CN101699353B - Colored carbon power and producing method thereof - Google Patents
Colored carbon power and producing method thereof Download PDFInfo
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- CN101699353B CN101699353B CN2009102725673A CN200910272567A CN101699353B CN 101699353 B CN101699353 B CN 101699353B CN 2009102725673 A CN2009102725673 A CN 2009102725673A CN 200910272567 A CN200910272567 A CN 200910272567A CN 101699353 B CN101699353 B CN 101699353B
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Abstract
The invention discloses a colored carbon power and a producing method thereof to solve the problems of the existing carbon power such as easy stickiness to roller, low resolution ratio and pigment rate, poor color and luster and higher power waste rate during printing and copying. The technical scheme comprises the colored carbon power is formed by agglutinating an anion type wax-containing polymer composite latex (A) and a cation type colorant-containing polymer composite latex (B), wherein the anion type wax-containing polymer composite latex (A) is obtained by polymerizing in-situ latex with wax grains and nano silica as cores, the cation type colorant-containing polymer composite latex (B) is obtained by polymerizing in-situ latex with colorant and nano silica as cores. The inventive is simple in technique, the resolution ratio and pigment rate of printing and copying by the prepared colored carbon power are high, power waste rate is low, and recycling and cleaning of carbon power are easy.
Description
Technical field
The present invention relates to a kind of duplicating machine and employed colored carbon powder of printer and manufacture method thereof of electrofax mode, relate to specifically a kind of printing, duplicating color and luster and resolution height, be easy to colored carbon powder that reclaims and clean and preparation method thereof.
Background technology
Colored carbon powder is that color laser printing, colored digital duplicate required crucial consumptive material, mainly is made up of resin, pigment, adjuvant etc.The traditional preparation process method of colored carbon powder is " fusion method ", be operations such as resin (being mainly the styrene-propene butyl acrylate copolymer), colorant (pigment or dyestuff), adjuvant (charge adjusting agent, mould release etc.) process melting mixing, low temperature mechanical crushing, air-flow pulverizing, classification, obtain the colored carbon powder of the about 10 μ m of granularity.Yet this preparation method exists defectives such as toner is difficult for the colored carbon powder grain size of evenly disperseing, preparing in resin and the shape homogeneity is poor, particle diameter is bigger, causes printing, easy roll banding when duplicating, resolution are low, shade deviation, useless powder rate are higher.And be the size that " suspension polymerization " that representative proposes controlled the colored carbon powder particle effectively with Canon company, flowing property, the charging performance of toner are significantly improved, improve the stability of toner photographic fixing, fixed performance, suppressed the print through phenomenon effectively.Makes printing, duplicating resolution and color and luster not good enough yet the weak point of " suspension polymerization " is the carbon dust broad particle distribution, carbon powder particle too circle causes remaining in the recovery of the carbon dust on the photoreceptor and cleans very difficulty.With Fuji Xerox, Konica-Minolta is that the company of representative has developed " emulsion polymerization/co-coagulation method ", adjustment by surfactant, shear rate can make powder granularity little of 5 μ m, even nanoscale, its Size Distribution narrows down, can control the shape of powder effectively by control flocculation, heat treatment process, thereby improved the resolution and the color and luster of colour print, duplicating, the carbon dust that the non-spherical structure of carbon powder particle helps on the photoreceptor reclaims and cleaning.Yet, in emulsion polymerization/co-coagulation method " and when preparing colored carbon powder, polymer emulsion and painted emulsion are difficult to make resin particle and colored particles evenly to disperse each other and stick in mixing, flocculation, thermal treatment; On the other hand, improve the consumption of wax for the anti-performance need of seal partially that improves colored carbon powder, but cause wax to be easy to move to carbon powder particles surface and pollution carrier and development sleeve simultaneously, and make pigment skewness in carbon dust, cause printing, duplicate the difficult quality raising.
Summary of the invention
The color and luster and the resolution height that the purpose of this invention is to provide a kind of printing, duplicating, useless powder rate is low, carbon dust reclaims the colored carbon powder that is easy to " strawberry shape " structure with cleaning.
The present invention also provides a kind of manufacture method of above-mentioned colored carbon powder.
