EP2490074A2 - Toner de développement d'image électrostatique - Google Patents
Toner de développement d'image électrostatique Download PDFInfo
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- EP2490074A2 EP2490074A2 EP10808329A EP10808329A EP2490074A2 EP 2490074 A2 EP2490074 A2 EP 2490074A2 EP 10808329 A EP10808329 A EP 10808329A EP 10808329 A EP10808329 A EP 10808329A EP 2490074 A2 EP2490074 A2 EP 2490074A2
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- Prior art keywords
- toner
- particles
- toner composition
- composition according
- prepared
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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
- G03G9/0802—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
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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
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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
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
-
- 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
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
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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
- G03G9/0821—Developers with toner particles characterised by physical parameters
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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
- G03G9/0827—Developers with toner particles characterised by their shape, e.g. degree of sphericity
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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
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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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/0975—Organic compounds anionic
Definitions
- the present invention relates to, in the toner including a binding resin, a coloring agent and a releasing agent, an electrostatic image developing toner, its composition, and a preparation method thereof.
- the electrostatic image developing toner is prepared by the method comprising:
- the toner prepared according to the method of the present invention has a narrow particle size distribution, has small consumption and imagery stability with high definition.
- a copy image or a printed image may be obtained by forming an electrostatic latent image on a photosensitive member by various means using photoconductive materials, developing the latent image using a toner and transferring the toner image to a transfer medium such as a paper as occasion demands, and fixing thereof by action of heat, pressure, heat and pressure, or solvent steam. Also, the abovementioned processes are repeated after cleaning the toner left on the photosensitive member without transfer using various means.
- the toner used for these purposes is generally a grinding toner made as a toner having a desired particle diameter obtained by fusing and mixing a coloring agent consist of a dye or a pigment of thermoplastics and uniformly dispersing thereof, and grinding finely and sorting thereof.
- the toner made by the abovementioned method has a good quality, it has some problems in view of imagery quality.
- the resin composition in which the coloring agent is dispersed is easily breakable enough to be finely grinded by an economical manufacturing device.
- the resin composition is easy to form particles having a wide particle diameter substantially in fine grinding rapidly, particularly may cause a seriously problem such as document pollution because there are relatively small particles thereof.
- a sorting process is performed in order to remove undesired particles, there is, in this case, a critical problem that it causes high production costs that production yield in manufacturing is low because of wide particle size distribution.
- Japanese Patent 1962-10231 , 1968-10799 , 1978-14895 provide the methods for product a toner by suspension polymerization.
- toner particles having a desired particle diameter are obtained by forming monomer composition by uniformly dissolving and dispersing polymerizable monomer, a coloring agent, polymerization starter, if required, cross-linker, charge control agents, and other addition agents, dispersing the monomer composition to aqueous-phase medium including dispersion stabilizer.
- the method has some advantages that it needs not the breakable property of the resin composition because of having not the grinding step, and can use soft materials, and also that the toner particles has uniform frictional electrification because the a coloring agent does not expose to the surface of the toner particles. Also, the method is very effective in the view of cost reduction such as energy save, production time shortening, process yield improvement, etc. because the sorting step can be omitted.
- the method has a disadvantage that the uniform electrification may be degraded and the development capability of the toner may be changed.
- the phenomenon is noticeable in case of copy or printing particularly in environment of high temperature and humidity.
- the method for spreading a resin on the surface layer of the toner particles such as described in Japanese Patent 1988-73277 , 1992-35662 is suggested.
- the method may prevent the abovementioned phenomenon affected by a coloring agent by making the thick of the spread layer be thicker, it has a serious problem that absolute value of the quantity of electron charge become smaller because the toner contains little composition having charge controllability. Such problem is being recognized and reported substantially in many case.
- the method for adhering charge control agents to the surface of the toner such as described in Japanese Patent 1990-62666 , 1990-630635 , 1987-273558 , and 1994-134437 is suggested.
- the method may cause a serious problem in operation as, in case of repeat of copy or printing, the charge control agents are separated from the surface of the toner particles in view of durability of the toner.
- Japanese Patent 1986-238846 , and 1994-197203 disclose the use of an electrostatic image developing toner containing the toner particles made by suspension polymerization method which performs dispersing polymerizable monomer composition containing polyester resin to water-borne medium and assembling thereof.
- it is expected to provide an electrostatic image developing toner having a better friction electrification, multiple operation, heat-resisting offset property and translucency.
- Improvement of low temperature fixing property is an important factor for performing high speed processing and full color printing by a printer and a copy machine.
- a toner obtained by a polymerization method wherein obtainment of toner particles of which the particle diameter has a sharp distribution and is very small may be relatively easy. It is essential that the toner used in a full color copy machine or a full color printer endures well a compound color in fixing step, thus, improvement of color reproduction or maintenance of transparency of OHP image is very important. Also, it is preferable that the color toner is made with the resin having better fusing property and lower molecular weight than a black-and-white toner.
- Wax having relatively high degree of crystallization for example, polyethylene wax and polypropylene wax are used as releasing agents of the black-and-white toner in order to improve heat-resisting offset property in fixing.
- polyethylene wax and polypropylene wax are used as releasing agents of the black-and-white toner in order to improve heat-resisting offset property in fixing.
- the full color toner because of high degree crystallization of the wax, transparency of image lowers in printing through OHP and serious problems occurs in high speed processing and low temperature fixing property.
- a toner particularly a color toner made by a polymerization method, it is required to provide a toner which is solvable smoothly the problems occurred all in development and fixing property.
- the object of the present invention is to provide an electrostatic image developing toner which solves the abovementioned problems, a composition of the toner and a preparation method of the composition.
