1-2) above, One skilled in the art can easily select.

  Reactive polymers include dimers to oligomers and polymers. From the viewpoint of network formation, a low molecular weight is preferable. Therefore, about 2-100 mer is preferable and about 2-50 mer is more preferable.

  The reactive monomer and the reactive polymer may be used alone or in combination. For example, functional group-containing reactive monomer-functional group-free reactive monomer, functional group-containing reactive monomer-functional group-free reactive polymer, functional group-containing reactive polymer-functional group-nonfunctional Combinations such as a reactive polymer containing a functional group, a reactive polymer containing a functional group and a reactive monomer containing no functional group are also possible. Furthermore, it is preferable to use a polymerization agent, a polymerization initiator and a polymerization aid suitable for the polymerization of these reactive monomers and reactive polymers.

(Iii-2-3) Polymerization agent, polymerization initiator and polymerization aid In this specification, the polymerization agent refers to a catalyst used for polymerization, the polymerization aid refers to a substance that promotes polymerization, and the polymerization initiator refers to polymerization. This refers to a chain initiator in the reaction. These polymerization agents, polymerization initiators and polymerization accelerators are not particularly limited, and compounds usually used by those skilled in the art are used depending on the monomer to be polymerized. A polymerization agent, a polymerization initiator, and a polymerization assistant can be used alone or in combination, but it is generally preferable to use them in combination.

  These polymerizers, polymerization initiators, and polymerization aids are formed by directly bonding the functional groups in the resin particles or aggregate particles without the presence of reactive monomers or reactive polymers. In some cases, the gap can be bonded only at the surface. For example, when an epoxy group and a carboxyl group are present on the surface of the resin particle, when potassium persulfate is used as a polymerization initiator and heated, it is between the epoxy group of the resin particle A and the carboxyl group of another resin particle B. The resin particles A and the resin particles B are bonded on the surface by the dehydration reaction. In this way, the resin particles can be bonded only on the surface.

  Examples of the polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate; hydrogen peroxide; azo initiators such as azobisisobutyronitrile; cumene hydroperoxide, t-butyl hydroperoxide, and the like. Organic peroxide: etc. are used. If necessary, a combination of persulfate or peroxide and a metal ion such as iron ion, a reducing agent such as sodium sulfoxylate, sodium pyrosulfite, or L-ascorbic acid may be used as a redox initiator. Good.

When a persulfate such as ammonium persulfate or potassium persulfate is used as a polymerization initiator, for example, sulfonate ion (—SO ₃ ⁻ ) or sulfate ester ion (—SO ₃ ⁻ ) is preferably used as the polymerization aid. . In this case, the surfactant having a sulfonate ion or a sulfate ester ion in the molecule functions as a polymerization aid.

  Examples of the surfactant having a sulfonate ion or a sulfate ester ion in the molecule include sodium dodecylbenzenesulfonate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalenesulfonate, sodium dioctylsulfosuccinate, sodium lauryl sulfate, polyoxy Examples include sodium ethylene alkyl ether sulfate.

(Iv) Release Agent From the viewpoint of forming a network between resin particles as shown in FIG. 1 and improving the durability of the toner, the release agent needs to be used as a release agent particle having a small particle size.

As the release agent, paraffin wax, polyolefin wax, modified wax having aromatic group, hydrocarbon compound having alicyclic group, natural wax, long chain hydrocarbon chain having 12 or more carbon atoms (CH ₃ (CH ₂ ) ₁₁ or CH ₃ (CH ₂ ) ₁₂ or more aliphatic carbon chains) and long chain carboxylic acids and esters thereof, long chain fatty acid metal salts (metal soaps), fatty acid amides, fatty acid bisamides, and the like are used. These may be used alone or in combination.

  Specific release agents include paraffin wax (manufactured by Nippon Oil Co., Ltd.), paraffin wax (manufactured by Nippon Seiwa Co., Ltd.), micro wax (manufactured by Nippon Oil Co., Ltd.), and microcrystalline wax (Nippon Seiwa). ), Hard paraffin wax (Nippon Seiwa Co., Ltd.), PE-130 (Hoechst), Mitsui High Wax 110P (Mitsui Petrochemical Co., Ltd.), Mitsui High Wax 220P (Mitsui Petrochemical ( ) Mitsui High Wax 660P (Mitsui Petrochemical Co., Ltd.), Mitsui High Wax 210P (Mitsui Petrochemical Co., Ltd.), Mitsui High Wax 320P (Mitsui Petrochemical Co., Ltd.), Mitsui High Wax 410P (Mitsui Petrochemical Co., Ltd.), Mitsui High Wax 420P (Mitsui Petrochemical Co., Ltd.), Modified Wax JC-1141 (Mitsui Petrochemical Co., Ltd.), Modified Wax JC-2130 (Mitsui Petrochemical Co., Ltd.) Co., Ltd.) JC-4020 (Mitsui Petrochemical Co., Ltd.), modified wax JC-1142 (Mitsui Petrochemical Co., Ltd.), modified wax JC-5020 (Mitsui Petrochemical Co., Ltd.), beeswax, carnauba wax, Examples include montan wax.

