WO2011082556A1 - 静电荷像显影用碳粉的制造方法 - Google Patents

静电荷像显影用碳粉的制造方法 Download PDF

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Publication number
WO2011082556A1
WO2011082556A1 PCT/CN2010/070524 CN2010070524W WO2011082556A1 WO 2011082556 A1 WO2011082556 A1 WO 2011082556A1 CN 2010070524 W CN2010070524 W CN 2010070524W WO 2011082556 A1 WO2011082556 A1 WO 2011082556A1
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WIPO (PCT)
Prior art keywords
wax
particles
colorant
toner
resin
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PCT/CN2010/070524
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English (en)
French (fr)
Inventor
朱顺全
李云峰
Original Assignee
湖北鼎龙化学股份有限公司
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Application filed by 湖北鼎龙化学股份有限公司 filed Critical 湖北鼎龙化学股份有限公司
Priority to EP10734888A priority Critical patent/EP2362269A1/en
Priority to US12/832,090 priority patent/US20110165511A1/en
Publication of WO2011082556A1 publication Critical patent/WO2011082556A1/zh

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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
    • G03G9/087—Binders for toner particles
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08782—Waxes
    • 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
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place

Definitions

  • the present invention relates to an electrostatic image image developing toner used in an electrophotographic copying machine and a printer, and more particularly to a toner for electrostatic image development which is excellent in fixability, roll resistance, and durability. Background technique
  • the electrostatic charge image developing toner which has been widely used in the past has been melted with a coloring agent such as carbon black or a pigment and a release agent such as a wax in a binder resin such as a styrene acrylic resin or a polyester resin. Mixing, then crushing.
  • a coloring agent such as carbon black or a pigment
  • a release agent such as a wax in a binder resin such as a styrene acrylic resin or a polyester resin.
  • the carbon powder obtained by the melt kneading/pulverization method has a limit on the control of the particle size of the carbon powder, and it is extremely difficult to produce a carbon powder having a particle diameter of substantially less than ⁇ or less, particularly 8 ⁇ m or less in a high yield, and it is difficult to achieve The demand for high resolution required for electrophotography in the future.
  • the wax having a low softening point is dispersed in the carbon powder, that is, the so-called oil-free fixing is a relatively common method, but in the conventional melt kneading/pulverizing method, if it is desired to contain a large amount of When the wax is detached, the wax is detached at the time of pulverization, and the surface wax of the carbon powder is excessively present, which causes problems such as contamination of the carrier or the developing sleeve, resulting in shortened life. Further, there is a problem that wax forms a film on the photoreceptor to cause image defects. Further, due to the detachment of the wax, there is a problem that the low-temperature fixing performance cannot be sufficiently exerted.
  • JP-A-2001-27821 proposes a method of preparing carbon powder by aggregating aggregate particles and colorant particles using wax particles as seeds. Since this method can make the toner contain a relatively large amount of wax to some extent, it is a good method for improving the fixability. However, this method has a problem that the dispersion of the colorant is lowered and the image density cannot be improved, and the detachment of the coloring agent is liable to occur, thereby causing contamination of the carrier and the developing sleeve, and there is a problem that durability is low. Summary of the invention
  • An object of the present invention is to provide a toner for electrostatic image development which has high sticking resistance and high durability in order to overcome the disadvantages of conventional carbon powder for electrostatic image development.
  • the method in which the resin particles are aggregated in an aqueous medium and melted to obtain a 'J carbon powder particle' can solve the above problems.
  • the present invention is a manufacturing method in which both a wax and a colorant are present inside the polymer particles at one stage.
  • a radical polymerizable monomer is added, and then the polymerized resin particles are agglomerated, whereby the aggregates of the polymer are agglomerated, and after that, a carbonation process can be formed by melting between the polymers.
  • the particles, therefore, the colorant and the wax may be dispersed in the toner in a state smaller than the polymer particles.
  • the constituent material which is difficult to melt such as wax is contained in the polymer particles before the aggregation stage, it is estimated that the above problem can be solved by being contained in the carbon powder without being detached during aggregation and fusion.
  • this method requires different manufacturing processes, not only the efficiency is low, but also in the polymerization stage, the molecular weight The adjustment of the coloring agent and the wax is likely to vary, and problems such as sticking at the time of fixing are likely to occur in long-term use.
  • a radical polymerizable monomer (monomer) is added to an aqueous dispersion of a wax particle of a colorant, and a core, that is, a seed, is polymerized, and a resin particle containing a colorant and a wax at the same time can be obtained. Formed in the water system at the same stage. Since it can be prepared in one stage, there is no problem that the resin characteristics of the resin-coated resin particles and the wax-incorporated resin particles do not differ, and since the thermal characteristics of the aggregation and the melting stage are also uniform, no wax is generated. And problems such as the detachment of the colorant.
  • the resin particle contains a colorant and a wax
  • the resin particle In order to gradually add a radical polymerizable monomer to an aqueous medium in which a wax particle is dispersed in a colorant, and then polymerize the radical polymerizable monomer to form a resin particle, the resin particle is further agglomerated in an aqueous medium, and is fused. Thereby, toner particles are produced.
  • the wax used in the present invention may be any of various types of well-known waxes, and specific examples thereof include hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin wax such as copolymerized polyethylene, paraffin wax or microcrystalline wax. , long-chain aliphatic-based ester waxes, carnauba wax, beeswax, such as behenic acid behenate, behenic acid behenate, octadecyl octadecyl ester, pentaerythritol Tetrabehenate Such as natural acid wax, oleic acid amide, stearic acid amide and other higher fatty acid amides.
  • hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin wax such as copolymerized polyethylene, paraffin wax or microcrystalline wax.
  • a wax having a melting point of 100 ° C or less is preferable, and a wax having a melting point of 40 - 90 ° C is preferable, and a wax having a melting point of 60 - 85 ° C is particularly preferable. If melting point When it exceeds 100 ° C, the effect of low-temperature fixability is lowered.
  • the colorant used in the present invention may be an inorganic pigment or an organic pigment, an organic dye or the like, or a combination thereof. Specific examples thereof are black colorants: carbon black, magnetite, titanium black, aniline black, nigrosine dye, and the like.
  • As the coloring agent for cyan Pigment Blue 15:3, Pigment Blue 15:4, etc. can be used.
  • the yellow coloring agent may be Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 138, Pigment Yellow 150, Pigment Yellow 155, Pigment Yellow 180, Pigment Yellow 185, Solvent Yellow 19 , Solvent Yellow 44, Solvent Yellow 77, Solvent Yellow 162, etc.
  • the coloring agent for magenta can be exemplified by Pigment Red 5, Pigment Red 48:1, Pigment Red 48:2, Pigment Red 48:3, Pigment Red 53:1, Pigment Red 57:1, Pigment Red 122, and the like.
  • the colorant is relatively polar, it is preferred to use a relatively polar wax in order to disperse the colorant in the wax.
  • the wax is preferably an ester wax.
  • a non-polar carbohydrate wax such as a paraffin wax
  • the affinity with the colorant may be lowered.
  • colorants are usually used in an amount of from 1 to 40 parts by weight, preferably from 2 to 30 parts by weight, per 100 parts by weight of the binder resin. Further, the wax is usually used in an amount of from 3 to 20 parts by weight based on 100 parts by weight of the binder resin.
  • the wax and the colorant may be melt-kneaded in a dry kneading apparatus such as a twin-screw extruder, a twin-roll or a three-roller to prepare a pigment-dispersed pellet in the wax. And then dispersing in an aqueous medium to modulate the wax particles in the colorant.
  • a coloring agent is added, that is, a media dispersing agent such as SC MILL is dispersed in a liquid state by using a sand mill, and then the liquid state is dispersed in an aqueous medium to prepare a coloring.
  • the colorant inner wax may be selected from at least one of a known cationic surfactant, an anionic surfactant, and a nonionic surfactant. In the presence of an active agent, it is dispersed and prepared in an aqueous medium. Two or more of these surfactants may be used in combination.
  • cationic surfactants are: lauryl ammonium chloride, dodecyl ammonium bromide, dodecyl tridecyl ammonium bromide, dodecyl pyridine chloride, dodecyl bromide Pyridine, cetyltrimethylammonium bromide, etc.; specific examples of anionic surfactants are sodium stearate, sodium dodecanoate, sodium lauryl sulfate, sodium dodecyl benzoate, twelve Metal salts of higher fatty acids such as sodium alkyl sulphate; etc.; specific examples of nonionic surfactants are: Poly(oxyethylene) Dodecy Ether, Poly(oxyethylene) Hexadecyl Ether ) , Poly(oxyethylene) Nonyl-Phenyl Ether, Poly(oxyethylene) Lauryl Ether, Polyoxyethylene Ether Resin Monooleate (Polyoxyethylene Ether) Sorbitan Mono-oleate Poly (oxyethylene) Ether
  • the wax in the colorant is dispersed in the presence of a surfactant and then used in the form of particles.