- the present invention relates to the electrostatic image developing toner which is prepared by the following method, and the preparation method comprising:
- the other object of the present invention is to provide a method to prepare a toner having a narrow particle size distribution, small consumption and good imagery stability with high definition.
- the coloring agent used in the present invention is preferably selected from known pigments which may be used in the toner and are used.
- black pigment yellow pigment, magenta pigment, cyan pigment as the pigments
- carbon black aniline black, nonmagnetic ferrite, and magnetite etc, as the black pigment.
- the carbon black for black pigment exists as an aggregate of very fine first particle, and is easy to be coarsened because of re-aggregation in being dispersed as pigment dispersion agent.
- a degree of re-aggregation of the carbon black particles has relevance to a large/small quantity of impurities contained in the carbon black, therefore it is very preferable that the quantity of impurities is contained to the extent that the polymerization is not prevented.
- the carbon black is made by Furnace method.
- a compound which represents Nitrogenous fused compound, Isoindolinone compound, Azo metal complex compound, Arylamine compound, etc. is used as the yellow pigments.
- C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 94, 95, 109, 110, 111, 128, 147, 150, 155, 168, 180, 194, etc. are used, and it is able even to use only one or mixed more than one of the Yellow Pigments for color mixture.
- Nitrogenous fused compound, Pyrrole compound, Anthraquinone, Quinacridone compound, Naphthol compound, Benzoimidazolone compound, Thio indigo compound, Perylene compound are used as the magenta pigment.
- C.I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 166, 169, 173, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, C.I. Violet 19 etc. are preferable.
- Quinacridoneseries Pigment represented by C.I. Pigment Red 122,202,207,209, C.I. Pigment Violet 19 is more preferable.
- C.I. Pigment Red 122 of the Quinacridoneseries Pigment is very preferable.
- Copper phthalocyanine compound and its derivatives, Anthraquinone compound etc. may be used as the cyan pigment.
- C.I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66 etc. and C.I. Pigment Green 7,36 etc. may be used particularly.
- Such a coloring agent may be used alone, in a mixture or in a solid solution.
- the coloring agent is suitably selected considering color, a degree of color saturation, brightness, weathering, OHP transparency, and dispersion property in the toner particles.
- the coloring agent may be added by 1 to 20 parts by weight based on 100 parts by weight of a bonding agent.
- the toner particles should be used with attention of a unique polymerizing inhibitory action or an aqueous phases transfer property contained in the coloring agent because it is made by polymerization method.
- Surface of the coloring agent may be modified by hydrophobic treatment using materials without polymerization inhibitory property.
- the carbon black has polymerization inhibitory property, thus it should be careful to use it.
- polar resins a polymer or copolymer having polar group
- polar monomer and polymerize thereof add a polar monomer and polymerize thereof, or mixed-add the polar resins and the polar monomer and polymerize thereof before manufacturing fine particles of suspension polymerization process.
- nitrogen-containing polymer such as ethyl of methacrylic dimethyl acid network, ethyl of metacrylic acid diethyl network, etc. or copolymer with styrene-unsaturated carbonic acid ester, etc. or nitrile-based monomer such as acrylonitrile, halogen-containing based monomer such as vinyl chloride, unsaturated carbonic acid such as acrylic acid or methacrylic acid etc. or a polymer such as unsaturated diacid, unsaturated diacid anhydride, nitrogen-containing monomer, etc. or copolymer with styrene-based monomer, etc. or polyester resins, or epoxy resins.
- the polyester resins are very preferable.
- the monomers having polar group which may be used in the present invention are as follows.
- the monomers having polar group are divided into acidic monomer and basic monomer.
- the acidic monomer is a polymerizable monomer having carboxyl group such as acrylic acid, methacrylic acid, itconic acid, maleic acid, fumaric acid, cinnamic acid, etc. or a polymerizable monomer having sulfonic acid group such as sulfonated styrene, etc. or a polymerizable monomer having sulfonamide group such as vinyl benzene sulfonamide, etc.
- the basic monomer is a nitrogen-containing heterocyclic polymerizable monomer such as aromatic vinyl compounds, vinyl pyridine, vinyl pyrrolidone etc. which have amino group such as styrene network.
- Such polar monomer may be used alone, or used in mixture. Also, it is possible that the polar monomer exists as salts with counter-ions. Among them, it is preferable to use the acidic monomer, more preferable to use acrylic acid or methacrylic acid.
- a ratio of an amount of the polar resins or the polar monomer or the mixture of the polar resins and the polar monomer in total amount of 100% by weight of polymerizable monomer consisting of binder resins as fine particles of suspension polymerization process or seeded polymerization process is an amount of 0.05% by weight to 20% by weight, more preferable 0.5% to 15% by weight.
- the raio is within the range, the fine particles of suspension polymerization process and seeded polymerization process to be gotten have improved stability is easy for a shape or a particle diameter of the particles to be controlled.
- the polymerizable monomer exists as a mixed layer, thus it is easy for assembly and polymerization stability to be deteriorated, also it causes the hardness of the generated resins particles surface layer to lower and properties of charge stability, durability, conservativeness, etc. as a toner to lower. Also, in the case of exceeding 20% by weight of the ratio, viscosity of the generated polimerizable monomer is too increased, therefore it is difficult to control the particle diameter of the desired assembling particles, and also cause the toner particles not to fuse and fixing property to damage seriously.
- Polymerizable monomers having polar group which may be used in the present invention are followed.
- styrene monomers such as styrene, chlorostyrene, dichlorostyrene, p-tert-butyl styrene, p-n-butyl styrene etc.
- acrylic acid ester monomers such as acrylic acid methyl, acrylic acid ethyl, acrylic acid propyl, acrylic acid n-butyl, acrylic acid iso butyl, acrylic acid hydrixy ethyl, acrylic acid ethylhexyl, etc.
