JP2008003357A - Toner kit for full-color electrostatic charge development and full-color toner kit for nonmagnetic one-component development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner kit for full-color electrostatic charge development having little difference in charges between colors and little change in charges and comprising yellow, magenta, cyan and black toners with high picture quality, and to provide a full-color toner kit for nonmagnetic one-component development using the above toner kit for full-color electrostatic charge development. <P>SOLUTION: The toner kit for full-color electrostatic charge development comprising a yellow toner, a magenta toner, a cyan toner and a black toner and containing at least a binder resin, a colorant and wax is characterized in that: the yellow toner contains an azo pigment as a colorant; the magenta toner contains an azo pigment and a quinacridone pigment as a colorant; the cyan toner contains a phthalocyanine pigment as a colorant; and the black toner contains an acidic carbon having a pH of 7 or lower as a colorant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a full-color electrostatic charge developing toner kit and a full-color toner kit for non-magnetic one-component development using the full-color electrostatic charge developing toner kit.

  With increasing demand in recent years, ensuring the long-term stability of color print images has become an increasingly important issue. In a color printer / copier, a toner kit consisting of four colors of yellow, magenta, cyan, and black is usually used, and the charging performance of the toner is adjusted by applying various external additives. However, the external additive has a large change in the adhesion state on the toner surface, and it is difficult to ensure image quality over a long period of time.

In this regard, as an external additive for pulverized toner, a method for suppressing the burying of the external additive by uniformly adding inorganic particles having a spacer effect to the toner surface and improving the durability stability of the image quality is described. (For example, refer to Patent Document 1). However, it is physically difficult to completely suppress the change in the adhesion state of the external additive during the endurance, and it is inevitable that a difference in color between toner charges gradually occurs. In view of the above situation, in order to reduce the color difference in toner charging performance and ensure long-term stability of image quality, it is most effective to reduce the chargeable color difference of the toner base itself before external addition. It is considered a means.
JP-A-11-295921

  An object of the present invention is to use a full-color electrostatic charge developing toner kit composed of yellow, magenta, cyan, and black having good image quality with little difference in charge amount between colors and charge fluctuation, and the full-color electrostatic charge developing toner kit. It is to provide a full color toner kit for non-magnetic one-component development.

  The above object of the present invention is achieved by the following configurations.

  1. In a full color electrostatic charge developing toner kit comprising a yellow toner, a magenta toner, a cyan toner and a black toner containing at least a binder resin, a colorant and a wax, the yellow toner contains an azo pigment as a colorant, and the magenta toner A full color characterized in that it contains an azo pigment and a quinacridone pigment as colorants, the cyan toner contains a phthalocyanine pigment as a colorant, and the black toner contains acidic carbon black having a pH of 7 or less as a colorant. Toner kit for electrostatic charge development.

  2. A full-color toner kit for non-magnetic one-component development, wherein the toner kit for full-color electrostatic charge development described in 1 is used.

  According to the present invention, a full-color electrostatic charge developing toner kit composed of yellow, magenta, cyan, and black having good image quality with little difference in charge amount between colors and charging fluctuations, and non-magnetic using the full-color electrostatic charge developing toner kit A full color toner kit for one-component development could be provided.

  The present invention is a full-color electrostatic charge developing toner kit comprising a yellow toner, a magenta toner, a cyan toner, and a black toner containing at least a binder resin, a colorant, and a wax, wherein the yellow toner contains an azo pigment as a colorant, The magenta toner contains an azo pigment and a quinacridone pigment as colorants, the cyan toner contains a phthalocyanine pigment as a colorant, and the black toner contains acidic carbon black having a pH of 7 or less. Features.

  Yellow toner is preferably used as a colorant. I. Pigment Yellow 74, and the magenta toner is preferably C.I. I. Pigment red 48: 3 and C.I. I. Pigment Red 122 and cyan toner as a colorant, preferably C.I. I. Pigment Blue 15: 3, and the black toner preferably contains acidic carbon black having a pH of 2 to 5 as a colorant.

  In a full color electrostatic charge developing toner kit combining these toners, the difference in color of the toner base charge amount is small, so that a long-term beautiful image can be obtained without widening the difference in color of the charging performance even after the endurance. It becomes possible. In addition, the following can be used as a pigment.

