WO1998025186A1 - Procede pour produire un toner polymere - Google Patents

Procede pour produire un toner polymere Download PDF

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Publication number
WO1998025186A1
WO1998025186A1 PCT/JP1997/004476 JP9704476W WO9825186A1 WO 1998025186 A1 WO1998025186 A1 WO 1998025186A1 JP 9704476 W JP9704476 W JP 9704476W WO 9825186 A1 WO9825186 A1 WO 9825186A1
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WIPO (PCT)
Prior art keywords
core
polymerizable monomer
toner
polymer
shell
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PCT/JP1997/004476
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English (en)
Japanese (ja)
Inventor
Nobuyasu Ota
Jun Hasegawa
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Nippon Zeon Co., Ltd.
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Publication date
Application filed by Nippon Zeon Co., Ltd. filed Critical Nippon Zeon Co., Ltd.
Publication of WO1998025186A1 publication Critical patent/WO1998025186A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/093—Encapsulated toner particles
    • G03G9/09392—Preparation thereof

Definitions

  • the present invention relates to a method for producing a polymerized toner, and more particularly, to a method for producing a polymerized toner suitable as an electrostatic image developing toner formed by electrophotography, electrostatic recording, or the like.
  • the present invention relates to a production method, a polymerization toner obtained by the production method, an image forming method using the polymerization toner, and an image forming apparatus containing the polymerization toner.
  • a two-component developer composed of toner and carrier particles is used.
  • the one-component developer includes a magnetic one-component developer containing magnetic powder and a non-magnetic one-component developer containing no magnetic powder.
  • a fluidizing agent such as colloidal force is often added independently to enhance the fluidity of the toner.
  • the toner generally, colored particles formed by dispersing a colorant such as carbon black or other additives in a binder resin and granulating the toner are used.
  • Toner production methods are roughly classified into a pulverization method and a polymerization method.
  • a synthetic resin, a colorant and, if necessary, other additives are melt-mixed, pulverized, and then classified to obtain particles having a desired particle size, thereby obtaining a toner.
  • various additives such as a coloring agent, a polymerization initiator, and, if necessary, a crosslinking agent and a charge controlling agent are added to the polymerizable monomer.
  • a polymerizable monomer composition in which an additive is uniformly dissolved or dispersed is prepared, and then dispersed in an aqueous dispersion medium containing a dispersion stabilizer using a stirrer to obtain a polymerizable monomer composition. Fine droplet particles are formed and then heated to carry out suspension polymerization to obtain toner having a desired particle size (polymerized toner).
  • an electrostatic latent image is substantially formed by toner.
  • an image forming apparatus such as an electrophotographic apparatus and an electrostatic recording apparatus
  • an image is formed on a uniformly charged photoconductor by forming an electrostatic latent image, and toner is attached to the electrostatic latent image.
  • the toner image is transferred to a transfer material such as transfer paper, and the unfixed toner image is then transferred to the toner image by various methods such as heating, pressing, and solvent vapor.
  • Fixed on the transfer material In the fixing process, in many cases, a transfer material on which a toner image has been transferred is passed between a heating roll (fixing roll) and a pressure roll, and the toner is heated and pressed to be fused on the transfer material.
  • the image formed by an image forming apparatus such as an electrophotographic copying machine is required to have higher definition year by year.
  • toner obtained by a pulverizing method has been the mainstream toner used in an image forming apparatus.
  • the pulverization method colored particles having a wide particle size distribution are easily formed. Therefore, in order to obtain satisfactory developing characteristics, it is necessary to classify the pulverized product to adjust the particle size distribution to a somewhat narrower range.
  • the classification itself is complicated and the yield is poor, and the toner yield is greatly reduced.
  • a polymerized toner having a desired particle size and particle size distribution can be obtained without performing pulverization or classification.
  • conventional polymerized toners have been used in recent years to speed up copying, to achieve full color, and to save energy. There was a problem that it was not possible to sufficiently respond to demands such as energy consumption.
  • the process that consumes energy is the fixing process after transferring the toner from the photoreceptor onto a transfer material such as transfer paper.
  • a heating roll heated to a temperature of 150 ° C. or higher is generally used to heat and melt the toner and fix the toner on the transfer material. Power is being used. It is required to lower the heating roll temperature from the viewpoint of energy saving. To lower the heating roll temperature, the toner must be able to fix at a lower temperature than before. That is, it is necessary to lower the fixing temperature of the toner itself. Using a toner that can fix at a lower temperature than before can reduce the heating roll temperature, but if the heating roll temperature is not so lowered, the fixing time will be shortened It can handle high-speed copying and high-speed printing.
  • the glass transition temperature of the binder resin constituting the toner may be reduced to meet the demands of the image forming apparatus such as energy saving and high-speed copying.
  • the toner is made of a binder resin having a low glass transition temperature
  • the toners may be connected during storage, transportation, or in the toner box of the image forming apparatus. Blocking occurs, making it easy to form aggregates, which is what is called poor storage stability.
  • Methods for lowering the melt viscosity of the toner include methods such as lowering the molecular weight of the binder resin and lowering the glass transition temperature compared to conventional binder resins for toner.
  • the toner is prone to blocking and becomes a poorly preserved toner.
  • Japanese Patent Application Laid-Open No. 3-136665 discloses a polymerizable monomer containing a colorant and a charge control agent.
  • a method of suspension polymerization in the presence of a macromonomer has been proposed.
  • a macromonomer is a relatively long linear molecule having a polymerizable functional group at an end of a molecular chain, for example, an unsaturated group such as a carbon-carbon double bond. According to this method, the macromonomer is incorporated as a monomer unit into the molecular chain of the produced polymer, so that a large number of macromonomers due to long linear molecules in the molecular chain are present.
  • the resulting polymer apparently becomes a high molecular weight polymer due to the entanglement of its branches, so-called physical crosslinking, so that the offset resistance of the polymerized toner is improved.
  • physical cross-linking by the macromonomer component differs from chemical cross-linking using a cross-linking monomer such as divinylbenzene, and has a loose cross-linking structure. The bridging structure is easily broken. Therefore, this polymerization toner is used when fixing using a heating roll. Is excellent in fixing property because it is easily melted. However, in the case of this polymerized toner, aggregation of the toner easily occurs during storage, and the storage stability is not satisfactory.
  • the conventional methods for lowering the fixing temperature of toner and improving the uniform melting property improve the fixing property of the obtained toner, but decrease the storage stability. Will occur.
  • a toner composed of a binder resin with a low glass transition temperature is coated with a polymer with a high glass transition temperature to prevent A so-called capsule-type toner, which solves the problem of preservation by improving the storage property, has been proposed.
  • Japanese Patent Application Laid-Open No. 60-173552 discloses a method of manufacturing a toner by using a jitter mill device on a surface of a spherical core particle having a fine particle diameter.
  • a method of forming a coating layer composed of a colorant or magnetic particles or a conductive agent and a binder resin As the core particles, a thermoplastic plastic transparent resin such as an acrylate resin or a styrene resin is used.
  • the gazette reports that this method provides a multilayer toner having excellent fluidity and improved functionality.
  • this method when nuclear particles having a low glass transition temperature are used, the nuclear particles themselves tend to aggregate.
  • the thickness of the binder resin to be attached to the core particles tends to be large. Therefore, in this method, it is difficult to obtain a toner having improved fixability and uniform melting property while maintaining storage stability.
  • Japanese Unexamined Patent Application Publication No. 2-2595967 discloses a cross-linking prepared by suspension polymerization in a solution in which a polymer for forcepsing, a charge controlling agent and a release agent are dissolved in an organic solvent. After the toner particles are added, a poor solvent is added, and the surface of the bridge toner particles is charged with a capsule containing a charge controlling agent and a release agent.
  • a method for producing an electrophotographic toner forming a coalescing coating has been proposed. However, in this method, since the solubility of the encapsulating polymer is reduced by dropping the poor solvent and the polymer is precipitated on the surface of the crosslinked toner particles, it is difficult to obtain spherical particles. According to this method, the capsule wall formed on the surface of the crosslinked toner particles is not uniform in thickness and relatively thick. As a result, the effect of improving the developing property and the fixing property is not sufficient.
  • Japanese Patent Application Laid-Open No. 57-45558 discloses that the core particles formed by polymerization are mixed and dispersed in a 1 to 40% by weight aqueous solution of a latex, and then the aqueous solution is dissolved.
  • a method for producing a toner for electrostatic image development in which an inorganic salt is added and a coating layer of fine particles obtained by emulsion polymerization is formed on the surface of nucleus particles.
