JP2012155336A - Production method of toner, toner, developer and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of an aqueous medium toner, particularly, a toner by an emulsion polymerization aggregation method, applicable for a toner, a developer and an image forming method, where the toner can achieve both of storage stability and fixing characteristics, is applicable as a color toner having a vivid hue, high transparency and image density, and has smooth surface property and superior shape property, and thereby, which has a stable charging performance even in a high humidity environment and has high durability capable of maintaining high precise picture quality even in repeated use.SOLUTION: The production method of a toner comprises at least forming a resin coating layer on a core particle surface by adding and melt-sticking fine particles of a coating resin to surfaces of core particles in a wet medium. In a cumulative volume grain size distribution of the coating resin fine particles measured by a dynamic light-scattering method, Dv50s in the distribution is 0.1 to 0.4 μm, and a width index SDs (μm) of the cumulative volume grain size distribution is in the range represented by an expression (1): 0.05<SDs<0.20.

Description

  The present invention relates to a method for producing a toner for forming an electrophotographic image, a toner obtained therefrom, a developer, and an image forming method using the same, and preferably allows both low-temperature fixability and storage stability to be achieved. The present invention relates to a toner manufacturing method suitable for electrophotography or electrostatic printing that is excellent in high-definition images.

  In electrophotography, generally, a photoconductor using a photoconductive substance is uniformly charged, an electric latent image is formed by means such as image exposure, and then the latent image is developed with toner. A visible image is formed and, if necessary, a toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat and pressure to obtain a copy or printed matter.

  In the production of toner, a so-called pulverization method, which is performed through mixing, kneading, pulverization, classification, external addition, and sieving steps of toner raw materials such as resins and colorants, has been widely performed conventionally. In response to the demand for higher functionality and higher image quality, aqueous medium toners that form toner particles in an aqueous medium, so-called polymerization toners, have been proposed. Among the polymerization toners, the emulsion polymerization aggregation method is attracting attention because of its high degree of freedom in controlling the particle size and shape. In the emulsion polymerization aggregation method, resin-colored fine particles (toner base particles) are formed through an aggregation / fusion process using an aqueous dispersion of polymer particles, a wax dispersion, and a colorant dispersion.

  However, in an emulsion polymerization aggregation method toner, if a large amount of wax is included for fixing at a low temperature, it cannot be avoided that these waxes are exposed on the surface of the toner particles after the fusing step. Proposes to coat the surface of the toner particles with a resin by adhering the resin fine particles to the surface of the aggregated particles and then fusing them in the aggregation step. In addition, the present applicant disclosed in Patent Document 2 that the aggregated particles are fused to form toner base particles, and then the resin particles are further adhered to the surface to form capsule toner, whereby the minimum necessary amount is obtained. We proposed a technology that can achieve both storage stability and low-temperature fixability by coating fine resin particles. These are still effective methods from the viewpoint of improving low-temperature fixability and storage stability in emulsion polymerization aggregation toners, but these days there are demands for higher performance and higher functionality. The situation is not enough.

  Although the present inventors consider that the suggestion of Patent Document 1 that the wax particles should be present in the vicinity of the surface of the toner particles to the extent that they are not exposed is actually important, Patent Document 1 further promoted this. There is no description about the specific method. As for the dispersion of the wax particle dispersion itself, for example, as disclosed in Patent Document 3, it is disclosed that a suitable average particle diameter of the wax particles is obtained by a dispersion treatment using a gorin type pressure homogenizer. Thus, as in Patent Document 1, since the wax particles are configured to be resin-coated after being contained only in the core particles by co-aggregation, they do not exist in the vicinity of the surface of the toner particles. It cannot be said that it is a proposal for functionalization.

  First, in the case of Patent Document 4, when the amount of added wax is large, the applicant of the present invention has a deterioration in toner particle size distribution and an increase in the amount of fine powder. In order to improve them, seed polymerization using wax particles as a seed is performed. As a result, the polymer particles showed a structure including a wax. Further, Patent Document 5 shows that the core toner surface is coated with wax-containing coating resin fine particles and fixed or fused in order to achieve oilless fixing. In particular, Patent Document 5 discloses a technical idea that the wax particles should be present in the vicinity of the surface of the toner particles to the extent that the wax particles are not exposed based on a more specific method. These are still considered to be effective proposals from the viewpoint of improving toner performance. However, it is considered that what kind of wax is present in the emulsion polymerization aggregation method toner in what configuration and state is one of the key technologies for the enhancement of functionality in the future. A more comprehensive and specific proposal is required to remain a fragmentary technique for either resin fine particle.

  Although there are various discussions on the surface properties and shape of the toner particles that are also related to the chargeability of the toner, the emulsion polymerization aggregation toner is originally produced by aggregating dispersed fine particles. The surface irregularities tend to be larger than that of the polymerization toner. In Patent Document 6, in order to improve the chargeability of the toner, attention is paid to the amount of the remaining surfactant on the toner surface, and in order to reduce this, the surface of the core particle having a shape factor of 0.90 or more in the dispersion is used. It is proposed to attach, heat, and fuse the coated resin fine particles to the surface. That is, if the shape of the core particles is distorted, the coating layer cannot be formed uniformly or a thick coating layer is required, so that the core particles should have a shape with few irregularities. However, in order to discuss the obtained toner surface properties, it is considered important to have the configuration or particle size distribution of the coated resin fine particles as the outermost surface. It only discloses that it can be obtained by a conventional method by a combination method or dissolution suspension method, and information other than the volume average particle size is not disclosed for the physical properties of the coated resin fine particles. In Patent Document 6, there is no technical idea that the wax should exist near the surface of the toner particles.

  On the other hand, in Patent Document 7 below, in a core-shell structure emulsion polymerization aggregation toner composed of core layer particles and shell particles forming a shell layer on the surface thereof, the core layer and the shell layer each contain a wax. A toner in which the melting point of the wax contained in the toner is higher than the melting point of the wax contained in the core layer is disclosed. As a result, both low-temperature fixing and blocking resistance (storage stability) can be achieved. However, in order to promote further low-temperature fixability, it is considered desirable that the wax particles near the surface have a lower melting point. Further, when the technology of this document is examined in detail, the production of the wax-containing resin particles is based on the “mini-emulsion method”, and this method uses a monomer liquid obtained by dissolving wax particles in a monomer as an aqueous medium. Since it is formed into oil droplets and undergoes radical polymerization, the wax particles are substantially limited to ester wax that can be dissolved in the monomer, and even if dispersibility can be ensured, it is difficult to obtain sufficient releasability. In this method, since it is inevitable that the wax particles are exposed on the surface after polymerization, a complicated structure is unavoidable, for example, by providing an outer layer of the resin coating on the obtained wax-containing layer to form composite resin particles. It is disadvantageous in terms of reproducibility and cost. Patent Document 7 does not disclose information other than the weight average particle diameter of the wax-containing resin particles, and it is impossible to know the particle size distribution of these particles considered to be closely related to the surface properties after coating.

  As described above, since there is almost no technique in view of how the coated resin fine particles for high functionality should be, further fixing characteristics (low temperature fixability, At present, there has been a wide range of applicable or optimal proposals for improving offset resistance, etc., and at the same time, obtaining a good shape by an easy method and further obtaining a high-definition image. In fact, the absence of such a proposal in the case of an aqueous medium toner, particularly an emulsion aggregation toner, is a drag on performance improvement, and expectations for the improvement are increasing.

JP-A-10-26842 JP 2001-209212 A JP 2005-2233 A JP 2001-27821 A JP 2001-235895 A JP-A-2005-300355 JP 2005-91706 A

  An object of the present invention is to provide a toner production method, a toner, a developer, and an image forming method that solve the above-described problems.

  A detailed object of the present invention is an aqueous medium toner, particularly an emulsion polymerization aggregation method toner, which has good storage stability in a high temperature and high humidity environment, and preferably has both fixing properties such as low temperature fixability and offset resistance. It is another object of the present invention to provide a toner production method that is optimal for a developer.

  Another detailed object of the present invention is an aqueous medium toner, particularly an emulsion polymerization aggregation method toner and a developer, which has a smooth and good surface property with little irregularity on the surface of the obtained toner, and is excellent in toner shape. It is to provide a method for manufacturing a toner.

  A detailed object of the present invention is an aqueous medium toner that is excellent in image characteristics as a color toner, such as having a clear hue, high transparency, and image density, and that can maintain stable performance with little change in charge in a high humidity environment, In particular, it is to provide an emulsion polymerization aggregation method toner and a toner production method optimal for a developer.

  Another detailed object of the present invention is to use a toner or a developer as described above in an image forming method including a latent image forming step, a developing step, and a transferring step, thereby preventing high-definition without causing filming or cleaning failure. It is an object to provide a highly functional image forming method capable of obtaining an image and having high durability even in repeated use.

  In order to achieve the above object, the present inventors have intensively studied the surface coating of an aqueous medium toner, particularly an emulsion polymerization aggregation method toner, and as a result, the spread of the particle size distribution of the coated resin fine particles is too broad. Even when the particle size distribution, which was considered natural, is sharp, the coating is not necessarily efficient. To solve the above problems comprehensively, the coated resin fine particles themselves have an appropriate particle size and an appropriate particle size distribution. In order for the wax particles to be present in the vicinity of the surface of the toner particles while achieving the broadening of the particle size distribution, it is necessary to have a state, and the specific wax particles are included in the coated resin fine particles. It has been found out that it is optimal to do so, and the present invention has been reached. That is, the present invention has the following characteristics.

At least in a method for producing a toner in which a resin coating layer is formed on the surface of a core particle by adding and fusing a coating resin fine particle on the surface of the core particle in a wet medium,
The Dv50s in the cumulative volume particle size distribution measured by the dynamic light scattering method of the coated resin fine particles is 0.1 to 0.4 μm, and the width index SDs (μm) of the cumulative volume particle size distribution is represented by the following formula (1). In range:
Formula (1) 0.05 <SDs <0.20
(However, the cumulative volume particle size distribution is accumulated from the small particle size side of the particle size fraction, Dv50s is the particle size (μm) at which the cumulative volume particle size distribution is 50%, and SDs is the cumulative volume particle size distribution. SDs = (Dv84s−Dv16s) / 2 where the particle size (μm) at the point of 84% is Dv84s and the particle size (μm) at the point of 16% is Dv16s. )
The core particles include at least polymer particles and a colorant;
A method for producing a toner, wherein the polymer particles include wax particles c therein.

  The present invention makes it possible to achieve both storage stability and fixing characteristics, and can be applied as a color toner such as having a clear hue, high transparency, and image density, and has a smooth surface and excellent shape. In particular, the toner has a stable charging performance even under high humidity and can maintain high-definition image quality even after repeated use, a toner having a high durability, a developer and an aqueous medium toner applicable to an image forming method, particularly an emulsion polymerization aggregation method toner. A manufacturing method is obtained.

1 is a diagram illustrating a schematic configuration of an apparatus according to a fixing test of the present invention.

  Hereinafter, the present invention will be described in detail.

In the present invention, the resin coating layer is formed on the surface of the core particles by adding the coating resin fine particles to the surface of the core particles and fusing them in a wet medium.
The core particles are pulverized core particles such as those obtained by kneading and classifying a binder resin and a colorant, a charge control agent, wax, etc., or freeze pulverized particles, binder resin component monomers and colorants, and a charge control agent. Suspension polymerization core particles obtained by suspension polymerization of a mixture such as wax, dissolved suspension core particles obtained by dissolving a polymer in a solvent and then dispersing in an aqueous system, and polymer particles obtained by emulsion polymerization of a binder resin component monomer ( Latex) and a dispersion such as a colorant are mixed and agglomerated to form aggregated core particles formed into an arbitrary particle diameter, or fused core particles obtained by further heat-sealing the aggregated particles. The core particles used in the present invention may be basically any type as long as the resin fine particles are dispersed in a wet medium, preferably in water. As the resin, polyester, styrene / acrylate copolymer, polyurethane or the like is used. Of these, polyesters and styrene / acrylate copolymers are preferred. A dispersion of a styrene / acrylate copolymer can be easily obtained by emulsion polymerization. In the case of polyester, it can be easily obtained by emulsifying and dispersing a polyester resin. A styrene / acrylate copolymer is particularly preferable.

  The volume average particle size of the core particles should be as small as possible in order to obtain a high-definition image, and is usually preferably 3 μm or more, more preferably 4 μm or more, and the upper limit is preferably It is good that it is 10 μm or less, more preferably 8 μm or less. A method for measuring the volume average particle diameter of the core particles will be described later.

  The wet dispersion medium in the present invention is a liquid having a function of dispersing and holding various particles, and should be appropriately set from known materials in accordance with the application purpose of the obtained particle dispersion. Specifically, water; alcohols such as methanol, ethanol, propanol and butanol; organic solvents such as acetone, methyl ethyl ketone, tetrahydrofuran, toluene and xylene; monomers such as styrene, butyl acrylate, 2-ethylhexyl acrylate and acrylic acid These are used alone or in combination. As an application of the aqueous medium toner, for example, in the case of suspension polymerization toner, the colorant is dispersed in the oil phase, that is, the monomer phase. Therefore, the monomers may be selected as the wet medium. Since the coagulation step in this case is carried out in an aqueous system, water may be selected as the wet dispersion medium. Among these, the present invention is most suitable for application to an emulsion polymerization aggregation method toner. Accordingly, water is preferred as the wet dispersion medium. The water quality is also related to the coarsening due to re-aggregation of finely divided particles, and if the conductivity is high, the dispersion stability with time tends to deteriorate. Therefore, the conductivity is preferably 10 μS / cm or less. In addition, it is preferable to use ion-exchanged water or distilled water that has been desalted to have a concentration of 5 μS / cm or less. The conductivity was measured using a conductivity meter (a personal SC meter model SC72 and a detector SC72SN-11 manufactured by Yokogawa Electric Corporation).

  In the present invention, since core particles having a uniform particle size can be easily obtained in a wet medium, among the above core particles, the core particles obtained by the emulsion polymerization aggregation method, that is, the above-described aggregated core particles or fused cores are used. The particles are preferred.

  Among these, the agglomerated core particles are obtained by aggregating at least polymer particles and a colorant in a wet medium. The fusion core particles are aggregated by aggregating at least the polymer particles and the colorant in a wet medium, and then the aggregated particles are heated to a temperature equal to or higher than the glass transition point (Tg) of the constituent resin. It is made by fusing.