- methacrylic acid ester monomers such as methacrylic acid methyl, methacrylic acid ethyl, methacrylic acid propyl, methacrylic acid n-butyl, methacrylic acid iso butyl, methacrylic acid hydroxyl ethyl, methacrylic acid ethylhexyl etc., acryl
- styrene monomer or the styrene monomer with one monomer or more than one monomer selected from acrylic acid ester monomers and methacrylic acid ester monomers in order to obtain good toner particles in a view of developing property and durability etc, in developing.
- the polymerizable monomers are generally used alone or appropriately with mixture for theoretical Glass Transition Temperature(Tg) to be 40 ⁇ 75° C which is disclosed at Polymer Handbook second edition III pp.139 ⁇ 192(Jone Wiley & sons private ).
- Tg Glass Transition Temperature
- toner particles it is one preferable type to add releasing agents as seeds and performing seeded polymerization when preparing seeded polymerization process particles.
- releasing agents When the releasing agents are being exposed on the toner surface, toners are easy to be agglomerated each other, and the toners may be fixed to a photo conductor when printing.
- the releasing agents are not exposed on the toner surface after agglomeration and large amount of wax can be used by containing the agent by seeded polymerization, and it may manufacture toner particles having high resolution and anti-offset property and also suitable to image forming device.
- Usable wax as a releasing agent used in the present invention is petroleum-based wax and its derivatives such as paraffin wax or styrene modified paraffin wax, micro crystal wax, petrolatum, montan-based wax and its derivatives, hydrocarbon wax and its derivatives by Fischer-Tropsch method, polyolefin wax and its derivatives represented by polyethylene, and natural wax and its derivatives such as carnauba wax, candelila wax, etc., and the derivatives contain block copolymer with oxide or vinyl-based monomer, and modified graft monomer. Also, fatty acids or compounds thereof such as higher aliphatic alcohol, stearate, palmitic acid, etc., acid amides wax, ester wax, plant-based wax, animal-based wax, etc. may be used.
- petroleum-based wax and its derivatives such as paraffin wax or styrene modified paraffin wax, micro crystal wax, petrolatum, montan-based wax and its derivatives, hydrocarbon wax and its derivatives by Fischer-Tropsch method,
- such wax component has a maximum heat absorption peak at 40°C to 110°C in heat up. It has a big efficiency of low temperature deposition and also shows an effective releasing property to have the maximum heat absorption peak in the temperature range. It is not preferable to exceed 110° C of the maximum heat absorption peak because the fixing temperature is climbing and low temperature offset is generated.
- DSC 200F3 of NETZSCH is used for measuring the maximum heat absorption peak of the wax component. Fusing point of indium and zinc is used for temperature correction of a detection part of the device, and the heat of fusion of indium is used for calorie correction. Sample for the measurement is aluminum cell, and the measurement is performed at 10 °C /minute of heat up rate.
- a content of the wax component as the releasing agent is an amount of 0.1 to 30% by weight, more preferable 0.5% to 20% by weight. Being less than 0.1% by weight of the content, it causes a releasing property to lower, so enough low temperature offset inhibitory effect is not shown. In case of exceeding 30% by weight, dispersion property of other material is deteriorated, or an aggravation of toner fluidity or a falling-off in image property is caused.
- charge control agent may be used in order to stabilize charge property of toner particles.
- the charge control agent may be used, particularly it is preferable to use a charge control agent which may have a rapid charging rate and keep stably uniform charging quantity.
- the charge control agent has a low polymerizable inhibition and has not any solubilized material to water-borne dispersion medium.
- metal compounds of aromatic series carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoeic acid, dicarboxylic acid, metallic salt or metal complex of azo dye or azo pigment, polymer compound having sulfonic acid or carboxyl acid in a branch, boron compounds, urea compounds, silicon compounds, carixareum, etc. are used as negative charge control agents, and nigrosine-based compounds, quaternary ammonium salts, polymer compounds having the quaternary ammonium salts in a branch, guanidine compounds, imidazole compounds, etc. are used as positive charge control agents.
- aromatic series carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoeic acid, dicarboxylic acid, metallic salt or metal complex of azo dye or azo pigment, polymer compound having sulfonic acid or carboxyl acid in a branch, boron compounds,
- charge control agent it is preferable to use with 0.5 to 10 parts by weight for 100 parts by weight of polymerizable monomer.
- charge control agent it is not essential to use charge control agent.
- charging quantity or charging rate may be controlled by actively using absence of restriction of layer pressure of the toner or frictional charging with developer bearing body(the abovementioned rotational sleeve).
- the emulsifier used as an aqueous dispersion stabilizer may be any of known emulsifiers, and it may be one or more than one surfactants in combination selected from a group consisting of cationic surfactant, anionic surfactant and non-ionic surfactant.
- the cationic surfactant may be, for example, dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridium chloride, dodecyl pyridium bromide, hexadecyl trimethyl ammonium bromide and the like.
- the anionic surfactant may be, for example, fatty acid salt such as sodium stearate, sodium dodecanate and the like, sodium dodecyl sulfate, sodium dodecyl benzenesulfonate, sodium lauryl lactate and the like.
- the non-ionic surfactant may be, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitant ether and the like.
- the amount of the emulsifier may be commonly 1 to 20 parts by weight for 100 parts by weight of the polymerizable monomer, preferably, and as a protecting colloid, one or more than one in combination selected from the group consisting of polyvinyl alcohols such as partly or completely safonified polyvinyl alcohol, cellulose derivatives such as hydroxyl ethyl cellulose, inorganic dispersing agent such as magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, aluminum phosphate, zinc phosphate, calcium phosphate tribasic, calcium hydrogen phosphate, calcium dihydrogen phosphate, and the like may be added to the emulsifier.