  As the long chain fatty acid metal salt (metal soap), zinc stearate, calcium stearate, magnesium stearate, zinc oleate, zinc palmitate, magnesium palmitate and the like are preferably used.

  Examples of the polyolefin wax include low molecular weight polypropylene, low molecular weight polyethylene, oxidized polypropylene, oxidized polyethylene, and the like. Specific examples of polyolefin waxes include, for example, Hoechst Wax PE520, Hoechst Wax PE130, Hoechst Wax PE190 (manufactured by Hoechst), Mitsui High Wax 200, Mitsui High Wax 210, Mitsui High Wax 210M, Mitsui High Wax 220, Mitsui High Wax Non-oxidized polyethylene wax such as 220M (Mitsui Petrochemical Industries), Sun Wax 131-P, Sun Wax 151-P, Sun Wax 161-P (Sanyo Chemical Industries), Hoechst Wax PED121, Hoechst Wax PED153, Hoechst Wax PED521, Hoechst Wax PED522, Ceridust 3620, Ceridust VP130, Ceridust VP5905, Ceridust VP9615A, Ceridust TM9610F, Ceridust 3715 (manufactured by Hoechst), Mitsui High Wax 420M Oxidized polyethylene wax such as Sun Wax E-300, Sun Wax E-250P (manufactured by Sanyo Chemical Industries), Hoechs t Non-oxidized polypropylene wax such as Wachs PP230 (Hoechst), Biscol 330-P, Biscol 550-P, Biscol 660P (Sanyo Chemical Industries), and Biscol TS-200 (Sanyo Chemical Industries, Ltd.) Oxidized polypropylene wax, such as

  These release agents can be used alone or in combination. As a mold release agent added as needed, the softening point (melting point) which is an endothermic main peak value in a DSC endothermic curve measured by “DSC120” manufactured by Seiko Instruments Inc. is preferably 40 to 130 ° C., preferably Is 50 to 120 ° C.

  1 to 3 parts by mass of the release agent is added to 100 parts by mass of the resin. When the amount of the release agent is less than 1 part by mass, the non-offset effect at the time of toner fixing cannot be obtained, and when it exceeds 3 parts by mass, the image forming apparatus member is likely to be contaminated.

(V) Toner Production Method The toner of the present invention forms, for example, a state in which the release agent particles exist in the gap formed by the resin particles contacting each other as shown in FIG. The resin particles are manufactured by forming a network. In order for the release agent particles to be present in the gaps between the resin particles, when the particle size of the resin particles is A and the particle size of the release agent particles is B, 0.13 ≦ B / A ≦ 0 It is necessary to adjust the sizes of the resin particles and the release agent particles so as to satisfy the relationship of .31. When B / A exceeds 0.31, release agent particles cannot be present between the resin particles. It is difficult to adjust release agent fine particles having a particle size of B / A of less than 0.13.

  In the present invention, first, an emulsion of resin particles and an emulsion of release agent particles satisfying the above particle size relationship are prepared. These emulsions are then mixed to form a network between the resin particles. What is necessary is just to determine the method of forming a network between resin particles according to the functional group in a resin particle. A network forming agent may be added to the dispersion medium (generally water) of the resin particle emulsion for reaction, or may be dispersed in advance in a dispersion medium for forming the resin particle emulsion.