  • the number average primary particle diameter of the wax particles in the coloring agent is preferably from 10 to 1,000 nm, preferably from 30 to 500 nm.
  • the number average primary particle diameter can be measured by Beckman Coulter's LS230.
  • the average primary particle diameter of the wax particles in the colorant is greater than 100 nm, the aggregation with the resin particles may be uneven, and it may be difficult to narrow the particle size distribution, which is disadvantageous for preparing the small particle size carbon powder.
  • the average primary particle diameter of the wax particles in the colorant is less than 10 nm, there is a problem that the wax content in the carbon powder is lowered, and there is a possibility that the effect of improving the sticking resistance at the time of low-temperature fixing is lowered.
  • the method of dispersing the colorant-incorporated wax particles in an aqueous medium is not limited, and for example, a device capable of dispersing by shearing and cavitation at a high-speed rotation such as a clearmix (product name of M disperser) can be used, and homogenization using TK can be used.
  • a device that disperses by high-speed rotation such as a device (manufactured by Miki Co., Ltd.), or a device that disperses by using a medium such as an SC mill (a product name of a pulverizer, manufactured by Mitsui Mining Co., Ltd.) and a sand mill.
  • the wax particles in the colorant it is preferred to use a method in which the wax is heated to a melting point or higher and then dispersed in an aqueous medium.
  • the coloring agent inner wax-coated particle dispersion is prepared, and then a radical polymerizable monomer is added, and it is added as necessary.
  • the polymerization initiator is subjected to a radical polymerization reaction to prepare resin particles containing a colorant and a wax, and then the particles are aggregated and fused to obtain a carbon powder.
  • the radical polymerizable monomer used in the present invention may be: styrene, ⁇ -mercaptobenzene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, 4-butylbenzene, 4 _ Styrene such as mercaptostyrene, decyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, decyl methacrylate, methacrylic acid Ethyl ester, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, ethyl hexyl methacrylate or the like (meta) acrylate.
  • styrene and butyl acrylate
  • a radical polymerizable monomer having a polar group may be used, and a radical polymerizable monomer having an acidic polar group may be a radical having a radical such as acrylic acid, methacrylic acid, maleic acid, fumaric acid or cinnamic acid.
  • the polymerizable monomer is used to crosslink a radical polymerizable monomer having a sulfonic acid group such as styrene, and particularly preferably acrylic acid or methacrylic acid.
  • a radically polymerizable monomer having a basic polar group may be exemplified by aminostyrene and its a meta-salt, a methyl pyridine, a vinylpyrrolidone, or the like, a nitrogen-containing complex ring-free radical polymerizable monomer, a bis-aminoethyl acrylate, a diethylaminoethyl methacrylate, or the like, an amino (meth) acrylate.
  • an amine salt-containing (meta) acrylate and an acrylamide, N-propyl acrylamide, N, N-dimercapto acrylamide, N, N-dipropyl acrylamide, N, N-dibutylacrylamide, acrylamide, and the like.
  • the glass transition temperature of the polymer is preferably from 40 to 70 °C. If the glass transition temperature exceeds 70 °C, the fixing temperature becomes too high, and the fixing property may be lowered. On the other hand, when the glass transition temperature of the polymer is less than 40 °C, the storage stability of the toner is deteriorated. , sometimes the problem of agglutination occurs.
  • a water-soluble polymerization initiator of persulfate such as potassium persulfate, sodium persulfate or ammonium persulfate, and a redox polymerization initiator which is combined with a reducing agent such as acidic sodium sulfite or ascorbic acid, hydrogen peroxide
  • a reducing agent such as acidic sodium sulfite or ascorbic acid, hydrogen peroxide
  • a water-soluble polymerization initiator such as t-butanol peroxide or cumyl hydroperoxide
  • a water-soluble polymerizable initiator and a ferrous salt or ascorbic acid A redox polymerization initiator or the like in which a reducing agent is combined.
  • These polymerization initiators may be added to the polymerization system before the addition of the radical polymerizable monomer, at the same time as the addition, and at any time after the addition, and these addition methods may be used in combination as necessary.
  • a chain transfer agent in order to adjust the molecular weight of the polymer, a chain transfer agent may be used as necessary.
  • the chain transfer agent are t-dodecyl mercaptan, n-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, carbon tetrachloride, chlorosilane Wait.
  • the chain transfer agent may be used singly or in combination of two or more kinds, and it is preferably used in an amount of not more than 5% by weight based on the maximum amount of the radical polymerizable monomer.
  • the number average particle diameter of the resin particles is preferably from 50 nm to 1,500 nm, more preferably from 70 to 700 nm.
  • the number average primary particle diameter can be measured using Beckman Coulter's LS230. When the number average primary particle diameter is less than 50 nm, since the wax content is small, there is a problem that the so-called release effect is poor. Further, when it is larger than 1500 nm, it is difficult to control the particle size of the carbon powder, and problems such as a wide particle size distribution may occur.
  • the toner of the present invention may be added with a charge control agent, and the charge control agent may be any one known in the art, and may be used singly or in combination.
  • a positively chargeable quaternary ammonium salt a negatively charged salt of a salicylic acid or an alkylsalicylic acid, a metal salt of a metal such as a metal, a metal complex, a metal salt of a benzoic acid, or a metal complex.
  • a substance, an amino compound, a phenol compound, a naphthol compound, an aminophenol compound or the like is preferred.
  • the amount of use may be determined depending on the desired charge amount of the toner, and is usually 0.01 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the binder resin.
  • the charge control agent may be used in a state where the colorant particles and the wax particles coexist, or the charge control agent may be dispersed in the aqueous medium alone, and the resin particles may be aggregated as a state of the dispersed particles.
  • the method of aggregating the resin particles is: heating the resin particle dispersion or adjusting the pH so that the dispersion is not stabilized and agglomerating, and then heating and melting; or adding agglomerated salt to agglomerate, and then heating and melting the method, etc. .
  • the method of adding agglomerated salt to agglomerate can form a stable agglomerated state, and is an excellent manufacturing method.
  • a monovalent or polyvalent metal salt can be used as the salt to be agglomerated.
  • the monovalent salt may, for example, be a sodium salt or a potassium salt, such as sodium chloride or potassium chloride; and the divalent metal salt may, for example, be magnesium chloride, magnesium sulfate, calcium chloride or sulfuric acid;
  • the metal salt of the valence may, for example, be aluminum hydroxide or aluminum chloride.
  • the aggregated salt is added below the glass transition temperature of the polymer particles, and then the temperature is raised as rapidly as possible and heated to a temperature higher than the glass transition temperature of the polymer particles.
  • the time until the temperature rise is preferably 1 hour or less.
  • the heating rate is preferably 0.25 ° C / min or more.
  • the upper limit is not particularly clear, but when the temperature is raised instantaneously, the salting out will be abruptly performed, and the problem of difficulty in controlling the particle size will occur. Therefore, it is preferable to be 5 ° C /min or less.
  • the colored particles can be separated from the aqueous medium by filtration and washing.
  • the filtration and washing methods include a centrifugal separation method, a vacuum filtration method using a suction device, and the like, and a method of filtering and washing using a filter press, etc., and are not particularly limited.
  • the dryer used in the project may be a spray dryer, a vacuum freeze dryer, a vacuum dryer, or the like, using a static shed dryer, a mobile shed dryer, a fluidized bed dryer, a rotary dryer, and a stirring type. Dryer, etc. is good.
  • the moisture content of the dried colored particles is preferably 5% by mass or less, more preferably 2% by mass or less.
  • the mashing apparatus may use a mechanical pulverizing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor.
  • the particles may be attached to the surface by adding the same or different kinds of binder resin emulsions. Modify the toner properties near the surface.
  • the carbon powder of the present invention may optionally use an additive such as a fluidizing agent, and the fluidizing agent may specifically be a fine powder such as hydrophobic silica, titanium oxide or aluminum oxide, usually with respect to the binder resin 100. It is preferably used in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight.
  • the average primary particle diameter of these flow agents is preferably from 5 to 80 nm.
