CN104375396A - Method for preparing color carbon powder by adopting suspension polymerization method - Google Patents
Method for preparing color carbon powder by adopting suspension polymerization method Download PDFInfo
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- CN104375396A CN104375396A CN201410570871.7A CN201410570871A CN104375396A CN 104375396 A CN104375396 A CN 104375396A CN 201410570871 A CN201410570871 A CN 201410570871A CN 104375396 A CN104375396 A CN 104375396A
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Abstract
The invention relates to a method for preparing color carbon powder by adopting a suspension polymerization method, and solves the problems that carbon powder is instable in quality and the selection of raw materials is limited in a traditional suspension polymerization method. According to the technical scheme, the method comprises the following steps: melting a coloring agent and resin, mixing the melt coloring agent and resin so as to obtain a mixture I, extruding the mixture I and crushing to obtain color master batch; adding the color master batch, wax and an initiator into monomers to obtain a mixture II, heating and stirring to dissolve the mixture II to obtain an organic phase containing the coloring agent, resin, initiator, wax and monomers; adding the organic phase into an aqueous solution containing a surface active agent, carrying out shearing dispersing on the organic phase in the aqueous solution to obtain turbid liquid, polymerizing the turbid liquid in a heating manner to obtain a color carbon powder matrix, finally filtering the color carbon powder matrix, washing the filtered color carbon powder matrix, drying, and mixing the color carbon powder matrix with additives to obtain the color carbon powder. The method is simple in procedure, low in process difficulty, easy to control, wide in raw material selection range and relatively few in adverse impact factors, and the obtained color carbon powder is relatively narrow in granularity distribution, relatively few in small particles and stable and reliable in quality.
Description
Technical field
The present invention relates to the preparation method of the development of static charge suspension polymerization colour of a kind of duplicating machine for electrofax mode and printer.
Background technology
Colored carbon powder is the important consumptive material needed for development of static charge color laser printer, colored digital duplicating machine, primarily of resin (comprising styrene-acrylic resin and vibrin etc.), colorant (pigment and dyestuff), adjuvant (charge adjusting agent, mould release etc.) composition.According to the difference of the color of carbon dust colorant used, carbon dust is divided into colored carbon powder and black carbon powder.The traditional preparation method of carbon dust is " comminuting method " (Physical), namely required resin, colorant, adjuvant through operations such as melting mixing, cryogenic mechanical pulverizing, air-flow crushing, classifications, obtain the carbon dust that granularity is about 10 μm.But, there is the high and colorant of the energy consumption not easily carbon powder particle size of dispersed in resin, preparation and the defect such as shape homogeneity is poor, particle diameter is larger in this preparation method, causes printing, easy roll banding when duplicating, the shortcoming such as resolution is low, shade deviation, powder rate of giving up are higher.The laser printer carbon dust used of current main flow is the high chemical method carbon dust of quality preservation substantially, the preparation of chemical method carbon dust mainly contains following three kinds of methods: emulsion polymerization/co-coagulation method (Konica-Minolta, Xerox, Fuji-Xerox), suspension polymerization (Canon, auspicious father-in-law) and PXP method (Ricoh)." emulsion polymerization/co-coagulation method " first prepares resin emulsion, dispersible pigment dispersion, wax dispersion respectively, making three kinds of particles aggregate to prepare colored carbon powder under so resin emulsion, dispersible pigment dispersion and wax dispersion being blended in the existence of agglutinant, there is the more and unfavorable factor that co-coagulation process control difficulties is higher of preparation process in the method; Take Canon as the preparation of the suspension polymerization colored carbon powder of representative be then that first in water, preparation is insoluble in the nano grade inorganic deflocculant of water, in water, dispersion granulation is carried out to the organic phase containing pigment, monomer with this inorganic colloid stabilizing agent again, then polymerization obtains colored carbon powder, the character of the inorganic colloid stabilizing agent in the method is subject to the impact of many factors in its preparation process, and the instability of inorganic colloid stabilizing agent character finally can cause the instability of carbon dust quality.On the other hand, in order to ensure carbon dust quality, the selection of raw material is also more limited to, when using common suspension polymerization to prepare colored carbon powder, because colorant does not process, there is a large amount of hydroxyls, acidity and basic group in colorants surface, the existence of these polar groups has strong inhibition to free radical polymerization, makes the colorant of a large amount of kind and type be difficult to use.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, there is provided that a kind of step is simple, technology difficulty is low, process easily controls, influence factor is few, the domain size distribution of the colored carbon powder obtained is narrower, and small-particle is few, steady quality adopts suspension polymerization to prepare the method for colored carbon powder reliably.