The manufacture method of colored carbon powder of the present invention comprises by anionic content of wax polymkeric substance complex emulsions (A) and cationicly contains colorant polymkeric substance complex emulsions (B) aggegation and form, described anionic content of wax polymkeric substance complex emulsions (A) is to be nuclear with wax particle and nano silicon, obtain by in-situ emulsion polymerization, the described cationic colorant polymkeric substance complex emulsions (B) that contains is to be nuclear with colorant and nano silicon, obtains by in-situ emulsion polymerization.
The present invention adopts the in-situ emulsion polymerization method, earlier preparing with wax particle and nano silicon respectively is nuclear, in the presence of anionic surfactant, obtain anionic content of wax polymkeric substance complex emulsions (A) by in-situ emulsion polymerization, and be nuclear with colorant and surface-treated silicon dioxide, in the presence of cationic surfactant, obtain the cationic colorant polymkeric substance complex emulsions (B) that contains by in-situ emulsion polymerization.
Then with above-mentioned (A) and (B) two components under beating action, need not flocculating agent, in the presence of non-ionic surfactant, rely on the yin, yang charge interaction to make their aggegations, again through conventional thermal treatment, filtration, drying, outside add auxiliary agent, make carbon dust of the present invention, this carbon dust has " strawberry shape " structure.
The present invention adopts emulsion polymerization in situ, polymerizable monomer and polymerization initiator are added in the water of external phase, and the adding nano silicon forms the nano silicon of disperse phase, because monomer is sl. sol. at aqueous phase, and its polymkeric substance is insoluble in whole system, so can take place with nano silicon and wax (or colorant) is the polyreaction of nuclear, the reaction beginning, elder generation's monomer pre-polymerization forms performed polymer, performed polymer polymerization then, performed polymer polymerization size progressively increase and stop reaction when reaching the particle diameter that needs.Because emulsion polymerization in situ is directly filling material to be added in the liquid monomer under polymerization state, silicon dioxide and wax (or colorant) as filling material are uniformly dispersed, thereby improved colour print, the resolution and the color and luster that duplicate, and do not need to improve especially the use amount of wax, do not exist the high wax that makes of use amount to be easy to move to surperficial carrier and the development sleeve of polluting of carbon powder particles owing to wax, and make colorant skewness in carbon dust, cause printing, duplicate the problem that difficult quality improves, and the powder that the present invention makes has " strawberry " shape, compare with the spherical powder of routine, its special shape is difficult for remaining on the photoreceptor, reclaims easy to clean.
Described anionic content of wax polymkeric substance complex emulsions (A) and cationic containing in the colorant polymkeric substance complex emulsions (B) are all contained nano silicon, its " ball " interaction energy has reduced carbon dust printing, duplicating the melting viscosity of process, helps improving the color and luster of colour print, duplicating; Play reinforcing agent and thixotropic agent simultaneously, help improving the resolution of colour print, duplicating.The particle diameter of described nano-silica two silicon is preferably 10-100nm, and addition is for accounting for anionic content of wax polymkeric substance complex emulsions (A) or the cationic 0.5-5% quality that contains colorant polymkeric substance complex emulsions (B) gross mass.
The employed wax of the inventive method can be senior fatty acid amides such as natural series wax, oleamide, stearic amide such as hydrocarbon waxes such as low molecular weight polyethylene wax, low-molecular-weight polypropylene wax, low-molecular-weight copolyalkenamer wax, paraffin, microcrystalline wax, behenic acid 20 diester, stearic acid octadecyl ester, Brazil wax, beeswax etc.
The employed colorant of the inventive method can be any of inorganic pigment or organic pigment, organic dyestuff, also can be its combination.The cyan colorant that can enumerate has the C.I. pigment blue 15: 3, pigment blue 15: 4 etc.; Yellow colorants has C.I. pigment yellow 74, pigment yellow 93, pigment yellow 94, pigment yellow 155, solvent yellow 16 2, pigment yellow 180, pigment yellow 185 etc.; Pinkish red colorant has C.I. pigment red 31, pigment red 122, paratonere 150, paratonere 184, paratonere 185, paratonere 57:1, paratonere 238, paratonere 269 etc.; Black colorant has carbon black, magnetic iron ore etc.