  • the carbon powder of the present invention can also be magnetite, ferrite, cerium oxide, barium titanate, and conductive
  • An inorganic fine powder such as titanium dioxide, a resistance adjusting agent such as a styrene resin or an acrylic resin, a slip agent or the like is used as an internal additive or an external additive.
  • the amount of these additives to be used can be appropriately selected depending on the desired properties, and is usually suitably from 0.05 to 10 parts by weight based on 100 parts by weight of the binder resin.
  • These additives are preferably used in a relatively large particle size, and the number average primary particle diameter is from 100 to 1000 nm.
  • the electrostatic charge image developing toner of the present invention can be used in the form of a two-component developer or a non-magnetic one-component developer.
  • the carrier may be a magnetic substance such as tantalum powder, magnetite powder or ferrite powder, or a material having a resin coating on the surface of these materials and a well-known substance such as a magnetic carrier.
  • a styrene resin, an acrylic resin, a styrene acrylic copolymer resin, a silicone resin, a denatured silicone resin, a fluororesin, or a mixture of these or the like can be generally used. detailed description
  • the mixture was dispersed to a number average primary particle diameter of 120 nm using a ClearMix, and cooled to 30 ° C to obtain a dispersion of behenic acid behenate particles in which carbon black was dispersed.
  • the particle size was measured using Beckman Coulter's LS230. Further, it is referred to herein as a colorant-incorporated wax particle (1) dispersion.
  • the behenic acid tetradecyl ester was changed to refined Brazil. Palm Carbide No. 1, and other conditions were the same to obtain a dispersion of purified carnauba wax No. 1 particles in which carbon black was dispersed.
  • the number average primary particle diameter is 105 nm. This is named as a colorant-coated wax particle (2) dispersion.
  • the behenic acid tetradecyl ester was changed to pentaerythritol Tetrabehenate, and the other conditions were the same to obtain pentaerythritol tetractalate (Cartaerythritol Tetrabehenate) in which carbon black was dispersed. ) Particle dispersion.
  • the number of primary primary particles is 145 nm. This is named as a colorant-containing wax particle (3) dispersion.
  • the carbon black was changed to the pigment red 122, and the other conditions were the same, and the purified carnauba wax No. 1 particle dispersion in which the pigment red 122 was dispersed was obtained.
  • the number average primary particle size is 135 nm. This is named as a colorant-containing wax particle (5) dispersion.
  • the carbon black was changed to the pigment red 122, and other conditions were the same to obtain a pentaerythritol Tetrabehenate particle dispersion in which the pigment red 122 was dispersed.
  • the number average primary particle diameter is 155 nm. This is named as a dispersion of wax particles (6) in the colorant.
  • the carbon black was changed to the pigment yellow 74, and the other conditions were the same, and the purified carnauba wax No. 1 particle dispersion in which the pigment yellow 74 was dispersed was obtained.
  • the number average primary particle diameter is 115 nm. This is named as a colorant-coated wax particle (8) dispersion.
  • the carbon black was changed to the pigment yellow 74, and other conditions were the same to obtain a pentaerythritol Tetrabehenate particle dispersion in which the pigment yellow 74 was dispersed.
  • the number average primary particle diameter is 145 nm. It is named as a dispersion of wax particles (9) in the colorant.
  • the carbon black was changed to the pigment red 122, and the other conditions were the same to obtain a dispersion of the behenic acid behenate particles in which the pigment red 122 was dispersed.
  • the number average primary particle size is 155 nm. This is named as a colorant-coated wax particle (14) dispersion.
  • the colorant-incorporated wax particle (1) dispersion liquid is placed in a glass reaction vessel having a stirring device, a heating and cooling device, a concentrating device, and a raw material input port, and heated to 40 ° C to add sodium dodecyl benzoate
  • a 5% aqueous solution of 800 g was added to the water-soluble polymerization initiator 1.2 g of potassium persulfate.
  • a monomer solution composed of 70 g of styrene, 20 g of butyl acrylate, and 10 g of methacrylic acid was dropped over 1 hour to carry out seed polymerization in which the wax particles ( 1 ) in the colorant were seeded.
  • the reaction was terminated after 7 hours. After completion of the reaction, the particle diameter was measured by cooling to 20 °C.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 220 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (1).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (2), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 230 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (2).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (3), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 250 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (3).
  • the colorant-incorporated wax particles (1) were changed to the colorant-incorporated wax particles (4), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the particle size of the colorant and the wax-incorporated resin particles was 240 nm.
  • the coloring agent and the wax-encapsulated resin particles are named as resins. Particle (4).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (5), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the particle size of the colorant and the wax-incorporated resin particles was 220 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (5).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (6), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 240 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (6).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (7), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 250 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (7).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (8), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 240 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (8).
  • the colorant-incorporated wax particles (1) were changed to use a coloring agent.
  • the wax particles (9) are encapsulated, and the coloring agent and the wax-incorporated resin particles are obtained under the same conditions.
  • the particle size of the colorant and the wax-incorporated resin particles was 230 nm.
  • the coloring agent and the wax-incorporated resin particles are named as resin particles (9).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (10), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 245 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (10).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (11), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 230 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (11).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (12), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 250 nm.
  • the coloring agent and the wax-incorporated resin particles are named as resin particles (12).
  • the colorant-incorporated wax particles (1) were changed to the colorant-incorporated wax particles (13), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the particle size of the colorant and the wax-incorporated resin particles was 260 nm.
  • the coloring agent and the wax-incorporated resin particles are named as resin particles (13).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (14), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 230 nm.
  • the coloring agent and the wax-incorporated resin particles are named as resin particles (14).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (15), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 240 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (15).
  • the colorant-incorporated wax particles (1) were changed to the colorant-containing wax particles (16), and the coloring agent and the wax-incorporated resin particles were obtained under the same conditions.
  • the colorant and the wax-incorporated resin particles had a particle diameter of 250 nm.
  • the coloring agent and the wax-incorporated resin particles were named as resin particles (16).
  • the temperature was then raised to 95 ° C and the shape was spheroidized using 5 hours. When the shape factor reached 0. 9 6 5 (measured using FPIA-3000), it was cooled to 20 °C. Then, it was filtered using a centrifugal separator, washed with water, and dried under reduced pressure with heating.
  • the obtained toner is referred to as toner 1.
  • the resin particles (1) were changed to the resin particles (2), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 2.
  • the resin particles (1) were changed to the resin particles (3), and the toner was obtained under the same conditions.
  • the obtained toner is named as toner 3.
  • the resin particles (1) were changed to the resin particles (4), and the toner was obtained under the same conditions.
  • the obtained toner is named as toner 4 .
  • the resin particles (1) were changed to the resin particles (5), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 5.
  • the resin particles (1) were changed to the resin particles (6), and the toner was obtained under the same conditions.
  • the obtained toner is named as toner 6.
  • the resin particles (1) were changed to the resin particles (7), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 7.
  • the resin particles (1) were changed to the resin particles (8), and others.
  • the toner is obtained under the same conditions.
  • the obtained toner was named as toner 8.
  • the resin particles (1) were changed to the resin particles (9), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 9 .
  • the resin particles (1) were changed to the resin particles (10), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 10.
  • the resin particles (1) were changed to the resin particles (11), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 11 .
  • the resin particles (1) were changed to the resin particles (12), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as carbon powder 12.
  • the resin particles (1) were changed to the resin particles (13), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 13 .
  • the resin particles (1) were changed to the resin particles (14), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 14 .
  • the resin particles (1) were changed to the resin particles (15), and the other conditions were the same to obtain carbon powder.
  • the obtained toner is named as toner 15 .
  • Toner preparation example 1 6 In the toner preparation example 1, the resin particles (1) were changed to the resin particles (16), and the other conditions were the same to obtain carbon powder. The obtained toner was named as toner 16.
  • a sodium dodecyl benzoate 5% aqueous solution of 600 g was added, and then a water-soluble polymerization initiator potassium persulfate 1.2 g was added.
  • a monomer solution consisting of 70 g of styrene, 20 g of butyl acrylate, and 10 g of methacrylic acid was added dropwise for one hour to carry out emulsion polymerization, and the reaction was terminated at 7 hours.
  • the mixture was cooled to 20 ° C to obtain a resin particle (Cl ) having a number average primary particle diameter of 130 nm.
  • the particle size growth was monitored, and 300 g of water and 10 g of sodium chloride were added at a time point when the particle diameter (median diameter of the volume standard: measured by Coulter Multi sizer ll manufactured by Beckman Coulter Co., Ltd.) reached 6.5 ⁇ m.