  Examples of azo yellow pigments used for producing yellow toner particles are shown below. The azo pigment is a general term for pigments having —N═N— (azo bond) in the molecule. For example, C.I. I. Pigment orange 13, C.I. I. Pigment orange 16, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. And CI Pigment Yellow 166.

  Examples of azo-based magenta pigments used in the production of magenta toner particles include C.I. I. Pigment red 3, C.I. I. Pigment red 31, C.I. I. Pigment red 41, C.I. I. Pigment red 48: 1-4, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 238, C.I. I. And CI Pigment Red 269.

  Examples of quinacridone-based magenta pigments used in the production of magenta toner particles include C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 207, C.I. I. Pigment violet 19 and the like.

  Examples of the phthalocyanine cyan pigment used for the production of cyan toner particles include C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16 or the like.

  For the production of black toner particles, acidic carbon black having a pH of 1 or more and less than 7, preferably pH 1-6, more preferably pH 2-5 is used. The pH of carbon black is the pH value of a suspension in which carbon black is dispersed in pure water. By containing carbon black having the above pH, it is possible to improve the charge rising characteristics including the charge amount distribution and the stability of the charge amount during repeated use. When neutral or alkaline carbon black having a pH of 7 or more is used, the above-described excellent charge rise property and charge stability over time cannot be obtained.

  The above-mentioned pigments can be used alone or in combination as desired. I. Pigment Yellow 74 as yellow toner, C.I. I. Pigment red 48: 3 and C.I. I. Pigment Red 122 as magenta toner, C.I. I. It is particularly preferable to use CI Pigment Blue 15: 3 for the cyan toner and acidic carbon black having a pH of 2 to 5 for the black toner.

  Next, materials used in the toner according to the present invention will be described.

"resin"
As the polymerizable monomer constituting the resin, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decyl Styrene, styrene derivatives such as pn-dodecylstyrene, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, methacrylic acid 2-ethylhexyl, stearyl methacrylate, lauryl methacrylate Methacrylic acid ester derivatives such as phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, acrylic N-octyl acid, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, acrylic ester derivatives such as phenyl acrylate, olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, fluorine Halogenated vinyls such as vinyl fluoride and vinylidene fluoride, vinyl esters such as vinyl propionate, vinyl acetate and vinyl benzoate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone, N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone, vinyl compounds such as vinyl naphthalene and vinyl pyridine, There are acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. These vinyl monomers can be used alone or in combination.

  Further, it is more preferable to use a combination of monomers having an ionic dissociation group as the polymerizable monomer constituting the resin. For example, it has a substituent such as a carboxyl group, a sulfonic acid group, a phosphoric acid group as a constituent group of the monomer, specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumar Acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrene sulfonic acid, allyl sulfosuccinic acid, 2-acrylamido-2-methylpropane sulfonic acid, acid phosphooxyethyl methacrylate, 3-chloro-2-acid phosphooxy And propyl methacrylate.

  Furthermore, polyfunctionality such as divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, etc. It is also possible to use a crosslinkable resin by using a functional vinyl.

  These polymerizable monomers can be polymerized using a radical polymerization initiator. In this case, an oil-soluble polymerization initiator can be used in the suspension polymerization method. Examples of the oil-soluble polymerization initiator include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile). ), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, Cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis (4,4-t- Butylperoxycyclohexyl) propane, tris (t Butyl peroxy) triazine peroxide polymerization initiator or a peroxide, such as and the like polymeric initiator having a side chain.

  Moreover, when using an emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, hydrogen peroxide and the like.

  In order to adjust the molecular weight of the resin, a commonly used chain transfer agent can be used. The chain transfer agent used is not particularly limited. For example, mercaptans such as octyl mercaptan, dodecyl mercaptan, t-dodecyl mercaptan, mercaptopropionate such as n-octyl-3-mercaptopropionate, terpinolene, Carbon tetrabromide and α-methylstyrene dimer are used.

  The surfactant that can be used when emulsion polymerization is performed using the radical polymerizable monomer is not particularly limited, but the following ionic surfactants are preferably used.

  Examples of ionic surfactants include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol-6 Sodium sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sodium sulfonate, etc.), sulfuric acid Ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearic acid) Potassium, calcium oleate), and the like.