The employed polymerizable monomer of the inventive method has styrene, α-Jia Jibenyixi, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, the special butyl ester of acrylic acid, the just own ester of acrylic acid, 2-EHA, lauryl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, isobutyl methacrylate, tert-butyl methacrylate, the just own ester of methacrylic acid, 1,3-butadiene, 1,2-butadiene etc.; Optimization styrene, butyl acrylate.Spendable polarity polymerizable monomer has acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid, itaconic acid etc.; Preferred acrylic acid, methacrylic acid.
Cationic surfactant of the present invention is at least a in amine salt type surfactant or the quaternary ammonium salt cationic surfactant, and amine salt type surfactant is as primary amine salt, secondary amine salt, tertiary ammonium salt type surfactant, hydramine, diamines or polyamines, the amine that contains acyl group, guanidine derivatives; The quaternary ammonium salt cationic surfactant that can enumerate has: DTAC, hexadecyltrimethylammonium chloride, OTAC, dodecyl benzyl dimethyl ammonium chloride, cetalkonium chloride, stearyl dimethyl benzyl ammonium chloride, DTAB, cetyl trimethyl ammonium bromide, the octadecyl trimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, cetyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide, the hexadecyldimethyl benzyl ammonium allyl ammonium chloride, chlorination N, N-dimethyl-N-benzyl-3-(stearoyl amido) propylamine, dibenzyl two (stearamide ethyl) ammonium chloride etc.Preferred quaternary ammonium salt cationic surfactant, more preferably zephiran.
Anionic surfactant of the present invention can also can be its combination at least a in metal carboxylate, Sulfonates, sulfuric ester salt and the structure mixed surfactant.That can enumerate has: aliphatic alcohol polyethenoxy ether carboxylate, odium stearate, sodium n-alkylbenzenesulfonate, sodium branched alkyl benzene sulfonate, diisopropyl sodium naphthalene sulfonate, nekal, alkyl sodium sulfonate, alpha-olefin sodium sulfonate, alpha-sulfo fatty acid ester, straight-chain alkyl sulfate, branched alkyl sodium sulphate, fatty alcohol polyoxyethylene ether sulfate etc.Preferred straight-chain alkyl sulfate, fatty alcohol polyoxyethylene ether sulfate.
Non-ionic surfactant of the present invention can be enumerated AEO, APES, polyoxyethylene carboxylate, alkanolamide, polyethenoxy alkanolamide etc.The preferred alkyl phenol polyethenoxy ether more preferably has the APES of 8～10 carbon atoms.
The employed polymerization initiator of in-situ emulsion polymerization can be enumerated among the present invention water-soluble persulfate initiators such as ammonium persulfate, potassium persulfate, sodium peroxydisulfate, and the redox initiator formed of these persulfates and acid sodium sulphite or ascorbic acid.
Beneficial effect:
1, carbon dust of the present invention has " strawberry shape " structure, and the size shape homogeneity is good, is difficult for remaining on the photoreceptor, it is low not only to reclaim easy to clean, useless powder rate, and has improved the resolution and the color and luster of colour print, duplicating.
2, utilize the method for in-situ emulsion polymerization, rely on the yin, yang charge interaction to make anionic content of wax polymkeric substance complex emulsions (A) and cationicly contain colorant polymkeric substance complex emulsions (B) aggegation, need not flocculating agent, process is more simple, reliably.
3, utilize silicon dioxide distinctive " ball " effect, reduce carbon dust and printing, duplicating the melting viscosity of process, thereby further improved the resolution and the color and luster of colour print, duplicating.
Embodiment
The preparation example 1 of anionic content of wax polymkeric substance complex emulsions
The preparation of wax dispersion: 30g wax (behenic acid 20 diester) and 7.5g lauryl sodium sulfate and 62.5g water are carried out stirring and dissolving under 90 ℃, then this potpourri is joined in the high speed dispersion agent fast and disperse, dispersion by 2h, obtain milky white wax dispersion, its particle diameter is 150nm.This particle diameter is measured by Beckman Coulter LS230.