  • the particle size growth is stopped.
  • the temperature was then raised to 95 ° C and the shape was spheroidized using 5 hours.
  • the carbon black was changed to use the pigment red 122, and the same conditions were used to obtain the comparative toner 2.
  • the carbon black was changed to use the pigment yellow 74, and the same conditions were used to obtain the comparative toner 3.
  • the carbon black was changed to use the pigment blue 15:3, and the same conditions were used to obtain the comparative toner 4.
  • toners were evaluated using a non-magnetic one-component printer.
  • the printer uses the ColorLaserJet 2605 from HP.
  • Durability evaluation Use the above printer to print text images with a pixel rate of 1% for yellow/magenta/cyan/black in high temperature and high humidity (33°C/85% RH environment), in one intermittent mode (after one print) 10 seconds of printing) 4,000 consecutive prints.
  • the image density (black) and the bottom ash concentration after the initial printing and 4000 sheets of printing were compared by the relative reflection density at which the paper reflection density was "0".
  • the color gamut formed by Y/M/C and B/G/R is compared under full-color visual observation.
  • the color gamut area obtained at the initial stage was compared to 100, and the color gamut area after 4000 sheets was compared.
  • Example 1 Toner 1/Toner 4/Toner 7/Toner 10
  • Example 3 Toner 3 / Toner 6 / Toner 9 / Toner 12
  • Example 4 Toner 13 / Toner 14 / Toner 15 / Toner 16
  • Comparative Example 1 Carbon powder for comparison 1 / Carbon powder for comparison 2 / Carbon powder for comparison 3 / Carbon powder for comparison 4 Evaluation results
  • the portrait is thick.
  • Example 1 1.41 0.000 100 1.40 0.000 99
  • Example 2 1.40 0.000 100 1.40 0.000 99
  • Example 3 1.41 0.000 100 1.41 0.000 99
  • Example 4 1.41 0.000 100 1.41 0.000 99 Comparative Example 1 1.38 0.000 100 1.26 0.006 87
  • the carbon powder of the present invention as described above can maintain stable performance for a long period of time.

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Description

静电荷像显影用碳粉的制造方法
技术领域
本发明涉及一种电子照相方式的复印机以及打印机所使用的静电荷像 显影用碳粉， 具体涉及一种定影性、 耐粘辊性、 耐久性优秀的静电荷像显影 用碳粉。 背景技术
在电子照相法中 ,过去一般广泛使用至今的静电荷像显影用碳粉都是在 苯乙烯丙烯酸树脂或者聚酯树脂等粘合树脂中将碳黑、颜料等着色剂以及蜡 等离型剂溶融混炼、 然后粉碎.分级制造而成。 但是， 上述溶融混炼 /粉碎 法得到的碳粉在碳粉粒径控制上存在限度， 高收率制造实质上 ΙΟμηι以下、 特别是 8μηι以下平均粒径的碳粉非常困难， 可以说不足以达成今后电子照 相所要求的高分辨度化的要求。
另外， 在混炼时， 将低软化点的蜡在碳粉中分散， 也就是所谓的无油定 影是比较一般的方法，但是以往的溶融混炼 /粉碎法中，如果希望包含入较 多量的蜡， 则会发生粉碎时蜡的脱离、碳粉表面蜡过剩存在， 从而引起载体 或者显影套筒的污染导致寿命缩短等问题。 而且还有蜡在感光体形成薄膜 (filming)从而发生图像缺陷等问题。 另外， 由于蜡的脱离， 还会存在无法充 分发挥其低温定影性能的问题。
在特开昭 6 3 - 18 6 253 号公报中， 为了克服粒径控制问题， 达成高分 辨率， 而提出使用乳化聚合 /凝集法的碳粉制造方法。 但是， 该方法是将树 脂粒子、 蜡粒子与着色剂粒子凝集的方法， 如果希望含有较多的蜡， 则会发 生蜡粒子的游离，如前所述，会引起对载体以及显影套筒的污染以及蜡在感 光体上形成薄膜等问题， 无法确保其耐久性。
另外，在特开 2001 - 27821号公报中，提出有通过以蜡粒子为种子的聚 合体粒子与着色剂粒子的凝集而调制碳粉的方法。由于该方法可以使得碳粉 中在某种程度上含有较多量的蜡， 因此在提高定影性上是一种很好的方法。 但是， 这种方法存在着色剂分散低下、 图像浓度无法提高的问题， 而且容易 发生着色剂的脱离，从而引起载体与显影套筒的污染，存在耐久性低下的问 题。 发明内容
本发明的目的是为了克服现有静电荷像显影用碳粉的缺点，提供一种拥 有高耐粘辊性与高耐久性的静电荷像显影用碳粉。
本发明者对上述问题进行锐意研究的结果发现，在着色剂内包蜡粒子分 散的水系媒体中逐渐添加游离基聚合性单体，然后使得上述游离基聚合性单 体聚合从而形成的树脂粒子， 进一步将该树脂粒子在水系媒体中凝集， 融着 从而得 'J碳粉粒子的制造方法可以解决以上问题。
也就是说，本发明是在一个阶段可以使得蜡与着色剂都存在于聚合体粒 子内部的制造方法。 对于内包着色剂的蜡粒子， 添加游离基聚合性单体， 然 后使得聚合的树脂粒子凝集的场合为聚合体互相的凝集，在这之后经过融着 工程， 通过聚合体间融着可以形成碳粉粒子， 因此， 着色剂与蜡也可以以比 聚合体粒子更小的状态在碳粉中分散。 另外， 由于像蜡这样难以融着的构成 材料也在凝集阶段之前内包于聚合体粒子中，因此在凝集以及融着时可以不 脱离的包含在碳粉中， 从而推定可以解决上述问题。 另外，也可以使用分别不同的方法制成着色剂内包树脂粒子与蜡内包树 脂粒子， 然后再使其凝集， 但是这种方法需要各自不同的制造工程， 不仅效 率很低， 而且在聚合阶段， 分子量的调整以及着色剂、 蜡的内包容易发生偏 差， 在长期使用中容易发生定影时粘辊等问题。
在本发明中，在内包着色剂的蜡粒子的水系分散液中添加游离基聚合性 单体（单体）， 以其为核也就是种子进行聚合， 可以使得同时内包着色剂与 蜡的树脂粒子在同一阶段在水系媒体中形成。 由于在一个阶段内可以调制， 因此构成着色剂内包树脂粒子与蜡内包树脂粒子的树脂特性不会发生存在 差异的问题， 由于凝集会合以及融着阶段的热特性也是一致的， 因此不会产 生蜡以及着色剂的脱离等问题。
本发明技术方案为至少使得树脂粒子在水系媒体中凝集从而制造含有 树脂、着色剂与蜡的静电荷像显影用碳粉的制造制造方法中， 该树脂粒子内 包着色剂以及蜡，并且该树脂粒子为在着色剂内包蜡粒子分散的水系媒体中 逐渐添加游离基聚合性单体，然后使得上述游离基聚合性单体聚合从而形成 的树脂粒子， 进一步将该树脂粒子在水系媒体中凝集， 融着从而制造碳粉粒 子。
本发明使用的蜡可以是众所周知的蜡中任意的种类， 具体的例子有： 低 分子量聚乙烯、 低分子量聚丙烯、共聚合聚乙烯等烯烃系蜡、 石蜡或微晶蜡 等碳氢化合物系蜡、 廿二酸二十二酯、 褐煤酸二十二酯、 十八酸十八酯、 季戊四醇四山 酸酯（ Pentaerythritol Tetrabehenate )等有长链脂肪族基的酯 系蜡、 巴西棕榈蜡、 蜜蜡等天然物系蜡、 油酸酰胺、 硬脂酸酰胺等高级脂肪 酸酰胺等。 这些蜡中， 为了提高低温定影性， 比较好的为融点 100°C以下的 蜡， 更好为融点 40 - 9 0°C的蜡， 特别好为融点 6 0 - 85°C的蜡。 如果融点 超过 100°C , 则低温定影性的效果会降低。