  Nonionic surfactants can also be used. Specifically, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, sorbitan ester Polymerization may be carried out in combination with the ionic surfactant described above as required.

  In the present invention, these are mainly used as an emulsifier at the time of emulsion polymerization, but may be used for other processes or purposes, for example, as a dispersing agent for associated particles.

"Release agent"
In the present invention, it is preferable that a release agent (hereinafter also referred to as wax) is contained in the toner in order to impart appropriate release properties to the toner and prevent the occurrence of offset. The mold release agent preferably has a melting point of 40 to 150 ° C, more preferably 50 to 110 ° C.

  By having a melting point within the above range, it has been confirmed that good fixability can be obtained and good offset resistance and durability can be obtained even when the fixing temperature is set to a low temperature.

  The melting point of the release agent can be determined by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant rate of temperature rise, for example, (10 ° C./min) is defined as the melting point.

  Examples of the release agent that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, and fatty acid ester wax. Partially saponified fatty acid ester wax, silicon varnish, higher alcohol and carnauba wax are preferably used.

  In the present invention, ester compounds represented by the following general formula are particularly preferred.

R _1- (OCO-R ₂ ) _n
In formula, n is an integer of 1-4, Preferably it is 2-4, More preferably, it is 3-4, More preferably, it is 4. R ₁ and R ₂ each represents a hydrocarbon group that may have a substituent. R ₁ has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ₂ has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

  In the present invention, the toner may be formed using a dispersion obtained by heating and stirring in an aqueous medium using a surfactant or a dispersant described later as a release agent. In this case, for example, it is possible to prepare a wax emulsion prepared by emulsifying the release agent, and add it together with the colorant dispersion when the resin particles are aggregated.

<Charge control agent>
The toner according to the present invention may contain a charge control agent as necessary. As the charge control agent, all known ones can be used, and examples thereof include a fluorine-based activator, a salicylic acid metal salt, a metal salt of a salicylic acid derivative, and the like. Specifically, a nigrosine dye Bontron 03, a quaternary ammonium, and the like. Bontron P-51 of the salt, Bontron S-34 of the azo metal complex compound, E-82 of the oxynaphthoic acid metal complex, E-84 of the salicylic acid metal complex, E-89 of the phenol condensate (above, Orient TP-302 of quaternary ammonium salt molybdenum complex (made by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, Copy charge of quaternary ammonium salt NEGVP2036, copy charge NX VP434 (Above, manufactured by Hoechst), LRA-901, LR-147 (made by Nippon Carlit Co., Ltd.) which is a boron complex, and other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt. It is done. Among these, azo metal complex compounds are preferable, and for example, those disclosed in paragraphs 0009 to 0012 of JP-A-2002-351150 are preferably used.

  In the present invention, the amount of charge control agent used is determined by the type of resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not limited in any way. However, it is preferably used in the range of 0.1 to 2 parts by mass with respect to 100 parts by mass of the resin. Preferably the range of 0.2-5 mass parts is good.

  In the present invention, a charge control agent is preferably contained in the vicinity of the toner surface. That is, by containing the toner in the vicinity of the toner surface, it is possible to effectively impart chargeability to the toner and to ensure that the toner fluidity is contained by not containing the charge control agent on the toner surface.

  As a specific content method, for example, there is a method of controlling the amount of the charge control agent added to the resin particles constituting the toner. That is, a method in which a large amount of charge control agent is added to the resin particles constituting the vicinity of the toner surface and the resin particles are aggregated so as to form the toner surface with resin particles to which no charge control agent is added, An example is a method in which resin particles containing a control agent are aggregated and then encapsulated with a resin component not containing a charge control agent on the surface of the aggregated particles.

  As a method of containing the resin particles, the dispersion diameter is adjusted by kneading with the resin. When it is detached, it may be added to the aqueous phase side and incorporated into the toner during the aggregation process or drying process.

<External additive>
The toner according to the present invention is preferably prepared by adding a small-diameter external additive and a large-diameter external additive. The addition of developer fluidity with a small-diameter external additive and transferability with a large-diameter external additive have the effect of suppressing the occurrence of image defects when a low-temperature fixing toner is used over a long period of time. is there.