The preparation of anionic content of wax polymkeric substance complex emulsions: the 5g lauryl sodium sulfate is dissolved in the 100g water, then it is added in the polymerization reaction kettle, with above-mentioned wax dispersion 25g and the surface treated nanometer SiO of 1.4g
2(Degussa R972, particle diameter 10～14nm) drops in the reactor respectively, be warmed up to 75 ℃, in reactor, add then the 1g potassium persulfate is dissolved in solution in the 50g water, then with 75g styrene, the 22g butyl acrylate, 3g methacrylic acid and 2g lauryl mercaptan potpourri add reactor gradually in 2h, temperature with system after adding is elevated to 80 ℃, under this temperature, react 3h, can obtain the original position complex emulsions of the content of wax and nano silicon, recording its particle diameter with the nano particle size instrument is 230nm, with it as emulsion (A-1).
Anionic content of wax polymkeric substance complex emulsions preparation example 2
The preparation of wax dispersion: with preparation example 1.
The preparation of anionic content of wax polymkeric substance complex emulsions: the 6g lauryl sodium sulfate is dissolved in the 100g water, then it is added in the polymerization reaction kettle, with above-mentioned wax dispersion 25g and the surface treated nanometer SiO of 14g
2(Degussa R974, particle diameter 10～14nm) drops in the reactor respectively, be warmed up to 75 ℃, in reactor, add then the 1g potassium persulfate is dissolved in solution in the 50g water, then with 75g styrene, the 22g butyl acrylate, 3g methacrylic acid and 2g lauryl mercaptan potpourri add reactor gradually in 2h, temperature with system after adding is elevated to 80 ℃, under this temperature, react 3h, the particle diameter of the anionic content of wax polymkeric substance complex emulsions that obtains is 225nm, and this complex emulsions is called complex emulsions (A-2).
Anionic content of wax polymkeric substance complex emulsions preparation example 3
In preparation example 1, except lauryl mercaptan being changed into n-octyl mercaptan, with surface treated nanometer SiO
2Addition changes into beyond the 5g, and other conditions are identical, and the particle diameter of the anionic content of wax polymkeric substance complex emulsions that obtains is 228nm, and this complex emulsions is called complex emulsions (A-3).
Anionic content of wax polymkeric substance complex emulsions preparation example 4
In preparation example 2, except methacrylic acid changed acrylic acid into, other conditions were identical, and the particle diameter of the anionic content of wax polymkeric substance complex emulsions that obtains is 220nm, and this complex emulsions is called complex emulsions (A-4).
The cationic colorant polymkeric substance complex emulsions preparation example 1 that contains
The preparation of colorant dispersion: at room temperature stir 30g carbon black (Cabot company) and 7.5g dodecane trimethyl ammonium chloride and 62.5g water pre-dispersed, then this dispersion liquid is joined in the high speed dispersion agent and disperse, dispersion by 2h, obtain dispersible pigment dispersion, its particle diameter is 120nm.
The cationic colorant polymkeric substance complex emulsions that contains prepares: 5g dodecane trimethyl ammonium chloride is dissolved in the 100g water, then it is added in polymerization reaction kettle, with above-mentioned dispersible pigment dispersion 25g and the surface treated nanometer SiO of 1.4g
2(Degussa R972, particle diameter 10～14nm) drops in the reactor respectively, be warmed up to 75 ℃, in reactor, add then the 1g potassium persulfate is dissolved in solution in the 50g water, then with 75g styrene, the 22g butyl acrylate, 3g methacrylic acid and 2g lauryl mercaptan potpourri add reactor gradually in 2h, temperature with system after adding is elevated to 80 ℃, under this temperature, react 3h, can obtain the cationic colorant polymkeric substance complex emulsions that contains of the content of wax and nano silicon, recording its particle diameter with the nano particle size instrument is 243nm, with it as complex emulsions (B-1).
The cationic colorant polymkeric substance complex emulsions preparation example 2 that contains
The preparation of colorant dispersion: with preparation example 1.
The cationic colorant polymkeric substance complex emulsions that contains prepares: the 6g hexadecyltrimethylammonium chloride is dissolved in the 100g water, then it is added in polymerization reaction kettle, with above-mentioned dispersible pigment dispersion 25g and the surface treated nanometer SiO of 14g
2(Degussa R972, particle diameter 10～14nm) drops in the reactor respectively, be warmed up to 75 ℃, in reactor, add then the 1g potassium persulfate is dissolved in solution in the 50g water, then with 75g styrene, the 22g butyl acrylate, 3g methacrylic acid and 2g lauryl mercaptan potpourri add reactor gradually in 2h, temperature with system after adding is elevated to 80 ℃, under this temperature, react 3h, can obtain the cationic colorant polymkeric substance complex emulsions that contains of the content of wax and nano silicon, recording its particle diameter with the nano particle size instrument is 250nm, with it as complex emulsions (B-2).