本发明所使用的着色剂可以为无机颜料或者有机颜料、 有机染料等， 也 可以是其组合。 其具体的例子有黑着色剂： 碳黑、 磁铁矿、 钛黑、 苯胺黑、 苯胺黑染料等。 青色用着色剂可以使用颜料蓝 15:3、 颜料蓝 15:4等。 另夕卜， 黄色用着色剂可以举出颜料黄 14、颜料黄 17、 颜料黄 93、 颜料黄 94、 颜 料黄 138、 颜料黄 150、 颜料黄 155、 颜料黄 180、 颜料黄 185、 溶剂 黄 19、 溶剂黄 44、 溶剂黄 77、 溶剂黄 162 等。 品红用着色剂可以举出 颜料红 5、 颜料红 48:1、 颜料红 48:2、 颜料红 48:3、 颜料红 53:1、 颜料 红 57:1、 颜料红 122 等。
由于着色剂极性比较高， 因此为了在蜡中分散含有着色剂， 最好使用比 较具有极性的蜡。
出于这种考虑，蜡最好为酯系蜡。在使用石蜡系蜡这样的非极性碳水化 合物蜡时， 由于极性低， 有发生与着色剂亲和性低下的可能性， 这时最好与 酯系蜡混合并用， 赋予其极性。
这些着色剂通常相对于粘合树脂 100重量份，使用 1 ~ 40重量份， 最好 为 2-30重量份。 另外， 蜡通常的使用数量为相对于粘合树脂 100重量份使 用 3-20重量份。
为了在蜡中分散着色剂， 可以使用将蜡与着色剂在双轴挤出机， 双辊或 者三辊等干式混炼装置中熔融混炼，调制在蜡中着色剂分散的颗粒（ pellet ), 然后在水系媒体中分散从而调制着色剂内包蜡粒子的方法。另外还有将蜡熔 融为液体状， 然后添加着色剂， 也就是说使用砂磨机， SC MILL等媒体分 散剂在液状下使其分散， 然后将保持该液态在水系媒体中分散，从而调制着 色剂内包蜡粒子的方法。 为了将本发明中使用的着色剂内包蜡粒子在水系媒体中稳定分散，可以 将上述着色剂内包蜡在周知的阳离子表面活性剂、 阴离子表面活性剂、非离 子表面活性剂中选择至少一种表面活性剂的存在下，在水系媒体中分散而调 制。也可以将这些表面活性剂的 2种以上并用。 阳离子表面活性剂的具体例 子有： 十二烷基氯化铵、 十二烷基溴化铵、 十二烷基三曱基溴化铵、 十二烷 基氯化吡啶、 十二烷基溴化吡啶、 十六烷基三曱基溴化铵等； 阴离子表面活 性剂的具体例子有硬脂酸钠、 十二酸钠、硫酸十二烷基钠、 十二烷基苯蹟酸 钠、十二烷基硫酸钠等高级脂肪酸的金属盐等； 非离子表面活性剂的具体例 子有： 聚氧乙烯十二醚（ Poly(oxyethylene) Dodecy Ether )、 聚氧乙烯十六醚 ( Poly(oxyethylene) Hexadecyl Ether ) , 聚氧 乙 烯壬基苯基醚 ( Poly(oxyethylene) Nonyl-Phenyl Ether )、 聚氧 乙烯十八烷基醚 ( Poly(oxyethylene) Lauryl Ether )、 聚氧乙烯醚山梨醇酐单油酸酯 （ Sorbitan Mono-oleate Poly(oxyethylene) Ether )、 糖姿酸酷 ( monodecanoate Sucrose ) 等。
本发明中， 着色剂内包蜡在表面活性剂的存在下分散后粒子化使用。着 色剂内包蜡粒子的数量平均一次粒径以 10 ~ 1000nm 为好， 优选为 30 ~ 500nm。 另外，数量平均一次粒径可以通过贝克曼库尔特公司的 LS230进行 测定。
如果着色剂内包蜡粒子的数量平均一次粒径大于 lOOOnm的时， 则与树 脂粒子的凝集会不均一，使得粒径分布变窄会很困难， 不利于调制小粒径碳 粉。 另外， 如果着色剂内包蜡粒子的数量平均一次粒径小于 10nm 时， 则存 在碳粉中的蜡含有量降低问题，有可能引起低温定影时耐粘棍性改善效果低 下的问题。 将着色剂内包蜡粒子在水系媒体中分散的方法并不限定，比如可以使用 clearmix (分散机商品名， M technique公司制 )这样的高速旋转通过剪断以 及气穴进行分散的装置、 使用 TK均质仪（特殊机化工业制 )这样的高速旋 转通过剪断进行分散的装置、 或者 SC mill (粉碎机商品名， 三井矿山株式 会社制） 以及砂磨机这样使用媒体进行分散的装置。
另外， 在分散着色剂内包蜡粒子时， 最好使用将蜡加热到融点以上， 然 后在水系媒体中分散的方法。
在着色剂内包蜡粒子的存在下添加游离基聚合性单体，然后使其聚合调 制树脂粒子时，先调制上述着色剂内包蜡粒子分散液， 然后添加游离基聚合 性单体， 根据必要性添加聚合开始剂， 进行游离基聚合反应， 调制含有着色 剂与蜡的树脂粒子， 然后将该粒子凝集、 融着， 从而得到碳粉。
本发明使用的游离基聚合性单体可以为： 苯乙烯、 α -曱基苯乙婦、 氯 苯乙烯、 二氯苯乙烯、 对叔丁基苯乙烯、 4-丁基苯乙婦、 4 _壬基苯乙烯等 苯乙烯类、 丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙酯、 丙烯酸 n -丁酯、 丙烯 酸异丁酯、 丙烯酸羟乙酯、 丙烯酸乙基己基酯、 异丁烯酸曱酯、 异丁烯酸乙 酯、 异丁烯酸丙酯、 异丁烯酸 n -丁酯、 异丁烯酸异丁酯、 异丁烯酸羟乙酯、 异丁烯酸乙基己基酯等（meta ) 丙烯酸酯等。 这其中， 苯乙烯、 丙烯酸丁酯 尤其好。
可以使用有极性基的游离基聚合性单体，有酸性极性基的游离基聚合性 单体可以举出丙烯酸、 异丁烯酸、 马来酸、 富马酸、 桂皮酸等有 «的游离 基聚合性单体，橫化苯乙烯等有磺酸基的游离基聚合性单体等，特别优选丙 烯酸或异丁烯酸。
另外， 有碱性极性基的游离基聚合性单体可以举出氨基苯乙烯以及其 4 级盐、 乙婦基吡啶、 乙烯吡咯烷酮等含有氮含有复素环游离基聚合性单体， 丙烯酸二曱胺基乙酯、 曱基丙烯酸二乙氨基乙酯等有氨基的（meta )丙烯酸 酯， 以及将这些氨基 4级化的有铵盐的 （meta ) 丙烯酸酯、 以及丙烯酰胺、 N—丙基丙烯酰胺、 N, N —二曱基丙烯酰胺、 N, N —二丙基丙烯酰胺、 N, N -二丁基丙烯酰胺、 丙烯酸胺等。
这些游离基聚合性单体可以单独或者混合使用，但是此时， 聚合体的玻 璃转移温度在 40 - 70°C为好。 玻璃转移温度如果超过 70 °C , 则定影温度变 得过高， 有时会发生定影性低下的问题； 另一方面， 聚合体的玻璃转移温度 不满 40°C时， 碳粉的保存稳定性变差， 有时会发生凝集的问题。
聚合开始剂可以使用过硫酸钾、过硫酸钠、过硫酸铵等过硫酸盐的水溶 性聚合开始剂以及这些过硫酸盐与酸性亚硫酸钠或者抗坏血酸等还原剂组 合的氧化还原聚合开始剂、 过氧化氢、 4,4'-偶氮-二 (4-氰)戊酸
( 4,4'-Azobis(4-cyanovaleric acid) )、 过氧化叔丁醇、 异丙苯基过氧化氢等水 溶性聚合开始剂、以及这些水溶性聚合性开始剂与亚铁盐或抗坏血酸等还原 剂组合的氧化还原聚合开始剂等。这些聚合开始剂可以在游离基聚合性单体 添加前、 与添加同时、 添加后的任何时期添加到聚合系中， 根据必要也可以 组合使用这些添加方法。
在本发明中为了调整聚合体的分子量可以根据必要使用链转移剂。该链 转移剂的具体的例子有 t一十二烷基硫醇、 n -十二烷基硫醇、 2 -巯基乙醇、 二异丙基黄原、 四氯化碳、 三氯溴化曱烷等。 链转移剂可以单独或者 2种类 以上并用， 相对于游离基聚合性单体最大使用不超过 5重量％为好。 当使用 量过多时， 伴随着分子量的降低， 游离基聚合性单体的残留会变多， 有可能 会发生刺鼻气味等问题。 树脂粒子的数量平均一次粒径以 50nm ~ 1500nm 为好， 更好为 70 ~ 700nm。 另外，数量平均一次粒径可以使用贝克曼库尔特公司的 LS230进行 测定。 该数量平均一次粒径不满 50nm时， 由于蜡含有量小， 会发生所谓离 型效果发挥差的问题。 另外， 比 1500nm更大时， 碳粉粒径控制困难， 有时 会发生粒径分布变得广泛等问题。
另外， 本发明的碳粉也可以添加电荷控制剂， 带电控制剂可以使用众 所周知的任意物质， 可以单独使用或者并用。 正电荷性以季胺盐为好、 负电 荷性以水杨酸或者烷基水杨酸的铬、 辞、 铝等的金属盐、 金属络合物、 苯曱 基酸的金属盐、 金属络合物、 氨基化合物、 苯酚化合物、 萘酚化合物、 氨基 苯酚化合物等为好。其使用量可以根据碳粉所希望的带电量决定，通常相对 于粘合树脂 100重量份使用 0.01 ~ 10重量份， 更好为使用 0.1 ~ 10重量份。
该电荷控制剂可以在上述着色剂粒子与蜡粒子共存的状态下使用，也可 以单独使得电荷调节剂在水系媒体中分散，作为分散粒子的状态与上述树脂 粒子凝集加入。
使得树脂粒子凝集的方法有： 对树脂粒子分散液进行加热或者调整 pH 使得分散不安定化并使其凝集， 然后再加热融着的方法； 或者添加凝集盐凝 集， 然后再加热融着的方法等。 其中， 添加凝集盐使其凝集的方法可以形成 稳定的凝集状态， 是一种优秀的制造方法。
使其凝集的盐可以使用 1价或者多价的金属盐。 具体的说， 1价盐可以 举出钠盐、钾盐等， 比如氯化钠、 氯化钾等； 2价的金属盐可以举出氯化镁、 硫酸镁、 氯化钙、 硫酸 4弓等； 3价的金属盐可以举出氢氧化铝、 氯化铝等。
将树脂粒子凝集、加热融着时，将凝集盐在聚合体粒子的玻璃转移温度 以下加入，然后尽可能快速的升温、加热到聚合体粒子的玻璃转移温度以上。 至该升温的时间最好为 1小时以下。 而且升温有必要快速进行，升温速度以 0.25°C /分以上为好。 上限并不特别明确， 但是瞬时提高温度， 则盐析会急 剧进行、 会发生粒径难以控制的问题， 因此 5°C /分以下为好。 通过该融着 工程可以得到聚合体粒子以及任意微粒子盐析 /融着后的会合粒子（着色粒 子） 的分散液。