Hereinafter, the core particles obtained by the emulsion polymerization aggregation method according to the present invention will be described in detail.
When producing toner mother particles by the emulsion polymerization aggregation method, usually a polymerization step of polymerizing polymer particles to obtain a polymer particle dispersion, a mixing step of mixing the polymer particle dispersion and the colorant particle dispersion, Aggregation step of adding a coagulant to the mixture and agglomerating to a predetermined particle size to obtain particle aggregates (aggregated particles), fusing step of overheating and fusing the agglomerated particles to form fused particles, and thereafter filtration and washing And a step of taking out toner mother particles such as a drying step. That is, a dispersion liquid containing polymer particles obtained by emulsion polymerization is mixed with a dispersion liquid such as a colorant, a wax, a charge control agent, and the like. These are aggregated core particles, and those obtained by heating and fusing are fused core particles.

  As the binder resin constituting the polymer particles of the core particles used in the emulsion polymerization aggregation method, one or more polymerizable monomers (vinyl monomers) that can be polymerized by the emulsion polymerization method may be appropriately used. Specific examples include monomers having no acidic or basic substituents and monomers having acidic or basic substituents. These monomers may be used alone or in combination. Also good.

  Each of the above monomers may be added separately at the time of polymerization, or a plurality of monomers may be mixed in advance and added simultaneously or polymerized. Furthermore, it is possible to change the monomer composition during the monomer addition. The monomer may be added as it is, or may be added as an emulsion mixed and adjusted in advance with water or a surfactant.

  Examples of the monomer having no acidic or basic substituent include styrenes such as styrene, methylstyrene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, pn-butylstyrene, and pn-nonylstyrene. Acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, Methacrylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N- Acrylamide, N, N-dibutyl acrylamide, acrylic acid amide and the like.

  On the other hand, as a monomer having an acidic or basic substituent, a monomer having a Bronsted acidic group (hereinafter, sometimes simply referred to as an acidic monomer or an acid monomer), or a monomer having a Bronsted basic group (hereinafter simply referred to as “monomeric monomer”). These monomers may be referred to as basic monomers), and these monomers are preferably used in combination with the monomers having no acidic or basic substituent.

  Examples of the acid monomer include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, monomers having a sulfonic acid group such as sulfonated styrene, and sulfonamides such as vinylbenzenesulfonamide. And monomers having a group. In addition, as the basic monomer, an aromatic vinyl compound having an amino group such as aminostyrene, a nitrogen-containing heterocyclic ring-containing monomer such as vinylpyridine or vinylpyrrolidone, or an amino group such as dimethylaminoethyl acrylate or diethylaminoethyl methacrylate ( And (meth) acrylic acid esters.

  These acidic monomers and basic monomers may be used alone or in combination, and may exist as a salt with a counter ion. Among them, in order to obtain negatively chargeable polymer particles, it is preferable to use an acidic monomer, more preferably acrylic acid and / or methacrylic acid. The total amount of acidic monomer and / or basic monomer in 100% by weight of all monomers constituting the binder resin as polymer particles is preferably 0.05% by weight or more, more preferably 0.5% by weight or more, More preferably, it is 1% by weight or more, preferably 10% by weight or less, more preferably 5% by weight or less.

  In order to obtain the polymer particles of the present invention, among the above-described monomers and the like, it is preferable to use an acidic monomer and another monomer in combination as a preferred embodiment. More preferably, acrylic acid and / or methacrylic acid is used as the acidic monomer, and a monomer selected from styrenes, acrylic esters, and methacrylic esters is used as the other monomer, and acidic monomers are more preferable. It is preferable to use acrylic acid and / or methacrylic acid as a monomer, and styrene and acrylic acid esters and / or methacrylic acid esters as other monomers, and particularly acrylic acid and / or methacrylic acid as acidic monomers. Is a combination of styrene and n-butyl acrylate as the other monomer.

  Further, when a cross-linked resin is used as the binder resin constituting the polymer particles, a polyfunctional monomer having radical polymerizability is used as the cross-linking agent shared with the above-mentioned monomers, for example, divinylbenzene, hexanediol diacrylate. , Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, diallyl phthalate, and the like. It is also possible to use a monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, acrolein and the like. Among these, radical polymerizable bifunctional monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable.

  These polyfunctional monomers may be used alone or in combination. When a crosslinked resin is used as the binder resin constituting the polymer primary particles, the blending ratio of the polyfunctional monomer in the total monomers constituting the resin is preferably 0.005% by weight or more, more preferably 0.1%. It is desirable that the content is not less than wt%, more preferably not less than 0.3 wt%, preferably not more than 5 wt%, more preferably not more than 3 wt%, still more preferably not more than 1 wt%.

  In emulsion polymerization, water is used as a preferred wet medium, and a surfactant (emulsifier) is dissolved therein. As the surfactant to be used, known ones can be used, but one or more surfactants selected from cationic surfactants, anionic surfactants and nonionic surfactants are used in combination. Can be used. Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

  The amount of the surfactant used may be an amount that allows the monomer to stably exist as droplets in water, but is usually 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer, For these surfactants, for example, one or two or more of polyvinyl alcohols such as partially or completely saponified polyvinyl alcohol and cellulose derivatives such as hydroxyethyl cellulose can be used in combination as a protective colloid.

  As a polymerization initiator as a free radical generation source for initiating emulsion polymerization, water-soluble initiators such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like, and these persulfates Redox initiator combined with a reducing agent such as sodium sulfite as a component of salt, hydrogen peroxide, 4,4'-azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydroperoxide, 2,2'-azobis Water-soluble polymerization initiators such as (2- (2-imidazolin-2-yl) propane) dihydrochloride, 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propionamide, and the like A redox initiator system using a water-soluble polymerizable initiator as a component and a reducing agent such as ferrous salt is used. The polymerization initiator is usually used in an amount of about 0.1 to 3 parts by weight with respect to 100 parts by weight of the polymerizable monomer, among which at least a part or all of the initiator is hydrogen peroxide or organic peroxide. It is preferable that it is a thing.

  In addition, one or two or more suspension stabilizers such as calcium phosphate, magnesium phosphate, calcium hydroxide, and magnesium hydroxide are usually used in an amount of 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer. May be.

  Any of the polymerization initiator and the suspension stabilizer may be added to the polymerization system at any time before, at the same time as or after the addition of the monomer, and these addition methods may be combined as necessary. good.

  In the emulsion polymerization, a known chain transfer agent can be used as necessary. Specific examples of such a chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, four Examples thereof include carbon chloride and trichlorobromomethane. The chain transfer agent may be used alone or in combination of two or more, and is usually used in the range of 5% by weight or less based on the total monomers. Further, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

  In the emulsion polymerization, the above monomers are polymerized in the presence of a polymerization initiator, and the polymerization temperature is usually 50 to 120 ° C, preferably 60 to 100 ° C, and more preferably 70 to 90 ° C.

  The particle size of the polymer particles of the resin dispersion obtained by emulsion polymerization can be measured by the dynamic light scattering method, and the particle at the point that becomes 50% when integrated from the small particle size side in the cumulative volume particle size distribution The diameter (cumulative 50% diameter) is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 3 μm or less, preferably 2 μm or less, more preferably 1 μm or less. desirable. When the particle size is less than the above range, it may be difficult to control the aggregation rate. When the particle size exceeds the above range, the particle size of the toner obtained by aggregation tends to be excessive, and the toner having the desired particle size is obtained. Is difficult to obtain, and may be inappropriate for applications requiring high resolution.

  The lower limit of Tg of the binder resin constituting the polymer particles by DSC (differential scanning calorimeter) method is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and the upper limit is preferably 90 ° C. or lower, more preferably. Is preferably 70 ° C. or lower. Here, when the Tg of the binder resin overlaps with the heat amount change based on other components, for example, the melting peak of the wax and cannot be clearly determined, when the toner is prepared in a state in which such other components are excluded. Of Tg.

  The acid value of the binder resin constituting the polymer particles is, as measured by the method of JISK-0070, the lower limit is preferably 3 mgKOH / g or more, more preferably 5 mgKOH / g or more, and the upper limit is preferably 50 mgKOH. / G or less, more preferably 30 mgKOH / g or less.

  The polymer particles thus obtained can be aggregated together with a colorant particle dispersion, a wax particle dispersion, a charge control agent particle dispersion, and the like, which will be described later, to form aggregated core particles.

  In addition, the method of making the wax particles exist in the aggregated particles is that the wax particles are included in the polymer particles in addition to the aggregation using the independent wax particle dispersion as described above, and coloring is performed. Aggregating the agent particle dispersion or the like to form aggregated core particles is also effective for reducing the fine powder of the particle size distribution of the obtained aggregated particles, and can be preferably employed. These may be used in combination.

  Examples of the wax particles (hereinafter referred to as wax particles c) include various non-polar or polar waxes, and one type may be selected from them, or a plurality of types may be used in combination.

  Nonpolar waxes include the following. Examples thereof include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax. Furthermore, silicone waxes that may be modified with an alkyl group or the like are also examples that can be suitably used.

  Examples of polar wax include the following. For example, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, and alcohols obtained by hydrolyzing these oxides, or block copolymers of these oxides; candelilla wax, carnauba wax, waxy wax, rice Plant waxes such as wax and jojoba wax; animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolactam; waxes based on fatty acid esters such as montanic acid esters and castor waxes Class: Deoxidized part or all of fatty acid ester such as deoxidized carnauba wax; and ester wax such as behenyl behenate and pentaerythritol tetrastearate. Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a long-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinal acid; stearyl alcohol Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or long chain alkyl alcohols having a long chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid Fatty acid amides such as amides and lauric acid amides; saturated fatty acid bisamides such as methylene bisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides and hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as lenbis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; Aromatic bisamides such as N, N'-distearylisophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soap); aliphatic hydrocarbons Wax grafted with vinyl monomers such as styrene and acrylic acid; partially esterified products of aliphatic and polyhydric alcohols such as behenic acid monoglyceride; hydroxyl groups obtained by hydrogenating vegetable oils and fats Methyl Este with Such compounds.

  The polar wax is preferably an ester wax from the viewpoint of compatibility and dispersibility in the polymer particles. However, from the viewpoint of releasability and charge stability of the finally obtained toner, it is optimal that the non-polar wax is included in the polymer particles. A hydrocarbon wax is preferred as the nonpolar wax. For example, petroleum waxes such as paraffin wax and microcrystalline wax; synthetic waxes such as Fischer-Tropsch wax; low molecular polyolefins obtained by radical polymerization of olefins under high pressure or Ziegler catalysts, metallocene catalysts, etc. under high pressures; high molecular weight polyolefins Polyolefins obtained by thermally degrading are preferred. Among them, petroleum wax is preferable, and paraffin wax is more preferable, and high purity purified product obtained by separating the wax by press sweating method, solvent method, vacuum distillation or fractional crystallization method is preferably used. .

  In order to improve the fixing property among these wax particles c, a low melting point wax is preferable. Specifically, the endothermic peak temperature of the wax measured by DSC is preferably 30 ° C. or higher, and 40 ° C. or higher. Is more preferable, and 60 ° C. or higher is particularly preferable. Moreover, 100 degrees C or less is preferable, 90 degrees C or less is still more preferable, and 85 degrees C or less is especially preferable. If the endothermic peak is too low, the wax tends to be exposed and sticky after fixing, and if the endothermic peak is too high, the fixability at low temperatures is poor. The wax preferably has a half-value width of an endothermic peak of preferably 20 ° C. or less, more preferably 15 ° C. or less, and still more preferably 12 ° C. or less. When the half-value width of the endothermic peak exceeds the above range, the wax does not melt rapidly at the time of fixing, so that a sufficient fixing reinforcing effect may not be exhibited. The lower limit of the half-value width of the endothermic peak is not limited, but is usually 2 ° C. or higher, preferably 5 ° C. or higher. Here, the half-value width of the endothermic peak of the wax means the peak width (° C.) at the position of half the endothermic peak height. In addition, the surface tension of the wax is also related to the releasability, but is preferably 35 mN / m or less, more preferably 30 mN / m or less, still more preferably 28 mN / m or less, preferably 20 mN / m. As mentioned above, it is desirable that it is 24 mN / m or more.

  In order to produce a wax dispersion using the above wax particles c, a predetermined amount of each of the wax particles c, the dispersant (the surfactant described above), water (deionized water), and the like are weighed, and the desired particles are obtained using a disperser. This can be done by performing a dispersion process until the diameter is reached.

  In this case, the disperser includes a rotary shear type homogenizer, a cavitron, a disk type disperser, a ball mill having a media, a sand mill, an attritor, a dyno mill, a DSP mill, a spike mill, a forced collision type gorin homogenizer, an optimizer, and more A sound wave irradiation type disperser or the like can be used.

  As a desirable mode, these wax particles c can be heated above the melting point and strong shear can be imparted by using a polymer electrolyte such as an ionic surfactant, polymer acid or polymer base as a dispersant in water. It is to produce a wax particle c dispersion by atomizing with a homogenizer or a pressure discharge type disperser.

  The 50% cumulative volume particle size distribution by the dynamic light scattering method of the dispersed wax particles c is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 3 μm or less. The thickness is preferably 2 μm or less, more preferably 1 μm or less. When the particle size of the wax particles c in the wax particle c dispersion is smaller than the above range, there is a problem that the wax particles c are not completely taken into the aggregated particles in the case where the wax c particle dispersion is used independently during the aggregation. Also in the wax-containing polymer particles described later, the wax content becomes too low, so that the effect of the wax is lowered, which is not preferable. In addition, if it is larger than the above range, the average particle size becomes too large, whether it is used independently or as an encapsulated polymer particle, it is used for applications that require high resolution as a toner. It is inappropriate and undesirable.

  The wax particle c dispersion obtained as described above can be used independently during aggregation. The wax particles c are usually preferably 1 part by weight or more, more preferably 3 parts by weight or more, and still more preferably 5 parts by weight or more with respect to 100 parts by weight of the polymer particles. There should be. In general, the amount is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight, and particularly preferably 15 parts by weight or less. It is good. If the amount of the wax particles c is too small than the above range, the low-temperature fixability and offset resistance of the obtained toner will be hindered. Since it tends to be impossible, it is not preferable.