  As the small-diameter external additive, those having a number average primary particle diameter of 10 to 60 nm are preferable, and specific examples thereof include silica, titania, alumina, strontium titanate particles and the like.

  Specific examples of the silica particles include R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150, H-200 manufactured by Hoechst. And TS-720, TS-530, TS-610, H-5, and MS-5 manufactured by Cabot Corporation.

  Examples of titania fine particles include T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, JA-1, and Fuji Titanium manufactured by Teika. TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T made by the company, IT-S, IT-OA, IT-OB, IT-OC made by Idemitsu Kosan Co., Ltd., etc. are mentioned.

  Examples of the alumina fine particles include RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd. and TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the large-diameter external additive, those having a number average primary particle diameter of 80 nm to 1 μm are preferable, and specific examples include general lubricants, organic fine particles, and inorganic fine particles having the above particle diameter.

  Examples of the lubricant include metal salts of higher fatty acids. Specific examples of the metal salts of such higher fatty acids include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, and the like; zinc oleate, manganese oleate, iron oleate, olein Oleic acid metal salts such as acid copper and magnesium oleate; palmitate metal salts such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; linoleic acid metal salts such as zinc linoleate and calcium linoleate; ricinol Examples include ricinoleic acid metal salts such as zinc acid and calcium ricinoleate.

  Examples of the organic fine particles include particles such as polystyrene, polymethyl methacrylate, styrene-methyl methacrylate copolymer, benzoguanamine, and melamine.

  As the inorganic fine particles having a large particle diameter, a dope such as titanium-doped silica is preferably used, and these inorganic fine particles are preferably hydrophobized with a silane coupling agent, a titanium coupling agent, or the like.

  The addition amount of the external additive is preferably 0.1 to 10.0% by mass with respect to the whole toner. As a method for adding the external additive, various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer can be used.

<Developer>
The toner according to the present invention can be used as a one-component developer, a non-magnetic one-component developer, or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be used. be able to. Further, it can be mixed with a carrier and used as a two-component developer. In this case, conventionally known materials represented by iron-containing magnetic particles such as iron, ferrite, and magnetite can be used as the magnetic particles of the carrier, but ferrite particles or magnetite particles are particularly preferable. The volume average particle diameter of the carrier is preferably 15 to 100 μm, more preferably 20 to 80 μm.

  The median diameter D50 of the volume-based distribution of the carrier can be measured using a laser diffraction particle size distribution measuring device “HELOS” (manufactured by SYMPATEC).

  The carrier is preferably a coating carrier in which magnetic particles are further coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicon resin, ester resin, fluorine-containing polymer resin, or the like is used. In addition, the resin for constituting the resin-dispersed carrier is not particularly limited, and a known resin can be used. For example, a styrene-acrylic resin, a polyester resin, a fluorine resin, a phenol resin, or the like is used. be able to.

  The mixing ratio of the carrier and the toner is preferably in the range of carrier: toner = 1: 1 to 50: 1 by mass ratio.

  Next, a toner manufacturing method according to the present invention will be described.

  The toner production method is preferably a method of producing a chemical toner that can easily control the particle size, particle size distribution, and shape factor of the release agent in the toner. The method for producing the chemical toner is not particularly limited, and examples thereof include a method in which resin particles are formed by an emulsion polymerization method, and the resin particles are assembled to produce a toner, and a method in which a toner is produced by suspension polymerization. A specific example of a production method in which resin particles are formed by an emulsion polymerization method and the resin particles are associated will be described later.

  Hereinafter, an example of a toner production method using an emulsion polymerization association method will be described in detail.

(1) Dissolution / dispersion step for dissolving or dispersing the release agent in the radical polymerizable monomer (2) Polymerization step for preparing a dispersion of resin particles (3) Resin particles and colorant particles in an aqueous medium Aggregation / fusion process for obtaining aggregated particles by aggregating and fusing (4) Aging the aggregated particles with thermal energy to adjust the shape, and adjusting the particle size, shape, distribution, and shape factor of the release agent, (5) Cooling step for cooling the toner base dispersion liquid (6) Solid-liquid separation of the toner base body from the cooled toner base dispersion liquid and surface activity from the toner base body (7) Drying step for drying the washed toner base (8) Step for adding an external additive.

  Hereinafter, each step will be described.