  • the charging characteristics of the toner are largely dependent on the environment due to the effect of a surfactant or an inorganic salt remaining on the fine particles, and the charging is reduced particularly under conditions of high temperature and high humidity. Had the disadvantage of doing so.
  • Japanese Patent Application Laid-Open No. 61-118578 discloses a suspension particle of a composition containing a vinyl monomer, a polymerization initiator and a colorant to obtain core particles.
  • a vinyl monomer which gives a polymer having hydrophilicity equal to or higher than that of the resin contained in the core particles and having a glass transition temperature higher than the glass transition temperature of the resin
  • a method for producing a polymer in which a body is polymerized to form a shell is adsorbed and grown on the core particles, so that the vinyl monomer absorbed into the core particles is polymerized to form a clear core.
  • Japanese Patent Application Laid-Open No. 7-128908 discloses that a monomer composition containing a polymerizable monomer, a colorant, and a releasing agent is directly subjected to suspension polymerization in an aqueous dispersion medium.
  • the mold release agent is contained in an amount of 10 to 40 parts by weight based on 100 parts by weight of the polymerizable monomer, and the surface of the toner is released after the polymerization process is completed.
  • a toner production method including a step of removing an agent is disclosed.
  • An object of the present invention is to have a low fixing temperature and a uniform melting property, excellent storage stability (blocking resistance), a narrow particle size distribution, and an environmental dependence of the charge amount.
  • An object of the present invention is to provide a method for producing a polymerized toner, which is small in size and hard to cause fogging and decrease in print density.
  • Another object of the present invention is to provide a method for producing a polymer toner capable of coping with high-speed copying and printing, achieving full color, and saving energy.
  • an object of the present invention is to provide a polymer capable of forming a toner image having excellent transparency (0 HP transmittance) when printed on a 0 HP sheet and fixed.
  • An object of the present invention is to provide a toner manufacturing method.
  • the present inventors have conducted intensive studies to overcome the problems of the known capsule toner, and as a result, granulated a polymerizable monomer composition for a core by a specific granulation method.
  • the droplets are polymerized to obtain core particles, and a shell capable of forming a polymer having a glass transition temperature higher than the glass transition temperature of the polymer component constituting the core particles in the presence of the core particles. It has been found that the above object can be achieved by a polymerized toner obtained by polymerizing a polymerizable monomer for use, and the present invention has been completed based on this finding.
  • a core polymerizable monomer containing at least a core polymerizable monomer and a colorant in an aqueous dispersion medium containing a dispersion stabilizer;
  • the body composition is passed through a gap between a rotor that rotates at a high speed and a stator that surrounds the rotor and has small holes or comb teeth, and is granulated.
  • the polymerizable unit for a granulated core is The droplets of the monomer composition are polymerized to obtain core particles.
  • a glass transition temperature higher than the glass transition temperature of the polymer component constituting the core particles is reduced.
  • a polymer having a core-shell type structure in which a polymer comprising a polymer layer covering a core particle is polymerized by polymerizing a polymerizable monomer for a seal capable of forming a polymer having the same Is provided.
  • the polymerizable monomer composition for a core is prepared such that the volume average particle size (dv) is 0.5 to 20 ⁇ ⁇ , the volume average particle size (d ⁇ ) and the number average particle size.
  • the present invention provides a manufacturing method for forming droplets having a ratio (dV / dp) to (dp) of 1 to 1.5.
  • a toner is attached to the surface of the photoreceptor on which the electrostatic latent image is formed to form a visible image, and then the visible image is transferred to a transfer material.
  • An image forming method comprising the steps of: (a) using the core-shell type polymerized toner as a toner as a toner;
  • a photoreceptor a unit for charging the surface of the photoreceptor, a unit for forming an electrostatic latent image on the surface of the photoreceptor, a unit for containing toner, and a photoreceptor for supplying the toner
  • the means for accommodating the toner includes: An image forming apparatus characterized by containing the above-described core-shell type polymerized toner is provided.
  • FIG. 1 is a diagram showing an example of a granulating apparatus used in the present invention.
  • FIG. 2 is a diagram showing an example of another granulating apparatus used in the present invention.
  • FIG. 3 is an enlarged view of a rotor and a stator of the granulating apparatus of FIG. BEST MODE FOR CARRYING OUT THE INVENTION>
  • the polymerized toner obtained by the production method of the present invention is a core-shell (capsule-type) colored polymer obtained by polymerizing a polymerizable monomer for sealing in the presence of core particles. Particles.
  • a polymerizable monomer composition for a core containing a polymerizable monomer for a core and a colorant is granulated in an aqueous dispersion medium containing a dispersion stabilizer to form fine droplets. Then, the droplets are polymerized to prepare core particles.
  • the droplets of the polymerizable monomer composition for a core in an aqueous dispersion medium have a volume flatness.
  • the average particle size (dv) is between 0.1 and 20 ⁇ m, preferably between 0.5 and 10 ⁇ m. If the droplets are too large, the particle size of the polymerized toner will be too large and the resolution of the image will be reduced.
  • the ratio (particle size distribution) of the volume average particle diameter (dv) and the Z number average particle diameter (dp) of the droplets of the polymerizable monomer composition for the core is usually from 1 to 3, preferably from 1 to 2. , More preferably from 1 to 1.5. If the particle size distribution of the droplets is wide, the fixing temperature varies, and defects such as fogging and filming occur.
  • the droplet preferably has a particle size distribution in the range of (volume average particle size ⁇ 1 m), preferably at least 50% by volume, more preferably at least 60% by volume. New
  • a rotor that rotates at a high speed a polymerizable monomer composition for a core containing at least a polymerizable monomer for a core and a colorant in an aqueous dispersion medium containing a dispersion stabilizer;
  • a volume average particle diameter Is 0.5 to 20 m, and the ratio (dVZdp) of the volume average particle diameter (dV) to the number average particle diameter (dp) is in the range of 1 to 1.5, quickly and stably.
  • Examples of the coloring agent used in the present invention include: carbon black, titanium white, nig mouth thin base, aniline bull, canoleco oil blue, cromuy ero, ultra rama limbo no. , Orient oil red, phthalocyanine blue, malachite green oxalate, etc .; cobalt, nickel, iron sesquioxide, ferric oxide And magnetic particles such as iron oxide manganese, iron oxide zinc, iron oxide nickel, and the like.
  • the following various coloring agents can be used.
  • Examples of colorants for magnetic toners include C.I.Direct Red 1C.I.Direct Red 4C.I. 1 C. I. Basic red 1 C. I. Modern red 30 C. I. Direct blue 1 C. I. Direct blue 1 C.
  • pigments include, for example, graphite, cadmium yellow, mineral fast yellow—, nepray yellow, nefton yellow S N-Zero Yellow G, Permanent Yellow NCG, Tar-Zin Lake, Red-Eyed Lead, Molybdenum Orange, ° —Mont-Orange Orange GTR Pyrazolone Range, Benzene Orange G, Cadmium Red, One Managed Red 4R, Watching Red Canoe Recipes, Salt Rake, Brilliant Carmine 3B, Mangan Purple, Fast Bayolet B, Methyl Bio Retray, Navy Blue, Black Bull , Alkali Blue Lake, Victorious Lake, Phthalion Anneal, Fast Scooter 1, Ind. Rem. BC, Chrom Green, Chromium Oxide, Vigment Green
  • magenta coloring pigments for full color toners include C.I. pigment red 12 3 4 5 6, 7, 8 9 and 10 1 1 1 2 1 3 1 4 1 5 , 16, 17 18, 19, 21 22, 23 30, 31 32, 37 38, 39, 40, 41 48, 49, 50 51 , 5 2 5 3 5 4, 5 5 5 7, 5 8 6 0, 6 3 6 4, 6 8, 8 1, 8 3 8 7 8 8 8 9 9 0 1 1 2 1 1 4, 1 2 2, 1 2 3, 1 6 3, 2 0 2, 2 0 6, 2 7, and
  • magenta dyes examples include CI Solvent Red 1,
  • magenta dyes include, for example, C.I. basic red 1,2,9,12,13,14,15,17,18,22,2 3, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; C.I. , 3, 7, 10, 14, 14, 15, 21, 25, 26, 27, and 28; and other basic dyes.
  • cyan color pigments for full color toners include CI Pigment Blue 1, 2, 3, 15, 16, and 17; CI Butt Bull C.I.A.I.D.B.I.45; and a copper phthalocyanine pigment in which 1 to 5 phthaloimidmethyl groups are substituted on a phthalocyanine skeleton.