  When the resin particles have only one type of functional group, a cross-linking agent, a reactive monomer or a reactive polymer is added to, for example, a mixed dispersion medium of a resin particle emulsion and a release agent particle emulsion and reacted. When the resin particles have two types of functional groups, the cross-linking agent, reactive monomer or reactive polymer having two reactive groups capable of reacting with the two types of functional groups are converted into resin particle emulsion and mold release. It may be added to the mixed dispersion medium of the agent particle emulsion and allowed to react. However, the two types of functional groups in the resin particles are set to a combination that can react with each other (for example, a carboxyl group and a glycidyl group), and a polymerization agent and a polymerization agent are mixed into the mixed dispersion medium of the resin particle emulsion and the release agent particle emulsion. An initiator and a polymerization aid may be added, followed by heating / dehydration or spray drying. A resin particle emulsion having only carboxyl groups and a resin particle emulsion having only epoxy groups are mixed, and a polymerization agent, a polymerization initiator and a polymerization aid are added to this dispersion medium, followed by heating / dehydration or spray drying. Also good. Spray drying is preferably used in view of the circularity of the toner. By such a method, a network is formed between the resin particles.

  Hereinafter, a specific method for producing a toner will be described with reference to the case of a styrene-methacrylate-acrylic acid copolymer resin, but the present invention is not limited to this, and in the production of other resins. Are used similarly.

(V-1) Preparation of Resin Particles It is preferable that toner particles contain an internal additive such as a colorant and a charge control agent in advance. Therefore, it is preferable to add an internal additive such as a colorant when preparing the resin particles.

(V-1-1) Colorant The colorant used in the present invention is not limited, and organic pigments, inorganic pigments, and dyes can be used. Examples thereof include pigments having various colors as shown below.

  Examples of the black colorant used in the present invention include carbon black, copper oxide, iron trioxide, manganese dioxide, aniline black, and activated carbon.

  Examples of the yellow colorant used in the present invention include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, for example, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used.

  Examples of magenta colorants used in the present invention include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Compounds. Specifically, for example, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, It is particularly preferable to use 202, 206, 220, 221, 254, 269 or the like.

  Examples of the cyan colorant used in the present invention include compounds represented by copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, for example, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly suitable.

  These colorants may be used alone or in combination of two or more, but it is desirable to use 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the toner particles. When the amount is more than 20 parts by mass, the toner fixing property and transparency are deteriorated. On the other hand, when the amount is less than 1 part by mass, a desired image density may not be obtained.

(V-1-2) Preparation of resin particles-1
A monomer mixture containing a polymerization initiator, a colorant, styrene, methacrylate, acrylic acid, and a colorant is added dropwise to an aqueous solution such as a surfactant and an emulsifier with stirring to prepare an emulsion containing polymer particles. If necessary, a monomer mixture of methacrylate and acrylic acid may be added dropwise to the emulsion with stirring. The resin particles in the resulting colored emulsion A have a carboxyl group.

(V-1-3) Preparation of resin particles-2
A monomer mixture containing a polymerization initiator, a colorant, styrene, methacrylate, glycidyl methacrylate and a colorant is added dropwise to an aqueous solution of a surfactant, an emulsifier and the like with stirring to prepare an emulsion containing polymer particles. If necessary, a monomer mixture of methacrylate and glycidyl methacrylate may be further added dropwise to the emulsion with stirring. The resin particles in the resulting colored emulsion B have an epoxy group.

(V-2) Preparation of release agent particles In order to retain the release agent between the resin particles, it is necessary to add the release agent as an emulsion. Examples of the method for emulsifying the release agent include a method in which the release agent is dissolved in an organic solvent and dispersed in water, or a method in which the release agent is dispersed in water and then heated to be emulsified. Commercial release agent emulsions can also be used. The release agent particles are prepared to have a particle size that satisfies the above relationship based on the size (particle size) of the resin particles.

(V-3) Dispersion (Emulsion) containing network forming agent
To the colored emulsion A (carboxyl group-containing) obtained in Preparation-1 of the resin particles, the release agent emulsion is mixed so that the release agent particles are 1 to 3 parts by mass per 100 parts by mass of the resin particles. Then, a crosslinking agent (for example, ethylene glycol diglycidyl ether) is added to prepare a dispersion containing the network forming agent.

  Alternatively, the colored emulsion A (carboxyl group-containing) obtained in resin particle preparation-1 and the colored emulsion B (epoxy group-containing) obtained in resin particle preparation-2 and the release agent emulsion are used as dispersion media. Charge and mix. The size of the release agent particles is adjusted so as to satisfy the above relationship with the size of the smaller one of the colored emulsion A and the colored emulsion B. A dispersion containing a network forming agent is prepared by dissolving potassium persulfate as a polymerization initiator and sodium dodecylbenzenesulfonate as a polymerization aid in the dispersion medium of these emulsions.