  In the present invention, it is more preferable to use the wax particles c in the form of being included in the polymer particles. Inclusion of the wax particles c in the polymer particles is facilitated by performing seed emulsion polymerization in which a monomer is added using the wax particles c in the wax particle c dispersion as a seed during the emulsion polymerization of the polymer particles. It can be carried out. In carrying out the seed emulsion polymerization to the wax particles c, the polymerization to the wax particle c seeds is advanced by sequentially adding the monomer constituting the polymer particles. At this time, the monomers may be added separately, or a plurality of monomers may be mixed and added in advance. Further, it is possible to change the monomer composition during the monomer addition. The monomer may be added as it is, but it is preferable to add it as an emulsion mixed and adjusted in advance with water or a surfactant. As the surfactant, one or two or more combined systems are selected from the above surfactants.

  In proceeding with seed emulsion polymerization, a certain amount of surfactant (emulsifier) may be added to the wax particle c dispersion. Further, the addition timing of the polymerization initiator may be any before the monomer addition, at the same time as the monomer addition, after the monomer addition, or may be a combination of these addition methods.

  The morphology of the wax-containing polymer particles obtained as described above may take any form such as a core-shell type, a phase separation type, an occlusion type, or a mixture of these forms. Particularly preferred is the core-shell type because the wax can be completely encapsulated. The wax particles c are usually preferably 1 part by weight or more, more preferably 3 parts by weight or more, and further preferably 5 parts by weight with respect to 100 parts by weight of the monomer constituting the polymer particles. It should be more than parts by weight. In general, the amount is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, still more preferably 20 parts by weight, and particularly preferably 15 parts by weight or less. It is good. If the amount of the wax particles c is too much or too little than the above range, it is not preferable because the seed emulsion polymerization does not proceed uniformly. In addition, components other than wax, such as pigments, charge control agents, etc., may be used as seeds at the same time within the scope of the present invention. Further, a colorant may be used by dissolving or dispersing in a monomer or wax.

  In the aggregation step in the emulsion polymerization aggregation method, compounding components such as polymer particles, colorant particles, and wax particles are mixed simultaneously or sequentially. In advance, a dispersion of each component, that is, a polymer particle dispersion ( Preparation of a colorant particle dispersion, a wax fine particle dispersion, a charge control agent dispersion, and the like, and mixing them to obtain a mixed dispersion. It is preferable from the viewpoint of the uniformity of the particle diameter.

  The colorant dispersion is preferably added with 10 to 30 parts by weight of the colorant and 1 to 15 parts by weight of the surfactant with respect to 100 parts by weight of water. The addition of the colorant dispersion at the time of emulsion aggregation is calculated and used so as to be 2 to 10% by weight in the finished mother particles after aggregation.

  In order to obtain a colorant dispersion, it is preferable to add a surfactant to water in order to disperse the colorant particles in water and keep the dispersion state stable. Examples of surfactants that can be used include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap, cationic surfactants such as amine salts and quaternary ammonium salts, Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols can be used. Among these, anionic surfactants such as anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The above surfactants may be used alone or in combination of two or more.

  Specific examples of the anionic surfactant include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonyl phenyl ether sulfate; lauryl sulfonate , Dodecylsulfonate, dodecylbenzenesulfonate, triisopropylnaphthalenesulfonate, sodium alkylnaphthalenesulfonate such as dibutylnaphthalenesulfonate, naphthalenesulfonate formalin condensate; monooctylsulfosuccinate, dioctylsulfosuccinate, lauric acid amidesulfonate, oleic acid amidesulfonate Sulfonates such as lauryl phosphate, isopropyl phosphate And phosphoric esters such as nonylphenyl ether phosphate; sodium dialkylsulfosuccinate such as sodium dioctylsulfosuccinate; disodium lauryl sulfosuccinate; and sulfosuccinates such as disodium lauryl polyoxyethylene sulfosuccinate;

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkylto Quaternary ammonium salts such as ammonium chloride; and the like.

  Specific examples of the nonionic surfactant include polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other alkyl ethers; Alkylphenyl ethers such as oxyethylene nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxy Alkylamines such as ethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as xylethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether, polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearin Alkanolamides such as acid diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And the like.

  Among these, since the stability of the colorant particles after dispersion can be maintained for a long time, it is preferable to use at least one anionic surfactant or at least anionic surfactant even when used in combination with other surfactants. It is preferable to include an agent. The amount of the surfactant used is usually 0.1 to 15 parts by weight with respect to 100 parts by weight of water, more preferably 0.5 to 10 parts by weight, and 1 to 5 parts by weight. It is best to do. When the amount of the surfactant used is larger than the above range, it becomes difficult to make the colorant finer, and the particle size distribution of the colorant of the present invention cannot be obtained. It is not preferable because reaggregation of agent particles cannot be suppressed.

The colorant particles used in the present invention are more uniformly aggregated when the difference in density from the polymer particles (about 1.1 to 1.3 g / cm ³ as resin particles) in the emulsion polymerization aggregation method is smaller, Accordingly, since the performance of the obtained toner is improved, the true density of the pigment particles measured by the pycnometer method specified in JIS K 5101-11-1: 2004 is less than 2.0 g / cm ^3. it is preferably, more preferably from 1.2~1.9g / cm ^3, particularly preferably from 1.3~1.8g / cm ^3. When the true density is large, the sedimentation property in an aqueous medium tends to deteriorate. In addition, in consideration of problems such as storage stability and sublimation, the colorant is preferably carbon black or an organic pigment.

  Examples of the above pigments include the following yellow pigments, magenta pigments, and cyan pigments. Carbon black was used as a black pigment, or the following yellow pigment / magenta pigment / cyan pigment was mixed to black. Things are used.

  Among these, carbon black as a black pigment exists as an aggregate of very fine primary particles, and when dispersed as a pigment dispersion, coarsening of particles due to reaggregation tends to occur. According to the study by the present inventors, the degree of reagglomeration of the carbon black particles is correlated with the amount of impurities contained in the carbon black (the degree of residual undecomposed organic matter). There was a tendency for coarsening due to re-aggregation. As a quantitative evaluation of the amount of impurities, the ultraviolet absorbance of the toluene extract of carbon black measured by the following method is preferably 0.05 or less, and more preferably 0.03 or less. Generally, carbon black produced by the channel method tends to have a large amount of impurities, and therefore, carbon black produced by the furnace method is preferred as the carbon black in the present invention.

  The ultraviolet absorbance (λc) of carbon black is determined by the following method. First, 3 g of carbon black was sufficiently dispersed and mixed in 30 ml of toluene. Filter using 5C filter paper. Thereafter, the filtrate was put into a quartz cell having a 1 cm square light absorption part, and the absorbance at a wavelength of 336 nm was measured using a commercially available ultraviolet spectrophotometer (λs), and the absorbance of only toluene as a reference was measured by the same method. From (λo), the ultraviolet absorbance is obtained by λc = λs−λo. Examples of commercially available spectrophotometers include an ultraviolet-visible spectrophotometer (UV-3100PC) manufactured by Shimadzu Corporation.

  As yellow pigments, compounds typified by condensed azo compounds, isoindolinone compounds and the like are used. Specifically, C.I. I. CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 150, 155, 168, 180, 185, etc. are preferably used. It is done.

  As the magenta pigment, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, 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, 202, 206, 207, 209, 220, 221, 238, 254, C.I. I. Pigment Violet 19 or the like is preferably used. Among them, C.I. I. Pigment red 122, 202, 207, 209, C.I. I. A quinacridone pigment represented by pigment violet 19 is particularly preferred. This quinacridone pigment is suitable as a magenta pigment because of its clear hue and high light resistance.

  As the cyan pigment, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like; I. Pigment Green 7, 36, etc. can be used particularly preferably.

  The amount of the colorant particles used in the colorant dispersion is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, particularly preferably 100 parts by weight of water. Is preferably 10 parts by weight or more. Further, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less, and particularly preferably 30 parts by weight or less. When the added amount of the colorant exceeds the above range, the concentration of the colorant is high, which is not preferable because the probability of reaggregation of particles during the dispersion increases. It is not preferable because it is difficult to obtain a particle size distribution.

  The inventors previously filed an application regarding a colorant particle dispersion in Japanese Patent Application No. 2006-89394. This reveals that the probability of exposure of the colorant particles to the mother particle surface is reduced by using a colorant dispersion having a specific particle size distribution, particularly in an emulsion polymerization aggregation toner. . Also in the present invention, excessive surface exposure of the colorant particles leads to inhibition of adhesion of the coating resin fine particles to the core particles in the subsequent step. Therefore, as the colorant dispersion in the present invention, Japanese Patent Application No. 2006-2006 It is optimal to use the technique described in 89394.

One of the gist of the above technique is a colorant dispersion comprising at least a wet dispersion medium and colorant particles, and the volume accumulation of the colorant particles in the colorant dispersion measured by a dynamic light scattering method. A colorant dispersion in which an average diameter Dv50 g (μm) satisfies the following formula (A) and a volume particle size distribution width index SDg of the colorant particles in the colorant dispersion satisfies the following formula (B).
Formula (A) 0.10 <Dv50g <0.30
Formula (B) 0.030 <SDg <0.090
(However, Dv50g represents the particle size (μm) where the volume particle size distribution cumulative curve of the colorant particles is 50%, and SDg is the particle size of the point where the volume particle size distribution cumulative curve of the colorant particles is 84%. SDv = (Dv84g-Dv16g) / 2 where (μm) is Dv84g and the particle size (μm) at the point of 16% is Dv16g, and the volume cumulative distribution is the small particle size side of the volume particle size distribution. To be accumulated)

Another one of the main points is a colorant dispersion comprising at least a wet dispersion medium and colorant particles, and the volume particle size distribution of the colorant particles in the colorant dispersion measured by a dynamic light scattering method is A colorant dispersion satisfying the following formulas (C), (D) and (E).
Formula (C) 0.10 <Dv50g <0.30
Formula (D) 1.0 <(Dv50 g / Dv10 g) / (Dv90 g / Dv50 g) <1.3
Formula (E) 0 <Pvg <2
(However, Dv 50 g represents the volume cumulative distribution 50% diameter (μm) of the colorant particles, Dv 10 g represents the volume cumulative distribution 10% diameter (μm) of the colorant particles, and Dv 90 g represents 90% of the volume cumulative distribution of the colorant particles. (Pvg represents the ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles, and the volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution)

  A charge control agent may be added to the toner used in the present invention in order to impart charge amount and charge stability. Conventionally known compounds are used as the charge control agent. Examples thereof include hydroxycarboxylic acid metal complexes, azo compound metal complexes, naphthol compounds, naphthol compound metal compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof. In consideration of adaptability to color toners (the charge control agent itself is colorless or light in color, and there is no color tone problem on the toner), quaternary ammonium salt compounds are used as positive charge, and salicylic acid or alkylsalicylic acid is used as negative charge. Metal salts with chromium, zinc, aluminum, boron, etc., metal complexes, metal salts of benzylic acid, metal complexes, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [ Hydroxynaphthalene compounds such as N- (4-chlorophenyl) amide] -3-hydroxynaphthalene] are preferred.

  When a charge control agent is contained in the toner in the emulsion polymerization aggregation method, the charge control agent is added together with a monomer or the like at the time of emulsion polymerization, or is added in the aggregation step together with polymer particles and a colorant, or the polymer particles and It can be blended by a method such as adding a colorant after agglomerating the colorant or the like to a particle size suitable for a toner. Among these, the charge control agent is emulsified and dispersed in water using a surfactant, and the cumulative volume particle size distribution of the charge control agent particles by the dynamic light scattering method is used as an emulsion of 0.01 to 3 μm. It is preferable to do. The addition of the charge control agent dispersion at the time of emulsion aggregation is calculated and used so as to be 0.1 to 5% by weight in the final aggregated mother particles after aggregation.

  In the aggregation step in the emulsion polymerization aggregation method, the above-described blending components such as polymer particles, colorant particles, wax, charge control agent and the like are mixed simultaneously or sequentially, but in advance a dispersion of each component, that is, A polymer particle dispersion (preferably including a wax), a colorant particle dispersion, a wax fine particle dispersion, and a charge control agent dispersion are prepared and mixed to obtain a mixed dispersion. It is preferable from the viewpoint of the uniformity of the composition and the uniformity of the particle diameter.

  The agglomeration treatment usually includes a method of heating in a stirring tank, a method of adding an aggregating agent such as an electrolyte, a method of combining these, and the like. The particle size is controlled, but the cohesive force can be increased by heating or adding an electrolyte. Among these, it is essential to add at least an aggregating agent when particles are aggregated with stirring to obtain particle aggregates approximately similar to the size of the toner.

As an aggregating agent to be added for agglomerating particles, either an organic salt or an inorganic salt may be used. Specifically, NaCl, KCl, LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO _{4 are used. , MgCl 2, CaCl 2, MgSO} 4, CaSO 4, ZnSO 4, Al 2 (SO 4) 3, Fe 2 (SO4) 3, CH 3 COONa, C 6 H 5 SO 3 Na and the like. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

  The addition amount of the flocculant varies depending on the type of flocculant, the target particle size, and the like, but is usually 0.05 to 25 parts by weight, preferably 0.1 to 100 parts by weight of the solid component of the mixed dispersion. -15 parts by weight, more preferably 0.1-10 parts by weight. When the addition amount is less than the above range, the progress of the agglutination reaction is slow, and fine particles of 1 μm or less remain after the agglomeration reaction, or the average particle size of the obtained particle aggregate does not reach the target particle size. If the above range is exceeded, rapid aggregation tends to occur, making it difficult to control the particle size, and the resulting aggregated particles may contain problems such as coarse powder and irregular shapes. is there. The aggregation temperature when the aggregation is performed by adding an aggregating agent is preferably equal to or lower than the Tg of the polymer particles, preferably 20 to 70 ° C, more preferably 30 to 60 ° C.

  The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order to reach the target particle size, the toner particles are usually held at the predetermined temperature for at least 30 minutes. Is desirable. The temperature rise until reaching a predetermined temperature may be raised at a constant rate within the above temperature range, or may be raised stepwise. Aggregation is carried out with stirring. For example, this stirring can be carried out in a reaction vessel having stirring blades such as paddle blades, squid blades, three retracted blades, Max blend blades, double helical blades, or with a homogenizer or homomixer. It can also be done.