  • yellow color pigments for full color toners include C.I. pigmentation yellow 1, 2, 3, 4, 5, 6, 7, 10, 10, 11, and 12 , 13, 14, 15, 16, 17, 23, 65, 73, 83, 138, and 180; C.I. , And 20; and the like.
  • dyes and pigments are the core polymerizable monomers 100 It is usually used in a proportion of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, relative to parts by weight.
  • the magnetic particles are generally used in an amount of 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymerizable monomer for core.
  • the polymerizable monomer for a core used in the present invention has a glass transition temperature of 80 ° C or less, preferably 10 to 70 ° C, more preferably 20 to 60 ° C. It can form a polymer.
  • the core polymerizable monomers can be used alone or in combination of two or more. If the polymerizable monomer for the core is capable of forming a glass transition temperature exceeding 80 ° C., the fixing temperature of the polymer toner will increase, the 0 HP permeability will decrease, and copying and copying will fail. It is not suitable for high-speed printing.
  • the glass transition temperature (T g) of a polymer is a calculated value (referred to as calculated T g) that is calculated according to the type of monomer used and the proportion used.
  • T g the Tg of a homopolymer formed from the monomer is defined as the Tg of the polymer in the present invention.
  • the monomer has a Tg of 100 It is said to form a polymer of ° c.
  • the Tg of the copolymer is determined according to the type of the monomer used and the usage ratio. calculate. For example, when 78% by weight of styrene and 22% by weight of n-butyl acrylate are used as monomers, styrene-n-butyl acrylate formed at this monomer ratio is used. Since the Tg of the monocopolymer is 50 ° C, this monomer is said to form a polymer having a Tg of 50 ° C.
  • a core capable of forming a polymer having a glass transition temperature of 80 ° C. or lower ⁇ Polymerizable monomer for use '' means that when multiple monomers are used, each of the monomers must form a polymer with a Tg of 80 ° C or less. It does not mean When one type of monomer is used, the homopolymer formed from the monomer must have a Tg of 80 ° C or less. However, when two or more types of monomers are used, it is sufficient that the Tg of the copolymer formed from the monomer mixture is 80 ° C or lower, and the monomer alone may be used. Polymers having a Tg of more than 80 ° C may be included.
  • the homopolymer of styrene has a Tg of 100 ° C., but the styrene is converted to a monomer that forms a low Tg polymer (eg, n-butyl acrylate).
  • a polymer having a Tg of 80 ° C or less can be formed by mixing and using styrene
  • styrene is used as the polymerizable monomer for the core. It can be used as a kind of
  • a vinyl monomer is usually used as the polymerizable monomer for the core.
  • the Tg of the polymer is adjusted to a desired range by using various vinyl monomers alone or in combination of two or more.
  • vinyl monomer used in the present invention examples include styrene monomers such as styrene, vinylintoluene, and methinorestyrene; and acrylic acid.
  • Norreic acid 2 ethylhexyl oleate, dimethyl oleate dimethylaminoethyl, acrylonitrile, methacrylonitrile, acrylamide, acrylamide, Derivatives of (meta) acrylinoleic acid such as methyl acrylamide; ethylene, Ethylenically unsaturated monoolefins such as
  • a combination of a styrene monomer and a derivative of (meth) acrylic acid is preferably used as the polymerizable monomer for the core.
  • Preferred examples include styrene and butyl acrylate (ie, n-butyl acrylate), and styrene and 2-ethylethyl acrylate (ie, 2— Ethyl hexyl acrylate).
  • the polymerizable monomer for the core it is preferable to use a crosslinkable monomer together with these vinyl monomers from the viewpoint of improving the storage stability of the polymerized toner.
  • the crosslinkable monomer include aromatic vinyl compounds such as divinylbenzene, divinylnaphthalene, and derivatives thereof; ethylene glycol dimethyl acrylate, and ethylene glycol. Diethylenically unsaturated carboxylic acid esters such as recall dimethacrylate; N, N — divinylaniline, divinyl ethers such as divinyl ether; compounds having three or more vinyl groups And the like.
  • These crosslinkable monomers can be used alone or in combination of two or more.
  • the crosslinkable The monomer may be used in an amount of usually 0.01 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the core polymerizable monomer. Desirable.
  • Macromonomers are relatively long molecules that have a polymerizable functional group at the end of the molecular chain (for example, an unsaturated group such as a carbon-carbon double bond). It is a linear molecule. Since the macromonomer has a vinyl polymerizable functional group at the terminal of the molecular chain, the number average molecular weight is usually from 1,000 to 300,000. Or a polymer is preferred.
  • Examples of the vinyl polymerizable functional group at the terminal of the molecular chain of the macromolecule include an acryloyl group and a methacryloyl group.
  • a methacryloyl group is preferred from the viewpoint of stiffness.
  • the macular monomer used in the present invention has a glass transition temperature higher than the glass transition temperature of the polymer obtained by polymerizing the core polymerizable monomer.
  • the level of T g between the polymer obtained by polymerizing the polymerizable monomer for core and the macromonomer is relative.
  • the macromonomer has a Tg of more than 70 ° C. Should be fine.
  • the core polymerizable monomer forms a polymer having a T g of 20 ° C.
  • the T g of a macromonomer is a value measured with a measuring instrument such as a normal DSC.
  • Examples of the macromonomer used in the present invention include styrene, styrene derivatives, methacrylate ester, acrylate ester, and acrylonitrile. Polymer obtained by polymerizing trinole, methacrylonitrile, etc., alone or in combination of two or more kinds; a macromonomer having a polysiloxane skeleton; Examples thereof include those disclosed on pages 4 to 7 of JP-A-203374. Of these macromonomers, those obtained by polymerizing hydrophilic ones, especially methacrylates or acrylates, alone or in combination of these. The resulting polymer is suitable for the present invention.
  • the amount of the macromonomer used is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, per 100 parts by weight of the polymerizable monomer for the core. And more preferably 0.05 to 1 part by weight. If the amount of the macromonomer used is small, it is difficult to improve the storability and the fixing property in a good balance. As the amount of macromonomer used increases, the fixability tends to decrease.
  • the core particles are preferably obtained by suspension polymerization of a vinyl monomer, a macromonomer, and a crosslinkable monomer as polymerizable components.
  • a polymerization initiator such as a polymerization initiator and a molecular weight regulator for polymerizing droplets of the core polymerizable monomer composition, and various additives such as a release agent and a pigment dispersant are used as cores. It can be mixed with polymerizable monomers for use.
  • radical polymerization initiator examples include potassium persulfate and ammonium persulfate.
  • Persulfates such as gum; 4,4-azobis (41-cyanovaleric acid), dimethyl-22'-azobis (2—methylpropironate), 22—azobis ( 2 — Amidinopropane) dihydrochloride, 22 2 — Azobis — 2 — Methinole N—1, 1 — Bis (hydroxylmethyl) 1 2 — Hydroxyshetylpro Pioamide, 2 2 '-azobis (24-dimethylbenzoylonitrile), 2 2'-azobisuisobutyronitrile, 1,1 'azobis (1-cyclo) Kisa down mosquitoes Norepo two Application Benefits Honoré) of which ⁇ zo compound; main Chiruechiruba one Okishi de, di one t one Puchirupaoki shea de, cetyl 0 - O key sheet de, di click Mi Honoré 0 - O key sheet de
  • oil-soluble radical initiators are preferred, and in particular, the 10-hour half-life temperature is 680 ° C., preferably 658 ° C.
  • An oil-soluble radical initiator selected from organic peroxides having a molecular weight of 250 or less is preferred.
  • t-butylbutyloxy-2-ethylhexanoet has low odor during printing of polymerized toner and low environmental destruction due to odors and other volatile components. Are particularly preferred.
  • the amount of the polymerization initiator to be used is usually 0.0013% by weight based on the aqueous dispersion medium. If the amount of the polymerization initiator used is less than 0.001% by weight, the polymerization rate is low, and if it exceeds 3% by weight, it is not economical.
  • the molecular weight modifier examples include t-decyl mercaptan, n Menolenic butanes such as dodecinolemenolecaptan, n-octylmenolecaptan; halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide; and the like. These molecular weight regulators can be added before or during the polymerization.
  • the molecular weight modifier is generally used in a proportion of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the core polymerizable monomer. .
  • the release agent examples include polyfunctional ester compounds such as pen-ester erythritol tetra-stearate; low-molecular-weight polyethylene, low-molecular-weight polypropylene, and low-molecular-weight. Low molecular weight polyolefins such as polybutylene; paraffin waxes; and the like.