[Dissolution / dispersion process]
This step is a step of preparing a radical polymerizable monomer solution of the release agent by dissolving or dispersing the release agent in the radical polymerizable monomer.

[Polymerization process]
In a preferred example of this polymerization step, a radical polymerizable monomer solution in which the release agent is dissolved or dispersed in an aqueous medium containing a surfactant is added, and mechanical energy is applied to form droplets. Then, the polymerization reaction is advanced in the droplets by radicals from the water-soluble radical polymerization initiator. In addition, you may add the resin particle as a core particle in the said aqueous medium.

  By this polymerization step, resin particles having a release agent, a hydrophilic resin, and a hydrophobic resin are obtained. Such resin particles may be colored particles or non-colored particles. The colored resin particles can be obtained by polymerizing a monomer composition containing a colorant. In addition, when using uncolored resin particles, the dispersion of the colorant particles is added to the dispersion of the resin particles in the fusion / ripening step described later, and the resin particles and the colorant particles are fused. By doing so, a toner base can be obtained.

[Aggregation / fusion process]
In water containing resin particles and colorant particles, a salting-out agent made of an alkali metal salt or alkaline earth metal salt is added as an aggregating agent having a critical aggregation concentration or more, and each particle is agglomerated and fused. To form associated particles. Further, in the aggregation / fusion process, internal additive particles such as release agent particles and charge control agents can be aggregated together with resin particles and colorant particles.

[Aging process]
Aging is preferably performed by thermal energy (heating). Specifically, it is a step of adjusting the shape of the associated particles and adjusting the particle size, distribution and shape of the release agent to form a toner base by heating and stirring the liquid containing the associated particles.

[Cooling process]
This step is a step of cooling the toner base dispersion. As a cooling treatment condition, cooling is performed at a cooling rate of 1 to 20 ° C./min. The cooling treatment method is not particularly limited, and examples thereof include a method of cooling by introducing a refrigerant from the outside of the reaction vessel, and a method of cooling by directly introducing cold water into the reaction system.

[Solid-liquid separation and washing process]
In this solid-liquid separation / washing step, a solid-liquid separation process for solid-liquid separation of the toner base from the dispersion of the toner base cooled to a predetermined temperature in the above-described step, and a solid-liquid separated toner cake (in a wet state) A cleaning process is performed to remove deposits such as a surfactant and a salting-out agent from an aggregate obtained by agglomerating a toner base in a cake form. The filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press or the like.

[Drying process]
This step is a step of drying the washed toner cake to obtain a dried toner base. Examples of dryers used in this process include spray dryers, vacuum freeze dryers, vacuum dryers, etc., stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers It is preferable to use a stirring dryer or the like. The moisture content of the dried toner base is preferably 5% by mass or less, and more preferably 2% by mass or less. In addition, when the toner bases subjected to the drying treatment are aggregated with a weak interparticle attractive force, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

[External process]
This step is a step in which an external additive is mixed with the dried toner base as necessary to produce a toner. As an external additive mixing device, a mechanical mixing device such as a Henschel mixer or a coffee mill can be used.

  The present invention can be applied to any of a toner produced by a pulverization method and a polymerized toner produced by a suspension polymerization and an emulsion association method.

  The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1
(Preparation of resin particle 1 dispersion)
An activator solution in which 7.08 g of an anionic activator (sodium dodecylbenzenesulfonate: SDBS) is dissolved in 2760 g of ion-exchanged water is put into a separable flask equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introduction device. Then, the internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream.

On the other hand, stearyl stearate 72.0g
Styrene 115.1g
n-Butyl acrylate 42.0g
Methacrylic acid 10.9g
Were heated and dissolved at 80 ° C. to prepare a monomer solution. Here, the two heated solutions were mixed and dispersed by a mechanical disperser having a circulation path to produce emulsified particles having a uniform dispersed particle size.

  Next, a solution in which 0.84 g of a polymerization initiator (potassium persulfate: KPS) was dissolved in 200 g of ion-exchanged water was added, and the resin particles were produced by heating and stirring at 80 ° C. for 3 hours. Subsequently, a solution prepared by dissolving 8.00 g of a polymerization initiator (KPS) and 10.0 g of 2-chloroethanol as a water-soluble chain transfer agent in 240 g of ion-exchanged water was added, and after 15 minutes, styrene 383 at 80 ° C. .6 g, a mixed solution of 140.0 g of n-butyl acrylate and 36.4 g of methacrylic acid (second monomer solution) was dropped over 120 minutes. After completion of dropping, the mixture was heated and stirred for 60 minutes and then cooled to 40 ° C. to obtain a dispersion of resin particles. This resin particle dispersion is referred to as “resin particle 1 dispersion”.