- polyvinyl alcohols such as partly or completely safonified polyvinyl alcohol
- cellulose derivatives such as hydroxyl ethyl cellulose
- inorganic dispersing agent such as magnesium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, aluminum phosphate, zinc phosphate, calcium
- the toner particles may be produced by using polymerization reaction.
- suspension polymerization method there are suspension polymerization method, emulsion polymerization method, emulsion associative polymerization method, dispersion polymerization method, suspension aggregation polymerization method, etc.
- a mixture except the releasing agent is process by suspension polymerization process to prepare fine particles, and the releasing agent is processed by seeded polymerization process to prepare fine particles, and then each fine particles are agglomerated into a desired size and fused by heat.
- the suspension seeded aggregation polymerization method is particularly preferred in view of degree of freedom of particle design and ease of control of particle size.
- a mixture except the releasing agent is process by suspension toner process to prepare fine particles, and separately, the releasing agent is processed by seeded polymerization process to prepare fine particles, and then each toner particle suspension and seeded polymerization particle suspension are mixed and agglomerated into a desired size and fused by heat, preferably.
- the fine particles polymerized by suspension polymerization process are produced by dispersing at least one selected from the group consisting of polymerizable monomers, polar resins, coloring agents except releasing agent in an water-borne dispersion medium mixed with one or a mixture of more than one selected from emulsifier, and organic and inorganic dispersion stabilizer, producing liquid droplet particles of polymerizable monomer composition, adding polymerization starter into the mixture before polymerization, adding thereof to the liquid droplet particles, and polymerizing polymerizable monomer components, and in the method for preparing fine particles by seeded polymerization process(S2), the seeded polymerization fine particles containing wax are produced by dispersing the releasing agent in an water-borne dispersion medium containing the emulsifier in advance and adding the releasing agent as a seed followed by polymerizing thereof using monomers for seeded polymerization.
- Toner particles having good degree of freedom of particle design and very uniform particle size distribution can be obtained by mixing the fine particle suspension prepared by suspension polymerization process and the fine particle suspension prepared by seeded polymerization process and agglomerating thereof using an agglomerating agent into a desired size, and then fusing thereof by heat. Because surface and shape of obtained toner particles are uniform and the releasing agents are not exposed on the surface, charging property and cohesion thereof are good, and good developing property is represented in electrostatic latent image developing in the electric photo process.
- polymerizable monomer mixture which is solved uniformly or dispersed using a homogenizer such as homogenizer, ball mill, colloid mill, ultrasonic homogenizer, etc. is suspended in the water-borne medium.
- a homogenizer such as homogenizer, ball mill, colloid mill, ultrasonic homogenizer, etc.
- high speed homogenizer such as high speed blender or ultrasonic homogenizer
- the polymerizable monomer mixture is stabilized by keeping the fine particle in the water borne medium in liquid droplet state in order to disperse uniformly the polymerizable monomer mixture in the water-borne dispersion medium.
- Polymerizable monomer droplets in stabilized fine particle state are polymerized with a polymerization starter.
- the temperature of polymerization is determined according to properties of matter of the polymerization starter, particularly a half-life temperature, the temperature is set at more than 40°C, generally 50 to 90°C and the polymerization is started.
- a water-soluble starter and an oil-soluble starter as the polymerization starter, wherein the half-life of the oil-soluble starter is 0.5 to 30 hours in polymerization reaction.
- persulfates such as peroxide, potassium persulfate, etc.
- organic peroxides such as benzoylperoxide, lauryl peroxide, etc.
- azo-group compounds such as 2,2'-azobis isobuthyronitrile, 2,2'-azobis(2,4-dimethylvaleronitile), etc., redox-group starter, etc. are used.
- azo-group compounds or organic peroxides are preferable.
- polymerization starter it is possible to obtain a polymer having a maximum in the range of weight average molecular weight 10,000 to 300,000 using quantity of 0.1 to 20 parts by weight of alone or more than one of polymerization starter for 100 parts by weight of polymerizable monomer, and to give preferable strength and proper fusing property to toner particles. Departing the half-life and addition quantity of the polymerization starter from the range, polymerizable monomers are not polymerized enough, or a good property of matter of the polymerized binding resins may have damage.
- the abovementioned polymerization starter may be added to the polymer whenever before adding the polymerizable monomer, simultaneously adding it, or after adding it, and such adding methods are performed with combined as demanded.
- a cross-linker may be added, and preferable adding quantity thereof is 0.001 to 15% by weight for 100 parts by weight of polymerizable monomer. Generally two more polymerizable compounds having a double band are used as the cross-linker.
- aromatic series divinyl compound such as divinylbenzen, divinylnaphthalene, etc., carboxylic acid ester having two double bands such as ethyleneglycole, diacrylate, ethyleneglycoledimethacrylate, 1,3-buthandioldimethacrylate, etc.
- compounds having three more vinyl groups such as divinyl aniline, divinyl ester, divinyl sulfide, divinyl sulfone, and divinyl compounds are used alone or with mixed.
- the adding quantity of the cross-linker being less than the range, it does not work enough. However, exceeding the range, the property of matter of binding resins may have bad influence.
- polymerization time being determined in view of polymerization conversion ratio, it is preferable that it is more than 30 minutes, generally 1 hour to 20 hours.
- the releasing agents can be mixed by uniformly dissolving or dispersing the releasing agent using a homogenizer such as high speed homogenizer, ball mill, colloid mill, ultrasonic homogenizer, etc. in the water-borne medium. At this time, the releasing agent dispersion is stabilized by keeping the fine particles in the water-borne.