The cationic colorant polymkeric substance complex emulsions preparation example 3 that contains
In preparation example 1, except carbon black being changed into pigment yellow 155, with surface treated nanometer SiO
2Addition changes into beyond the 5g, and other conditions are identical, and the cationic particle diameter that contains colorant polymkeric substance complex emulsions that obtains is 215nm, and this complex emulsions is called complex emulsions (B-3).
The cationic colorant polymkeric substance complex emulsions preparation example 4 that contains
In preparation example 2, except carbon black being changed into paratonere 184, other conditions are identical, and the cationic particle diameter that contains colorant polymkeric substance complex emulsions that obtains is 235nm, and this complex emulsions is called complex emulsions (B-4).
The cationic colorant polymkeric substance complex emulsions preparation example 5 that contains
In preparation example 1, except changing carbon black into pigment blue 15: 4, other conditions are identical, and the cationic particle diameter that contains colorant polymkeric substance complex emulsions that obtains is 240nm, and this particle is called complex emulsions (B-5).
Carbon dust preparation example 1
100g joins in the reactor with complex emulsions (A-1), regulating the speed that stirs is 500rpm, under agitation in 20 minutes, join in the reactor gradually complex emulsions (B-1) then, begin to heat up after stirring 30min, by 30min the temperature of system is raised to 60 ℃, stirring rate with system is reduced to 200rpm then, begin the variation of the particle diameter of detection architecture then, when the particle diameter of agglutination particle increases to 7 μ m, in system, add non-ionic surfactant X-405 (DOW Chemical), then stirring rate is increased to 400rpm, be warmed up to 95 ℃ then and carry out spheroidization, when the sphericity arrival 0.96 (using FPIA-3000 to measure) of particle was above, the centrifugal separator filtration was used in cooling, wash, the heating drying under reduced pressure.Particle after the drying is added the additive processing promptly get carbon dust.The carbon dust that obtains is called carbon dust (T-1).
Carbon dust preparation example 2
In carbon dust preparation example 1, except complex emulsions (B-1) is replaced by complex emulsions (B-2), non-ionic surfactant changes into beyond the lauryl alcohol polyoxyethylene ether, the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-2).
Carbon dust preparation example 3
In carbon dust preparation example 1, except complex emulsions (B-1) being replaced by complex emulsions (B-3), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-3).
Carbon dust preparation example 4
In carbon dust preparation example 1, except complex emulsions (B-1) being replaced by complex emulsions (B-4), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-4).
Carbon dust preparation example 5
In carbon dust preparation example 1, except complex emulsions (B-1) being replaced by complex emulsions (B-5), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-5).
Carbon dust preparation example 6
In carbon dust preparation example 1, except complex emulsions (A-1) is replaced by complex emulsions (A-2), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-6).
Carbon dust preparation example 7
In carbon dust preparation example 1, except complex emulsions (A-1) being replaced by complex emulsions (A-3), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-7).
Carbon dust preparation example 8
In carbon dust preparation example 1, except complex emulsions (A-1) being replaced by complex emulsions (A-4), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-8).
Carbon dust preparation example 9
In carbon dust preparation example 3, except complex emulsions (A-1) being replaced by complex emulsions (A-2), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-9).
Carbon dust preparation example 10
In carbon dust preparation example 4, except complex emulsions (A-1) being replaced by complex emulsions (A-2), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-10).
Carbon dust preparation example 11
In carbon dust preparation example 5, except complex emulsions (A-1) being replaced by complex emulsions (A-2), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-11).
Carbon dust preparation example 12
In carbon dust preparation example 3, except complex emulsions (A-1) being replaced by complex emulsions (A-3), the identical carbon dust that obtains of other conditions.The carbon dust that obtains is called carbon dust (T-12).