  As described above, aggregated core particles according to the present invention can be obtained. In addition, the volume-based arithmetic mean diameter of the core particles by the Coulter method is usually preferably 3 μm or more, more preferably 4 μm or more, and particularly preferably 5 μm or more. Further, it is preferably 10 μm or less, more preferably 8 μm or less, and particularly preferably 7 μm or less. If the particle size is too small, surface coating with the coating resin fine particles in the subsequent process tends not to be performed uniformly. If the particle size is too large, the surface coating itself with the coating resin fine particles is not a problem, but the obtained toner has a high definition. This is not preferable because the image cannot be reproduced.

  In the emulsion polymerization aggregation method, in order to increase the stability of the particle aggregate obtained in the aggregation step, a fusion step is performed in which the particles are heated and integrated so as to cause fusion between the aggregated particles. The temperature of the fusing step is usually not less than Tg of the polymer constituting the polymer particles, preferably not less than 5 ° C higher than the Tg, more preferably not less than 10 ° C higher than the Tg, More preferably, the temperature is 20 ° C. or more higher than the Tg, preferably 80 ° C. or less, more preferably 50 ° C. or less than the Tg. The time required for the fusing step varies depending on the shape of the target toner, but after reaching the glass transition temperature of the polymer constituting the polymer particles, usually 0.1 to 10 hours, preferably 1 to 1 hour. It is desirable to hold for 6 hours.

  In the emulsion polymerization aggregation method, it is preferable to add a surfactant or raise the pH value of the aggregation liquid after the above aggregation process, preferably before the fusion process or during the fusion process. As the surfactant used here, one or more surfactants that can be used for producing the above polymer particles can be selected and used, but particularly when the polymer particles are produced. It is preferable to use the same surfactant as that used. The addition amount in the case of adding the surfactant is not limited, but is preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, further preferably 3 parts by weight with respect to 100 parts by weight of the solid component of the mixed dispersion. Part or more, preferably 20 parts by weight or less, more preferably 15 parts by weight or less, and still more preferably 10 parts by weight or less. After the aggregation process, by adding a surfactant before the completion of the fusing process or by increasing the pH value of the aggregation liquid, it is possible to suppress the aggregation of the particle aggregates aggregated in the aggregation process, In some cases, it is possible to suppress the generation of coarse particles in the toner after the fusing process.

  By such heat treatment, the particles in the aggregate are fused and integrated, the surface of the toner particles as the aggregate is smoothly changed, and the shape is also nearly spherical. The particle aggregate before the fusion process is considered to be an aggregate due to electrostatic or physical aggregation of the particles, but after the fusion process, the polymer particles constituting the particle aggregate are fused together. In addition, the shape of the toner particles can be made nearly spherical. According to such a fusion process, by controlling the temperature and time of the fusion process, the shape of the particles is agglomerated, the potato type with advanced fusion, the spherical with advanced fusion, etc. Depending on the purpose, various shapes of toner can be manufactured.

  As described above, the fused core particles according to the present invention can be obtained. The volume-based arithmetic average diameter (volume average diameter) of the core particles by the Coulter method is preferably the same as that of the above-described aggregated core particles.

  In the present invention, coated resin fine particles are adhered to the surface of the above-mentioned aggregated core particles or fused core particles, and are fused to coat the core particles to form toner base particles.

  Therefore, as a coating method in the present invention, the core particles are aggregated particles obtained by aggregating at least polymer particles and a colorant in a wet medium, and the resin particles for coating are added to the aggregated particles and fused. And a method of forming a resin coating layer on the surface of the aggregated particles. Further, the core particles are aggregated in a wet medium by aggregating at least the polymer particles and the colorant, and then heated to a temperature equal to or higher than the glass transition point (Tg) of the resin constituting the aggregated particles. It may be a fusion particle formed by adhesion, and a method of forming a resin coating layer on the surface of the fusion particle by further adding a resin fine particle for coating to the surface and fusing it.

  In the present invention, when the amount of the wax is increased, the low-temperature fixability is improved, but the wax particles are easily exposed on the surface of the core particles particularly when added as independent particles at the time of aggregation. However, the deterioration of performance can be prevented by coating the surface of the core particles with resin fine particles.

  As the coating resin fine particles, any known resin can be adopted, but it is preferable that the coating resin fine particles are prepared by polymerizing monomers similar to those used for the polymer particles described above. Among these, it is more preferable to include a polymerizable acid as a monomer because particles can be stably formed. The polymerizable acid is the same as that used for the polymer particles, but is preferably acrylic acid and / or methacrylic acid. Accordingly, examples of the resin include styrene-acrylic acid copolymer resin, styrene-methacrylic acid copolymer resin, styrene-acrylic acid ester-acrylic acid terpolymer resin, styrene-acrylic acid ester-methacrylic acid terpolymer. An original copolymer resin, a methacrylic acid ester-acrylic acid ester-acrylic acid terpolymer resin, a methacrylic acid ester-acrylic acid ester-methacrylic acid terpolymer resin, etc. can be used, preferably styrene and acrylic. It is good that it is a terpolymer resin of acid ester or methacrylic acid ester and acrylic acid or methacrylic acid. It is also preferable to use crosslinked resin fine particles containing a polyfunctional monomer as a raw material.

  The Tg of the resin serving as the base of the coated resin fine particles is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and preferably 110 ° C. or lower, more preferably. Is preferably 90 ° C. or lower. When the Tg is lower than 50 ° C., the storage stability of the toner becomes unstable, and when the Tg is higher than 110 ° C., the fixing energy increases and low temperature fixability cannot be obtained.

  The amount of the coating resin fine particles used is usually preferably 1 part by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight with respect to 100 parts by weight of the core particles. Or less, more preferably 30 parts by weight or less, and particularly preferably 10 parts by weight or less. If the amount of the coating resin fine particles used is less than the above, the core particle surface is not sufficiently covered, and if it is more than the above, the coating layer is increased and the thickness is increased, and the cost performance is reduced. In general, as the coating with resin fine particles increases, the fusion time of fine particles increases, and the residual fine particles that do not adhere increase, which adversely affects the subsequent process and the production efficiency deteriorates, and the shape becomes close to a spherical shape. For this reason, problems such as defective cleaning may occur. In the present invention, when the amount of the coating resin fine particles used is small, the fixability and the shape can be controlled.

  The coated resin fine particles according to the present invention include wax particles (hereinafter referred to as wax particles s) inside the polymer particles as in the case of the polymer particles described above, but the surface of the toner particles is not exposed unless the wax particles s are exposed. It is desirable because the technology of the present invention that should be in the vicinity can be embodied in a straight line and can exert a remarkable effect on the low-temperature fixing property or the offset resistance. As the wax particles s included in the coating resin fine particles, the same particles as the wax particles c used for the polymer particles of the core particles can be used. Among them, the nonpolar wax has a wide fixing temperature range. The fixability tends to be remarkably improved. Accordingly, the wax particles s encapsulated in the coated resin fine particles are optimally nonpolar wax. A hydrocarbon wax is preferred as the nonpolar wax. For example, petroleum waxes such as paraffin wax and microcrystalline wax; synthetic waxes such as Fischer-Tropsch wax; low molecular polyolefins obtained by radical polymerization of olefins under high pressure or Ziegler catalysts, metallocene catalysts, etc. under high pressures; high molecular weight polyolefins Polyolefins obtained by thermally degrading are preferred. Among them, petroleum wax is preferable, and paraffin wax is more preferable, and high purity purified product obtained by separating the wax by press sweating method, solvent method, vacuum distillation or fractional crystallization method is preferably used. .

  As the nonpolar wax particles included in the coated resin fine particles of the present invention, the oil content (residual oil content) measured by the method described in JIS K2235 (1991) is preferably 0.1% by mass or less. The oil content is defined as the amount of sample dissolved (% by mass) at −32 ° C. with respect to methyl ethyl ketone as the residual oil content in the wax.

  Further, as the nonpolar wax particles included in the coated resin fine particles of the present invention, the penetration at 25 ° C. measured by the method described in JIS K2235 (1991) is preferably 10 mm or less. The penetration degree represents the hardness of the wax, and is expressed as a depth (mm) at which a specified needle vertically enters the sample at a test temperature of 25 ° C.

  These wax particles s are preferably low melting point waxes. Specifically, the endothermic peak temperature of the wax measured by DSC is preferably 30 ° C or higher, more preferably 40 ° C or higher, and 60 ° C or higher. Particularly preferred. Moreover, 100 degrees C or less is preferable, 90 degrees C or less is still more preferable, and 85 degrees C or less is especially preferable. If the melting point is too low, the wax tends to be exposed and sticky after fixing, and if the melting point is too high, the fixability at low temperatures is poor.

  The amount of wax contained in the coating resin fine particles is usually preferably 2 parts by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight with respect to 100 parts by weight of the monomer constituting the coating resin. The amount is preferably not more than parts by weight, more preferably not more than 25 parts by weight. If the added amount of wax particles is less than 2 parts by weight, the oilless fixability cannot be sufficiently exerted, and if it is more than 50 parts by weight, the effect of imparting oilless fixability is sufficiently exerted, but the toner strength is lowered or the storage stability is improved. This is not preferable because the property becomes unstable, the amount of wax used increases and the cost reduction effect decreases, and the production of the wax-encapsulated coated resin fine particles becomes difficult. In order to effectively exhibit low-temperature fixability, the wax content of the coating resin fine particles may be larger than the wax particle content of the polymer particles or the core particles, but usually from the viewpoint of storage stability. The wax content of the coated resin fine particles is desirably smaller than the wax content of the polymer particles or the core particles.

  The particle diameter of the coated resin fine particles varies depending on the particle diameter of the core particles. However, according to the study by the present inventors, the optimum value for the core particles having an average particle diameter of 3 to 10 μm is The cumulative 50% value Dv50s of the cumulative volume particle size distribution by the dynamic light scattering method is preferably 0.1 μm or more, more preferably 0.15 μm or more, and preferably 0. The thickness is preferably 4 μm or less, more preferably 0.3 μm or less. If the particle diameter of the coated resin fine particles is too small, the suction force to the core particles is weak, so that the adsorption is not sufficient, and if the particle diameter of the coated resin fine particles is too large, the fine particles interfere with each other to the core particles. In any case, the core particles are not stably coated with the coated resin fine particles, which is not preferable.

In addition, the width index SDs (μm) of the cumulative volume particle size distribution measured by the dynamic light scattering method of the coating resin fine particles needs to be in the range of the following formula (1).
Formula (1) 0.05 <SDs <0.20
(However, the cumulative volume particle size distribution is accumulated from the small particle size side of the particle size fraction, Dv50s is the particle size (μm) at which the cumulative volume particle size distribution is 50%, and SDs is the cumulative volume particle size distribution. SDs = (Dv84s−Dv16s) / 2 where the particle size (μm) at the point of 84% is Dv84s and the particle size (μm) at the point of 16% is Dv16s. )

  The above SDs are indices (width indices) indicating the spread of the volume particle size distribution of particles measured by the dynamic light scattering method, and the smaller the numerical value, the smaller the spread of the distribution. The lower limit of SDs in formula (1) is more preferably 0.08 or more, and particularly preferably 0.09 or more. The upper limit is more preferably 0.15 or less.

  According to the experiments by the present inventors, when the coated fine particles are obtained by emulsion polymerization with a monomer alone that does not include the wax particles s, the width index SD is as very narrow as 0.02 to 0.04, and 0 .05 will not be exceeded. Further, even if the wax particles s are included, if the wax is polar wax particles, the particle width index SD is about 0.05 to 0.07 and exceeds 0.08. There is nothing. However, the coated fine particles including a specific nonpolar wax have a very broad distribution with a width index SD (SDs) of 0.08 or more, and surprisingly such a broad particle size distribution. The coated particles match the core particles such as the emulsion-polymerized agglomerated particles having an average particle size of about 3 to 10 μm and irregularities on the surface, and efficiently coat so as to fill the valleys. It has been found that the surface property can be improved smoothly and a good shape can be achieved, and as a result, a highly functional coating can be achieved with a relatively small amount of coating.

  Considering the size of the above-mentioned width index SDs by the mechanism of seed emulsion polymerization that encloses wax particles, the seed emulsion polymerization involves the presence of wax particles as seeds in the emulsifier micelles, and as microdroplets in the system. The existing monomer droplets are supplied to the wax particle micelles, where the wax particles partially dissolve or swell so that the monomers are sequentially impregnated, and the radicals generated in the aqueous phase reach the monomers in the micelles and the seed polymerization proceeds. It is considered a thing. Therefore, the polar index of particles SDs obtained is such that, as polar wax particles, those that are well compatible with monomers, particularly those containing polymerizable acid monomers, and that are more likely to partially dissolve or swell, the polymerization proceeds smoothly. On the other hand, it is considered that the width index SDs becomes large because the polymerization is difficult to proceed when the polymer is difficult to partially dissolve or swell with respect to the monomer, such as a nonpolar wax. Note that the fact that the oil content of the wax particles is small or the penetration is small works to increase the width index SDs.

  When the coating resin fine particles are in the above-mentioned SDs range, the particle size distribution of the resin particles for coating the core particles is not excessively sharp and broad, and varies within an appropriate range. Therefore, in the process in which the coating resin fine particles fill the unevenness of the surface of the core particle having an average particle diameter of 3 to 10 μm, especially the emulsion polymerization aggregation method core particle having an uneven shape on the surface thereof, the depth of the unevenness It is considered that particles having a size corresponding to the size of the particles adhere efficiently, and as a result, the surface after coating is smoothed and the shape of the resulting particles is improved.

  Regarding the particle diameter of the coating resin fine particles, the ratio of particles of 0.1022 μm or less in the cumulative volume particle size distribution measured by the dynamic light scattering method is preferably 20% or less, more preferably 10% or less. More preferably, it should be 5% or less, particularly preferably 0%. This means that the ratio of particles of about 100 nm or less is small by a certain amount, but if these particles are larger than the above range, the particles tend to reaggregate in the resin fine particle dispersion, and the dispersion is stable over time. This is not only a factor that deteriorates the properties, but also because these particles do not participate in coating as coated particles and are likely to remain as independent particles in the system, which causes a load of washing and filtration in the subsequent process. is there.