(Preparation of yellow colorant dispersion 1)
5 g of anionic surfactant sodium n-dodecyl sulfate was dissolved in 160 g of ion-exchanged water with stirring. While stirring this solution, C.I. I. Pigment Yellow 74 and 20 g were gradually added and dispersed using Claremix (M Technique Co., Ltd.) to give a dispersion of colorant particles having a dispersion diameter of 220 nm (hereinafter referred to as “yellow colorant dispersion”). 1)).

(Preparation of magenta colorant dispersion 1)
In the preparation of the “yellow colorant dispersion 1”, C.I. I. Pigment Yellow 74, 20 g instead of C.I. I. Pigment red 48: 3 and C.I. I. “Magenta colorant dispersion 1” was prepared in the same manner except that 10 g of CI pigment red 122 was used.

(Preparation of Cyan Colorant Dispersion 1)
In the preparation of the “yellow colorant dispersion 1”, C.I. I. Instead of CI Pigment Yellow 74, C.I. I. “Cyan colorant dispersion 1” was prepared in the same manner except that CI Pigment Blue 15: 3 was used.

(Preparation of black colorant dispersion 1)
In the preparation of the “yellow colorant dispersion 1”, C.I. I. Pigment Yellow 74, acid-treated pH 5 C.I. I. “Black colorant dispersion 1” was prepared in the same manner except that CI Pigment Black 7 was used.

<< Preparation of Yellow Toner Particles 1 >>
1500 g of the “resin particle 1 dispersion”, 2000 g of ion-exchanged water, and “yellow colorant dispersion 1” are placed in a 5 L four-necked flask equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device and stirred. . After adjusting to 30 degreeC, 5 mol / L sodium hydroxide aqueous solution was added to this solution, and pH was adjusted to 10.0. Next, an aqueous solution in which 52.6 g of magnesium chloride hexahydrate was dissolved in 72 g of ion-exchanged water was added at 30 ° C. for 10 minutes with stirring. Thereafter, after standing for 3 minutes, temperature increase was started, and the temperature was increased to 90 ° C. in 6 minutes (temperature increase rate = 10 ° C./min).

  In this state, the particle size was measured with “Coulter Counter TA-II” (manufactured by Beckman Coulter), and when the volume-based median diameter reached 6.5 μm, 115 g of sodium chloride was dissolved in 700 g of ion-exchanged water. The particle growth was stopped, and the mixture was further heated and stirred at a liquid temperature of 90 ° C. ± 2 ° C. for 6 hours for fusion. Then, it cooled to 30 degreeC on the conditions of 6 degreeC / min, hydrochloric acid was added, pH was adjusted to 2.0, and stirring was stopped. The produced toner particles were subjected to solid-liquid separation, and washing with ion exchange water was repeated four times (the amount of ion exchange water was 15 L), and then dried with 40 ° C. warm air to obtain yellow toner particles. This is designated as “yellow toner particles 1”.

<< Preparation of Magenta Toner Particles 1 >>
“Magenta toner particles 1” were obtained in the same manner as in the preparation of “yellow toner particles 1” except that “magenta colorant dispersion 1” was used instead of “yellow colorant dispersion 1”.

<< Preparation of Cyan Toner Particles 1 >>
“Cyan toner particles 1” were obtained in the same manner as in the production of “yellow toner particles 1” except that “cyan colorant dispersion 1” was used instead of “yellow colorant dispersion 1”.

<< Preparation of Black Toner Particles 1 >>
“Black toner particles 1” were obtained in the same manner as in the production of “yellow toner particles 1” except that “black colorant dispersion 1” was used instead of “yellow colorant dispersion 1”.