Technical scheme comprises the following steps: comprise the following steps:
1) colorant and resin through melting mixing, extrude, pulverize and obtain Masterbatch;
2) in monomer, add Masterbatch, wax and initiating agent, heating stirring and dissolving, obtains the organic phase containing colorant, resin, initiating agent, wax, monomer;
3) add step 2 to containing in the aqueous solution of suspension stabilizer) organic phase first carry out low velocity shear dispersion, and then by high speed shear dispersion obtain suspension;
4) by step 3) described suspension intensification polymerization obtains colored carbon powder parent, then through filtering washing, dry, mixing additive obtains colored carbon powder.
Described step 1) in, in control Masterbatch, colorant particle size dispersion is to 50-600nm.
Described step 2) in, the heating-up temperature in described heating stirring and dissolving is 40-80 DEG C.
Described step 3) in, described suspension stabilizer is surfactant.
Described step 3) in, described surfactant is at least one in anionic surfactant, cationic surfactant, non-ionic surfactant, synthetic polymer spreading agent or natural polymer spreading agent.
Described step 3) in, the described surfactant addition as suspension stabilizer is 0.5 weight portion ~ 5 weight portion relative to monomer 100 weight portion.
Described step 3) in, the rotating speed of low velocity shear dispersion is 2000rpm ~ 8000rpm, and the rotating speed of described high speed shear dispersion is 10000rpm ~ 20000rpm.
Described step 4) in, the temperature of suspension intensification polymerization is 50 degree ~ 98 degree.
The present invention first colorant and resin through melting mixing, extrude, pulverize and obtain Masterbatch, colorant can be made well dispersed by pre-prepared Masterbatch; Again Masterbatch, wax and initiating agent are heated stirring and dissolving in monomer and obtain organic phase, then in organic phase being added containing surfactant water, homogenous disperse obtains suspension, suspension is heated to uniform temperature polymerization and obtains carbon powder particles dispersion liquid, obtain colored carbon powder finally by technological processs such as filtration washing, drying, mixing additives.This preparation method's step is simple, stable technical process, easily operate, and does not specially require, adopt the inventive method good to the adaptability of raw material to the selection of resin, colorant, wax, surfactant.In above-mentioned technological process, the organic surfactant of the creationary employing of inventor substitutes existing inorganic deflocculant completely, inventor's research shows, surfactant has the ability of stronger stably dispersing suspended particles, and can produce and the higher characteristic of purity by volume industrial, when it is for suspension stabilizer, effectively can ensure the stability of suspension polymerization system and the quality of prepared carbon dust.Thus solve the problem that inorganic deflocculant character instability finally causes carbon dust quality instability, wider to the selectivity of raw material.In principle, structurally all there is hydrophobic part and hydrophilic segment in organic surfactant and inorganic deflocculant (as calcium phosphate and magnesium hydroxide colloidal), such amphiphilic structure determines both and all can use as dispersion stabilizer.Compared with inorganic colloid, organic surface active agent has the longer hydrophobic long-chain of segment and the easy Ionized hydrophilic head base had compared with forceful electric power lotus, hydrophobic long-chain makes surfactant can be adsorbed in suspension oil droplets firmly, have and then provide stronger static charge repulsive force (non-ionic surfactant then provides strong steric hindrance repulsion by longer hydrophilic segment) between suspension oil droplet compared with the hydrophilic head base of forceful electric power lotus, make organic surface active agent have the ability of better stably dispersing suspension system.Inorganic colloid spreading agent inevitably runs into some unfavorable factors in the preparation (as the temperature of room temperature, system, feed purity, operation control, settling time, the change of settling temperature etc. aspect), these unfavorable factors then can cause the change of the inorganic colloid stabilizing agent character in crystal formation, size and reunion degree etc. prepared, and the uncertainty of these properties finally result in the instability of carbon dust character.The breakthrough employing surfactant of the present invention is as the dispersion stabilizer of suspension polymerization, there is due to surfactant the purity of the chemicals of specific chemical constitution and easily guarantee, prepared the colored carbon powder that quality is good, and process for suspension polymerization has good technology stability.