然后， 通过过滤、 洗净可以将着色粒子从水系媒体中分离。 这里过滤、 洗净方法有离心分离法、使用吸虑器等进行的减压过滤法、使用压滤机等进 行过滤以及洗净的方法， 这里并不特别限定。
然后将洗净处理的着色粒子滤饼干燥处理， 得到干燥的着色粒子的工 程。 该工程使用的干燥机可以举出喷雾干燥器、 真空冻结干燥机、 减压干燥 机等、 以使用静置棚干燥机、 移动式棚干燥机、 流动层干燥机、 回转式干燥 机、 搅拌式干燥机等为好。 干燥的着色粒子的水分以 5质量％以下为好， 更 好为 2质量％以下。 另夕卜， 干燥处理的着色粒子之间以较弱的粒子间引力凝 集时， 可以对该凝集体进行解碎处理。这里的解碎处理装置可以使用气流粉 碎机、亨舍尔搅拌机、磨咖啡机 (coffee mill)、食品加工机等机械式解碎装置。
在制造本发明的碳粉时，在凝集粒子的粒径实质上成长为最终的碳粉粒 径之后，还可以通过添加同种或者不同种类的粘合树脂乳浊液使得粒子附着 于表面， 从而修饰表面附近的碳粉性状。
另夕卜，本发明的碳粉可以根据必要使用流动化剂等添加剂，其流动化剂 具体的可以举出疏水性二氧化硅、 氧化钛、 氧化铝等微粉末， 通常相对于粘 合树脂 100重量份使用 0.01 ~ 5重量份， 以使用 0.1 ~ 3重量份为好。这些流 动化剂的数量平均一次粒径以 5 ~ 80nm为好。
另外， 本发明的碳粉还可以将磁铁矿、 铁氧体、 氧化铈、 钛酸锶、 导电 性二氧化钛等无机微粉末或苯乙烯树脂、 丙烯酸树脂等电阻调節剂、滑剂等 作为内添剂或者外添剂使用。这些添加剂的使用量可以根据所希望的性能适 宜选定， 通常相对于粘合树脂 100重量份， 以 0.05 ~ 10重量份程度为合适。 这些添加剂使用比较大粒径的为好， 其数量平均一次粒径为 100 ~ 1000nm。
本发明的静电荷像显影用碳粉可以以双组分系显影剂或者非磁性单组 分系显影剂的形态使用。 当作为双组分系显影剂使用的场合， 载体可以使用 鉄粉、磁铁矿粉、铁氧体粉等磁性物质或者在这些物质表面有树脂涂层的物 质以及磁性载体等众所周知的物质。树脂涂层载体的覆盖树脂一般所知的可 以使用苯乙烯系树脂、丙烯酸系树脂、苯乙烯丙烯酸共聚合系树脂、硅树脂、 变性硅树脂、 氟树脂， 或者这些的混合物等。 具体实施方式
着色剂内包培粒子调制例 1
在二十二酸二十二酯 lOOg中添加碳黑 50g, 使用亨舍尔搅拌机干式混 合， 然后在双辊机中熔融混炼， 使得二十二酸二十二酯中分散有碳黑。 熔融 混炼后冷却， 得到分散有碳黑的二十二酸二十二酯。 然后， 将上述分散有碳 黑的二十二酸二十二酯 30g加热到 85 °C使得二十二酸二十二酯熔解， 然后 投入加热到 85°C的十二烷基苯蹟酸钠的 5 % (重量百分比）水溶液 200g中， 使用 ClearMix使其分散为数量平均一次粒径 120nm, 冷却到 30°C , 得到分 散有碳黑的二十二酸二十二酯粒子分散液。 该粒径使用贝克曼库特公司的 LS230测定。 另外， 这里将其命名为着色剂内包蜡粒子（1 )分散液。
着色剂内包培粒子调制例 2
在着色剂内包蜡粒子调制例 1中，将二十二酸二十二酯变更为精制巴西 棕榈蜡 1号，其他条件相同得到分散有碳黑的精制巴西棕榈蜡 1号粒子分散 液。 其数量平均一次粒径为 105nm。 将其命名为着色剂内包蜡粒子（2 )分 散液。
着色剂内包培粒子调制例 3
在着色剂内包蜡粒子调制例 1中，将二十二酸二十二酯变更为季戊四醇 四山嵛酸酯 （ Pentaerythritol Tetrabehenate ), 其他条件相同得到分散有碳黑 的季戊四醇四山 酸酯（ Pentaerythritol Tetrabehenate )粒子分散液。 其数量 平均一次粒径为 145nm。 将其命名为着色剂内包蜡粒子 （3 )分散液。
着色剂内包培粒子调制例 4
在着色剂内包蜡粒子调制例 1中， 将碳黑变更为颜料红 122, 其他条件 相同得到分散有颜料红 122的二十二酸二十二酯粒子分散液。其数量平均一 次粒径为 145nm。 将其命名为着色剂内包蜡粒子（4 )分散液。
着色剂内包培粒子调制例 5
在着色剂内包蜡粒子调制例 2中， 将碳黑变更为颜料红 122, 其他条件 相同得到分散有颜料红 122的精制巴西棕榈蜡 1号粒子分散液。其数量平均 一次粒径为 135nm。 将其命名为着色剂内包蜡粒子（5 )分散液。
着色剂内包培粒子调制例 6
在着色剂内包蜡粒子调制例 3中， 将碳黑变更为颜料红 122, 其他条件 相同得到分散有颜料红 122 的季戊四醇四山 酸酯 （ Pentaerythritol Tetrabehenate )粒子分散液。 其数量平均一次粒径为 155nm。 将其命名为着 色剂内包蜡粒子 （ 6 )分散液。
着色剂内包培粒子调制例 7
在着色剂内包蜡粒子调制例 1 中， 将碳黑变更为颜料黄 74, 其他条件 相同得到分散有颜料黄 74的二十二酸二十二酯粒子分散液。 其数量平均一 次粒径为 135nm。 将其命名为着色剂内包蜡粒子（7 )分散液。
着色剂内包培粒子调制例 8
在着色剂内包蜡粒子调制例 2中， 将碳黑变更为颜料黄 74, 其他条件 相同得到分散有颜料黄 74的精制巴西棕榈蜡 1号粒子分散液。 其数量平均 一次粒径为 115nm。 将其命名为着色剂内包蜡粒子（8 )分散液。
着色剂内包培粒子调制例 9
在着色剂内包蜡粒子调制例 3 中， 将碳黑变更为颜料黄 74, 其他条件 相同得到分散有颜料黄 74 的季戊四醇四山嵛酸酯 （ Pentaerythritol Tetrabehenate )粒子分散液。 其数量平均一次粒径为 145nm。 将其命名为着 色剂内包蜡粒子 （ 9 )分散液。
着色剂内包培粒子调制例 10
在着色剂内包蜡粒子调制例 1中，将碳黑变更为颜料蓝 15:3 ,其他条件 相同得到分散有颜料蓝 15:3 的二十二酸二十二酯粒子分散液。 其数量平均 一次粒径为 125nm。 将其命名为着色剂内包蜡粒子（10 )分散液。
着色剂内包培粒子调制例 11
在着色剂内包蜡粒子调制例 2中，将碳黑变更为颜料蓝 15:3 ,其他条件 相同得到分散有颜料蓝 15:3的精制巴西棕榈蜡 1号粒子分散液。 其数量平 均一次粒径为 105nm。 将其命名为着色剂内包蜡粒子（11 )分散液。
着色剂内包培粒子调制例 12
在着色剂内包蜡粒子调制例 3中，将碳黑变更为颜料蓝 15:3 ,其他条件 相同得到分散有颜料蓝 15:3 的季戊四醇四山嵛酸酯 （Pentaerythritol Tetrabehenate )粒子分散液。 其数量平均一次粒径为 135nm。 将其命名为着 色剂内包蜡粒子 （ 12 )分散液。
着色剂内包培粒子调制例 13
在二十二酸二十二酯 lOOg 于 9 0°C加热熔解的物质中作为分散助剂添 加卵磷脂 0.05g, 然后使用砂磨机一边高速分散一边逐渐添加碳黑 50g。 然 后、 使用砂磨机分散一直到碳黑数量平均一次粒径到 80nm以下。 在热时从 砂磨机分离、 冷却后得到分散有碳黑的二十二酸二十二酯。 然后， 将上述分 散有碳黑的二十二酸二十二酯 30g加热到 85 °C使得二十二酸二十二酯熔解， 然后投入加热到 85 °C的十二烷基苯横酸钠的 5 %水溶液 200g 中， 使用 ClearMix使其分散为数量平均一次粒径 120nm, 冷却到 30°C , 得到分散有 碳黑的二十二酸二十二酯粒子分散液。该粒径使用贝克曼库特公司的 LS230 测定。 另外， 这里将其命名为着色剂内包蜡粒子（ 13 )分散液。
着色剂内包培粒子调制例 14
在着色剂内包蜡粒子调制例 13 中， 将碳黑变更为颜料红 122 , 其他条 件相同得到分散有颜料红 122的二十二酸二十二酯粒子分散液。其数量平均 一次粒径为 155nm。 将其命名为着色剂内包蜡粒子（14 )分散液。
着色剂内包培粒子调制例 15
在着色剂内包蜡粒子调制例 13中， 将碳黑变更为颜料黄 74, 其他条件 相同得到分散有颜料黄 74的二十二酸二十二酯粒子分散液。 其数量平均一 次粒径为 145nm。 将其命名为着色剂内包蜡粒子（15 )分散液。
着色剂内包培粒子调制例 1 6
在着色剂内包蜡粒子调制例 13中， 将碳黑变更为颜料蓝 15:3 , 其他条 件相同得到分散有颜料蓝 15:3 的二十二酸二十二酯粒子分散液。 其数量平 均一次粒径为 135nm。 将其命名为着色剂内包蜡粒子（16 )分散液。 树脂粒子调制例 1
将着色剂内包蜡粒子 （1 )分散液装入拥有搅拌装置、 加热冷却装置、 浓缩装置以及各原料投入口的玻璃制反应容器中， 加热到 40°C , 添加十二 烷基苯橫酸钠的 5 %的水溶液 800g , 再加入水溶性聚合开始剂过硫酸钾 1.2g。 加温到 85 °C之后， 使用 1小时滴下由苯乙烯 70g、 丙烯酸丁酯 20g、 异丁烯酸 10g构成的单体溶液， 进行以着色剂内包蜡粒子（ 1 ) 为种子的种 子聚合。 7小时后结束反应。 反应结束后， 冷却到 20°C测定粒径。 该着色剂 以及蜡内包树脂粒子的粒径为 220nm。将该着色剂以及蜡内包树脂粒子命名 为树脂粒子（ 1 )。
树脂粒子调制例 2
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（2 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 230nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 2 )。
树脂粒子调制例 3
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（ 3 ) , 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 250nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 3 )。