[Preparation of Toner Kit 1]
The “yellow toner particles 1”, “magenta toner particles 1”, “cyan toner particles 1”, and “black toner particles 1” were each subjected to external addition processing by the following method. First, 1% by mass of hydrophobic silica (number average primary particle size = 12 nm, degree of hydrophobicity = 68) and 1% by mass of hydrophobic titanium oxide (number average primary particle size = 20 nm, degree of hydrophobicity = 63) are added. , “Henschel mixer” (manufactured by Mitsui Miike Chemical Co., Ltd.). Thereafter, coarse particles were removed using a sieve having an opening of 45 μm. A set of “yellow toner particles 1”, “magenta toner particles 1”, “cyan toner particles 1”, and “black toner particles 1” subjected to the above processing is referred to as “toner kit 1”.

Example 2
(Preparation of yellow colorant dispersion 2)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Instead of CI Pigment Yellow 74, C.I. I. “Yellow colorant dispersion 2” was prepared in the same manner except that CI Pigment Yellow 83 was used.

(Preparation of magenta colorant dispersion 2)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Pigment Yellow 74, 20 g instead of C.I. I. Pigment red 185 and C.I. I. “Magenta colorant dispersion 2” was prepared in the same manner except that 10 g of CI pigment red 19 was used.

(Preparation of Cyan Colorant Dispersion 2)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Instead of CI Pigment Yellow 74, C.I. I. “Cyan colorant dispersion 2” was prepared in the same manner except that CI Pigment Blue 16 was used.

<< Preparation of Yellow Toner Particles 2 >>
In the production of “yellow toner particles 1” in Example 1, “yellow toner particles 2” were obtained in the same manner except that “yellow colorant dispersion 2” was used instead of “yellow colorant dispersion 1”. It was.

<< Preparation of Magenta Toner Particles 2 >>
In the production of “yellow toner particles 1” in Example 1, “magenta toner particles 2” were obtained in the same manner except that “magenta colorant dispersion 2” was used instead of “yellow colorant dispersion 1”. It was.

<< Preparation of Cyan Toner Particles 2 >>
In the production of “yellow toner particles 1” in Example 1, “cyan toner particles 2” was obtained in the same manner except that “cyan colorant dispersion 2” was used instead of “yellow colorant dispersion 1”. It was.

[Preparation of Toner Kit 2]
In the production of “toner kit 1” of Example 1, “yellow toner particle 2”, “magenta toner particle 2”, “magenta toner particle 1” instead of “yellow toner particle 1”, “magenta toner particle 1”, “cyan toner particle 1”, “ “Toner kit 2” was prepared in the same manner except that “Cyan toner particles 2” were used.

Comparative Example 1
(Preparation of yellow colorant dispersion 3)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Instead of CI Pigment Yellow 74, C.I. I. “Yellow colorant dispersion 3” was prepared in the same manner except that CI Pigment Yellow 117 was used.

(Preparation of magenta colorant dispersion 3)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Instead of CI Pigment Yellow 74, C.I. I. “Magenta colorant dispersion 3” was prepared in the same manner except that CI Pigment Red 185 was used.

(Preparation of Cyan Colorant Dispersion 3)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Instead of CI Pigment Yellow 74, C.I. I. “Cyan colorant dispersion 3” was prepared in the same manner except that CI Pigment Blue 25 was used.

(Preparation of black colorant dispersion 2)
In the preparation of “Yellow Colorant Dispersion 1” in Example 1, C.I. I. Pigment Yellow 74 instead of basified C.I. I. “Black colorant dispersion 2” was prepared in the same manner except that CI Pigment Black 7 was used.

<< Preparation of Yellow Toner Particles 3 >>
In the production of “yellow toner particles 1” of Example 1, “yellow toner particles 3” were obtained in the same manner except that “yellow colorant dispersion 3” was used instead of “yellow colorant dispersion 1”. It was.

<< Preparation of magenta toner particles 3 >>
In the production of “yellow toner particles 1” in Example 1, “magenta toner particles 3” were obtained in the same manner except that “magenta colorant dispersion 3” was used instead of “yellow colorant dispersion 1”. It was.

<< Preparation of Cyan Toner Particles 3 >>
“Cyan toner particles 3” were obtained in the same manner as in the preparation of “yellow toner particles 1” except that “cyan colorant dispersion 3” was used instead of “yellow colorant dispersion 1”.