And, first colorant and resin are carried out melting mixing and manufacture Masterbatch, reach the resin-coating modification of resin to the physics and chemistry of colorants surface, improve the degree of scatter of colorant in subsequent process in monomer and flour-carbon resin, thus effectively improve the print quality of colored carbon powder.
Colorant used in the present invention is not particularly limited, can be inorganic pigment or organic pigment, organic dyestuff any one, also can be its combination.The cyan colorant that can enumerate has pigment blue 15: 3, pigment blue 15: 4 etc.; Yellow colorants has pigment Yellow 12, pigment yellow 17, pigment yellow 74, pigment yellow 93, pigment yellow 94, pigment yellow 155, solvent yellow 16 2, pigment yellow 180, pigment yellow 185 etc.; Magenta colorant has pigment red 31, pigment red 122, paratonere 150, paratonere 184, paratonere 185, paratonere 57:1, paratonere 238, paratonere 256, paratonere 269 etc.; Black colorant has carbon black, magnetic iron ore, aniline etc.Colorant concentrations is 1 weight portion ~ 15 weight portion relative to polymerizable monomer (abbreviation monomer) 100 weight portions usually.
The inventive method is prepared the resin that Masterbatch uses and is not particularly limited, and can be styrene-acrylic resin, vibrin etc.; The preparation method of resin is not particularly limited, and can be polycondensation reaction, bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, melt polymerization or interfacial polycondensation etc.
The polymerizable monomer that the present invention uses can be the polymerizable monomer of nonpolarity base or the polymerizable monomer having polar group.
The polymerizable monomer of described nonpolarity base can exemplify as styrene, α-methyl styrene, chlorostyrene, dichlorostyrene, p-tert-butylstyrene, 4-butylstyrene, the phenylethylenes such as 4-nonylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid n-butyl ester, isobutyl acrylate, hydroxy-ethyl acrylate, ethylhexylacrylate, methylmethacrylate, ethyl methacrylate, methacrylate propyl ester, methacrylate n-butyl ester, methacrylate isobutyl ester, hydroxy ethyl methacrylate, methacrylate ethylhexyl etc. (meta) acrylate etc., this is optimization styrene wherein, butyl acrylate.
The described polymerizable monomer having the polymerizable monomer of polar group can select polar acidic base or the polymerizable monomer having basic polar base, the polymerizable monomer of described polar acidic base can enumerate the polymerizable monomer that acrylic acid, methacrylic acid, methacrylate, maleic acid, fumaric acid, cinnamic acid etc. have carboxyl, sulfonated phenylethylenes etc. have sulfonic polymerizable monomer etc., preferred sodium p styrene sulfonate, acrylic acid, methacrylate, there is the polymerizable monomer of basic polar base can enumerate aminostyryl and its 4 grades of salt, acrylamide, allylamine, vinyl pyrimidine, N,N-DMAA, vinyl pyrrolidone, acrylate methyl esters, acrylate, acrylate propyl ester, acrylic acid diethylamino methyl esters, acrylic acid diethylamino ethyl ester, acrylic acid diethylamino propyl ester, acrylyl oxy-ethyl-trimethyl salmiac, acrylyl oxy-ethyl-trimethyl ammonium bromide, acryloxyethyldimethyl benzyl ammonium chloride, acryloxyethyldimethyl Benzylphosphonium Bromide ammonium, acryloxypropyl trimethyl ammonium chloride, acryloxypropyl trimethylammonium bromide, Methacrylamide, N, N-dimethylmethacryl amide, dimethylamine methyl esters, dimethylaminoethyl methacrylate, dimethylamine propyl ester, methacrylic acid diethylamino methyl esters, diethyl aminoethyl methacrylate, methacrylic acid diethylamino propyl ester, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, methylacryoyloxyethyl trimethylammonium bromide, methacryloxypropyl trimethyl ammonium chloride, methacryloxypropyl trimethylammonium bromide, methylacryloxyethyldimethyl benzyl ammonium chloride, methylacryoyloxyethyl dimethylbenzyl ammonium bromide, preferred aminostyryl, dimethylaminoethyl methacrylate, MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
These polymerizable monomers can be used alone or as a mixture.