树脂粒子调制例 4
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（ 4 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 240nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 4 )。
树脂粒子调制例 5
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（ 5 ) , 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 220nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 5 )。
树脂粒子调制例 6
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（ 6 ) , 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 240nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 6 )。
树脂粒子调制例 7
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（7 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 250nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 7 )。
树脂粒子调制例 8
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（ 8 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 240nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 8 )。
树脂粒子调制例 9
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（ 9 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂及 蜡内包树脂粒子的粒径为 230nm。将该着色剂及蜡内包树脂粒子命名为树脂 粒子（ 9 )。
树脂粒子调制例 10
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子 （10 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 245nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（10 )。
树脂粒子调制例 11
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（11 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 230nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（11 )。
树脂粒子调制例 12
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（12 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 250nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（ 12 )。
树脂粒子调制例 13
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（13 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 260nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（ 13 )。 树脂粒子调制例 14
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子 （14 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 230nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（ 14 )。
树脂粒子调制例 15
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子 （15 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 240nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（15 )。
树脂粒子调制例 1 6
在树脂粒子调制例 1 中， 将着色剂内包蜡粒子（1 ) 变更为使用着色剂 内包蜡粒子（16 ), 其他条件相同得到着色剂及蜡内包树脂粒子。 该着色剂 及蜡内包树脂粒子的粒径为 250nm。将该着色剂及蜡内包树脂粒子命名为树 脂粒子（16 )。
碳粉调制例 1
将上述树脂粒子（ 1 )的分散液在 30°C—边搅拌， 一边将氯化镁水溶液 (浓度 = 20 % ) 300g使用 30分钟滴下， 然后升温到 80°C。 监视粒径成长， 在粒径（体积基准的中值径： 使用贝克曼库尔特公司制库尔特 Multi sizer ll 测定）到达 6 .5μηι的时间点上， 添加水 300g, 使得粒径成长停止。 然后升 温到 9 5°C , 使用 5 小时使得形状球形化。 在形状系数到达 0. 9 6 5 (使用 FPIA-3000测定）时， 冷却到 20°C。 然后使用离心分离器过滤、 水洗净、 加 热减压干燥。 对于干燥后的粒子 100g 添加疏水性二氧化硅 ( Hexamethyldisilazane处理、 数量平均一次粒径 = 12nm ) lg、 疏水性二氧 化钛（三曱基辛基硅烷处理、 数量平均一次粒径 =25nm) 0.5g、 使用亨舍尔 混合机混合。 得到的碳粉称为碳粉 1。
碳粉调制例 2
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（2), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 2。
碳粉调制例 3
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（3), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 3。
碳粉调制例 4
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（4), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 4。
碳粉调制例 5
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（5), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 5。
碳粉调制例 6
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（6), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 6。
碳粉调制例 Ί
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（7), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 7。
碳粉调制例 8
在碳粉调制例 1 中， 将树脂粒子（1 ) 变更为使用树脂粒子（8), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 8。
碳粉调制例 9
在碳粉调制例 1中， 将树脂粒子（1 ) 变更为使用树脂粒子（9 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 9。
碳粉调制例 10
在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 10 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 10。
碳粉调制例 11
在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 11 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 11。
碳粉调制例 12
在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 12 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 12。
碳粉调制例 13