In a further preferred embodiment of the present invention, both the polymer particles and the coating resin fine particles include nonpolar wax particles. In the method for producing a toner in which the core particles include polymer particles, the polymer particles include wax particles c, and the coating resin fine particles include wax particles s, the DSC endothermic peak of the wax particles c and s. The temperature satisfies the following formula (2).
Formula (2) Tpc> Tps
(However, Tpc represents the DSC endothermic peak temperature (° C.) of the wax particles p included in the polymer particles, and Tps represents the DSC endothermic peak temperature (° C.) of the wax particles c included in the coated resin fine particles. )
As a result, the coated particle side wax, which is relatively easy to melt at low temperatures, is relatively close to the surface and thus has low temperature fixability, and the polymer particles, that is, the core particle side wax, can have high temperature side offset resistance. As a result, the fixable temperature range is expanded. Among these, Tpc is preferably higher than Tps by 3 ° C or more, more preferably 5 ° C or more.

In addition, as a desirable embodiment of the present invention, the core particles include polymer particles, and Tg of the polymer particles and the coating resin fine particles satisfies the following formula (3).
Formula (3) Tgc <Tgs
(However, Tgc represents Tg (° C.) of polymer particles, and Tgs represents Tg (° C.) of coated resin fine particles.)
The Tg of the polymer particles and the coated resin fine particles is as described above, but when compared with the Tg of the base resin, the Tg of the resin constituting the coated resin fine particles is the same as that of the resin constituting the polymer particles. A temperature higher than Tg, preferably higher than 5 ° C., more preferably higher than 10 ° C. is preferable because it improves the storage stability of the final toner base particles.

  The method of dispersing these wax particles s in a wet medium and the method of encapsulating the wax particles s in the coated resin fine particles (seed emulsion polymerization) should be performed by the same method as described in the section of polymer particle production. Can do.

  Among them, the coated resin fine particles in the present invention are preferably performed by a specific method for supplying the monomer to the wax particle s seed. That is, the monomer component constituting the wax particle s and the resin of the coated resin fine particle is dispersed in a wet medium to form a dispersion, and the monomer constituting the resin of the coated resin fine particle using the wax particle s as a seed. This is preferable because the preferred width index SDs of the coated resin fine particles can be achieved by the technique of performing seed polymerization with the components. Specifically, a wax particle dispersion, an emulsifier aqueous solution, and the like are charged into a reaction vessel, and a part of the polymerization initiator is added as necessary while heating and stirring. Thereafter, while stirring the system, the monomer constituting the coated resin fine particles is added to and mixed with the emulsifier aqueous solution to form fine droplets and a polymerization initiator (as an aqueous solution) for a predetermined time (2 to 2). It is a method of dripping over 10 hours) and completing seed polymerization. According to this method, since droplets of the monomer are gradually supplied into the system, the swelling of the wax particles by the monomer gradually proceeds, so that the particle size distribution of the obtained resin particles may be excessively sharpened. Absent. Further, since the monomer is dispersed in advance as droplets and is gradually supplied, rapid polymerization does not occur, so that the particle size distribution of the obtained resin particles is not excessively broadened. In particular, when a nonpolar wax particle dispersion is used as a seed, it is preferable because the above-described particle size distribution width index SDs can be easily achieved.

In the core particles and coated resin fine particles described above, preferred embodiments in the present invention are as follows, and are desirable in this order.
(1) Aggregation in which the coated resin fine particles are obtained by seed polymerization using a nonpolar wax as a seed, and the core particles are agglomerated based on polymer particles obtained by seed polymerization using a nonpolar wax as a seed Core particles or fused core particles fused with the core particles (2) The coated resin fine particles are obtained by seed polymerization using a non-polar wax as a seed, and the core particles are obtained by seed polymerization using a polar wax as a seed. Aggregated core particles obtained by agglomerating the obtained polymer particles as a base, or fused core particles obtained by fusing them are obtained by seed polymerization using a nonpolar wax as a seed. , Agglomerated core particles obtained by co-aggregation based on polymer particles whose core particles do not have wax and nonpolar wax particles, or fused core particles obtained by fusing them (4) Agglomerated core particles obtained by co-aggregation based on polymer particles and polar wax particles in which the core particles are obtained by seed polymerization using a nonpolar wax as a seed. Alternatively, fused core particles obtained by fusing them

  After the above steps are completed, the core particles are completely coated with the coating resin fine particles, and then solid-liquid separation (such as a filtration operation such as a centrifugal separation method or a filter press method) is performed by a known method to collect the formed particles. Then, after washing as necessary, operations such as drying and crushing are performed to obtain toner mother particles.

In the present invention, in each dispersion of polymer particles, coated resin fine particles, and wax particles, the volume particle size distribution of particles and the cumulative distribution thereof are measured by a dynamic light scattering method. This method obtains the particle size distribution by detecting the speed of Brownian motion of finely dispersed particles, irradiating the particles with laser light, and detecting light scattering (Doppler shift) with different phases according to the speed. It is. The value of the volume particle size of these particles is a value when the particles are stably dispersed in the aqueous system, and does not mean the particle size of the powder or wet cake before dispersion. In actual measurement, the above volume particle size was measured using the following settings using an ultrafine particle size distribution measuring apparatus (Nikkiso Co., Ltd., UPA-EX150, hereinafter abbreviated as UPA) using a dynamic light scattering method. went.
Measurement upper limit: 6.54 μm
Measurement lower limit: 0.0008 μm
Number of channels: 52
Measurement time: 100 sec.
Particle permeability: Transmitted particle refractive index: 1.59
Particle shape: Spherical density (g / cm ³ ): 1
Dispersion medium type: WATER
Dispersion medium refractive index: 1.333
At the time of measurement, the colorant dispersion was diluted with pure water so that the sample concentration index was in the range of 0.01 to 0.1, and measured with a sample subjected to dispersion treatment with an ultrasonic cleaner.

The particles in the colorant particle dispersion are similarly measured using UPA under the following conditions.
Measurement upper limit: 6.54 μm
Measurement lower limit: 0.0008 μm
Number of channels: 52
Measurement time: 100 sec.
Particle permeability: Absorbing particle refractive index: N / A (not applicable)
Particle shape: Non-spherical density (g / cm ³ ): 1
Dispersion medium type: WATER
Dispersion medium refractive index: 1.333

  Other components (particles) such as a fluidity improver, a cleaning aid, a lubricant, or an abrasive can also be externally added to the toner base particles thus obtained as external additives.

  In order to control fluidity and developability, external additives added to the toner particle surface include metal oxides such as alumina, silica, titania, zinc oxide, zirconium oxide, cerium oxide, talc, hydrotalcite, and the like. Hydroxides, metal titanates such as calcium titanate, strontium titanate and barium titanate, nitrides such as titanium nitride and silicon nitride, carbides such as titanium carbide and silicon carbide, organics such as acrylic resins and melamine resins A particle etc. are mentioned, It is possible to combine two or more. Among them, silica, titania, and alumina are preferably used alone or in combination, and more preferably those subjected to a hydrophobic surface treatment with, for example, a silane coupling agent or a silicone compound. In particular, those subjected to surface treatment with a silicone compound are preferred from the viewpoint of maintaining the charge amount. The number average primary particle diameter by the electron microscopy is preferably in the range of 1 to 500 nm, more preferably in the range of 5 to 100 nm. Further, those having a small particle diameter (number average primary particle diameter in the range of less than 1 to 30 nm) and those having a large particle diameter (number average primary particle diameter in the range of 30 to 500 nm) Are preferably used in combination so that the particle size difference is 10 nm or more, more preferably 30 nm or more. The total amount of the external additive added is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight with respect to 100 parts by weight of the toner particles.

  Examples of the lubricant include fatty acid amides such as ethylene bisstearylamide and oleic acid amide; fatty acid metal salts such as zinc stearate and calcium stearate; Examples of the abrasive include the aforementioned silica, alumina, cerium oxide, and the like. The average particle size of these particles is usually at most 1 μm (that is, 1 μm or less), preferably 0.01 to 1 μm.

  In toners, particularly aqueous medium toners such as emulsion aggregation toners, the shape is close to a sphere and the particle surface is smooth, so it is difficult to firmly attach these external additives. Therefore, as the external addition device, a high-speed fluid mixer in which a stirring blade rotates at a high speed is used, and the device itself can be controlled at 30 to 55 ° C. through a medium whose temperature is adjusted to the jacket, preferably water, around the mixer. Is preferable. As a result, the particle surface is softened in the external additive device, and adhesion of the external additive is promoted and strengthened.

  Examples of the high-speed fluid mixer include Henschel mixers FM-300 and FM-500 manufactured by Mitsui Mining Co., Ltd., and Supermixers SMB-500 and SMG-500 manufactured by Kawata Corporation.

  The chargeability of the emulsion polymerization aggregation method toner may be positively charged or negatively charged, but is preferably used as a negatively chargeable toner. Control of the chargeability of the toner can be adjusted by selection and content of the resin monomer and charge control agent, selection and addition amount of the external additive, and the like.

  The arithmetic average particle diameter (Dv) obtained from the volume particle size distribution of the toner obtained by the toner production method of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and particularly preferably. It is good that it is 5 μm or more. Further, it is preferably 10 μm or less, more preferably 8 μm or less, and particularly preferably 7 μm or less. Further, the lower limit of the content ratio of fine powder particles having a volume particle size of 5.04 μm or less is preferably 0.1% or more, more preferably 0.5% or more, and particularly preferably 1% or more. The upper limit is preferably 10% or less, more preferably 7% or less, and particularly preferably 5% or less. The lower limit of the content ratio of the fine particles having a number particle size of 5.04 μm or less is preferably 0.5% or more, more preferably 1% or more, particularly preferably 3% or more, and the upper limit is preferably 20%. % Or less, more preferably 15% or less, and particularly preferably 10% or less. Furthermore, the content of coarse particles having a volume particle size of 12.7 μm or more is preferably 2% or less, more preferably 1% or less, and particularly preferably 0.5% or less. It is most preferable that particles having a volume particle size of 5.04 μm or less and a volume particle size of 12.7 μm or more, in particular, coarse particles having a volume particle size of 12.7 μm or more are essentially not present at all. In addition, since the removal process requires equipment, it is desirable to control within the above range. When the volume average particle size or the particle content exceeds the above range, it may not be suitable for high-resolution image formation, and when it is less than the above range, handling as a powder tends to be difficult. Also, these ranges function well for surface coating with the coated resin fine particles of the present invention. Furthermore, the value (Dv / Dn) obtained by dividing Dv by the arithmetic average particle diameter (Dn) obtained from the number particle size distribution is preferably 1.0 to 1.25, more preferably 1.0 to 1.20, Preferably it is 1.0-1.15, and the one near 1.0 is desirable. A toner having a sharper particle size distribution tends to have a more uniform chargeability between particles. Therefore, Dv / Dn of an electrostatic charge image developing toner for achieving high image quality and high speed is in the above range. Is preferred.

  The toner particle size measuring device uses a Coulter Counter Multisizer II (manufactured by Beckman Coulter, Inc.), an interface (manufactured by Nikki) that outputs the number distribution and volume distribution, and a general personal computer. Connect and prepare 1% NaCl aqueous solution as the electrolyte using special grade or first grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and measured using a Coulter counter Multisizer II type with a 100 μm aperture. The volume and number of toners are measured to calculate a volume distribution and a number distribution, and a volume average diameter Dv and a number average diameter Dn are obtained, respectively.

  The toner of the present invention, particularly the toner produced by the emulsion polymerization aggregation method, can be produced with a smooth surface and a more spherical shape, but the average circularity is preferably 0.940 or more, More preferably, it is 0.950 or more, Especially preferably, it is 0.960 or more. The closer to a sphere, the less the localization of the charge amount in the particles and the developability tends to be uniform, but since it is difficult to produce a perfect spherical toner, the average circularity is Preferably it is 0.995 or less, More preferably, it is 0.990 or less. According to the production method of the present invention, it is possible to easily produce toner particles in the above-mentioned circularity range.

The circularity in the present invention is used as a simple method for quantitatively expressing the particle shape. In the present invention, the circularity is measured by using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. The circularity of the obtained particles is obtained by the following equation (1).
Circularity a = L0 / L (1)
[In the formula, L0 represents the circumference of a circle having the same projected area as the particle image, and L represents the particle image when image processing is performed at an image processing resolution of 512 × 512 (0.3 μm × 0.3 μm pixels). Indicates the perimeter. ]

  The circularity used in the present invention is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the circularity.

  Furthermore, the measurement device used in the present invention, “FPIA-2100”, has a thinner sheath flow (7 μm → 4 μm) than “FPIA1000” which has been used to calculate the shape of the toner. ) And the magnification of the processed particle image, and further improved the processing resolution of the captured image (256 × 256 → 512 × 512), so that the accuracy of toner shape measurement has been improved, thereby more reliably capturing fine particles. It is a device that has achieved. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

  As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impurities in the container have been removed in advance, and a measurement sample is 0. Add about 1-0.5g. The suspension in which the sample is dispersed is irradiated with ultrasonic waves (50 kHz, 120 W) for 1 to 3 minutes, the dispersion concentration is set to 1.2 to 2 million pieces / μl, and the flow type particle image measurement apparatus is used. The circularity distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.

  The outline of the measurement is as follows.

  The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat flow cell (thickness: about 200 μm). The strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to form an optical path that passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.

  Further, at least one of the peak molecular weights in the gel permeation chromatography (hereinafter sometimes abbreviated as GPC) of the THF soluble content of the toner is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 3 It is desirable that it is 10,000 or more, preferably 150,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less. When the peak molecular weight is lower than the above range, the mechanical durability in the non-magnetic one-component development method may be deteriorated. When the peak molecular weight is higher than the above range, the low temperature fixability and the fixing strength are deteriorated. There is a case. The THF-insoluble content of the toner is preferably 10% or more, more preferably 20% or more, and preferably 60% or less, more preferably when measured by a gravimetric method using Celite filtration described later. It should be 50% or less. If it is not within the above range, it may be difficult to achieve both mechanical durability and low-temperature fixability.

  The peak molecular weight of the toner is measured under the following conditions using a measuring apparatus: HLC-8120GPC (manufactured by Tosoh Corporation).

  The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min.

  The toner is dissolved in THF and filtered through a 0.2 μm filter, and the filtrate is used as a sample.

Measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6 mass%. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ are used, and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, in order to accurately measure the molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, μ-styragel 500, 10 ³ , manufactured by Waters, A combination of 10 ⁴ and 10 ^{5 and} a combination of shodex KA801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK are preferable.

  When used as a two-component developer, the toner particles and carrier particles can be mixed and used. Any known carrier particles can be used.