  By defining the relationship between the particle diameters of the resin particles (colored emulsion) and the release agent particles within the above range, and the addition amount of the release agent particles is 1 to 3 parts by mass per 100 parts by mass of the resin particles, the network In the dispersion (emulsion) containing the forming agent, it is considered that each particle is dispersed in the state shown in FIG. 2, and a network is formed between the resin particles by performing the next spray drying in this state. The release agent is held in the gap between the resin particles.

(V-4) Spray drying The dispersion containing the network-forming agent is then washed as necessary and spray dried. Although there is no restriction | limiting in particular in the spray-drying method, Drying apparatuses, such as a spray-dryer which has a spray-dry system, a piezo-type discharge system, or a spray-dryer which has a thermal jet discharge system, are used. Among these, a spray dryer having a spray drying method and a piezoelectric discharge method is preferably used.

  The piezo-type discharge method is a method in which electrical energy is converted into mechanical energy using a piezo element while the dispersion is heated, and the dispersion is ejected quantitatively. A typical thermal jet discharge method is the bubble jet (registered trademark) discharge method, where the heat generated by the heater formed in the nozzle is applied to the dispersion to heat the dispersion and use the expansion energy. Then, the dispersion is sprayed. In any method, the dispersion liquid is quantitatively heated, and the resin particles constituting the adhering particles are melted and melted together by heating, and the toner particles having a uniform particle diameter are recovered by being ejected from the nozzle. The

  In this spray drying, a dehydration reaction occurs between the epoxy group in the crosslinking agent and the carboxyl group in the resin particle, and the resin particles are crosslinked. As a result, aggregated particles (toner particles) that are aggregates of resin particles in which the release agent is held in the gaps between the resin particles are obtained. In addition, it is thought that the particles 12 and 14 as shown in FIG. 1 are formed by the heating at the time of spray drying.

(V-5) Preparation of toner An external additive is added to the obtained toner particles for the purpose of improving the chargeability and fluidity of the toner. Examples of the external additive include negatively chargeable silica fine particles, titanium oxide, metal soap, and positively chargeable silica fine particles.

  As the negatively chargeable silica fine particles, generally negatively chargeable silica fine particles having an average particle size of 4 to 120 nm, preferably 5 to 50 nm, and more preferably 6 to 40 nm are used. The negatively chargeable silica fine particles are preferably hydrophobized from the viewpoint of improving the fluidity and chargeability of the toner. Examples of the hydrophobic negatively chargeable silica fine particles include commercially available RX200 (average particle size of 12 nm), RX50 (average particle size of 40 nm) manufactured by Nippon Aerosil Co., Ltd., TG811F, TG810G, and TG308F manufactured by Cabot Corporation. Is used. A combination of negatively chargeable silica fine particles having different average particle diameters may be used.

  The addition amount of the negatively chargeable silica fine particles is generally 0.5 to 2.0 parts by mass, preferably 0.7 to 1.5 parts by mass with respect to 100 parts by mass of the toner particles. In the present specification, the average particle diameter of fine particles means a volume average particle diameter unless otherwise specified.

  The titanium oxide fine particles are used as necessary for adjusting the charge of the toner. Although there is no restriction | limiting in particular in the magnitude | size of a titanium oxide microparticle, It is preferable that a particle size or the magnitude | size of a major axis is a magnitude | size of 10-30 nm. The titanium oxide fine particles are added in an amount of 0.2 to 2.0 parts by weight, preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the toner particles. The addition of the titanium oxide fine particles and the positively chargeable silica fine particles in a mass ratio of 1: 3 to 3: 1 can adjust the charge without causing an extreme decrease in the electric resistance of the toner. In terms, it is preferable.

  The surface of the titanium oxide fine particles is hydrophobic in order to reduce the change in chargeability with respect to the change in the external environment of the toner (that is, maintain stable chargeability) and improve the fluidity of the toner. ,preferable. As the hydrophobic titanium oxide fine particles, STT-30S manufactured by Titanium Industry Co., Ltd. is used.

  Metal soap is added as necessary for the purpose of improving the fluidity of the toner, improving the binding property of the external additive, and preventing toner aggregation. For example, magnesium stearate, calcium stearate, zinc stearate and the like can be mentioned. The metal soap preferably has a volume average particle diameter or major axis diameter of 0.5 to 10 μm, and more preferably 1 to 5 μm. The metal soap is added in an amount of 0.1 to 1.0 part by weight, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the toner particles.