在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 13 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 13。
碳粉调制例 14
在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 14 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 14。
碳粉调制例 15
在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 15 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 15。
碳粉调制例 1 6 在碳粉调制例 1中， 将树脂粒子（ 1 )变更为使用树脂粒子（ 16 ), 其他 条件相同得到碳粉。 将得到的碳粉命名为碳粉 16。
比较用碳粉 1
将十二烷基苯横酸钠 5 %水溶液 200g加热到 85°C , 然后添加二十二酸 二十二酯 15g加热到 85°C熔解的物质， 使用 ClearMix进行分散。 在数量平 均一次粒径分散到 120nm的阶段结束分散， 冷却到 30°C , 得到二十二酸二 十二酯分散液（ A1 )。
然后， 在十二烷基苯蹟酸钠 5 %水溶液 200g 中添加碳黑 8g, 使用 ClearMix进行分散。 在数量平均一次粒径分散到 lOOnm的阶段结束分散， 得到碳黑分散液（Bl )。
在具备搅拌装置、 加热冷却装置、 浓缩装置、 以及各原料投入口的玻璃 制反应容器中添加十二烷基苯蹟酸钠 5 %水溶液 6 00g, 然后添加水溶性聚 合开始剂过硫酸钾 1.2g,加温到 85°C后使用一小时滴下由苯乙烯 70g、 丙烯 酸丁酯 20g、 异丁烯酸 10g构成的单体溶液进行乳化聚合， 7小时候结束反 应。 反应结束后冷却到 20°C , 得到数量平均一次粒径为 130nm的树脂粒子 ( Cl )。
将上述二十二酸二十二酯分散液（ A1 )、 碳黑分散液（B1 )在上述树脂 粒子（C1 )的分散液中 30°C混合、 一边搅拌一边使用 30分钟滴下氯化镁水 溶液（浓度 = 20 %重量百分比） 300g, 然后升温到 80°C。 监视粒径成长， 在粒径（体积基准的中值径： 使用贝克曼库尔特公司制库尔特 Multi sizer ll 测定 )到达 6 .5μηι的时间点上， 添加水 300g以及氯化钠 10g, 使得粒径成 长停止。 然后升温到 9 5°C , 使用 5小时使得形状球形化。 在形状系数到达 0. 9 6 5 (使用 FPIA-3000测定） 时， 冷却到 20°C。 然后、 使用离心分离器 过滤、 水洗净、 加热减压干燥。 对于干燥后的粒子 100g添加疏水性二氧化 硅（ Hexamethyldisilazane (六曱基二硅氮烷)处理、数量平均一次粒径 = 12nm ) lg、 疏水性二氧化钛（三曱基辛基硅烷处理、 数量平均一次粒径 = 25nm ) 0.5g使用亨舍尔混合机混合。 得到的碳粉称为比较用碳粉 1。
比较例用碳粉 2
在比较用碳粉 1中，将碳黑变更为使用颜料红 122,其他使用同样条件， 得到比较用碳粉 2。
比较例用碳粉 3
在比较用碳粉 1中， 将碳黑变更为使用颜料黄 74, 其他使用同样条件， 得到比较用碳粉 3。
比较例用碳粉 4
在比较用碳粉 1中，将碳黑变更为使用颜料蓝 15:3 ,其他使用同样条件， 得到比较用碳粉 4。
评价
使用上述得到的碳粉实施定影性（粘辊性）与耐久性评价。
这些碳粉使用非磁性单组分方式的打印机进行评价。打印机使用的是惠 普公司制 ColorLaserJet 2605。
粘棍性评价：
使用该打印机在低温低湿（ 10°C / 10 % RH环境）下进行黄 /品红 /青 /黑各色的像素率为 10 %的点图案 （全像素率 = 40 %的半色调图像）连续 印刷 1000张， 然后将电源在 OFF的状态下停止 1晚。 在后一天一早在白纸 上印字、 通过目视评价定影部是否有碳粉的吐出。
耐久性评价 使用上述打印机在高温高湿（33°C/85%RH环境）下进行黄 /品红 / 青 /黑各色的像素率为 1%的文字图像印刷， 在 1枚间歇模式（ 1张印字后 休息 10秒的方法） 下连续印字 4000张。 对初期以及 4000张印字后的图像 浓度（黑） 以及底灰浓度通过以纸反射浓度为 「0」 的相对反射浓度进行比 较。 然后， 在全彩色目视下对 Y/M/C以及 B/G/R形成的色域进行比 较。 比较以初期得到的色域面积为 100, 以 4000张后的色域面积来进行比 较。
碳粉使用了以下组合。
实施例 1: 碳粉 1/碳粉 4/碳粉 7/碳粉 10
实施例 2: 碳粉 2/碳粉 5/碳粉 8/碳粉 11
实施例 3: 碳粉 3 /碳粉 6 /碳粉 9 /碳粉 12
实施例 4: 碳粉 13 /碳粉 14 /碳粉 15 /碳粉 16
比较例 1： 比较用碳粉 1 /比较用碳粉 2 /比较用碳粉 3 /比较用碳粉 4 评价结果
Figure imgf000023_0001
初期 4000张后 画像浓 画像浓
底灰浓度 色域 底灰浓度 色域 度（黑） 度（黑） 实施例 1 1.41 0.000 100 1.40 0.000 99 实施例 2 1.40 0.000 100 1.40 0.000 99 实施例 3 1.41 0.000 100 1.41 0.000 99 实施例 4 1.41 0.000 100 1.41 0.000 99 比较例 1 1.38 0.000 100 1.26 0.006 87
如上所述本发明的碳粉可以长期维持稳定的性能。

Claims

权 利 要 求 书
1、 一种静电荷像显影用碳粉的制造方法， 包括至少使得树脂粒子在水 系媒体中凝集从而制造含有树脂、着色剂与蜡的静电荷像显影用碳粉， 其特 征在于， 该树脂粒子内包着色剂以及蜡， 并且该树脂粒子为在着色剂内包蜡 粒子分散的水系媒体中逐渐添加游离基聚合性单体，然后使得上述游离基聚 合性单体聚合从而形成的树脂粒子， 进一步将该树脂粒子在水系媒体中凝 集， 融着从而得到碳粉粒子。
PCT/CN2010/070524 2010-01-06 2010-02-05 静电荷像显影用碳粉的制造方法 WO2011082556A1 (zh)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186253A (ja) 1987-01-29 1988-08-01 Nippon Carbide Ind Co Ltd 静電荷像現像用トナ−
JP2001027821A (ja) 1998-06-24 2001-01-30 Mitsubishi Chemicals Corp 静電荷像現像用トナー
US20070134583A1 (en) * 2005-12-10 2007-06-14 Samsung Electronics Co., Ltd. Method of preparing toner and toner prepared using the method
CN101061440A (zh) * 2004-11-22 2007-10-24 三菱化学株式会社 静电荷图像显影用调色剂的制造方法以及静电荷图像显影用调色剂
CN101097411A (zh) * 2006-06-30 2008-01-02 三星电子株式会社 制备调色剂的方法以及利用该方法制备的调色剂
CN101256367A (zh) * 2008-03-06 2008-09-03 湖北鼎龙化学有限公司 静电荷显影用碳粉及其制造方法
CN101315526A (zh) * 2008-07-17 2008-12-03 湖北鼎龙化学股份有限公司 静电荷显影用碳粉的制造方法
JP2008299086A (ja) * 2007-05-31 2008-12-11 Canon Inc トナー及び画像形成方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63186253A (ja) 1987-01-29 1988-08-01 Nippon Carbide Ind Co Ltd 静電荷像現像用トナ−
JP2001027821A (ja) 1998-06-24 2001-01-30 Mitsubishi Chemicals Corp 静電荷像現像用トナー
CN101061440A (zh) * 2004-11-22 2007-10-24 三菱化学株式会社 静电荷图像显影用调色剂的制造方法以及静电荷图像显影用调色剂
US20070134583A1 (en) * 2005-12-10 2007-06-14 Samsung Electronics Co., Ltd. Method of preparing toner and toner prepared using the method
CN101097411A (zh) * 2006-06-30 2008-01-02 三星电子株式会社 制备调色剂的方法以及利用该方法制备的调色剂
JP2008299086A (ja) * 2007-05-31 2008-12-11 Canon Inc トナー及び画像形成方法
CN101256367A (zh) * 2008-03-06 2008-09-03 湖北鼎龙化学有限公司 静电荷显影用碳粉及其制造方法
CN101315526A (zh) * 2008-07-17 2008-12-03 湖北鼎龙化学股份有限公司 静电荷显影用碳粉的制造方法

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