The present invention can be anionic surfactant, cationic surfactant, non-ionic surfactant, synthetic polymer spreading agent, natural polymer spreading agent as the surfactant that suspension stabilizer uses, and also can be the combination of these surfactants.Cationic surfactant has DTAC, DTAB, cetylpyridinium chloride, dodecylpyridinium bromide, hexadecyltrimethylammonium chloride, cetyl trimethyl ammonium bromide etc.Anionic surfactant has the slaine etc. of the higher fatty acid such as odium stearate, sodium laurate, sodium dodecylsulphonate, neopelex, lauryl sodium sulfate, dodecyl diphenoxy ethers sodium disulfonate, sodium laureth sulfate.Non-ionic surfactant has polyoxyethylene ten diether (Poly (oxyethylene) Dodecy Ether), polyoxyethylene margaron (Poly (oxyethylene) Hexadecyl Ether), ethylene nonyl phenyl ether (Poly (oxyethylene) Nonyl-Phenyl Ether), Poly (oxyethylene) polyoxyethylene stearyl base ether (Lauryl Ether), polyoxyethylene ether sorbitan mono-oleic acid ester (Sorbitan Mono-oleate Poly (oxyethylene) Ether), CT-1695 (monodecanoate Sucrose) etc.Synthetic polymer spreading agent has the amphipathic nature polyalcohol of the polymerizable monomer containing above-mentioned acidity or basic polar base in structure.Natural polymer spreading agent has the natural polymers such as gelatin, algin, albumen, the cellulose derivative such as methylcellulose, hydroxypropyl methylcellulose, the polyvinyl alcohol (PVA) of partial alcoholysis.Preferred DTAC, neopelex, methylcellulose.In the present invention, the use amount of described surfactant is 0.5 weight portion ~ 5 weight portion relative to monomer 100 weight portion, the particle diameter of carbon dust too much can be caused too little, and likely because too many salt causes the instability of suspension system to occur a large amount of bits, cross the particle diameter that can cause carbon powder particle at least too large, and the dispersion stabilization of suspended particle can be caused to cause slagging scorification not due to the minimizing of consumption.
The initiating agent that the inventive method uses can be oil-soluble initiator, azo-initiator, peroxide initiating agent or redox type initiators.Object lesson has azoisobutyronitrile, ABVN, benzoyl peroxide, dilauroyl peroxide, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two (2-ethylhexyl) peroxy dicarbonate, peroxy dicarbonate two hexadecyl ester, peroxy dicarbonate 24 ester, cumyl peroxyneodecanoate, new peroxide tert-butyl caprate, peroxidating pivalic acid tert-pentyl ester, peroxide tert pivalate ester, peroxidating-2-ethyl acid tert-pentyl ester, peroxidating-2-ethyl acid the tert-butyl ester, tert-butyl hydroperoxide isobutyrate, peroxidating thiacyclohexane.Preferred azoisobutyronitrile, ABVN, peroxide tert pivalate ester, more preferably ABVN, initiator amount is 0.1 weight portion ~ 10 weight portion relative to polymerizable monomer 100 weight portion usually.
The wax that the inventive method uses is not particularly limited, can be the higher fatty acid amides etc. such as natural series wax, oleamide, stearic amide such as the 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, pentaerythrite four behenate, Brazil wax, beeswax, preferred stearic acid octadecyl ester.
Wax is 1 weight portion ~ 40 weight portion relative to polymerizable monomer 100 weight portion usually, and with 2 weight portion ~ 35 weight portions as well, 5 weight portion ~ 30 weight portions are better.When addition is very few, release time fixing is not enough, and sticky rod phenomenon likely occurs.In addition, time too much, can wax be adhered on developer or carrier, the low problem of permanance likely occurs.
Additive of the present invention can be one or more in hydrophobic monox, titanium dioxide, aluminium oxide, cerium oxide, strontium titanates, resin microsphere, and those skilled in the art can carry out choice and operation according to specific needs.
In present invention process process, described step 1) in, it is 50-600nm that colorant is preferably ground to particle diameter, the particle diameter of colorant is crossed conference and is caused the coloration efficiency of colorant to reduce, and the particle diameter of colorant is excessive also can cause adverse effect to the stability of follow-up suspension, and the colorant that the too small meeting of colorant particle diameter causes particle diameter meticulous causes colouring power not high to the reflection potential of light not.