  • a polyfunctional ester compound is preferable, and a polyfunctional ester compound comprising an alcohol having three or more functional groups and a carboxylic acid is particularly preferable.
  • trifunctional or higher polyhydric alcohol examples include aliphatic alcohols such as glycerin, phenol erythritol, pentaglycerol, etc .; Alicyclic alcohols such as sodium, quesole and inositol; aromatic alcohols such as tris (hydroxymethyl) benzene; D —Erylose, L—Arabinose, D—Mannose, D—Galactose, D—Funorectose, L—Ramnose, Sacca Sugars such as rose, maltose, lactose, etc .; sugars such as elitrite, D-traits, Larabit, adonite, xylite, etc. Alcohol; etc. can be mentioned. Of these, pentaerythritol is preferred.
  • Carboxylic acids include, for example, acetic acid, butyric acid, cabronic acid, phenanoic acid, hydropruric acid, perargonic acid, hydroprurinic acid, undecanoic acid, ⁇ , myristic, stearic, margaric, arachidic, cerotic, melicic, eric, brassic Aliphatic carboxylic acids such as acid, sorbic acid, linoleic acid, linolenic acid, behenylic acid, tetratolic acid, xymenic acid; Alicyclics such as hexane carboxylate, hexahydrous sulfonic acid, hexahydroterephthalate, 3,4,5,6-tetrahydro phthalate Carboxylic acid; benzoic acid, toluic acid, cumic acid, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid, Aromatic carboxylic acids such as hemi
  • Aromatic carboxylic acids are more preferred.
  • stearic acid and myristic acid are particularly preferred.
  • the plurality of carboxylic acids bonded to the trifunctional or higher functional alcohol may be different or the same.
  • the difference between the maximum value and the minimum value of the number of carbon atoms in a plurality of carboxylic acids is 9 or less, preferably 5 or less.
  • polyfunctional ester compounds include pentaerythritol tetrastearate, pentaerythritol torelate, mirristate, and glycerol. ⁇ Trial arachinic acid, etc. can be mentioned.
  • the polyfunctional ester compound is preferably one that easily dissolves in the polymerizable monomer.
  • penstrate and pentose erythritol tetrastrate, and pentose erythritol torelate teramistate are preferred. Pentate elimination is particularly preferred. Ordinary resins are ground when mixed with polymerizable monomers.
  • the release agent is used in an amount of usually 0.1 to 40 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polymerizable monomer. If the amount of the release agent is too small, the effect of improving the low-temperature fixing property is small, and if it is too large, the blocking resistance is reduced.
  • Lubricants such as oleic acid and stearic acid; and dispersion aids such as silane-based or titanium-based cutting agents for the purpose of uniform dispersion of the colorant in the core particles. May be used.
  • Such a lubricant or dispersant is generally used in a proportion of about 1100 to 1Z1, based on the weight of the colorant.
  • the polymerization of the droplets of the polymerizable monomer composition for the core is performed in an aqueous medium containing a dispersion stabilizer (also referred to as a dispersant).
  • a dispersion stabilizer also referred to as a dispersant
  • a vinyl monomer, a macromolecule, a crosslinkable monomer, a radical polymerization initiator, a coloring agent, and other additives selected as needed are mixed to form a Paul Miller or the like.
  • a mixed solution (hereinafter, referred to as a raw material liquid) is prepared by dispersing the raw material more uniformly, and then the raw material liquid is poured into an aqueous medium containing a dispersion stabilizer, and a high shear force mixing device is used. After dispersing and granulating into fine droplets, polymerization is usually carried out at a temperature of 30 to 200 ° C.
  • the dispersion stabilizer preferably used in the present invention contains a hardly water-soluble metal compound.
  • poorly water-soluble metal compounds include sulfuric acid Sulfates such as lithium and calcium sulfates; carbonates such as barium carbonate, calcium carbonate and magnesium carbonate; phosphates such as calcium phosphate; aluminum oxide And metal oxides such as titanium oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide.
  • dispersants containing colloids of poorly water-soluble metal hydroxides are preferred because they can narrow the particle size distribution of the polymer particles and improve the sharpness of images. is there.
  • a dispersion stabilizer containing a colloid of a sparingly water-soluble metal hydroxide is suitable for improving the fixing property and the storage stability of the toner. It is.
  • the dispersion stabilizer containing a colloid of a poorly water-soluble metal hydroxide is not limited by its manufacturing method, but can be adjusted by adjusting the pH of an aqueous solution of a water-soluble polyvalent metal compound to 7 or more. Colloids of the resulting poorly water-soluble metal hydroxides, especially colloids of poorly water-soluble metal hydroxides formed by the reaction of a water-soluble polyvalent metal compound with an alkali metal hydroxide in the aqueous phase It is preferable to use a password.
  • the colloid of the poorly water-soluble metal compound used in the present invention has a particle size distribution D 5 () (cumulative value of 50% of the particle size distribution ) of 0.5 // m or less, and D 9 () (90% cumulative value of the number particle size distribution) is preferably 1 m or less.
  • D 5 () cumulative value of 50% of the particle size distribution
  • D 9 () (90% cumulative value of the number particle size distribution) is preferably 1 m or less.
  • the dispersion stabilizer is generally used in a proportion of 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer for core. If this ratio is too small, it is difficult to obtain sufficient polymerization stability, and a polymer aggregate is easily generated. Conversely, if this ratio is too large, the viscosity in the aqueous dispersion medium increases, and the distribution of the polymerized toner particles is unfavorably widened.
  • a dispersion stabilizer containing a water-soluble polymer can be used.
  • the water-soluble polymer include, for example, polyvinyl alcohol, methyl cellulose, gelatin, and the like.
  • it is not necessary to use a surfactant but it can be used in order to stably carry out polymerization within a range where the environmental dependence of the charging characteristics does not become large.
  • the polymerizable monomer composition for a core has a fine particle size by flowing through a gap between a high-speed rotating rotor and a stator surrounding the rotor and having small holes or comb teeth. Into droplets. That is, in the present invention, a granulating apparatus including a rotor and a stator is used for granulating the polymerizable monomer composition for a core.
  • Examples of the rotor include a stirring blade attached to an ordinary stirrer and a comb-shaped ring as shown in FIG.
  • the rotor rotates at high speed.
  • the rotation speed is usually between 4,000 and 25,000 rpm, preferably between 10,000 and 25,000.
  • the rotation speed is the measured value displayed by the rotation sensor.
  • a stator having small holes or comb teeth is used as the stator.
  • the small hole may be a round hole or a slit.
  • Examples of the comb teeth include those having the shape of the stator 102 shown in FIG.
  • the size of the round hole, the width of the slit, or the length (width) in the rotational direction of the comb teeth is usually 0.2 to 10 mm, preferably 0.5 to 5 mm. If the size or width is too wide, it becomes difficult to granulate the liquid particles finely and uniformly, and if it is too narrow, the throughput cannot be increased.
  • the stator is provided so as to surround the outside of the rotor.
  • the size of the gap between the rotor and the stator is usually 0.1 to 1.3 mm, preferably It is 0.2 to 1.0 mm.
  • a specific example of a device having a high-speed rotating rotor and a stator surrounding the rotor and having small holes or comb teeth is CLEAR MIX (c1earmix) manufactured by Aemtechnic Co., Ltd. And Ebara Milda-1 manufactured by EBARA CORPORATION.
  • FIG. 1 is an explanatory diagram showing the structure of the Ebara Milder.
  • the rotor 101 is a ring having comb teeth. This ring rotates at high speed.
  • a stator 102 composed of a ring having comb teeth concentric with the rotor and surrounding the rotor is provided outside the annular rotor 101. The rotor 101 and the stator 102 are combined with a slight gap therebetween due to the difference between the inner and outer diameters.
  • the polymerizable monomer composition for the core dispersed in the aqueous dispersion medium containing the dispersion stabilizer enters the inside of the rotor 101 arranged in the casing from the liquid inlet 103, When flowing from the high-speed rotating rotor 101 to the outer stator 102, the rotor and the stator cause shearing force, collision, pressure fluctuation, and cavitating force. Or, it is ejected into the casing from the gap between the rotor and stator comb teeth under the action of the pottery core. By repeating these actions, droplets having a small particle size and a narrow particle size distribution are formed. The dispersion containing the droplets is discharged from the liquid outlet 104.