- a homogenizer such as high speed homogenizer, ball mill, colloid mill, ultrasonic homogenizer, etc.
- the releasing agent dispersions in stabilized fine particle state are polymerized with polymerization monomer and a polymerization starter.
- the temperature of polymerization is determined according to properties of matter of the polymerization starter, and the temperature is set at more than 40°C, generally 50 to 95°C and the polymerization is started.
- a water-soluble starter and an oil-soluble starter as the polymerization starter, wherein the half-life of the oil-soluble starter is 0.5 to 30 hours in polymerization reaction.
- persulfates such as peroxide, potassium persulfate, etc.
- organic peroxides such as benzoylperoxide, lauryl peroxide, etc.
- azo-group compounds such as 2,2'-azobis isobuthyronitrile, 2,2'-azobis(2,4-dimethylvaleronitile), etc., redox-group starter, etc. are used.
- organic peroxides or azo-group compounds are preferable.
- polymerization starter it is possible to obtain a polymer having a maximum in the range of weight average molecular weight 10,000 to 300,000 using quantity of 0.1 to 20 parts by weight of alone or more than one of polymerization starter for 100 parts by weight of polymerizable monomer, and to give preferable strength and proper fusing property to toner particles. Departing addition quantity of the polymerization starter from the range, polymerizable monomers are not polymerized enough, or a good property of matter of the polymerized binding resins may have damage.
- the abovementioned polymerization starter may be added to the polymer whenever before adding the polymerizable monomer, simultaneously adding it, or after adding it, and such adding methods are performed with combined as demanded.
- a cross-linker may be added, and preferable adding quantity thereof is 0.001 to 15% by weight for 100 parts by weight of polymerizable monomer. Generally two more polymerizable compounds having a double bond are used as the cross-linker.
- aromatic divinyl compound such as divinylbenzen, divinylnaphthalene, etc., carboxylic acid ester having two double bonds such as ethyleneglycole, diacrylate, ethyleneglycoledimethacrylate, 1,3-buthandioldimethacrylate, etc.
- compounds having three more vinyl groups such as divinyl aniline, divinyl ester, divinyl sulfide, divinyl sulfone, and divinyl compounds are used alone or with mixed.
- the adding quantity of the cross-linker being less than the range, it does not work enough. However, exceeding the range, the property of matter of binding resins may have bad influence.
- polymerization time being determined in view of polymerization conversion ratio, it is preferable that it is more than 30 minutes, generally 1 hour to 30 hours.
- the average particle diameter(D50) of the fine particles prepared by suspension polymerization process and seeded polymerization process may be 50 nm to 10 ⁇ m , and preferably, 100 nm to 5 ⁇ m.
- the average particle diameter(D50) of the fine particles prepared by suspension polymerization process and seeded polymerization process is less than 50 nm, there are some difficulties that much aggregation agents are needed, and also much fine particles may be contained. Meanwhile, in the case that it exceeds 10 ⁇ m , there is a problem that the size of the particles after aggregation is too coarse so that the particles are scattered and a resolution is lowered in electrophotographic process, thereby final image has a bad influence.
- the dispersion of the fine particles prepared by suspension polymerization process and the dispersion of the fine particles prepared by seeded polymerization process produced by the polymerization are mixed and gone through aggregation process using a proper aggregation agent to have a desired particle diameter.
- An aggregation treatment used in the aggregation process is generally a method for heating in a blender, a method for adding an electrolyte, and a method combined thereof, etc.
- the electrolyte is any one of organic material or inorganic material.
- it is an inorganic salts having monovalent metallic cations such as NaCl, KCl, LiCl, Na 2 SO 4 , K 2 SO 4 , Li 2 SO 4 , CH 3 COONa, C 6 H 5 SO 3 Na, etc.
- an inorganic salts having divalent metallic cations such as MgCl 2 , CaCl 2 , MgSO 4 , CaSO 4 , ZnSO 4 , etc.
- an inorganic salts having trivalent metallic cations such as Al 2 (SO 4 ) 3 , Fe 2 (SO 4 ) 3 , etc.
- inorganic salts having multivalent metallic cations it is preferable to use inorganic salts having multivalent metallic cations in view of a high speed and high yield. Also, it is preferable to use the inorganic salts having monovalent metallic cations in view of controlling the speed of aggregation growth. What is used as the electrolyte may control an aggregation property by using one selected of inorganic salts having monovalent, divalent, trivalent metallic cations or with mixed thereof. Particularly, it is very preferable to select properly one of inorganic salts having divalent or trivalent metallic cations so that the aggregation property of the particles has a high speed, and then to select inorganic salts having monovalent metallic cations so as to control the aggregation speed.
- the electrolytes not at the same time but slowly in intermittent or continuous method. While the adding time is different according to a kind of the electrolytes and quantity to be used thereof, it is preferable for addition to be carried out during one more minutes. Generally, when the electrolytes being put at the same time, it is difficult to control the aggregation of the particles because the aggregation starts suddenly. Also, a desired toner particles and particle diameter distribution cannot be obtained because there remain many fine particles or too many aggregates.
- temperature of the aggregation process is 0°C to 90°C, more preferably 5°C to 80°C.
- To control the temperature of the aggregation process is one method for control the particle diameter and shape of special range of the present invention. It is possible for the aggregation process to be carried out by controlling pH or by adding polar organic solution such as alcohol.
- fusing process temperature by heat is preferably more than glass transfer temperature(Tg) of first suspension toner particles in micron state, more preferable is more Tg+5°C and less than Tg+50°C. Also, while time needed in the fusing process is different according to the shape of toner, it is preferable that it is generally 0.1 to 20 hours after arriving at more glass transfer temperature of fine particles prepared by suspension polymerization process and seeded polymerization process. It is more preferable to be kept during 0.5 to 15 hours.