  Among them, the carrier particles have a weight average particle size of 15 to 60 μm, preferably 20 to 45 μm, and carrier particles smaller than 22 μm are 20% or less, preferably 0.05 to 15%, more preferably 0.1 to 12 %, And carrier particles smaller than 16 μm are 3% or less, preferably 2% or less, more preferably 1% or less.

  The coarse powder amount of a carrier of 62 μm or more needs to be 0.2 to 10% in close correlation with the sharpness of the image. When the weight average particle diameter of the carrier is less than 15 μm, the fluidity of the carrier is lowered, the mixing property with the toner is deteriorated, and fogging easily occurs. When the carrier average particle diameter exceeds 60 μm, the toner carrying ability is lowered. In addition, toner scattering tends to occur. Further, if the amount of fine powder increases, carrier adhesion tends to occur, and if the amount of coarse powder increases, fog and image density decrease tend to occur.

  Examples of carrier particles used in the present invention include surface oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth magnetic metals and their alloys or oxides; ferrites; magnetic powders And a resin carrier in which is dispersed.

  The surface of the carrier particles is preferably coated with a coating material containing a resin for the purpose of controlling charge imparting characteristics and carrier resistance characteristics.

  The coating material on the surface of the carrier particles varies depending on the toner material. For example, amino (meth) acrylic resins, (meth) acrylic resins, copolymers of these resins and styrene resins, (meth ) A copolymer of acrylic resin and fluorine resin, silicone resin, polyester resin, fluorine resin, polytetrafluoroethylene, monochlorotrifluoroethylene polymer and polyvinylidene fluoride, among which silicone resin, fluorine resin or A copolymer or mixture of a fluororesin and a (meth) acrylic resin can maintain a high chargeability over a long period of time, and the coating amount of these coating materials may be appropriately determined so that the charge imparting characteristics of the carrier particles are satisfied. In general, the total amount is 0.1 to 30% by weight, preferably 0.3 to 0, which is the percent by weight.

  As a method of forming the resin coating layer on the surface of the magnetic carrier core particles, the resin composition is dissolved in an appropriate solvent, the magnetic carrier core particles are immersed in the resulting solution, and then the solvent is removed, dried, A method of baking at high temperature; or a method of floating magnetic carrier core particles in a fluidized system, spraying and applying a solution in which the resin composition is dissolved, drying and baking at high temperature; simply magnetic carrier core particles and resin Any method of mixing a powder of the composition or an aqueous emulsion can be used.

  The resin carrier is a magnetic powder-dispersed resin carrier in which magnetic powder such as iron powder, ferrite, and iron oxide is dispersed in resin. Examples of the resin for dispersing the magnetic powder include styrene (meth) acrylic copolymer, polyester resin, epoxy resin, styrene-butadiene copolymer, acid resin, and melamine resin. The dispersion amount of the magnetic powder is preferably 20 to 80 wt% in the total amount of the resin carrier.

  When a two-component developer is prepared by mixing a carrier and a toner, the mixing ratio can be appropriately selected according to the purpose, but the toner concentration in the two-component developer is usually 1 to 15% by weight. When the content is preferably 3 to 12% by weight, more preferably 5 to 10% by weight, usually good results are obtained. When the toner concentration is less than 1% by weight, the image density is low, and when it exceeds 15% by weight, fog and in-machine scattering tend to increase, and the service life of the two-component developer tends to be reduced.

  The image forming method of the present invention includes an electrostatic latent image forming step, a toner image forming step, and a transfer step. Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of forming the toner image by developing the electrostatic latent image with a toner layer or a developer layer on a developer carrier. The toner layer or developer layer is not particularly limited as long as it contains the toner or developer of the present invention. The transfer step is a step of finally transferring the toner image onto a transfer medium (paper or the like). Among them, the toner or developer according to the present invention is suitable for image formation including a full color development system because it can achieve both fixing characteristics and storage stability, and in particular, an image including a full color tandem development system suitable for high-speed image formation. Ideal for formation.

  The transferred toner image is then fixed on the transfer target in a fixing process using thermal means. As a fixing device in the fixing process, heat generated from a normal heating / pressure roll is used. Although roll fixing is also preferable, in order to achieve maximum energy saving and high speed by making the best use of the fixing characteristics of the toner of the present invention, belt fixing that allows a wide fixing nip is preferable. In belt fixing, either the heating side or the pressure side may be formed by a belt, and a sheet heating element or IH (electromagnetic induction heating) may be adopted as an internal heating source in addition to a halogen lamp. Good.

  A belt fixing device that can be used in the present invention will be described. As shown in FIG. 1, the fixing device typically includes a fixedly supported low heat capacity heater 3, a cylinder 2 made of a heat resistant mold, a fixing belt 1, and a pressure roller 5. In general, the fixing belt 1 slides and rotates by frictional force generated by driving the pressure roller 5 and moves without causing wrinkles. As the material of the fixing belt 1, a known heat-resistant film can be used. Specifically, for example, polyimide, polyetherimide, PES, or PFA is used, and at least the image contact side thereof includes PTFE, PFA, or the like. An endless belt in which a release layer obtained by adding a conductive agent to the fluororesin is preferably used. The total thickness of the fixing belt 1 is usually 20 to 150 μm, preferably 30 to 100 μm. Moreover, the thickness of a mold release layer is 1-20 micrometers normally, Preferably it is 5-15 micrometers. The heater 3 performs on / off control of the heater 3 by the thermistor 4 so that the surface temperature of the fixing belt 1 becomes a predetermined temperature. The unfixed toner 6 on the recording material P is fixed by the heat and pressure of the heater 3 through the belt 1 when passing through the nip, and becomes a fixed toner 7.

Specific examples of the present invention will be described below in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
In the following examples, “parts” means “parts by weight”. Various measurements in the present invention were measured by the following methods.

[Particle size distribution of polymer particles, coated resin particles, wax particles, colorant particles]
It was measured with UPA described in the text. Unless otherwise noted, measurements were made immediately after the end of production of these dispersions.

[Re-agglomeration of colorant dispersion]
After the colorant dispersion was manufactured, the dispersion 1L was weighed in a plastic container and allowed to stand as it was, and after 48 hours, the container was shaken up and down 10 times, and then the ratio of the particle size of 0.972 μm or more in the volume distribution of the colorant particles Pvg (%) was measured again and evaluated by taking a ratio between the value and the value immediately after production, and was ranked as follows, and Δ or more was regarded as acceptable. Desirably, it is more than ○.
A: Increase ratio is less than 1.2 times (reaggregation property is very small)
○: Increase ratio is 1.2 times or more and less than 2 times (reaggregation property is small)
Δ: Increase ratio is 2 times or more and less than 3 times (Re-aggregation is slightly high, but there is no big problem in actual use)
×: Increase ratio is 3 times or more (high re-aggregation property and unbearable)

[Thermal properties of wax]
Measured by using a DSC120 model manufactured by Seiko Denshi Co., Ltd., in accordance with JIS K7121, with a sample amount of 10 mg, raising the temperature in the range of 5 to 120 ° C. at 10 ° C./min, and then lowering (cooling) at 10 ° C./min. did. From the figure when the horizontal axis is temperature and the vertical axis is calorie balance, the measurement was performed according to the following criteria.
(1) Endothermic peak temperature: Temperature (° C) corresponding to the peak of the melting peak
(2) Endothermic peak half-width: Peak width (° C.) at a position of half the melting peak height

[Surface tension of wax]
Measurement was performed by a contact angle method using Zisman-plot using four liquids of tetrachloroethane, 1-methylnaphthalene, diiodomethane, and α-bromonaphthalene.

[Toner particle size distribution]
Measured with Multisizer II described in the text.

[Toner insoluble in THF (THF)]
1 g of sample was added to 50 g of THF, and allowed to stand at 25 ° C. for 24 hours. The mixture was filtered with 10 g of Celite through a glass filter (11GP100 manufactured by SIBATA). The amount insoluble in THF was calculated by subtracting from the above.

[Peak molecular weight of toner solubles in THF]
It measured using HLC-8120 described in the text using the filtrate in the above-mentioned THF insoluble matter measurement.

[Polymer particles, coated resin fine particles, toner glass transition temperature (Tg)]
It was measured by DSC7 manufactured by PerkinElmer. 10 mg of sample is put in an aluminum pan, heated from 30 ° C. to 100 ° C. in 7 minutes, rapidly cooled from 100 ° C. to −20 ° C., and heated from −20 ° C. to 100 ° C. in 12 minutes. The Tg value observed when the temperature was increased was used. When there are a plurality of endothermic peaks, the lowest endothermic peak temperature is defined as Tg. The polymer particles and the coating resin fine particles are measured by drying the water in the dispersion, and when the endothermic peak of the wax particles interferes, a polymer without wax particles is prepared.

[Softening point of toner (Sp)]
Using a flow tester (CFT-500, manufactured by Shimadzu Corporation), about 1 g of the sample was heated to a rate of temperature increase of 3 ° C / min. Applying a load of 30 kg / cm ^{2 with} a plunger with an area of 1 cm ² while heating at, and extruding from a die with a hole diameter of 1 mm and a length of 10 mm, this draws a plunger stroke-temperature curve, and the height of the S-shaped curve When h is h, the temperature corresponding to h / 2 was taken as the softening point.

[Average circularity of toner]
The shape of the toner was measured with FPIA-2100 described in the text.

[Live-action evaluation]
Evaluation of the non-magnetic one-component toner was performed using a commercially available tandem full-color printer, and in the single-color image evaluation (5% printing), up to about 6000 sheets were repeatedly photographed for image evaluation and durability evaluation. Further, full-color image evaluation was also performed as described later. This printer has a data processing resolution of 600 dpi and includes four color cartridges of cyan, yellow, magenta, and black. In each color cartridge, an electrostatic latent image is formed on the OPC photosensitive member by laser writing, and the development process is non-magnetic. The electrostatic latent image is developed by a one-component contact development method to form a toner image. Then, the transfer paper is conveyed by the transfer belt, and the toner images are sequentially transferred onto the transfer paper in the above color order. The toner image is fixed by a flexible belt method (surface release layer material is PFA) heated on the heating side as a fixing device, and is passed through a nip formed between the elastic pressure roller. Done.

  For evaluation as a two-component developer, a commercially available tandem MFP was used, and full-color image evaluation was performed by repeatedly taking up to about 20000 sheets. This MFP has a data processing resolution of 600 dpi and includes four yellow, magenta, cyan, and black imaging units. In each color imaging unit, electrostatic latent image formation using an LED printer head is performed on a 30φ OPC photoreceptor. Made. In the development process, an electrostatic latent image on the photoreceptor is developed by a non-contact development method using a mixture of toner and silicone-coated ferrite particles having an average particle diameter of about 50 μm (toner concentration 8 wt%) for each color. It has a configuration in which toner image formation is performed. The toner image is directly transferred onto the transfer belt by the intermediate transfer belt method and then transferred onto the paper at once. The fixing of the toner image is performed as a fixing device by passing the paper through a nip portion formed between the fixing side and the elastic pressure roller. A PFA tube is used on the surface of both the heating side and the pressure side.

  Using the above-described actual photographing apparatus, a durability test for a specified number of sheets was performed in an environment of a temperature of 23 ° C. and a humidity of 55% RH, and image density and fogging of a print sample were evaluated numerically (described later) and banding (halftone) The image quality items such as the degree of dot-like band density unevenness) and others were visually evaluated.

[Evaluation of image density and fog]
The image density was measured with a reflection spectral densitometer (X-rite 504, manufactured by SDG Co., Ltd.) for the solid portion of the print sample obtained in the actual image evaluation. The image density is preferably within 0.15, more preferably within 0.10, with respect to the initial stage during actual shooting. If the change in image density exceeds 0.15, an uncomfortable feeling (overdeveloped or insufficiently developed) is felt, which is not preferable. For the fog, a colorimeter (ZE2000, manufactured by Nippon Denshoku Co., Ltd.) was used, and the difference in Hunter whiteness shown below was measured for the paper before and after the live action. The fog is preferably within 1.5, more preferably within 1.0 throughout the live action. If the fog exceeds 1.5, the sharpness of the image becomes inferior.
Hunter whiteness W (L * a * b *) = 100 − [(100−L *) ² + a * ² + b * ² ] ^1/2

[Fixability test]
In the fixing test, a fixing machine having the structure shown in FIG. 1 was used for the fixing test. In this fixing machine, a fixing belt (φ30 mm) 1 is fitted on the outer periphery of a cylinder portion 2 and is slidably rotated by driving of a pressure roller (φ30 mm) 5. A ceramic heater 3 is installed in the fixing nip N. The belt 1 is obtained by forming a release layer of a conductive primer (10 μm thickness) and a PFA resin (10 μm thickness) on a polyimide film (50 μm thickness). The pressure roller 5 is a silicone rubber elastic layer (3 nm thick) coated with a PFA resin release layer (30 μm thick), and the pressure is 10 kgf. The heater 3 has an output of 800 W and is set so that the surface temperature of the fixing belt can be adjusted in steps of 10 ° C. in the range of 100 to 200 ° C. Separately, a belt-like solid is printed on plain paper (A4 size) P having a basis weight of about 80 g / m ^{2 with} a toner adhesion amount of about 0.6 mg / cm ² to obtain a print image of unfixed toner 6. The fixing speed is 100 mm / s. The fixed image is acquired in increments of 10 ° C. within the above temperature range, and the temperature range where the toner on the recording paper after fixing is sufficiently adhered to the recording paper without fixing the belt at the time of fixing is the fixing temperature range. And When the lower limit temperature of the fixing temperature at which this offset does not occur is TL and the upper limit temperature is TU, ΔT = TU−TL is the fixing temperature range. ΔT is preferably 70 ° C. or higher, and practically problematic at 50 ° C. or lower.

[transparency]
For the three colors of magenta, cyan, and yellow toners, using the same fixing machine as that for which the fixing temperature width was measured, an unfixed toner image (toner adhesion amount of about 0.6 mg / cm ² ) on the OHP sheet was fixed at a fixing speed of 25 mm. / S, after fixing at 180 ° C., the transmittance was measured in the wavelength range of 400 nm to 700 nm with a spectrophotometer (U-3210 manufactured by Hitachi, Ltd.), and the transmittance at the wavelength with the highest transmittance was measured. Transparency was evaluated using the difference (maximum transmittance−minimum transmittance) between the transmittance (minimum transmittance (%)) at the wavelength with the lowest transmittance (maximum transmittance (%)) as a value. If the transmittance was 65% or more, the transparency was judged good.