  • FIG. 2 and FIG. 3 are diagrams showing the structure of the clear mix.
  • the rotor 201 is a stirring blade that can be rotated at a rotation speed of usually 4,500 to 21,500 rpm.
  • Reference numeral 2 denotes an annular member provided with a number of slit-like small holes.
  • the gap between the rotor and the stator is usually between 0.1 and 1.3 mm.
  • Polymerizable monomer group for core dispersed in aqueous dispersion medium containing dispersion stabilizer The product is supplied to the gap between the rotor 201 and the stator 202 from the liquid inlet 204 shown in FIG.
  • the rotor and stator are surrounded by, for example, a pot of about 500 cc (pressurized vacuum attachment; casing) and a temperature sensor. 06, a cooling jacket 207, and a cooling coil 208 are arranged around it.
  • the supplied mixture is subjected to the action of the shear force, the collision property, the pressure fluctuation, the cavity or the potential core by the rotor and the stator, and from the small hole of the stator into the pot. Spouts.
  • droplets having a small particle size and a narrow particle size distribution are formed.
  • the dispersion containing the droplets is discharged from the liquid outlet 205.
  • the dispersion discharged from the liquid outlet is supplied into the polymerization tank.
  • the amount of the aqueous dispersion medium containing the polymerizable monomer composition for the core to be passed through these granulators is usually 10 to 300 seconds, preferably 30 to 25 seconds, as indicated by the residence time. 0 seconds, more preferably 50 to 240 seconds.
  • the polymerizable monomer composition for core is contained at the liquid inlet of the granulating device.
  • An aqueous dispersion medium is continuously supplied, and after a certain residence time, discharged from a liquid outlet and charged into a polymerization reaction tank, droplets of a polymerizable monomer composition for a core having a certain particle diameter are obtained. It is possible to rapidly and stably prepare an aqueous dispersion medium in which is dispersed.
  • the aqueous dispersion medium containing the polymerizable monomer composition is supplied to a granulation container equipped with a stirrer having a high shearing force, and the mixture is stirred and granulated.
  • a dispersion containing droplets of the polymerizable monomer composition for a core having a desired particle size and particle size distribution is stably supplied in a short time to the polymerization tank.
  • the polymerization conversion in the polymerization step for obtaining the core particles, is usually at least 80%, preferably at least 85%, more preferably at least 90%. If the polymerization conversion rate in this step is less than 80%, a large amount of the core polymerizable monomer remains, so even if the sealing polymerizable monomer is added and polymerized, Since the copolymer of the polymerizable monomer for the shell and the polymerizable monomer for the core covers the surface of the core particles, the Tg difference between the core and the shell is small. The storage stability of the resulting polymerized toner is reduced.
  • the volume average particle size (dv) of the core particles is usually 0.5 to 20 2111, preferably 1 to 10 ⁇ 111. If the core particles are too large, the resolution of the image will decrease.
  • the ratio (particle size distribution) of the volume average particle size (dv) and the Z number average particle size (dp) of the core particles is usually 1.7 or less, preferably 1.5 or less, more preferably 1.5% or less. 1.4 or less.
  • the particle size distribution (dv / cip) of the generated core particles is 1.5 or less, and in many cases, 1.4 or less.
  • a polymerizable monomer for a shell is polymerized in the presence of the core particle to form a polymer layer (sill) on the surface of the core particle.
  • the polymerizable monomer for a seal used in the present invention comprises core particles. It forms a polymer having a glass transition temperature higher than the glass transition temperature of the polymer component.
  • the Tg of the polymer obtained from the polymerizable monomer for core and the Tg of the polymer component constituting the core particles (typically, the Tg of the polymer obtained from the polymerizable monomer for core ) Is relative.
  • the polymerizable monomer for sealing a monomer that forms a polymer having a glass transition temperature exceeding 80 ° C, such as styrene or methyl methacrylate, is usually used. Use each alone or in combination of two or more. However, when the glass transition temperature of the polymer component of the core particle is much lower than 80 ° C, the polymerizable monomer for sealing forms a polymer at 80 ° C or lower. It may be something. It is necessary to set the glass transition temperature of the polymer composed of the polymerizable monomer for sealing so as to be at least higher than the glass transition temperature of the polymer component of the core particles. is there.
  • the glass transition temperature of the polymer obtained from the polymerizable monomer for sealing is usually from 50 to 120 ° C, preferably from 50 to 120 ° C, in order to improve the storage stability of the polymer. It is between 60 and 110 ° C, more preferably between 80 and 105 ° C. If the glass transition temperature of the polymer composed of the polymerizable monomer for sealing is too low, the glass transition temperature is lower than the glass transition temperature of the polymer component constituting the core particles. Even if it is high, storage stability may decrease.
  • the glass transition temperature of the polymer component of the core particles can be expressed by the calculated T g of the polymer formed from the polymerizable monomer for the core in many cases.
  • the difference in glass transition temperature between the polymer composed of the polymerizable monomer for core and the polymer composed of the polymerizable monomer for shell is usually 10 ° C. or more, and is preferably. It is preferably at least 20 ° C, more preferably at least 30 ° C.
  • the polymerizable monomer for shell In the system dispersion medium, it is preferable to carry out suspension polymerization after forming the droplets having the smaller number average particle diameter of the core particles.
  • the particle size of the droplets of the polymerizable monomer for the shell increases, the storage stability tends to decrease.
  • a mixture of the polymerizable monomer for shell and an aqueous dispersion medium is finely dispersed using, for example, an ultrasonic emulsifier. Perform processing. It is preferable to add the aqueous dispersion thus obtained to an aqueous dispersion medium in which core particles are present.
  • the polymerizable monomer for shell is not particularly limited by the solubility in water of 20. However, when the polymerizable monomer for shell having a solubility in water at 20 ° C of 0.1% by weight or more is used, Since the monomer having high solubility in water easily migrates to the surface of the core particle quickly, it is easy to obtain a polymerized toner having good storability.
  • a polymerizable monomer for sealing having a solubility in water at 20 ° C. of less than 0.1% by weight when used, the transfer to the core particles is delayed, and the monomer is formed into fine droplets. It is preferable to polymerize by adding to the reaction system.
  • a polymerizable monomer for a shell having a solubility in water at 20 ° C of less than 0.1% by weight when used, an organic solvent having a solubility in water at 20 ° C of 5% by weight or more is used in the reaction system.
  • the polymerizable monomer for shells is transferred to the core particles quickly, and it becomes easier to obtain a polymerized toner with good storage stability o
  • Monomers for shells having a solubility in water at 20 ° C of less than 0.1% by weight include styrene, butinorea acrylate, and 2-ethylhexyl acrylate. , Ethylene and propylene.
  • Examples of the sealing monomer having a solubility in water at 20 ° C of 0.1% by weight or more include methyl methacrylate and methyl crelate (meta).
  • Organic solvents that are preferably used when a shell monomer having a solubility in water of less than 0.1% by weight are selected from the group consisting of methanol, ethanol and Isopropyl alcohol, n-propyl alcohol, butyl alcohol, etc. ⁇ ; grade alcohol; acetone, methylethyl ketone, etc .; tetrahydrofuran Cyclic ethers such as lan and dioxane; ethenoles such as dimethinolle and tenenoles; aldehydes such as methylethylformaldehyde; and aldehydes such as methylthioformaldehyde.
  • the organic solvent is added in such an amount ratio that the solubility of the polymerizable monomer for shell in a dispersion medium (total amount of water and the organic solvent) becomes 0.1% by weight or more.
  • the amount of the organic solvent used depends on the type of the organic solvent and the type and amount of the polymerizable monomer for the shell, but is usually 0.1 to 50 parts by weight based on 100 parts by weight of the aqueous dispersion medium. Parts, preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight.
  • the order in which the organic solvent and the polymerizable monomer for the shell are added to the reaction system is not particularly limited, but the transfer of the polymerizable monomer for the shell to the core particles is promoted, and the polymerization having good storage stability is performed. In order to make it easier to obtain a toner, it is preferable to add an organic solvent to the reaction system first, and then add a polymerizable monomer for shell.
  • the solubility in water at 20 ° C is firstly determined. 0.1% by weight or more of a monomer is added for polymerization, then an organic solvent is added, and then a monomer having a solubility in water at 20 ° C of less than 0.1% by weight is added. I prefer to do it.
  • This addition method according to this, in order to adjust the fixing temperature of the polymerization toner, the Tg of the polymer obtained from the polymerizable monomer for shell polymerized in the presence of the core particles and the amount of the monomer added were adjusted. It can be controlled appropriately.