Described step 2) in, it is because wax can be dissolved in the monomer containing resin, colorant preferably in this temperature range that heating for dissolving temperature is preferably 40-80 DEG C, the too low wax of temperature then can not be dissolved in monomer preferably, and temperature is too high, likely causes the thermal polymerization of monomer.
Described step 3) in, surfactant existence under, adopt low speed and high speed shear dispersion supending respectively, the rotating speed of described low velocity shear dispersion is 2000rpm ~ 8000rpm, the rotating speed of described high speed shear dispersion is 10000rpm ~ 20000rpm, due to the existence of surfactant, make oil phase stable dispersion in water be that particle diameter is suspended oil droplet the tiny of 10 ~ 100 microns of sizes by low velocity shear, then make the tiny particle diameter being suspended oil droplet be reduced to particle diameter 5 ~ 10 microns required by carbon dust further by high speed shear dispersion.
Described step 4) in, the temperature of suspension intensification polymerization is 50 degree ~ 98 degree, too high meeting causes the fast decoupled of initiating agent, cause the molecular weight of resin in suspension polymerization carbon dust too low, thus cause carbon dust in print procedure, have the phenomenon of sticky printer fixing roller, the too low meeting of polymerization temperature causes the reaction time oversize, causes production efficiency to reduce, and the polymerization of monomer can be caused incomplete simultaneously.
Beneficial effect:
1, the invention provides one surfactant as suspension stabilizer, prepare development of static charge colored carbon powder by suspension polymerization.Using surfactant as the dispersion stabilizer of suspension polymerization, avoid some unfavorable factors that common suspension polymerization runs into when preparing inorganic colloid spreading agent, the change of the inorganic colloid stabilizing agent character prepared by the change as the temperature of room temperature, system, feed purity, operation control aspect causes, finally causes the problem of the change of carbon dust performance index.The inventive method preparation process is simple, technology difficulty is low, process easily controls, process is simple, reliable.
2, this method has carried out special parcel process with resin to colorant when preparing Masterbatch, resin is made to be adsorbed in colorants surface by physics or chemical action, the Application Range of colorant is substantially increased by this parcel process to colorant, also improve the dispersiveness of colorant in monomer and flour-carbon resin simultaneously, make carbon dust show good printing effect and permanance.
Embodiment
In following embodiment, described " part " refers to parts by weight, and described percentage is percent by weight.
The preparation example 1 of resin
60 parts of toluene, 40 parts of isopropyl alcohols, the styrene of 59 parts, the butyl acrylate of 29 parts, the aminostyryl of 12 parts, initiating agent azoisobutyronitriles of 2 parts are dropped into successively in reactor, stir, be warming up to 75 DEG C of reactions 10 hours, decompression distillation is except desolventizing, cooling obtains pale yellow transparent resin, matter average molecular weight Mw=40830, glass temperature Tg=72 degree, is referred to as resin 1.
The preparation example 2 of resin
60 parts of toluene, 40 parts of isopropyl alcohols, the styrene of 58 parts, the butyl acrylate of 32 parts, the sodium p styrene sulfonate of 10 parts, initiating agent ABVNs of 2 parts are dropped into successively in reactor, stir, be warming up to 67 DEG C of reactions 10 hours, decompression distillation is except desolventizing, cooling obtains pale yellow transparent resin, matter average molecular weight Mw=48670, glass temperature Tg=65 degree, is referred to as resin 2.
The preparation example 1 of Masterbatch
50 parts of carbon black (Monarch 700 are dropped in melting mixing machine, Cabot, Cabot) and 50 parts of resins 1, through melting mixing, extrude, fragmentation obtains Masterbatch 1, is 116nm with the particle diameter that nano particle size instrument records carbon black in toluene after being dissolved by Masterbatch 1.
The preparation example 2 of Masterbatch
43 parts of pigment red 146 (SUNBRITE RED 146 are dropped in melting mixing machine, Japanese ink, DIC) and 57 parts of resins 1, through melting mixing, extrude, fragmentation obtains Masterbatch 2, is 434nm with the particle diameter that nano particle size instrument records pigment red 146 in toluene after being dissolved by Masterbatch 2.
The preparation example 3 of Masterbatch
47 parts of pigment yellow 185 (Paliotol Gelb D 1155 are dropped in melting mixing machine, BASF, BASF) and 53 parts of resins 1, through melting mixing, extrude, fragmentation obtains Masterbatch 3, is 376nm with the particle diameter that nano particle size instrument records pigment yellow 185 in toluene after being dissolved by Masterbatch 3.