- fine particles prepared by suspension polymerization process and seeded polymerization process are fused and integrated by heat.
- particle aggregates before fusing process are aggregate by electrostatic or physical aggregation
- various types of toner such as the shape for toner particles to be aggregated, for example, a potato type or sphere type may be obtained by controlling temperature and time, etc. of fusing process through the fusing process.
- the toner aggregate gone through each abovementioned processes is sorted into solid/ liquid according to a known method, and a desired toner particles may be obtained by collecting the particle aggregate, washing and drying thereof as demanded.
- the additive is metal oxide such as alumina, silica, titanium dioxide, zinc oxide, zirconium oxide, cesium oxide, talcum, hydrotalcite, etc., metal titanate such as hydroxide, calcium titanate, strontium titanate, barium titanate, etc., nitride such as titanium nitride, silicon nitride, etc., acrylic carbide based resins such as titanium carbide, silicon carbide, etc., organic particles such as melamine resins, and the mixture thereof. Silica, titanium dioxide, alumina among them is preferable.
- the surface is more preferable to be treated by silane coupling agent or silicon oil, and so on. It is preferable that average first particle diameter is in range of 500 nm, more preferable 5 to 100 nm. Also, in the range, an additive having the small particle diameter and an additive having the large particle diameter are preferable to be used together.
- Total mixed quantity of the additive is preferable to be in range of 0.05 to 10 parts by weight for 100 parts by weight of the toner particles, more preferable 0.1 to 5 parts by weight.
- the toner of the present invention obtained by the abovementioned methods is for distribution of charging quantity to be sharp in comparison to prior toner.
- the distribution of charging quantity is related to particle diameter of toner and position of charge control agent.
- charging quantity became wide.
- the wide distribution of charging quantity makes it difficult to control with a desired developing condition, makes the ratio of low charging particles of high charging particles increase, and thus results in various image faults.
- the present invention is easy to control particle diameter and rounded image by producing particles by processing a mixture except the releasing agent by suspension polymerization process to prepare fine particles, and by producing particles by separately processing the releasing agent by seeded polymerization process followed by mixing and agglomerating the suspension polymerization particle suspension and the seeded polymerization particle suspension into a desired size, and fusing thereof by heat. Also, the present invention provides an electrostatic image developing toner having uniform distribution of particle size in comparison to prior toner producing processes and, thus its toner consumption is low and is useful to an electro photographic process requiring high resolution.
- Anionic surfactant SDBS (Sodium Dodecyl Benzene Sulfonate) 20% aqueous solution 0.1 part and ion-exchanged water 300 parts were added to a stirrer, a heat-cooling device, a reflux device and a detachable reactor abled to insert each raw material (volume: 2 L), and stirred using TK type homomixer Mark (made by Primix) at 5,000 RPM in the condition of heating to 60° C under nitrogen gas flow to obtain water-borne dispersion medium.
- TK type homomixer Mark made by Primix
- a polymerizable monomer compounds was prepared by heating thereof at 60° C .
- a polymerizable monomer compounds is prepared by solving 4 parts of 2,2'-azobis(2,4-dimethylvaleronitril) as a polymerization starter in the styrene with maintaining 60° C , and then adding thereof to the polymerizable monomer compounds.
- a micronized polymerizable monomer mixture in dripped state was prepared by putting the abovementioned polymerizable monomer mixture into the water-borne dispersion medium solution under nitrogen gas flow, and stirring thereof at 10,000 RPM for 10 minutes at 60°C using TK type homomixer Mark II(made by Primix).
- Fine particle suspension was prepared by stirring the polymerizable monomer mixture in dripped state not to sink or float after changing into Teflon stirring blade, and simultaneously carrying out polymerization for 5 hours at 75°C.
- average particle diameter (D50) is 0.83 ⁇ m .
- Preparation Example 1 The process of Preparation Example 1 was repeated except for changing Carbon black(first particle diameter 31nm) 5 parts to Cyan pigment(C.I. PB 15:3, made by Dainippon) 6 parts in the process of dispersing and dissolving the polymerizable monomer mixture of Preparation Example 1 to prepare cyan pigment fine particle suspension.
- average particle diameter (D50) is 0.75 ⁇ m.
- Preparation Example 1 The process of Preparation Example 1 was repeated except for changing Carbon black(first particle diameter 31nm) 5 parts to magenta pigment(PIGMENT RED122, made by Dainippon) 6 parts in the process of dispersing and dissolving the polymerizable monomer mixture of Preparation Example 1 to prepare magenta pigment fine particle suspension.
- average particle diameter(D50) is 0.82 ⁇ m.
- Preparation Example 1 The process of Preparation Example 1 was repeated except for changing Carbon black(first particle diameter 31nm) 5 parts to yellow pigment(PIGMENT YELLOW 180, made by Dainippon) 6 parts in the process of dispersing and dissolving the polymerizable monomer mixture of Preparation Example 1 to prepare magenta pigment fine particle suspension.
- average particle diameter(D50) is 0.75 ⁇ m.
- SDBS Sodium Dodecyl Benzene Sulfonate
- the releasing agent dispersion prepared as described above 35 parts and ion-exchanged water 250 parts were added to a stirrer, a heat-cooling device, a reflux device and a detachable reactor abled to insert each raw material (volume: 2 L), and stirred while heating to 90 °C under nitrogen gas flow.
- the resulting solution was cooled to room temperature to obtain milk white releasing agent fine particle dispersion.
- average particle diameter(D50) is 0.7 ⁇ m .