  • the polymerizable monomer for a seal is preferably used by mixing a charge control agent.
  • the charge control agent is used to improve the chargeability of the polymerization toner.
  • various positively or negatively chargeable charge control agents can be used.
  • Specific examples of the charge control agent include Nigrosin N 01 (manufactured by Orient Chemical Company), Niguchi Shin EX (manufactured by Orient Chemical Co.), and Spirobra TRH (manufactured by Hodogaya Chemical Co., Ltd.), T-77 (manufactured by Hodogaya Chemical Co., Ltd.), Bottron S-34 (manufactured by Orient Kagaku), Bottron E--8 4 (manufactured by Orient Chemical Co., Ltd.).
  • the charge control agent is used in an amount of usually from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, based on 100 parts by weight of the polymerizable monomer for the shell. Can be
  • a polymerization system for shell is used in a reaction system of the polymerization reaction performed to obtain the core particles.
  • O Polymerization method can be listed o
  • the polymerizable monomer for the shell may be added to the reaction system all at once or continuously or intermittently by using a pump such as a bumper pump. Can be added.
  • a water-soluble radical initiator When adding the polymerizable monomer for shell, it is preferable to add a water-soluble radical initiator in order to easily obtain a polymer toner having a core-shell type structure. New When adding the polymerizable monomer for the shell, When the polymer initiator is added, the water-soluble radial initiator enters near the outer surface of the core particles to which the polymerizable monomer for shell has migrated, and the polymer layer ( Is likely to be formed.
  • water-soluble radical initiator examples include persulfates such as lithium persulfate and ammonium persulfate; 4,4-azobis (4-cyanovaleric acid); 2,2 — Azobis (2 — amidinopropane) dihydrochloride, 2, 2 — azobis 1 2 — methyl N — 1, 1 — bis (hydroxymethyl) 1 2
  • examples thereof include azo-based initiators such as droxyshetyl propioamide; combinations of oil-soluble initiators such as cumoxide and redox catalysts; and the like.
  • the amount of the water-soluble radical initiator used is usually 0.001-1% by weight based on the aqueous medium.
  • the weight ratio of the polymerizable monomer for core to the polymerizable monomer for shell is usually 40 Z 60 to 99. 9 / 0.1, preferably. Is 60 Z 40-99. 5 / 0.5, more preferably 80 / 20-99 Z 1. If the proportion of the polymerizable monomer for the shell is too small, the effect of improving the storage stability is small, and if it is too large, the effect of reducing the fixing temperature and improving the 0 HP permeability is small. You.
  • the polymerized toner of the present invention has a volume average particle size of usually l to 20 ⁇ m, preferably 3 to 15 / m, and a particle size distribution (volume average particle size Z number average particle size).
  • the particle size is usually 1.6 or less, preferably 1.5 or less, and is a spherical particle having a sharp particle size distribution.
  • the polymer toner of the present invention is a polymer particle having a core-shell type structure comprising a core particle and a sealant covering the core particle.
  • the average thickness of the shell is usually from 0.001 to 1.0 / m, preferably from 0.05 to 0.05 / m. ⁇ 0.5 m. If the thickness of the seal is too large, the fixability is reduced, and if it is too thin, the storage stability is reduced.
  • the core particle diameter and shell thickness of the polymerized toner can be observed with an electron microscope, the particle size and shell thickness selected at random from the observation photograph are directly measured. It can be obtained by measuring. If it is difficult to observe the core particles and the shell with an electron microscope, at the stage of forming the core particles, measure the particle size of the core particles in the same manner as described above using an electron microscope.
  • the particle size of the polymer particles is measured by an electron microscope or a coater counter after the core particles are coated with the sealant.
  • the average thickness of the shell can be determined from the measured and the change in particle size before and after coating the shell.
  • the thickness of the shell can be calculated from the particle size of the core particles and the amount of the monomer used to form the shell.
  • the toluene insoluble content is usually 50% by weight or less, preferably 20% by weight or less, and more preferably 10% by weight or less. .
  • the toluene-insoluble matter is defined as the polymer obtained by pressing and solidifying the polymerization toner, placing the polymer in a wire mesh basket of 80 mesh, and heating for 24 hours at room temperature in toluene. After immersion in a basket, the dry weight of the solid matter remaining in the basket was measured and expressed as a percentage by weight relative to the polymer.
  • the ratio of the major axis r1 to the minor axis rs (r1 / rs) of the polymerized toner of the present invention is usually from 1 to 1.25, preferably from 1 to 1.20, more preferably from 1 to 1.20. It is 1 to 1.15. If this ratio is increased, the resolution of the image is reduced, and the friction between the toners is increased when the toners are stored in the toner storage section of the image forming apparatus. However, durability tends to decrease due to peeling of the external additive. (Developer)
  • the polymerized toner of the present invention may be used as it is as a developer, but is usually used as a developer in combination with an external additive such as a fluidizing agent or an abrasive.
  • an external additive such as a fluidizing agent or an abrasive.
  • the external additive adheres to the surface of the polymerized toner.
  • the external additive has a function of increasing the fluidity of the polymerized toner or suppressing the formation of a toner film on a photoreceptor by a polishing action.
  • inorganic particles and organic resin particles are typical.
  • the inorganic particles include silica, aluminum oxide, titanium oxide, zinc oxide, tin oxide, barium titanate, and sodium titanate. And other particles.
  • Organic resin particles include methacrylate polymer particles, acrylate polymer particles, styrene-methacrylate copolymer particles, and styrene-a Core particles in which the core is formed of a styrene polymer and the core is a methacrylate ester polymer and the core is a styrene-type particle. You.
  • inorganic oxide particles are preferable, silica particles are more preferable, and hydrophobically treated silica particles are particularly preferable.
  • the external additive and the polymerized toner are charged into a mixer such as a hen-shell mixer and stirred.
  • the usage amount of the external additive is not particularly limited, but is usually about 0.1 to 6 parts by weight based on 100 parts by weight of the polymerization toner.
  • the fixing temperature is usually from 80 to 180 ° C., preferably from 100 to 150 ° C., and more preferably from 100 to 13 ° C. It can be reduced to a temperature as low as 0 ° C, does not aggregate during storage, and has excellent storage properties. (Image forming device)
  • An image forming apparatus to which the polymerized toner of the present invention is applied includes: a photoconductor, a unit for charging the surface of the photoconductor, a unit for forming an electrostatic latent image on the surface of the photoconductor, a unit for containing toner (developer), It has means for supplying toner and developing the electrostatic latent image on the surface of the photoreceptor to form a toner image, and means for transferring the toner image from the surface of the photoreceptor to a transfer material.
  • FIG. 4 shows a specific example of such an image forming apparatus.
  • a photosensitive drum 1 as a photosensitive member is mounted on the image forming apparatus so as to be rotatable in the direction of arrow A.
  • the photosensitive drum 1 has a photoconductive layer provided on the outer peripheral surface of a conductive support drum.
  • the photoconductive layer is composed of, for example, an organic photoreceptor, a selenium photoreceptor, a zinc oxide photoreceptor, and an amorphous silicon photoreceptor.
  • a charging port 2 as a charging unit
  • a laser-light irradiating device 3 as a latent image forming unit
  • a developing unit as a developing unit
  • a roll 4 a transfer roll 10 as a transfer means, and a cleaning device (not shown) are arranged as required.
  • the charging roll 2 is for uniformly and uniformly charging the surface of the photosensitive drum 1 positively or negatively.
  • the surface of the photosensitive drum 1 is charged by applying a voltage to the charging roll 2 and bringing the charging roll 2 into contact with the surface of the photosensitive drum 1.
  • the charging roll 2 can be replaced by charging means using corona discharge.
  • the laser beam irradiator 3 irradiates the surface of the photosensitive drum 1 with light corresponding to the image signal, and irradiates the uniformly charged surface of the photosensitive drum 1 with a predetermined pattern.
  • As another latent image forming means there is a means composed of an LED array and an optical system.
  • the developing roll 4 is for attaching toner to the electrostatic latent image of the photosensitive drum 1, and in the case of reversal development, the toner is attached only to the light irradiation portion, and in the case of regular development, the toner is attached. Then, a bias voltage is applied between the developing roll 4 and the photosensitive drum 1 so that the toner adheres only to the non-irradiated portion.
  • a developing roll 4 and a supply roll 6 are provided in a casing 9 in which the toner 7 is accommodated.
  • the developing roll 4 is disposed so as to be in close contact with the photosensitive drum 1 so as to be partially in contact therewith, and rotates in the direction B opposite to the photosensitive drum 1.