[Toner charge amount]
The charge amount of the non-magnetic one-component toner is 23 ° C. and 55% RH in an environment of 23 ° C. and 55% RH. After the image check print is obtained for a predetermined number of sheets, the toner on the developing roller of the cartridge is q / m meter (Trek Japan, Model The toner on the roller was sucked onto the filter paper (Whatman Grade 1) using 210HS), and the charge amount per unit weight of toner was determined from the displayed capacitance and the toner weight on the sucked filter paper.

<Preparation of wax particle dispersion A1>
27 parts (540 g) of nonpolar wax particles A1 having the characteristics shown in Table 1, 2.8 parts of stearyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 20% sodium dodecylbenzenesulfonate aqueous solution (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen) 1.9 parts of S20A (hereinafter abbreviated as 20% DBS aqueous solution) and 68.3 parts of demineralized water were heated to 90 ° C. and stirred for 10 minutes using a homomixer (Mark II f model, manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, this dispersion was heated to 90 ° C., and circulation emulsification was started under a pressure condition of 25 MPa using a homogenizer (manufactured by Gorin Co., Ltd., 15-M-8PA type). The wax particle dispersion A1 (emulsion solid content concentration = 30.2%) was prepared by dispersing until the 50% diameter was about 0.25 μm.

<Preparation of wax particle dispersions A2 to A6>
Except for changing the wax particles A1 used in the preparation of the wax particle dispersion A1 to the wax particles A2 to A6 having the characteristics shown in Table 1, the wax particle dispersions A2 to A6 were prepared in exactly the same manner as the preparation of A1. Produced.

<Preparation of wax particle dispersion A7>
27 parts (540 g) of wax particles A7 shown in Table 1, 1.9 parts of a 20% DBS aqueous solution, and 71.1 parts of demineralized water were placed in a 3 L stainless steel container and heated to 90 ° C. and homomixer (Special Machine Industries Co., Ltd.) (Production Mark II f model) and stirred for 10 minutes. Next, this dispersion was heated to 99 ° C., and circulation emulsification was started under a pressure condition of 45 MPa using a homogenizer (manufactured by Gorin Co., Ltd., 15-M-8PA type). A wax particle dispersion A7 (emulsion solid content concentration = 27.4%) was prepared by dispersing until the% diameter reached about 0.25 μm.

<Preparation of wax particle dispersion B1>
30 parts (600 g) of wax particles B1 having the characteristics shown in Table 1, 2.8 parts of 20% DBS aqueous solution, and 67.2 parts of demineralized water were heated to 90 ° C. and homomixer (Mark II, manufactured by Tokushu Kika Kogyo Co., Ltd.). f model) for 10 minutes. Next, this dispersion was heated to 90 ° C., and circulation emulsification was started under a pressure condition of 25 MPa using a homogenizer (manufactured by Gorin, 15-M-8PA type), and the particle size distribution was measured while measuring the particle diameter with UPA. A wax particle dispersion B1 (emulsion solid content concentration = 30.6%) was prepared by dispersing until the 50% cumulative diameter reached about 0.25 μm.

  Table 2 shows the particle size of the wax particles in the obtained wax particle dispersion.

-Dv50 represents the volume particle size distribution cumulative 50% value measured by UPA.
・ SD is calculated from the volume particle size distribution data measured by UPA using the following formula.
SD = (Dv84−Dv16) / 2
However, Dv84 represents a volume particle size distribution accumulated 84% value, and Dv16 represents a volume particle size distribution accumulated 16% value.
-The ratio of particles of 0.1022 μm or less represents the ratio (%) of particles having a volume particle size distribution cumulative value of 0.1022 μm or less.
・ In the above measurement, the cumulative value is calculated from the small particle size.

<Preparation of polymer particle dispersion A1>
35. Wax particle dispersion A1 is placed in a reactor (with an internal volume of 21 liters, an inner diameter of 250 mm, a height of 420 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and raw material / auxiliary charging devices. The mixture was heated to 90 ° C. under a nitrogen stream (6 parts by weight (712.12 g) and 259 parts of demineralized water were added and stirred).

  Thereafter, the following mixture of monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization while stirring was continued. The time when the mixture of the monomers and the emulsifier aqueous solution was started to be dropped was set as the polymerization start, and the following initiator aqueous solution was added over 4.5 hours from 30 minutes after the start of the polymerization. The aqueous solution of the agent was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Monomers]
Styrene 76.8 parts (1535.0 g)
Butyl acrylate 23.2 parts Acrylic acid 1.5 parts Tetrachlorobromomethane 1.0 part Hexanediol diacrylate 0.7 part

[Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part demineralized water 67.1 parts

[Initiator aqueous solution]
8% aqueous hydrogen peroxide solution 15.5 parts 8% L (+)-ascorbic acid aqueous solution 15.5 parts

[Additional initiator aqueous solution]
8% L (+)-ascorbic acid aqueous solution 14.2 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer particle dispersion A1. The solid content concentration of the dispersion was 21.1% by weight. Table 2 shows the particle size of the polymer particles in the dispersion. The Tg of particles obtained by polymerizing these monomers without wax particles was 62.5 ° C.

<Preparation of polymer particle dispersion A2>
The wax particle dispersion A2 is 35. placed in a reactor (inner volume 21 liters, inner diameter 250 mm, height 420 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device. The mixture was heated to 90 ° C. under a nitrogen stream (6 parts by weight (712.12 g) and 259 parts of demineralized water were added and stirred).

  Thereafter, the following mixture of monomers and an aqueous emulsifier solution was added over 5 hours from the start of polymerization while stirring was continued. The time when the mixture of the monomers and the emulsifier aqueous solution was started to be dropped was set as the polymerization start, and the following initiator aqueous solution was added over 4.5 hours from 30 minutes after the start of the polymerization. The aqueous solution of the agent was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Monomers]
92.5 parts of styrene (1850.0 g)
Butyl acrylate 7.5 parts Acrylic acid 1.5 parts Tetrachlorobromomethane 1.0 part Hexanediol diacrylate 0.6 part

[Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part demineralized water 67.1 parts

[Initiator aqueous solution]
8% aqueous hydrogen peroxide solution 15.5 parts 8% L (+)-ascorbic acid aqueous solution 15.5 parts

[Additional initiator aqueous solution]
8% L (+)-ascorbic acid aqueous solution 14.2 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain milky white polymer particle dispersion A2. The particle size of the polymer particles in this dispersion is shown in Table 2. The Tg of the particles obtained by polymerizing these monomers without wax particles was 80.0 ° C.

<Preparation of polymer particle dispersions A3 to A7, B1>
Polymer particle dispersions A3 to A6 are prepared in exactly the same manner as A2 except that the wax particle dispersion A2 used in the preparation of the polymer particle dispersion A2 is changed to wax particles A3 to A7 and B1, respectively. did. The particle size of the polymer particles in these dispersions is shown in Table 2.

  After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer particle dispersion B1. The solid content concentration was 18.2% by weight. Table 2 shows the particle size of the polymer particles in this dispersion.

<Preparation of polymer primary particle dispersion C1>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device (inner volume 21 liters, inner diameter 250 mm, height 420 mm) 2.0% 20% DBS aqueous solution 2.0 weight And 317 parts of demineralized water, heated to 90 ° C. under a nitrogen stream, and 3.2 parts of 8% hydrogen peroxide aqueous solution and 3.2 parts of 8% L (+)-ascorbic acid aqueous solution were stirred together. Added. 5 minutes later, polymerization of the following mixture of monomers and emulsifier aqueous solution was started (from the time when 3.2 parts of 8% hydrogen peroxide aqueous solution and 3.2 parts of 8% L (+)-ascorbic acid aqueous solution were added all at once. After 5 minutes), the following initiator aqueous solution was added over 6 hours from the start of polymerization, and the internal temperature was maintained at 90 ° C. for 1 hour with further stirring.

[Monomers]
Styrene 88.0 parts (1760.0 g)
Butyl acrylate 12.0 parts Acrylic acid 1.5 parts Tetrachlorobromomethane 0.5 parts Hexanediol diacrylate 0.4 parts

[Emulsifier aqueous solution]
20% DBS aqueous solution 1.5 parts Demineralized water 66.4 parts

[Initiator aqueous solution]
8% aqueous hydrogen peroxide solution 18.9 parts 8% L (+)-ascorbic acid aqueous solution 18.9 parts

  After completion of the polymerization reaction, the mixture was cooled to obtain milky white polymer particle dispersion C1. The solid content concentration was 19.5% by weight. Table 2 shows the particle size of the polymer particles in this dispersion. The Tg of the particles was 75.0 ° C.

<Preparation of Colorant Particle Dispersion A (for Black)>
Carbon black produced by a furnace method in which a 300 L internal volume container equipped with a stirrer (propeller blade) has a UV absorbance of 0.02 as a colorant particle and a true density is 1.8 g / cm ^3. (Mitsubishi Chemical Corporation, Mitsubishi Carbon Black MA100S) 20 parts (40 kg), 20% DBS aqueous solution 1 part, nonionic surfactant (Kao Corporation, Emulgen 120) 4 parts, ion exchange with electrical conductivity of 2 μS / cm 75 parts of water was added and predispersed to obtain a pigment premix solution.

  The volume particle size distribution cumulative 50% diameter of the carbon black in the dispersion after premixing measured by UPA was 90 μm. The premix solution was supplied as a raw material slurry to a wet bead mill and subjected to one-pass dispersion.

In this wet bead mill, a rotor disk is rotatably arranged in a vertical cylindrical stator, a medium is filled in a space formed by the stator and the rotor disk, and the medium moves by the rotating rotor. The media beads are separated by a centrifugal separator disposed on the stator. In addition, the inner diameter of the stator was 75 mmφ, the separator diameter was 60 mmφ, the distance between the separator and the disk was 15 mm, and zirconia beads having a diameter of 90 μm (true density 6.0 g / cm ³ ) were used as dispersion media. Since the effective internal volume of the stator is 0.5 liter and the filling volume of the media is 0.35 liter, the media filling rate is 70%. The rotation speed of the rotor disk is constant (the peripheral speed of the rotor tip is 11 m / sec), and the premix slurry is continuously supplied from the supply port by a non-pulsating metering pump at a supply rate of 50 liters / hr and continuously from the discharge port. The colorant particle dispersion A of black color was obtained by discharging the liquid. The solid content concentration of the colorant dispersion A was 24.2% by weight, and the measurement results of the particle size are shown in Table 3.

<Preparation of Colorant Particle Dispersion B (for Magenta)>
The colorant particles were mixed with a quinacridone pigment having a true density of 1.5 g / cm ³ . I. Except for changing to Pigment Red 122 (manufactured by Clariant Japan, Hostaperm Pink E-WD), preliminary dispersion was performed in the same manner as the colorant particle dispersion A to obtain a pigment premix solution. Thereafter, the premix solution was used as a raw material slurry and dispersed in a wet bead mill similar to the colorant particle dispersion A, but here, not a one-pass operation but a circulation operation was performed. In the circulation operation, the dispersion slurry extracted by the raw material pump from the raw material tank for storing the premix product is supplied to the wet bead mill and pulverized by stirring with the media in the mill, and then the media is removed by the separator. It is separated and discharged, followed by a route returning to the raw material tank, and is circulated and crushed. The conditions for the bead mill are that zirconia beads having a diameter of 50 μm (true density: 6.0 g / cm ³ ) are used as a dispersion medium, and that cooling water of about 10 ° C. is circulated through the jacket outside the stator. It is the same. A magenta colorant particle dispersion B was obtained when a predetermined particle size was reached by circulation operation. The measurement results of the particle size are shown in Table 3.

<Preparation of colorant particle dispersion C (for cyan)>
As the colorant particles, C.I. having a true density of 1.6 g / cm ³ . I. A cyan colorant particle dispersion C was obtained in the same manner as the colorant dispersion particle dispersion B, except that the pigment was changed to CI Pigment Blue 15: 3 (manufactured by Clariant Japan, Hostaperm Blue B2G). The measurement results of the particle size are shown in Table 3.

<Preparation of colorant particle dispersion D (for yellow)>
As the colorant particles, C.I. having a true density of 1.5 g / cm ³ . I. A yellow colorant particle dispersion D was obtained in the same manner as in the preparation of the colorant dispersion particle dispersion B, except that the pigment yellow 93 (Chrophtal Yellow 3G, manufactured by Nagase Sangyo Co., Ltd.) was used. The measurement results of the particle size are shown in Table 3.

Dv10g, Dv16g, Dv50g, Dv84g, and Dv90g represent the particle size (μm) at which the colorant particle has a volume particle size distribution cumulative value of 10%, 16%, 50%, 84%, and 90%, respectively.
SDg is expressed as SDg = (Dv84g−Dv16g) / 2.
Pvg represents the ratio (%) of the particle size of 0.972 μm or more in the volume distribution of the colorant particles.
-The volume cumulative distribution is accumulated from the small particle size side of the volume particle size distribution.

  Using each of the above particle dispersions, formation of aggregated core particles or fused core particles and adhesion / fusion of the coated resin fine particles are performed. In practice, the coating with the coating resin fine particles after the formation of the agglomerated core particles or the fused core particles is carried out as it is, but for convenience of explanation, it is described in sections.

<Production of Aggregated Core Particle A (Black)>
Polymer particle dispersion A1 95 parts as solid content (998.2 g as solid content)
Colorant particle dispersion A 6 parts as colorant solids
20% DBS aqueous solution Using 0.1 parts of the above components as solids, aggregated core particles were produced by the following procedure.

Polymer particle dispersion A1 and 20% in a mixer (volume 12 liter, inner diameter 208 mm, height 355 mm) equipped with a stirrer (double helical blade), heating / cooling device, concentrating device, and raw material / auxiliary charging device A DBS aqueous solution was charged and mixed uniformly at an internal temperature of 12 ° C. for 5 minutes. Subsequently, while continuing stirring at an internal temperature of 12 ° C., 0.52 parts of 5% aqueous solution of ferrous sulfate as FeSO ₄ · 7H ₂ O was added over 5 minutes, and then the colorant fine particle dispersion A was added over 5 minutes. The mixture was uniformly mixed at an internal temperature of 12 ° C., and a 0.5% aqueous solution of aluminum sulfate was added dropwise under the same conditions (the solid content with respect to the resin solid content was 0.10 parts). Thereafter, the temperature was raised to 53 ° C. over 75 minutes, and further raised to 56 ° C. over 170 minutes to obtain agglomerated core particles A. When the volume distribution arithmetic mean diameter Dv by Multisizer II was measured, it was 6.7 μm.