The preparation example 4 of Masterbatch
65 parts of green pigment 15:4 (Hostaperm Blue BT are dropped in melting mixing machine, Clariant, Clariant) and 35 parts of resins 1, through melting mixing, extrude, fragmentation obtains Masterbatch 4, is 498nm with the particle diameter that nano particle size instrument records green pigment 15:4 in toluene after being dissolved by Masterbatch 4.
The preparation example 5 of Masterbatch
26 parts of carbon black (MA-100 are dropped in melting mixing machine, Mitsubishi Chemical, MitsubishiChemical) and 74 parts of resins 2, through melting mixing, extrude, fragmentation obtains Masterbatch 5, is 180nm with the particle diameter that nano particle size instrument records carbon black in toluene after being dissolved by Masterbatch 5.
The preparation example 6 of Masterbatch
63 parts of pigment red 122 (PIGMENT RED 3090 are dropped in melting mixing machine, adret pigment, SANYO) and 37 parts of resins 2, through melting mixing, extrude, fragmentation obtains Masterbatch 6, is 570nm with the particle diameter that nano particle size instrument records pigment red 122 in toluene after being dissolved by Masterbatch 6.
The preparation example 7 of Masterbatch
40 parts of pigment yellow 180 (PIGMENT YELLOW JHGT are dropped in melting mixing machine, adret pigment, SANYO) and 60 parts of resins 2, through melting mixing, extrude, fragmentation obtains Masterbatch 7, is 235nm with the particle diameter that nano particle size instrument records pigment yellow 180 in toluene after being dissolved by Masterbatch 7.
The preparation example 8 of Masterbatch
45 parts of green pigment 15:3 (Fastogen Blue FB5301 are dropped in melting mixing machine, Japanese ink, DIC) and 55 parts of resins 2, through melting mixing, extrude, fragmentation obtains Masterbatch 8, is 379nm with the particle diameter that nano particle size instrument records green pigment 15:3 in toluene after being dissolved by Masterbatch 8.
In Masterbatch, the particle diameter of colorant is listed as follows:
Carbon dust preparation example 1
In reactor, drop into 66 parts of styrene, 16 parts of butyl acrylates and 10 parts of Masterbatch 1 stirring at room temperature be uniformly dissolved; Then in still, drop into 8.5 parts of stearic acid octadecyl esters (Japanese grease, NOF), be heated to 70 degree and stir fusing evenly, then in still, drop into 1.64 parts of ABVN stirring and dissolving, obtain organic phase.
The deionized water of 200 parts, the methylcellulose of 2 parts is dropped into successively in reactor, stirring is warming up to 50 degree and is uniformly dissolved, with HOMOMIXER (spectrum Lai Mikesi under 6000rpm rotating speed, PRIMIX) circulation homogeneous surfaces aqueous surfactant solutions, in 50 degree of condition downhill reaction stills, drop into organic phase, carry out dispersion 10 minutes; Then homogeneous speed is brought up to 15000rpm, homogeneous 50 minutes; 67 degree are warming up to after homogeneous, stir polymerization to cool after 8 hours, use hydro-extractor filters, spend deionized water 6 times, 55 degree of lower vacuum drying, namely add additive process to dried particle obtains black carbon powder, the particle diameter of this carbon dust is 7.5 μm, distribution of particles is 2.01, and sphericity is 0.982, in carbon dust containing the resin of 87%, the carbon black of 5% and 8% wax.
Carbon dust preparation example 2
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 2, wax stearic acid octadecyl ester changes Tissuemat E POLYWAX 400 (Bake Hughes into, BAKER HUGHES), other conditions are constant, add additive process namely obtain red carbon powder to dried particle, the particle diameter of this carbon dust is 7.9 μm, distribution of particles is 1.78, and sphericity is 0.988, in carbon dust containing the resin of 87.7%, the pigment red 146 of 4.3% and 8% wax.
Carbon dust preparation example 3
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 3,66 parts of styrene change 57.4 parts of styrene into, 16 parts of butyl acrylates change 24.6 parts of butyl acrylates into, wax stearic acid octadecyl ester changes Tissuemat E POLYWAX 400 (Bake Hughes into, BAKER HUGHES), other conditions are constant, additive process is added to dried particle and namely obtains Yellow carbon powder, the particle diameter of this carbon dust is 6.8 μm, distribution of particles is 1.59, and sphericity is 0.981, in carbon dust containing the resin of 87.3%, the pigment yellow 185 of 4.7% and 8% wax.