  The positively chargeable silica fine particles are used as necessary for adjusting the charge of the toner. The positively chargeable silica fine particles used in the present invention are not particularly limited. The volume average particle diameter of the positively chargeable silica fine particles is preferably 10 to 50 nm, more preferably 15 to 40 nm in consideration of fluidity and the like. The positively chargeable silica fine particles are preferably hydrophobized from the viewpoint of maintaining chargeability and improving fluidity. As the hydrophobic positively chargeable silica fine particles, commercially available NA50H manufactured by Nippon Aerosil Co., Ltd., TG820F manufactured by Cabot Co., Ltd., etc. are used. The positively chargeable silica fine particles are added in an amount of 0.1 to 1.0 parts by weight, preferably 0.2 to 0.8 parts by weight, based on 100 parts by weight of the toner particles, if necessary.

  In addition, for example, external additives commonly used by those skilled in the art other than those described above, such as inorganic fine particles added for the purpose of controlling chargeability and improving fluidity, are also used.

  The external addition process is performed by adding a predetermined amount of the above external additive to the toner particles and performing, for example, a stirring / mixing process using a Henschel mixer.

  The toner of the present invention can be used in any type of image forming apparatus. An image forming apparatus using a one-component toner or an image forming apparatus using a two-component toner may be used. Further, it may be a contact developing type image forming apparatus or a non-contact type image forming apparatus. A one-component contact type image forming apparatus that can use the toner of the present invention is described in detail in, for example, Japanese Patent Application Laid-Open No. 2002-202622. The image forming apparatus of the present invention includes a latent image carrier on which an electrostatic latent image typified by a photoreceptor is formed; toner is applied to the latent image carrier to develop the electrostatic latent image on the latent image carrier. At least a developing device having a toner carrying member typified by a developing roll to be conveyed; and a toner regulating member for regulating the amount of toner carried to the latent image carrying member by the toner carrying member. The toner of the present invention is accommodated in a toner accommodating portion, conveyed from the toner accommodating portion to a developing roll (toner carrier), and supplied to the photosensitive member (latent image carrier) via the developing roll (toner carrier). And transferred to form an image. The toner regulating member adjusts the toner supply amount so that excessive supply from the developing roll (toner carrier) to the photosensitive member (latent image carrier) is not performed.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not restrict | limited to this Example.

  The particle diameters of the resin particle emulsion and the wax emulsion were measured using a Nikkiso Microtrac UPA150. The toner particles and the volume average particle diameter of the toner were measured with Multisizer III (manufactured by Coulter).

(Production Example 1: Preparation of colored emulsion)
(Production Example 1-1) Preparation of Colored Emulsion 1 In a reaction vessel (capacity 3 liters; with a stirrer, reflux condenser, dropping device, and thermometer), 1000 parts by mass of distilled water, polyoxyethylene nonylphenol ether (HLB = 14) 10 parts by mass and 10 parts by mass of sodium lauryl sulfate were charged and stirred in a nitrogen atmosphere at a temperature of 30 to 40 ° C. and 40 to 60 rpm to dissolve the contents and heated to 85 ° C.

  While maintaining the temperature of the contents at 85 ° C., 3 parts by mass of potassium persulfate was added, 260 parts by mass of styrene, 270 parts by mass of n-butyl acrylate and 5 parts by mass of sodium acrylate, CI Pigment Blue 15: 334 mass A soft monomer mixture consisting of parts was dropped over 2 hours and then polymerized by maintaining at 85 ° C. for 1 hour to prepare an emulsion containing soft polymer particles.

  Next, a hard monomer mixture composed of 290 parts by weight of methyl methacrylate and 5 parts by weight of sodium acrylate was dropped into the emulsion over 2 hours, and then held at 85 ° C. for 1 hour. Then, it cooled to normal temperature, 25% ammonia water was added as a neutralizing agent, pH was adjusted to 8-9, and the colored emulsion 1 was obtained. The ratio of the soft monomer mixture to the hard monomer mixture was 64:36 (% by mass). The average particle size of the colored emulsion 1 was 130 nm.

(Production Example 1-2) Preparation of Colored Emulsion 2 In a reaction vessel (capacity 3 liters; with stirrer, reflux condenser, dropping device, and thermometer), 1000 parts by mass of distilled water, polyoxyethylene nonylphenol ether (HLB = 14) 10 parts by mass and 6 parts by mass of sodium lauryl sulfate were charged and stirred in a nitrogen atmosphere at a temperature of 30 to 40 ° C. and 40 to 60 rpm to dissolve the contents and heated to 85 ° C.