  • the supply roll 6 comes into contact with the developing roller 4 and rotates in the same direction C as the developing port to supply toner to the outer periphery of the developing port 4.
  • a stirring means (stirring blade) 8 for stirring the toner is installed in the casing 9.
  • a developing roll blade 5 as a layer thickness regulating means is provided. Is arranged.
  • This blade 5 is made of conductive rubber stainless steel and injects electric charge into the toner, so that the voltage of
  • the case 9 of the image forming apparatus accommodates the polymerization toner 7 of the present invention.
  • the polymerization toner 7 may contain an additive such as a fluidizing agent.
  • the polymerized toner of the present invention has a core-shell structure, and the shell of the surface layer is a polymer having a relatively high glass transition temperature. Since it is formed of, the surface has low adhesiveness, and aggregation in the casing 9 during storage is suppressed. Further, since the polymer toner of the present invention has a relatively short particle size distribution, when a toner layer is formed on the developing roll 4, the toner thickness is controlled by the layer thickness regulating means 5. Substantially a single layer can be obtained, thereby improving image reproducibility.
  • the transfer roll 10 is for transferring the toner image formed on the surface of the photosensitive drum 1 by the developing roll 4 onto the transfer material 11.
  • Examples of the transfer material 11 include paper and resin sheets such as 0HP sheets.
  • a corona discharge device or a transfer belt can be used as the transfer means.
  • the toner image transferred onto the transfer material 11 is fixed on the transfer material by fixing means.
  • the fixing means usually comprises a heating means and a pressure bonding means. More specifically, the fixing means is usually composed of a combination of a heating roll (fixing roll) 12 and a pressure roll 13.
  • the transfer material 11 onto which the toner image has been transferred is passed between the heating roll 12 and the pressure roll 13 to melt the toner, and at the same time, is pressed onto the transfer material 11 To fix.
  • the polymerized toner of the present invention is used as the toner, even if the heating temperature by the heating means is low, the toner is easily melted and lightly pressed by the pressure bonding means. Then, the toner becomes smooth and fixed to the surface of the transfer material, enabling high-speed printing or copying. Further, the toner image fixed on the OHP sheet has excellent OHP transparency.
  • the cleaning device is for cleaning the transfer residual toner remaining on the surface of the photosensitive drum 1, and includes, for example, a cleaning blade. Be composed. This cleaning device does not necessarily need to be installed in the case where a method of performing cleaning at the same time as development by the development roll 4 is employed.
  • the image forming apparatus illustrated in FIG. 4 includes, for one photoreceptor, a unit for charging the surface of the photoreceptor, a unit for forming an electrostatic latent image on the surface of the photoreceptor, a unit for containing a superposed toner, It has a means for supplying a polymerization toner and developing an electrostatic latent image on the surface of the photoreceptor to form a toner image, and a means for transferring the toner image from the surface of the photoreceptor to a transfer material.
  • the image forming apparatus of the present invention surrounds one photoreceptor, and the surface of the photoreceptor corresponds to magenta, yellow, blue, and black.
  • At least four means for forming an electrostatic latent image and at least four means for accommodating the superimposed toner corresponding to magenta, yellow, blue and black, and the polymerized toner Supplying and developing each electrostatic latent image on the photoreceptor surface to form a toner image
  • At least four means for forming an electrostatic latent image and at least four means for accommodating the superimposed toner corresponding to magenta, yellow, blue and black, and the polymerized toner Supplying and developing each electrostatic latent image on the photoreceptor surface to form a toner image.
  • a step of attaching a toner to the surface of the photoreceptor on which the electrostatic latent image is formed to form a visible image, and then transferring the visible image to a transfer material The polymerized toner of the present invention is used as a toner.
  • the volume average particle diameter (dV) and the particle size distribution of the polymer particles that is, the ratio (dv / dp) between the volume average particle diameter and the number average particle diameter (dp), are determined by using a multi-sizer (manufactured by Kor Yuichi Co., Ltd.). ). The measurement by the multisizer was performed under the conditions of an aperture diameter: 50 m, a medium: Isoton II, a concentration: 10%, and the number of particles to be measured: 50, 000.
  • the shell is thick, it can be measured with a multisizer or an electron microscope, but in the case of the thin shell, the calculation was made using the following formula.
  • Equation (iv) is obtained from equation (iii).
  • the volume resistivity of the toner is measured using a dielectric loss meter (trade name: TRS-10 And Ando Electric Co., Ltd.) at a temperature of 30 ° C and a frequency of 1 kHz.
  • Toner image evaluation was performed on a printer that was modified so that the temperature of the fixing roll part of a commercially available non-magnetic one-component developing printer could be changed.
  • the temperature at which the fixing rate was 80% was evaluated as the fixing temperature.
  • the fixing test was performed by changing the temperature of the fixing roll of the printer, measuring the fixing rate at each temperature, and determining the relationship between the constant temperature fixing rates.
  • the fixation rate was calculated from the ratio of the image density before and after the tape peeling operation in the solid black area on the test paper printed with the remodeled printer. That is, assuming that the image density before tape removal is before ID and the image density after tape removal is after ID, the fixing rate can be calculated by the following equation.
  • Fixing rate (%) (after ID and before ID) X I 0 0
  • the tape peeling operation is to apply an adhesive tape (Scout Mending Tape 810-3-18) manufactured by Sumitomo SLIM Co., Ltd. to the measurement area of the test paper, and extrude it at a constant pressure to adhere it. Then, a series of operations to peel off the adhesive tape in the direction along the paper at a constant speed. The image density was measured using a reflection image densitometer manufactured by McBeth, Inc.
  • the toner sample placed in a closed container, seal it, submerge it in a thermostatic water bath whose temperature is controlled at 55 ° C, remove it after a certain period of time, and aggregate it. This was done by weighing the toner.
  • the sample removed from the container was transferred onto a 42-mesh sieve so as not to destroy the structure as much as possible, and the sample was measured using RE 0 STAT of a powder measuring machine (manufactured by Hosokawa Mikuguchi). After setting the vibration intensity to 4.5 and vibrating for 30 seconds, the weight of the toner remaining on the sieve was measured, and the weight of the aggregated toner was measured. And the amount.
  • the aggregation rate (% by weight) of the toner was calculated from the weight of the aggregated toner and the weight of the sample.
  • the storage stability of the toner was evaluated on the following four levels.
  • ⁇ aggregation rate is less than 5% by weight
  • the aggregation rate is 5% by weight or more and less than 10% by weight
  • the aggregation rate is 10% by weight or more and less than 50% by weight
  • the aggregation rate is 50% by weight or more.
  • the temperature of the fixing roll of the modified printer was set to 170 ° C, and printing was performed using a commercially available 0 HP (Transparency Lance 1) sheet by Uchida Yoko Co., Ltd. Was evaluated for 0 HP permeability.
  • the printed 0 HP sheet was placed on an O HP apparatus, and the appearance of the color was visually observed and evaluated according to the following criteria.
  • Continuous printing is performed from the initial stage using the printer described above.
  • ⁇ The number of continuous prints that can maintain the above image quality is 10,000 or more
  • the number of continuous prints that can maintain the above image quality is 5,000 or more and less than 10,000, and the continuous print number that can maintain the above image quality is less than 5,000.
  • the raw material liquid is added to the magnesium hydroxide colloid dispersion obtained above, and the mixture is stirred and mixed using a propeller-type stirrer. Further, while stirring and mixing, t-butyl vinyl oxide is added. —4 parts of ethyl hexanoate was added to obtain a mixture of the polymerizable monomer composition for the core.
  • a 500 cc pressurized vacuum attachment, a rotor (rotor R-2), and a stator (screen S-1.0-224) are attached ( The gap between the rotor and the stator is 0.2 mm), and a granulator (CLEARMIX CLM-0.8S: Emtech) operating at a rotor speed of 21,100 rpm
  • the mixture was supplied at a flow rate of 30 kg Zhr using a pump to granulate droplets of the monomer composition for core.
  • the residence time was 60 seconds.
  • the volume average particle diameter of droplets is about 5.0 m, the volume average particle diameter
  • the ratio of Z number average particle diameter is about 1.18, and the number of droplets in the range of volume average particle diameter ⁇ 1 m is about 70 m % By volume.