- An agglomerating process, heat fusing process, washing and drying process and addition process were performed as follows in a stirrer, a heat-cooling device, a reflux device and a detachable reactor abled to insert each raw material (volume: 2 L) to prepare a black toner.
- the aggregation process carried out by slowly adding 5 parts of aluminum sulfate solution of 0.5 weight% thereto for 5 minutes until average particle diameter(D50) of final toner particles reaches to 6.5 ⁇ m .
- the resulting solution was heated to 80 °C for 1 hour followed by stirring at 150 RPM for 3 hours while maintaining the temperature at 80 °C.
- Decompression filtering was carried out by cooling slurry obtained after the abovementioned heat fusing process, and then, after enough washing thereof many times using ion exchanged water 500 part, black toner particles, wherein average particle diameter(D50) was 6.8 ⁇ m and the degree of rounding is 0.958, were obtained by drying thereof at 45 °C decompression dryer during 24 hours.
- Black toner particle having good fluidity is obtained by mixing hydrophobic silica(R972, made by Degu) 1 part with 100 parts of the black toner particles using multipurpose small mixing grinder(made by Mitsui mine).
- An agglomerating process, heat fusing process, washing and drying process and addition process were performed as follows in a stirrer, a heat-cooling device, a reflux device and a detachable reactor abled to insert each raw material (volume: 2 L) to prepare a cyan toner.
- the aggregation process carried out by slowly adding 5 parts of aluminum sulfate solution of 0.5 weight% thereto for 5 minutes until average particle diameter(D50) of final toner particles reaches to 6.5 ⁇ m.
- the resulting solution was heated to 80° C for 1 hour followed by stirring at 150 RPM for 3 hours while maintaining the temperature at 80 °C .
- Decompression filtering was carried out by cooling slurry obtained after the abovementioned heat fusing process, and then, after enough washing thereof many times using ion exchanged water 500 part, cyan toner particles, wherein average particle diameter(D50) was 6.7 ⁇ m and the degree of rounding is 0.951, were obtained by drying thereof at 45 °C decompression dryer during 24 hours.
- Cyan toner particle having good fluidity is obtained by mixing hydrophobic silica(R972, made by Degu) 1 part with 100 parts of the cyan toner particles using multipurpose small mixing grinder(made by Mitsui mine).
- An agglomerating process, heat fusing process, washing and drying process and addition process were performed as follows in a stirrer, a heat-cooling device, a reflux device and a detachable reactor abled to insert each raw material (volume: 2 L) to prepare a magenta toner.
- the aggregation process carried out by slowly adding 5 parts of aluminum sulfate solution of 0.5 weight% thereto for 5 minutes until average particle diameter(D50) of final toner particles reaches to 6.5 ⁇ m .
- the resulting solution was heated to 80 °C for 1 hour followed by stirring at 150 RPM for 3 hours while maintaining the temperature at 80 °C.
- Decompression filtering was carried out by cooling slurry obtained after the abovementioned heat fusing process, and then, after enough washing thereof many times using ion exchanged water 500 part, magenta toner particles, wherein average particle diameter(D50) was 6.7 ⁇ m and the degree of rounding is 0.948, were obtained by drying thereof at 45 °C decompression dryer during 24 hours.
- Magenta toner particle having good fluidity is obtained by mixing hydrophobic silica(R972, made by Degu) 1 part with 100 parts of the cyan toner particles using multipurpose small mixing grinder(made by Mitsui mine).
- An agglomerating process, heat fusing process, washing and drying process and addition process were performed as follows in a stirrer, a heat-cooling device, a reflux device and a detachable reactor abled to insert each raw material (volume: 2 L) to prepare a yellow toner.
- the aggregation process carried out by slowly adding 5 parts of aluminum sulfate solution of 0.5 weight% thereto for 5 minutes until average particle diameter(D50) of final toner particles reaches to 6.5 ⁇ m .
- the resulting solution was heated to 80 °C for 1 hour followed by stirring at 150 RPM for 3 hours while maintaining the temperature at 80 °C.
- Decompression filtering was carried out by cooling slurry obtained after the abovementioned heat fusing process, and then, after enough washing thereof many times using ion exchanged water 500 part, yellow toner particles, wherein average particle diameter(D50) was 6.5 ⁇ m and the degree of rounding is 0.950, were obtained by drying thereof at 45 °C decompression dryer during 24 hours.
- Yellow toner particle having good fluidity is obtained by mixing hydrophobic silica(R972, made by Degu) 1 part with 100 parts of the cyan toner particles using multipurpose small mixing grinder(made by Mitsui mine).
- water-borne dispersion medium containing hydoxyapatite(generation theorectical quantity: 1.5 parts by weight) which is insoluble microparticular dispersion stabilizer was obtained by stirring the abovementioned components at 10,000 RPM using TK type homomixer Mark (made by Primix).
- a polymerizable monomer compounds was prepared by heating thereof at 60 °C.
- a polymerizable monomer compounds was prepared by dissolving 4 parts of 2,2'-azobis(2,4-dimethylvaleronitril) as a polymerization starter in the styrene with maintaining 60 °C, and then adding thereof to the polymerizable monomer compounds.
- a polymerizable monomer mixture in dripped state was prepared by putting the abovementioned polymerizable monomer compounds into the inorganic dispersion medium solution under nitrogen gas flow, and stirring thereof at 6,000 RPM for 10 minutes at 60 °C using TK type homomixer.
- Toner particles were prepared by stirring the polymerizable monomer mixture in dripped state not to sink or float after changing into Teflon stirring blade, and simultaneously carrying out polymerization for 8 hours at 70°C.
- Decompression filtering was carried out by cooling slurry obtained after the abovementioned fusing process, adding 5N hydrochloric acid for pH to maintain below 2, thereby for the inorganic dispersion medium to be solved.