  While maintaining the temperature of the content at 85 ° C., 3 parts by weight of potassium persulfate was added, and 260 parts by weight of styrene, 270 parts by weight of n-butyl acrylate and 5 parts by weight of acrylate, CI Pigment Blue 15: 334 parts by weight The resulting soft monomer mixture was added dropwise over 2 hours and then polymerized by holding at 85 ° C. for 1 hour to prepare an emulsion containing soft polymer particles.

  Next, a hard monomer mixture composed of 290 parts by weight of methyl methacrylate and 5 parts by weight of acrylate was dropped into the emulsion over 2 hours, and then held at 85 ° C. for 1 hour. Then, it cooled to normal temperature, 25% ammonia water was added as a neutralizing agent, and it adjusted to pH 8-9, and the colored emulsion 2 was obtained. In addition, the ratio of a soft monomer mixture and a hard monomer mixture is 64:36 (mass%). The average particle diameter of the colored emulsion 2 was 300 nm.

(Production Example 1-3) Preparation of Colored Emulsion 3 In a reaction vessel (capacity 3 liters; with stirrer, reflux condenser, dropping device, and thermometer), 1000 parts by mass of distilled water, polyoxyethylene nonylphenol ether (HLB = 14) 10 parts by mass and 2 parts by mass of sodium lauryl sulfate were charged and stirred in a nitrogen atmosphere at a temperature of 30 to 40 ° C. and 40 to 60 rpm to dissolve the contents and heated to 85 ° C.

  While maintaining the temperature of the content at 85 ° C., 3 parts by weight of potassium persulfate was added, and 260 parts by weight of styrene, 270 parts by weight of n-butyl acrylate and 5 parts by weight of acrylate, CI Pigment Blue 15: 334 parts by weight The resulting soft monomer mixture was added dropwise over 2 hours and then polymerized by holding at 85 ° C. for 1 hour to prepare an emulsion containing soft polymer particles.

  Next, a hard monomer mixture composed of 290 parts by weight of methyl methacrylate and 5 parts by weight of acrylate was dropped into the emulsion over 2 hours, and then held at 85 ° C. for 1 hour. Then, it cooled to normal temperature, 25% ammonia water was added as a neutralizing agent, and it adjusted to pH 8-9, and the colored emulsion 3 was obtained. In addition, the ratio of a soft monomer mixture and a hard monomer mixture is 64:36 (mass%). The average particle size of the colored emulsion 3 was 500 nm.

(Production Example 1-4) Preparation of colored emulsion 4 In a reaction vessel (capacity 3 liters; with a stirrer, a reflux condenser, a dropping device, and a thermometer), 1000 parts by mass of pure water and sodium dodecylbenzenesulfonate 4.5 A mass part was charged and stirred in a nitrogen atmosphere at a temperature of 30 to 40 ° C. and 40 to 60 rpm to dissolve the contents, and the temperature was raised to 70 ° C.

  While maintaining the temperature of the content at 70 ° C., 4.5 parts by mass of potassium persulfate was added, 60 parts by mass of styrene, 90 parts by mass of n-butyl acrylate and 30 parts by mass of glycidyl methacrylate, CI Pigment Blue 15: 3 55 A mixture consisting of parts by mass was added dropwise over 2 hours, and then polymerized by maintaining at 70 ° C. for 1 hour to produce an emulsion.

  Next, a mixture composed of 330 parts by mass of styrene, 380 parts by mass of n-butyl acrylate and 20 parts by mass of methyl acrylate was dropped into the emulsion over 3 hours, and then held at 70 ° C. for 1 hour. Then, it cooled to normal temperature and added aqueous ammonia as a neutralizing agent, and adjusted pH to 7.5, and the colored emulsion 4 was obtained. The average particle size of the colored emulsion 4 was 150 nm.

(Production Example 2: Preparation of wax emulsion)
(Production Example 2-1) Preparation of Wax Emulsion 1 Paraffin wax (melting point 85 ° C., no acid value) 100 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 20 parts by mass, and ion exchange A wax emulsion 1 was obtained by mixing 1000 parts by mass of water using a homogenizer manufactured by Gorin under conditions of 100 ° C. and 60 kg / cm ² and then cooling. The average particle size of the wax emulsion 1 was 20 nm.

(Production Example 2-2) Preparation of Wax Emulsion 2 Paraffin wax (melting point 85 ° C., no acid value) 100 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 10 parts by mass, and ion exchange A wax emulsion 2 was obtained by mixing 1000 parts by weight of water using a homogenizer manufactured by Gorin under conditions of 100 ° C. and 60 kg / cm ² and then cooling. The average particle size of the wax emulsion 2 was 45 nm.