  • the aqueous dispersion of the granulated core polymerizable monomer composition was placed in a reactor equipped with a stirring blade, and the polymerization reaction was started at 90 ° C., and the polymerization conversion reached 98%. Occasionally, 1 part was sampled, and the rest was added with the above-mentioned polymerizable monomer for shell and 1 part of a 1% aqueous solution of potassium persulfate, and the reaction was continued for 3 hours. ⁇ Polymer particles with a shell structure was obtained.
  • the sampled core particles had a volume average particle size of 6.3 m, a volume average particle size (dV) and a Z number average particle size (dp) of 1.18.
  • the volume average particle diameter of the core-shell type polymer particles is 6.9 m, and the volume average particle diameter (dV) / number average particle diameter (dp) is 1.20, 1 to 1/3. Was 1.1 and the toluene-insoluble content was 3%.
  • toner To 100 parts of the polymerized toner obtained as described above, 0.3 part of a hydrophobized colloid darica (trade name: R—202, manufactured by Nippon Aerosil Co., Ltd.) was added. To prepare a developer (hereinafter simply referred to as toner). When the volume resistivity of the toner thus obtained was measured, it was 11.4 (1 og ⁇ ocm).
  • Table 1 shows the evaluation results of the polymerized toner obtained as described above. In other image evaluations, an image having a high image density, no fog, no unevenness, and an extremely good resolution was obtained.
  • Example 3 A polymerized toner was obtained in the same manner as in Example 1 except that the number of rotations of the rotor was changed to 15 and OOO rpm. The results are shown in Table 1. In the image evaluation, an image having a high image density, no fog, no unevenness, and an extremely good resolution was obtained. [Example 3]
  • Polymerized toner was obtained in the same manner as in Example 1 except that the supply flow rate of the mixed solution was changed to 20 kg / hr. The results are shown in Table 1.
  • Example 1 In the same manner as in Example 1, except that granulation was performed with a TK homomixer operating at a rotational speed of 1200 rpm instead of granulating with clear mix in Example 1, As a result, a polymerized toner was obtained.
  • Table 1 In the granulation using this TK homomixer, the volume average particle size of the droplets was 7.1 m, and the volume average particle size Z number average particle size was 1.52. table 1
  • the polymerization temperature obtained by the production method of the present invention was set to a fixing temperature of 120 to 130 ° C. It is possible to reduce it, and it is also excellent in preservability. In addition, the dependence of the charge amount on the environment is small, and it is difficult to cause fogging and decrease in print density.
  • the polymerized toner obtained in Comparative Example 1 does not have a sufficient balance between the effect of lowering the fixing temperature and the storage stability, has a large environmental dependence of the charge amount, and has a low image evaluation. It is.
  • Example 1 instead of granulating with clear mix, a rotor having comb teeth and a stator having comb teeth similar to the rotor having comb teeth were used.
  • a polymerized toner was obtained in the same manner as in Example 1 except that granulation was performed using a working ebaramyelda. In addition,. The residence time in the granulation step was 70 seconds. The results are shown in Table 2.
  • a polymerization toner was prepared in the same manner as in Example 1 except that the butyl acrylate used in the core polymerizable monomer composition was changed to 2-ethylhexyl acrylate. Obtained. The results are shown in Table 2.
  • the polymerizable monomer composition is added to the dispersion medium, and the mixture is dispersed with a TK homomixer at 70 ° C., and a granulation apparatus (Ebara Milder) operating at a rotation speed of 5,000 rpm is used.
  • a granulation apparatus Ebara Milder
  • Ebara Corporation Ebara Corporation with a pump at 180 kg / hr to granulate the dispersion, polymerize it at 70 ° C, polymerize, wash and dry to obtain polymerized toner.
  • a developer toner was obtained in the same manner as in Example 1. The results are shown in Table 2.
  • a polymerized toner was obtained in the same manner as in Example 1 except that the shell monomer was not added. The results are shown in Table 2.
  • the fixing temperature was reduced to 120 to 130 ° C.
  • the storage capacity is excellent and the storage capacity is less dependent on the environment, and the occurrence of fogging and lowering of the print density are unlikely to occur.
  • the polymerization toner obtained in Comparative Example 2 does not have a sufficient balance between the effect of lowering the fixing temperature and the storage stability, has a large environmental dependence of the charge amount, and has a poor image evaluation. It is low.
  • the polymerized toner obtained in Comparative Example 3 had a low fixing temperature, but had no seal, and therefore had poor storage stability and low image evaluation.
  • Example 1 was repeated in the same manner as in Example 1 except that instead of 7 parts of black rubber, 5 parts of a magenta pigment (a pigment 122) were used. Got a ner. The results are shown in Table 3.
  • Example 1 was repeated in the same manner as in Example 1 except that 5 parts of yellow quinophthalone pigment (Vigment Yellow 1338) was used in place of 7 parts of black pigment. Polymerized toner was obtained. Table 3 shows the results.
  • Example 1 was repeated in the same manner as in Example 1 except that 5 parts of cyan paint (Vigment Blue 15: 3) were used instead of 7 parts of carbon black. A polymer toner was obtained. The results are shown in Table 3.
  • the polymerization toners obtained by the production method of the present invention can reduce the fixing temperature to 120 to 130. It is possible and has excellent storage properties. In addition, the amount of charge is less dependent on the environment, and is less likely to cause fogging and decrease in print density.
  • the present invention has a low fixing temperature, a uniform melting property, and Provided is a method for producing a polymerized toner having excellent properties.
  • Use of the polymerized toner according to the production method of the present invention enables high-speed copying and printing, full colorization, and energy saving. Further, the polymerized toner of the present invention shows excellent transparency when printed on an HP sheet and fixed.
  • the polymerized toner of the present invention can form a high-quality image without fogging or a decrease in print density.
  • an image forming method using a polymerized toner having such excellent characteristics, and an image forming apparatus containing the polymerized toner there is provided.

Abstract

L'invention concerne un procédé qui permet de produire un toner polymère ayant une structure coeur/enveloppe. Selon le procédé, on fait passer une composition de monomère polymérisable formant le coeur, constituée au moins d'un monomère polymérisable formant le coeur et d'un colorant, dans un espace compris entre un rotor tournant à une vitesse élevée et un stator entourant ledit rotor et présentant de petits orifices ou des dents de peigne, dans un milieu de dispersion aqueux qui contient un stabilisant de dispersion, de façon à former des gouttelettes de ladite composition; on polymérise les gouttelettes de façon à obtenir des particules coeur; puis, en présence desdites particules coeur, on polymérise un monomère polymérisable formant l'enveloppe, capable de former un polymère dont la température de transition vitreuse est plus élevée que celle du polymère constituant les particules coeur, de façon à former des enveloppes constituées de couches de polymères recouvrant les particules coeur. L'invention concerne également un toner polymère obtenu par ledit procédé, un procédé permettant de former des images au moyen dudit toner, ainsi qu'un dispositif imageur contenant ledit toner.
PCT/JP1997/004476 1996-12-05 1997-12-05 Procede pour produire un toner polymere WO1998025186A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8/340677 1996-12-05
JP34067796 1996-12-05

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WO1998025186A1 true WO1998025186A1 (fr) 1998-06-11

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10428187B2 (en) 2015-03-19 2019-10-01 Bridgestone Corporation Method for producing mixture

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5962870A (ja) * 1982-10-04 1984-04-10 Canon Inc トナ−の製造方法
JPS61118758A (ja) * 1984-11-15 1986-06-06 Konishiroku Photo Ind Co Ltd トナ−の製造方法
JPH03136065A (ja) * 1989-10-23 1991-06-10 Kao Corp 静電荷像現像用トナー及びその製造方法
JPH07128908A (ja) * 1993-10-29 1995-05-19 Canon Inc 静電荷像現像用トナー及びその製造方法
JPH08305084A (ja) * 1995-03-03 1996-11-22 Nippon Zeon Co Ltd 静電荷像現像用トナーの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5962870A (ja) * 1982-10-04 1984-04-10 Canon Inc トナ−の製造方法
JPS61118758A (ja) * 1984-11-15 1986-06-06 Konishiroku Photo Ind Co Ltd トナ−の製造方法
JPH03136065A (ja) * 1989-10-23 1991-06-10 Kao Corp 静電荷像現像用トナー及びその製造方法
JPH07128908A (ja) * 1993-10-29 1995-05-19 Canon Inc 静電荷像現像用トナー及びその製造方法
JPH08305084A (ja) * 1995-03-03 1996-11-22 Nippon Zeon Co Ltd 静電荷像現像用トナーの製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10428187B2 (en) 2015-03-19 2019-10-01 Bridgestone Corporation Method for producing mixture

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