<< Preparation of Black Toner Particles 2 >>
In the production of “yellow toner particles 1” in Example 1, “black toner particles 2” were obtained in the same manner except that “black colorant dispersion 2” was used instead of “yellow colorant dispersion 1”. It was.

[Preparation of Toner Kit 3]
In the production of “toner kit 1” in Example 1, “yellow toner particle 3”, “yellow toner particle 1”, “magenta toner particle 1”, “cyan toner particle 1”, “black toner particle 1” instead of “yellow toner particle 1”, “ “Toner kit 3” was prepared in the same manner except that magenta toner particles 3 ”,“ cyan toner particles 3 ”, and“ black toner particles 2 ”were used.

Comparative Example 2
[Preparation of Toner Kit 4]
“Toner Kit 4” was prepared in the same manner as in “Toner Kit 1” in Example 1, except that “Yellow Toner Particle 3” was used instead of “Yellow Toner Particle 1”.

Comparative Example 3
[Preparation of Toner Kit 5]
In the production of “toner kit 1” of Example 1, “yellow toner particle 2”, “magenta toner particle 1”, “cyan toner particle 1”, “black toner particle 1” instead of “yellow toner particle 1”, “magenta toner particle 1”, “ “Toner kit 5” was prepared in the same manner except that magenta toner particles 2 ”,“ cyan toner particles 3 ”, and“ black toner particles 2 ”were used.

Comparative Example 4
[Preparation of Toner Kit 6]
In the production of “toner kit 1” of Example 1, “yellow toner particle 3”, “magenta toner particle 3”, “magenta toner particle 1” instead of “yellow toner particle 1”, “magenta toner particle 1” and “cyan toner particle 1” A “toner kit 6” was produced in the same manner except that the “cyan toner particles 3” were used.

Comparative Example 5
[Preparation of Toner Kit 7]
In the production of “toner kit 1” in Example 1, “magenta toner particles 3” and “black toner particles 2” were used in place of “magenta toner particles 1” and “black toner particles 1”. “Toner kit 7” was prepared.

[Evaluation]
The following items were evaluated for the “toner kits 1 to 7” produced above. As an evaluation machine, a commercially available printer magiccolor 2300DL (manufactured by Konica Minolta Business Technologies, Inc.) employing an electrophotographic method was used.

(Charge amount, color difference)
The charge amount of the toner was evaluated by the following method using a charge amount measuring device “Blow-off type TB-200” (manufactured by Toshiba Corporation). First, it is blown with nitrogen gas for 10 seconds under a blow pressure of 4.9 × 10 ⁴ Pa with a blow-off charge measuring device (for example, TB-200: manufactured by Toshiba Chemical Co.) equipped with a 400 mesh stainless steel screen. The charge amount (μC / g) is calculated by dividing the measured charge by the flying toner mass.

  Regarding the inter-color difference in the initial charge amount, the case of less than 10 μC / g was evaluated as “◎”, 10-20 μC / g was evaluated as “◯”, and the case where the above was not satisfied was evaluated as “X”.

(Charge fluctuation)
Further, the fluctuation range from the initial charge amount after printing 3000 sheets is less than 10 μC / g for all colors, ◯, the one having 10-20 μC / g is marked with ◯, and the one not satisfying the above is marked with ×. .

(Image quality)
Visual evaluation was performed on the image after printing 3000 sheets. ◎ If it is inferior to the initial image in any environment ◎, if it can not be visually discerned, but slightly minor image failure occurs when observed with a loupe, if there is an obvious image defect Was marked with x.

  From Table 2, it can be seen that the toner kit for developing a full color electrostatic charge according to the present invention has little difference in charge amount between colors and charge fluctuation and good image quality.

Claims (2)

In a full color electrostatic charge developing toner kit comprising a yellow toner, a magenta toner, a cyan toner and a black toner containing at least a binder resin, a colorant and a wax, the yellow toner contains an azo pigment as a colorant, and the magenta toner A full color characterized in that it contains an azo pigment and a quinacridone pigment as colorants, the cyan toner contains a phthalocyanine pigment as a colorant, and the black toner contains acidic carbon black having a pH of 7 or less as a colorant. Toner kit for electrostatic charge development. A full-color toner kit for non-magnetic one-component development, wherein the toner kit for full-color electrostatic charge development according to claim 1 is used.