Carbon dust in the embodiment of the invention is tested, and its result is as follows:
| The performance title | Development density | Bottom ash | Useless powder rate | Consumption (mg) | Resolution (line is right/mm) |
| Embodiment 1 | 1.35 | 0.001 | 7％ | 20 | 6 |
| Embodiment 2 | 1.34 | 0.003 | 10％ | 29 | 12 |
| Embodiment 3 | 1.3 | 0.001 | 12％ | 25 | 6 |
| Embodiment 4 | 1.47 | 0.002 | 8％ | 27 | 12 |
| Embodiment 5 | 1.45 | 0.003 | 5％ | 28 | 12 |
| Embodiment 6 | 1.39 | 0.004 | 9％ | 22 | 12 |
| Embodiment 7 | 1.41 | 0.003 | 6％ | 24 | 6 |
| Embodiment 8 | 1.42 | 0.005 | 8％ | 28 | 6 |
| Embodiment 9 | 1.38 | 0.008 | 7％ | 22 | 6 |
| Embodiment 10 | 1.37 | 0.003 | 10％ | 21 | 6 |
| Embodiment 11 | 1.40 | 0.004 | 11％ | 23 | 12 |
| Embodiment 12 | 1.42 | 0.001 | 6％ | 24 | 6 |
Brief summary: as seen from the above table, carbon dust development density of the present invention and resolution height, bottom ash, useless powder rate and the existing carbon dust of consumption are low simultaneously.
Claims (2)
1. the manufacture method of the colored carbon powder of " strawberry shape " structure, it is characterized in that, comprise by anionic content of wax polymkeric substance complex emulsions (A) and cationicly contain colorant polymkeric substance complex emulsions (B) aggegation and form, described anionic content of wax polymkeric substance complex emulsions (A) is to be nuclear with wax particle and surface-treated nano silicon, obtain by in-situ emulsion polymerization, the described cationic colorant polymkeric substance complex emulsions (B) that contains is to be nuclear with colorant and surface-treated nano silicon, obtains by in-situ emulsion polymerization.
2. the colored carbon powder of " strawberry shape " structure is characterized in that, is made by the described manufacture method of claim 1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| CN2009102725673A CN101699353B (en) | 2009-10-29 | 2009-10-29 | Colored carbon power and producing method thereof |
| EP10734886.4A EP2495616B1 (en) | 2009-10-29 | 2010-05-04 | Color toner and preparation method thereof |
| PCT/CN2010/072419 WO2011050605A1 (en) | 2009-10-29 | 2010-05-04 | Colorful carbon powder and preparation method thereof |
| US12/832,100 US8221954B2 (en) | 2009-10-29 | 2010-07-08 | Color toner and method for preparing the same |
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| CN2009102725673A CN101699353B (en) | 2009-10-29 | 2009-10-29 | Colored carbon power and producing method thereof |
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| CN101699353A CN101699353A (en) | 2010-04-28 |
| CN101699353B true CN101699353B (en) | 2011-10-26 |
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| CN102603952B (en) * | 2012-03-02 | 2014-04-16 | 中国科学院化学研究所 | Resin, resin nanoemulsion and preparation methods thereof |
| CN103869644A (en) * | 2014-02-28 | 2014-06-18 | 湖北鼎龙化学股份有限公司 | Polyester type color powdered ink and preparation method thereof |
| CN105005183B (en) * | 2015-08-11 | 2019-11-22 | 湖北鼎龙控股股份有限公司 | The compound electrostatic image toner preparation processes of styrene-acrylic resin/polyester resin |
| CN105838110B (en) * | 2016-03-31 | 2017-08-25 | 江西金环颜料有限公司 | A kind of preparation method of laser 3D printing high temperature black ceramic paint |
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| CN101256367A (en) * | 2008-03-06 | 2008-09-03 | 湖北鼎龙化学有限公司 | Carbon powder for development of static charge and method for manufacturing the same |
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| CN101256367A (en) * | 2008-03-06 | 2008-09-03 | 湖北鼎龙化学有限公司 | Carbon powder for development of static charge and method for manufacturing the same |
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| JP特开2002-82486A 2002.03.22 |
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Address after: 430015 Hubei city of Wuhan province Hankou Jianghan Road No. 8 Jinmao Building 19 Patentee after: Hubei Dinglong Cmi Holdings Ltd Address before: 430015 Hubei city of Wuhan province Hankou Jianghan Road No. 8 Jinmao Building 19 Patentee before: Hubei Dinglong Chemical Co., Ltd. |