(Production Example 2-3) Preparation of Wax Emulsion 3 Paraffin wax (melting point 85 ° C., no acid value) 100 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 8 parts by mass, and ion exchange A wax emulsion 3 was obtained by mixing 1000 parts by weight of water using a homogenizer manufactured by Gorin under conditions of 100 ° C. and 50 kg / cm ² and then cooling. The average particle size of the wax emulsion 3 was 75 nm.

(Production Example 2-4) Preparation of Wax Emulsion 4 Paraffin wax (melting point 85 ° C., no acid value) 100 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 5 parts by mass, and ion exchange A wax emulsion 4 was obtained by mixing 1000 parts by weight of water using a homogenizer manufactured by Gorin under conditions of 100 ° C. and 30 kg / cm ² and then cooling. The average particle size of the wax emulsion 4 was 250 nm.

(Production Example 2-5) Preparation of wax emulsion 5 Paraffin wax (melting point: 85 ° C., no acid value) 100 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 30 parts by mass, and ion exchange A wax emulsion 5 was obtained by mixing 1000 parts by weight of water using a homogenizer manufactured by Gorin under conditions of 100 ° C. and 70 kg / cm ² and then cooling. The average particle size of the wax emulsion 5 was 8 nm.

Production Example 2-6 Preparation of Wax Emulsion 6 A wax emulsion 6 was obtained in the same manner as in Production Example 2-1, except that low molecular weight polyethylene was used in place of the wax emulsion 1 paraffin wax. The average particle size of the wax emulsion 6 was 21 nm.

(Production Example 2-7) Preparation of wax emulsion 7 A wax emulsion 7 was obtained in the same manner as in Production Example 2-1, except that carnauba wax (acid number 15) was used instead of the paraffin wax of wax emulsion 1. It was. The average particle size of the wax emulsion 7 was 21 nm.

(Example 1)
2 parts by weight of wax emulsion 1 and 8 parts by weight of ethylene glycol glycidyl ether were added to 100 parts by weight of Colored Emulsion 1, stirred, and then spray dried at 100 ° C. The toner particles 1 were obtained by washing twice with ion exchange water and vacuum drying.

  The external additive was applied to the toner particles 1 and a 20 L type Henschel mixer. As an external additive, 1 part by mass of negatively chargeable small particle size silica RX200 (Nippon Aerosil Co., Ltd. average particle size of 12 nm) and negatively chargeable large particle size silica RX50 (Japan) are used per 100 parts by mass of toner particles 1. 0.5 parts by mass of Aerosil Co. average particle size 40 nm) and 0.5 parts by mass of titanium oxide STT-30S (average particle size 20 nm) were used. In addition, as the negatively chargeable silica (negatively chargeable small particle size silica, negatively chargeable large particle size silica), those subjected to surface treatment (hydrophobization treatment) with hexamethyldisilazane were used. As a result, toner 1 was obtained.

(Evaluation of toner)
The obtained toner was evaluated for filming property, fixing property and particle strength. The results are shown in Table 1. In addition, each evaluation method and the symbol shown in Table 1 are as follows.

(Filming property)
The filming property was agitated for 1 hour in a state where toner was set in a developing unit of a commercially available laser printer (IBM 4019) adopting a one-component developing method and adjusted so as not to be developed on the photoreceptor. The filming state of the toner on the developing sleeve was visually observed. The evaluation was as follows according to the filming occurrence.
○: No filming occurred.
Δ: Filming occurs, but there is no practical problem.
X: Filming remarkably occurs, and there is a problem in practical use.

(Fixability test)
A color laser printer KL-2010 manufactured by Konica Corporation was modified and used to fix the image. The fixing device (fixing unit) is a heat roller fixing device including a heating roller and a pressure roller. However, this fixing device (fixing unit) was removed and modified so that it can be driven independently by an external driving device and the fixing nip passage time can be adjusted. The roller (fixing roller) on the side in contact with the toner image on the paper was modified so that the temperature could be controlled from 100 ° C. to 230 ° C. Using this fixing device, the image for fixing property evaluation was passed so that the heating roller side would be an unfixed toner adhesion surface, and fixed under the condition of a nip passage time of 50 msec. The image for fixing evaluation was prepared as follows using a color laser printer LP-3000C manufactured by Seiko Epson Corporation. First, J paper manufactured by Fuji Xerox Office Supply Co. is used as an evaluation paper, and a so-called solid image is formed by uniformly adhering the prepared toner on the paper, and the toner adhesion amount in the solid image becomes 0.4 mg / cm ^2. The image forming conditions were adjusted as described above, and then a solid image was formed in a 20 mm square area at a position 10 mm from the leading edge of the paper, and this image was used as an image for fixing property evaluation.