<Production of Aggregated Core Particle B (Magenta)>
Aggregated core particles B were obtained in exactly the same manner as in the production of the aggregated core particles A, except that the colorant particle dispersion A was changed to the colorant particle dispersion B. Dv was 6.5 μm.

<Production of Aggregated Core Particle C (Cyan)>
Aggregated core particles C were obtained in exactly the same manner as in the production of the aggregated core particles A, except that the colorant particle dispersion A was changed to the colorant particle dispersion C. Dv was 6.5 μm.

<Production of Aggregated Core Particle D (Yellow)>
Aggregated core particle D was obtained in exactly the same manner as in the production of aggregated core particle A, except that colorant particle dispersion A was changed to colorant particle dispersion D. Dv was 6.6 μm.

<Production of Aggregated Core Particle E (Black)>
Agglomerated core particles E were obtained in exactly the same manner as in the production of the agglomerated core particles A except that the polymer particle dispersion A2 was used instead of the polymer particle dispersion A1 in the production of the agglomerated core particles A. Dv was 6.7 μm.

<Manufacture of toner base particles 1 (black) by coating on aggregated core particles A>
After the formation of the agglomerated core particles A, polymer particle dispersion A2 (5 parts as a solid content) was added as coating resin fine particles over 3 minutes, and held there for 60 minutes. Subsequently, a 20% DBS aqueous solution (6 parts as a solid content) was added over 10 minutes, and then the temperature was raised to 90 ° C. over 30 minutes and held for 60 minutes. As a result, the coating resin fine particles are fused to the core particles, and coating is performed. Then, the slurry obtained by cooling to 30 ° C. over 20 minutes was extracted, and suction filtration was performed with an aspirator using 5 types C (No5C manufactured by Toyo Roshi Kaisha, Ltd.) filter paper. The cake remaining on the filter paper is transferred to a stainless steel container having an internal volume of 10 L equipped with a stirrer (propeller blade), and 8 kg of ion-exchanged water having an electric conductivity of 1 μS / cm is added and stirred at 50 rpm, and then uniformly dispersed. Stirred for 30 minutes.

  Subsequently, suction filtration is performed with an aspirator using the above filter paper, and the solid matter remaining on the filter paper is again provided with a stirrer (propeller blade) and a container with an internal volume of 10 L containing 8 kg of ion-exchanged water having an electric conductivity of 1 μS / cm. The mixture was uniformly dispersed by stirring at 50 rpm and kept stirring for 30 minutes. When this process was repeated 5 times, the electrical conductivity of the filtrate was 2 μS / cm.

  The obtained cake was spread on a stainless steel pad so as to have a height of 20 mm, and dried in an explosion-proof blower dryer set at 40 ° C. for 48 hours to obtain toner mother particles 1.

<Manufacture of toner base particles 2 to 8 (black) by coating on aggregated core particles A>
Toner base particles 2 to 8 were obtained in the same manner as in the manufacture of toner base particles 1 except that polymer particle dispersions A2 to A7, B1, and C1 were used as the coating resin fine particles.

<Manufacture of toner base particles 9 (magenta) by coating the aggregated core particles B>
Except for changing the agglomerated core particles to agglomerated core particles B, toner mother particles 9 were obtained in exactly the same manner as in the production of toner mother particles 1.

<Manufacture of toner base particles 10 (cyan) by coating on aggregated core particles C>
Except for changing the agglomerated core particles to agglomerated core particles C, toner mother particles 10 were obtained in exactly the same manner as in the production of toner mother particles 1.

<Manufacture of toner base particles 11 (yellow) by coating on aggregated core particles D>
Except for changing the agglomerated core particles to agglomerated core particles D, toner mother particles 11 were obtained in exactly the same manner as in the production of toner mother particles 1.

<Manufacture of toner base particles 12 (black) by coating on aggregated core particles E>
Toner base particles 12 were obtained in the same manner as in the production of toner base particles 1 except that the aggregate core particles were changed to aggregate core particles E and the coated resin fine particles were changed to polymer particles A1.

Then, the manufacture example using a fusion core particle is shown.
<Manufacture of fused core particle A (for black)>
After confirming the particle size in the same manner as in the production of the aggregated core particle A using the material used in the aggregated core particle A, the temperature is further raised to 95 ° C. in order to promote the fusion / bonding of the aggregated core particle A. For 5 hours, and then the slurry was cooled to obtain fused core particles A. The Dv measured by Multisizer II was 6.8 μm.

<Manufacture of fused core particles B (for magenta), C (for cyan), D (for yellow)>
Using the materials used for the agglomerated core particles B to D, respectively, and confirming the particle size in the same manner as in the production of the agglomerated core particles B to D, and thereafter the fused core particles in the same manner as the fused core particles A. B to D were obtained. The Dv measured by Multisizer II was 6.7, 6.6, and 6.6 μm, respectively.

<Manufacture of toner base particles 13 (black) by coating the fused core particles A>
After the formation of the fused core particle A, polymer particle dispersion A2 (5 parts as a solid content) was added as coating resin fine particles over 3 minutes, and held as it was for 60 minutes. Subsequently, a 20% DBS aqueous solution (6 parts as a solid content) was added over 10 minutes, and then the temperature was raised to 90 ° C. over 30 minutes and held for 60 minutes. As a result, the coating resin fine particles are fused to the core particles, and coating is performed.
In the following post-treatment, toner base particles 13 were obtained in the same manner as toner base particles 1.

<Manufacture of toner base particles 14 (magenta) by coating the fused core particles B>
Except for changing the fused core particles to fused core particles B, toner mother particles 14 were obtained in exactly the same manner as in the production of the toner mother particles 13.

<Manufacture of toner base particles 15 (cyan) by coating the fused core particles C>
Except for changing the fused core particles to fused core particles C, toner mother particles 15 were obtained in exactly the same manner as in the production of the toner mother particles 13.

<Manufacture of toner base particles 16 (yellow) by coating the fused core particles D>
Except for changing the fused core particles to fused core particles D, toner mother particles 16 were obtained in exactly the same manner as in the production of toner mother particles 13.

  Using the toner base particles 1 to 16, an external addition process for forming a non-magnetic one-component toner was performed.

<Manufacture of nonmagnetic one-component toners 1 to 16>
In the external addition, 0.5 parts of silica fine particles having an average primary particle size of 50 nm hydrophobized with dimethyl silicone oil are added to 100 parts of each toner base particle, and the average primary particles hydrophobized with dimethyl silicone oil. Add 1.0 part of silica fine particles with a diameter of 12 nm, pass hot water of 45 ° C. through the outer jacket, stir and mix with a temperature controlled FM20 type Henschel mixer (Mitsui Mining Co., Ltd.), and sieve opening 45 μm The non-magnetic one-component toners 1 to 16 using the toner base particles were obtained through the operation of removing the coarse particles with the vibration sieve device. Table 4 shows a summary of various physical properties of each toner.

  Among these, the nonmagnetic one-component toners 2, 3, 4, 5, and 7 tend to be slightly inferior in average circularity as compared with the nonmagnetic one-component toners 1 and 6, and the nonmagnetic one-component toner 8 The average circularity tended to be considerably inferior.

Examples using these toners are shown below.
[Examples 1 to 14, Comparative Example 1]
Using these non-magnetic one-component toners 1 to 16, single-color images of each toner were evaluated with the tandem full-color printer. In addition, a fixability test of each toner was also performed. The color toner was confirmed for transparency. The evaluation results are shown in Table 5.

  According to Table 5, Examples 1, 6, 8 to 9, and 12 to 15 had the most excellent image density / fogging / charge amount change, no problem in image quality, and good fixing characteristics. In comparison, Examples 2 to 5, 7 and 11 showed no change in practical use, but there was a slight change, and the fixing temperature range tended to decrease somewhat. In Comparative Example 1, the image evaluation, change in charging property, and fixing property did not reach the standard.

[Example 15]
Using each color toner of non-magnetic one-component toners 1, 9, 10 and 11 with the above-mentioned tandem type full color printer, according to the pattern of identification number N5 defined in JIS X9201: 2001 (high-definition color digital standard image) A full color image was continuously formed about 2000 times to evaluate the image.

  As a result, a clear full-color image was obtained through 2000 sheets with good image density, fog, resolution, and the like. In the meantime, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade of the non-magnetic one-component developing machine, and the mechanical durability was good.

[Example 16]
A full color image evaluation similar to that of Example 15 was performed using each color toner of the non-magnetic one-component toners 13, 14, 15 and 16.

  As a result, a clear full-color image was obtained through 2000 sheets with good image density, fog, resolution, and the like. In the meantime, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, no toner fusion to the developing roller or blade of the non-magnetic one-component developing machine, and the mechanical durability was good.

[Example 17]
Each toner of 1, 9, 10, and 11 used as a non-magnetic one-component toner is mixed with silicone-coated Cu—Zn type ferrite particles having an average particle diameter of about 50 μm using a V-type mixer. A two-component developer for each color was prepared (toner concentration 8 wt%). These developers were loaded into each developer of the tandem MFP, and about 20,000 full-color image formation tests were performed at a full-color printing rate of about 20% using these toners as replenishing toners.

  As a result, through 20000 sheets, a clear full-color image having a good image density, fog, resolution, and the like was exhibited. Meanwhile, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, and mechanical durability was also good.

[Example 18]
Each color developer was obtained in the same manner as in Example 17 except that each of the 13, 14, 15 and 16 color toners used as the non-magnetic one-component toner was used, and the same full color image formation test as in Example 17 was conducted. .

  As a result, through 20000 sheets, a clear full-color image having a good image density, fog, resolution, and the like was exhibited. Meanwhile, there was no image contamination due to photoconductor filming or internal contamination due to a decrease in toner charge, and mechanical durability was also good.

DESCRIPTION OF SYMBOLS 1 Fixing belt 2 Cylinder 3 Heater 4 Thermistor 5 Pressure roller 6 Unfixed toner 7 Fixed toner N Nip part P Recording material

Claims (19)

At least in a method for producing a toner in which a resin coating layer is formed on the surface of a core particle by adding and fusing a coating resin fine particle on the surface of the core particle in a wet medium,
The Dv50s in the cumulative volume particle size distribution measured by the dynamic light scattering method of the coated resin fine particles is 0.1 to 0.4 μm, and the width index SDs (μm) of the cumulative volume particle size distribution is represented by the following formula (1). In range:
Formula (1) 0.05 <SDs <0.20
(However, the cumulative volume particle size distribution is accumulated from the small particle size side of the particle size fraction, Dv50s is the particle size (μm) at which the cumulative volume particle size distribution is 50%, and SDs is the cumulative volume particle size distribution. SDs = (Dv84s−Dv16s) / 2 where the particle size (μm) at the point of 84% is Dv84s and the particle size (μm) at the point of 16% is Dv16s. )
The core particles include at least polymer particles and a colorant;
A method for producing a toner, wherein the polymer particles include wax particles c therein.   2. The toner production method according to claim 1, wherein a ratio of particles of 0.1022 μm or less in a cumulative volume particle size distribution measured by a dynamic light scattering method of the coated resin fine particles is 20% or less.   The core particle is an agglomerated particle obtained by aggregating at least polymer particles and a colorant in a wet medium, and a resin particle for coating is added to the agglomerated particle and fused to form a resin on the surface of the agglomerated particle. The toner manufacturing method according to claim 1, wherein a coating layer is formed.   The core particles are agglomerated by aggregating at least polymer particles and a colorant in a wet medium, and then heated to a temperature equal to or higher than the glass transition point (Tg) of the resin constituting the agglomerated particles. 3. The resin-coated layer according to claim 1, wherein the resin-coated layer is formed on the surface of the fused particles by adding and melting the coated resin fine particles on the surface of the fused particles. The method for producing the toner according to item.   The method for producing a toner according to claim 1, wherein at least a monomer constituting the resin of the coating resin fine particles contains a polymerizable acid.   6. The toner production method according to claim 1, wherein the coating resin fine particles include wax particles s therein.   The toner production method according to claim 6, wherein a DSC endothermic peak temperature of the wax particles s is in a range of 30 to 100 ° C. 8.   The toner manufacturing method according to claim 6, wherein the wax particles s are nonpolar waxes.   The toner manufacturing method according to claim 1, wherein the wax particles c are polar wax particles.   The toner manufacturing method according to claim 1, wherein the wax particles c are nonpolar wax particles. In the toner manufacturing method in which the core particles include polymer particles, the polymer particles include wax particles c, and the coating resin fine particles include wax particles s, the DSC endothermic peak temperature of the wax particles c and s has a DSC endothermic peak temperature. The toner production method according to claim 1, wherein the following formula (2) is satisfied.
Formula (2) Tpc> Tps
(However, Tpc represents the DSC endothermic peak temperature (° C.) of the wax particles c included in the polymer particles, and Tps represents the DSC endothermic peak temperature (° C.) of the wax particles s included in the coated resin fine particles. ) 12. The toner according to claim 1, wherein the core particles include polymer particles, and Tg of the polymer particles and the coating resin fine particles satisfies the following formula (3). Production method.
Formula (3) Tgc <Tgs
(However, Tgc represents Tg (° C.) of polymer particles, and Tgs represents Tg (° C.) of coated resin fine particles.)   12. The method for producing a toner according to claim 6, wherein the residual oil content of the wax particles s is 0.1% by mass or less.   12. The toner manufacturing method according to claim 6, wherein a penetration of the wax particles s at 25 ° C. is 10 mm or less.   The monomer components constituting the wax particles s and the resin of the coated resin fine particles are each dispersed in a wet medium to form a dispersion. The toner production method according to claim 6, wherein seed polymerization is performed.   A toner manufactured by the toner manufacturing method according to claim 1.   A developer comprising the toner according to claim 16 and a carrier.   Forming an electrostatic latent image on the electrostatic latent image bearing member; developing the electrostatic latent image with a toner layer on the toner bearing member to form a toner image; and An image forming method including a step of transferring to a toner, wherein the toner layer contains the toner according to claim 16.   Forming an electrostatic latent image on the electrostatic latent image carrier, developing the electrostatic latent image with a developer layer on the developer carrier to form a toner image, and transferring the toner image An image forming method comprising a step of transferring onto a body, wherein the developer layer contains the developer according to claim 17.