- Black compared toner 1 having good fluidity was obtained by mixing hydrophobic silica 1 part with 100 parts of the compared toner particles 1 using multipurpose small mixing grinder(made by Mitsui mine).
- Toner 0.5 g and carrier 9.5 g were put into a PE bottle, and mixed using a Turbula Mixer at 150 RPM for 5 minutes. Then charge-to-mass ratio of the resulting mixture was measured using a suction toner charge-to-mass ratio measuring apparatus(made by TREK, Model : 210HS-2).
- the method for producing a toner composition according to the present invention is easy to control particle diameter and rounded image, and also provides an electrostatic image developing toner having uniform distribution of particle size in comparison to prior toner producing processes and, thus its toner consumption is low and is useful to an electro photographic process requiring high resolution.
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- Physics & Mathematics (AREA)
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- Developing Agents For Electrophotography (AREA)
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KR1020090073671A KR101126576B1 (ko) | 2009-08-11 | 2009-08-11 | 정전하상 현상용 토너 |
PCT/KR2010/005220 WO2011019180A2 (fr) | 2009-08-11 | 2010-08-10 | Toner de développement d'image électrostatique |
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EP2490074A2 true EP2490074A2 (fr) | 2012-08-22 |
EP2490074A4 EP2490074A4 (fr) | 2014-07-09 |
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EP10808329.6A Withdrawn EP2490074A4 (fr) | 2009-08-11 | 2010-08-10 | Toner de développement d'image électrostatique |
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Country | Link |
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EP (1) | EP2490074A4 (fr) |
KR (1) | KR101126576B1 (fr) |
CN (1) | CN102576201B (fr) |
WO (1) | WO2011019180A2 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107015451A (zh) * | 2017-05-08 | 2017-08-04 | 天津市合成材料工业研究所有限公司 | 一种具有渐变结构的电子照相显影用墨粉及其制备方法 |
Families Citing this family (4)
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KR101693087B1 (ko) * | 2014-12-31 | 2017-01-04 | 충북대학교 산학협력단 | 정전하상 현상용 토너 및 그 제조 방법, 화상 형성 방법 |
CN107111263B (zh) * | 2015-01-14 | 2020-11-10 | 花王株式会社 | 静电图像显影用调色剂制造方法 |
JP7175592B2 (ja) * | 2017-07-28 | 2022-11-21 | 富士フイルムビジネスイノベーション株式会社 | 静電荷像現像用トナー、静電荷像現像剤、トナーカートリッジ、プロセスカートリッジ、画像形成装置及び画像形成方法 |
US10409185B2 (en) * | 2018-02-08 | 2019-09-10 | Xerox Corporation | Toners exhibiting reduced machine ultrafine particle (UFP) emissions and related methods |
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EP1109069A2 (fr) * | 1999-12-15 | 2001-06-20 | Mitsubishi Chemical Corporation | Toner pour le développement d'images électrostatiques et procédé de sa farbrication |
EP1231519A2 (fr) * | 2001-02-09 | 2002-08-14 | Mitsubishi Chemical Corporation | Procédé de production de toner pour le développement d'images électrostatiques |
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US2297691A (en) | 1939-04-04 | 1942-10-06 | Chester F Carlson | Electrophotography |
JPS4223910B1 (fr) | 1965-08-12 | 1967-11-17 | ||
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JPS61238846A (ja) | 1985-04-17 | 1986-10-24 | Showa Denko Kk | 架橋性組成物 |
JPH0727253B2 (ja) | 1986-05-22 | 1995-03-29 | 富士ゼロックス株式会社 | 電子写真用感光体 |
JPH0719085B2 (ja) | 1986-09-17 | 1995-03-06 | 株式会社リコー | デジタルカラ−画像形成装置 |
JPH0262666A (ja) | 1988-08-29 | 1990-03-02 | Nec Corp | 文生成方式 |
JP2787687B2 (ja) | 1988-08-30 | 1998-08-20 | ティーディーケイ株式会社 | 静電潜像現像剤および現像方法 |
US5559168A (en) * | 1988-08-30 | 1996-09-24 | Nippon Shokubai Co., Ltd. | Method for production of microfine colored particles and electrophotographic toner using the particles |
JP2809480B2 (ja) | 1990-05-31 | 1998-10-08 | ユニ・チャーム株式会社 | 吸収性物品の表面シート |
KR960005188B1 (ko) * | 1990-07-24 | 1996-04-22 | 가부시끼가이샤 니혼쇼꾸바이 | 전자사진용 토너 |
JPH06134437A (ja) | 1992-10-22 | 1994-05-17 | Plando Kenkyusho:Kk | 廃棄物の反応処理方法及びその装置 |
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-
2010
- 2010-08-10 EP EP10808329.6A patent/EP2490074A4/fr not_active Withdrawn
- 2010-08-10 CN CN201080042142.4A patent/CN102576201B/zh not_active Expired - Fee Related
- 2010-08-10 WO PCT/KR2010/005220 patent/WO2011019180A2/fr active Application Filing
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EP1231519A2 (fr) * | 2001-02-09 | 2002-08-14 | Mitsubishi Chemical Corporation | Procédé de production de toner pour le développement d'images électrostatiques |
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Also Published As
Publication number | Publication date |
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CN102576201B (zh) | 2014-01-15 |
KR20110016127A (ko) | 2011-02-17 |
KR101126576B1 (ko) | 2012-03-20 |
WO2011019180A2 (fr) | 2011-02-17 |
CN102576201A (zh) | 2012-07-11 |
EP2490074A4 (fr) | 2014-07-09 |
WO2011019180A3 (fr) | 2011-06-16 |
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