While changing the surface temperature of the fixing roller step by step, pass an unfixed image sample and check whether or not (part of the image) has transferred to the fixing roller after passing through the fixing roller. Judgment was made visually. The presence or absence of an offset at each temperature was examined, and the temperature at which the offset occurred was regarded as the offset temperature and evaluated as follows.
○: No offset occurs even at 210 ° C or higher.
Δ: Offset occurs at 190 ° C. or higher and lower than 210 ° C.
X: Offset occurs at less than 190 ° C.

(Particle strength test)
The strength of the toner particles was measured as follows. Toner was set in a developing unit of a commercially available laser printer (IBM 4019) adopting a one-component developing method, and stirred for 1 hour in a state adjusted so as not to be developed on the photoreceptor. The toner was taken out and the particle size distribution of the toner was measured using a flow type particle image analyzer (manufactured by Toa Medical Electronics Co., Ltd., FPIA-2000). At that time, the value represented by the following formula was used as the particle strength index.

This particle strength index indicates the degree of generation of fine powder of 1 μm or less, and the smaller the value, the higher the strength. The particle strength was evaluated according to the following criteria. The results are shown in Table 1.
○: Particle strength index is less than 5 (no toner disintegration)
Δ: Particle strength index of 5 or more and less than 10 (some toners are crushed, but there is no practical problem)
X: Particle strength index is 10 or more (toner is often crushed)

(Examples 2-5, Comparative Examples 1-12)
Using the colored emulsions 1 to 4 and the wax emulsions 1 to 7 produced above, toners were prepared in the same manner as in Example 1 except that the combinations shown in Table 1 were used. Fixability and particle strength were evaluated. The results are shown in Table 1.

  The particle size A of the resin particles and the particle size B of the release agent particles satisfy the relationship of 0.13 ≦ B / A ≦ 0.31, and the release agent particles are 1 to 100 parts by mass of the resin particles. The toners of Examples 1 to 5 to which 3 parts by mass are added have no filming, excellent fixability, and excellent particle strength. On the other hand, although the addition amount of the release agent particles satisfies the above range, Comparative Examples 1 to 6 in which the particle size does not satisfy the above relationship have no practical problems with respect to filming and fixing properties. It can be seen that the strength is low. Further, it can be seen that although Comparative Example 7, 9 and 11 in which the particle size satisfies the above relationship but the release agent content is too high, filming occurs although the fixability and particle strength are not problematic in practice. Further, it can be seen that Comparative Examples 8, 10 and 12 in which the content of the release agent is too low have poor fixability.

  From the above results, the toner of the present invention is a toner with high sphericity in which the resin particles are bonded to each other on the surfaces of the resin particles, and a release agent is held between the resin particles. It is understood that the occurrence of filming is less than that of the agglomerated particles, the durability and the fixing property are excellent, and the manufacturing method is simple.

  Since the toner of the present invention is easy to manufacture, has good filming properties, and has excellent durability and fixing properties, it is widely used as a toner for electrophotography.

FIG. 3 is a schematic diagram showing a structure of a toner of the present invention. FIG. 4 is a schematic diagram showing a state when a resin particle emulsion and a release agent particle emulsion are mixed during the production of the toner of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Toner 11 Resin particle 12, 13, 14, 15 Aggregate 16 Network 17 Interface 18 Release agent

Claims (4)

  A toner containing aggregate particles having a resin particle mass, wherein the resin particle mass has a shape in which the resin particles melt or contact each other with a boundary surface, and the aggregate particles have a network structure. And a toner having a release agent held in a gap between the resin particles.   The toner according to claim 1, wherein the network structure is formed by a network forming agent.   The toner according to claim 1, wherein the network forming agent is a crosslinking agent. A method for producing a toner according to any one of claims 1 to 3,
Preparing a dispersion of resin particles having a functional group and release agent particles;
Blending into the dispersion a network forming agent capable of reacting with the functional group to form a network between resin particles; and
Spray drying the dispersion;
The particle size A of the resin particles and the particle size B of the release agent particles satisfy the relationship of 0.13 ≦ B / A ≦ 0.31.
A method wherein 1 to 3 parts by mass of the release agent particles are added to 100 parts by mass of the resin particles.

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