Carbon dust preparation example 4
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 4, 66 parts of styrene change 61.5 parts of styrene into, 16 parts of butyl acrylates change 20.5 parts of butyl acrylates into, wax stearic acid octadecyl ester changes behenic acid 20 diester (Japanese grease into, NOF), initiating agent 1.64 parts of ABVNs change 2.5 parts of azoisobutyronitriles into, polymerization temperature 67 degree changes 75 degree into, other conditions are constant, additive process is added to dried particle and namely obtains cyan carbon dust, the particle diameter of this carbon dust is 7.2 μm, distribution of particles is 2.36, sphericity is 0.985, containing the resin of 85.5% in carbon dust, the wax of the green pigment 15:4 and 8% of 6.5%.
Carbon dust preparation example 5
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 5, other conditions are constant, additive process is added to dried particle and namely obtains black carbon powder, the particle diameter of this carbon dust is 6.5 μm, distribution of particles is 1.89, and sphericity is 0.985, in carbon dust containing the resin of 89.4%, the carbon black of 2.6% and 8% wax.
Carbon dust preparation example 6
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 6, 66 parts of styrene change 63.1 parts of styrene into, 16 parts of butyl acrylates change 18.9 parts of butyl acrylates into, the wax stearic acid octadecyl ester of 8% changes behenic acid 20 diester (the Japanese grease of 5.5% into, NOF), initiating agent 1.64 parts of ABVNs change 5 parts of peroxide tert pivalate esters into, polymerization temperature 67 degree changes 75 degree into, other conditions are constant, additive process is added to dried particle and namely obtains red carbon powder, the particle diameter of this carbon dust is 7.3 μm, distribution of particles is 1.43, sphericity is 0.975, containing the resin of 88.2% in carbon dust, the pigment red 122 of 6.3% and the wax of 5.5%.
Carbon dust preparation example 7
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 7, initiating agent 1.64 parts of ABVNs change 5 parts of peroxide tert pivalate esters into, polymerization temperature 67 degree changes 75 degree into, and other conditions are constant, adds additive process namely obtain Yellow carbon powder to dried particle, the particle diameter of this carbon dust is 6.5 μm, distribution of particles is 1.33, and sphericity is 0.979, in carbon dust containing the resin of 88%, the pigment yellow 180 of 4.0% and 8% wax.
Carbon dust preparation example 8
In carbon dust preparation example 1, change Masterbatch 1 into Masterbatch 8, the wax stearic acid octadecyl ester of 8% changes Tissuemat E POLYWAX 600 (the Bake Hughes of 6% into, BAKERHUGHES), other conditions are constant, add additive process namely obtain cyan carbon dust to dried particle, the particle diameter of this carbon dust is 6.1 μm, distribution of particles is 2.37, and sphericity is 0.981, the wax containing the resin of 89.5%, the green pigment 15:3 and 6% of 4.5% in carbon dust.
Carbon dust prepares comparative example 1
In reactor, drop into 66 parts of styrene, 16 parts of butyl acrylates and 10 parts of Masterbatch 1 stirring at room temperature be uniformly dissolved; Then in still, drop into 8.5 parts of stearic acid octadecyl esters (Japanese grease, NOF), be heated to 70 degree and stir fusing evenly, then in still, drop into 1.64 parts of ABVN stirring and dissolving, obtain organic phase.
In reactor, drop into the deionized water of 200 parts successively, the concentration of 150 parts is the Na of 0.1mol/L
3pO
4aqueous solution, stirs and is warming up to 40 degree, and with HOMOMIXER (spectrum Lai Mikesi, PRIMIX) circulation homogeneous under 6000rpm rotating speed, in still, drip 35 parts of concentration is the CaCl of 1mol/L
2aqueous solution, time for adding is 30 minutes, obtains Ca
3(PO4)
2inorganic colloid spreading agent.In 50 degree of condition downhill reaction stills, drop into organic phase, homogeneous speed is brought up to 15000rpm, homogeneous 50 minutes; 67 degree are warming up to after homogeneous, stir polymerization to cool after 8 hours, use hydro-extractor filters, spend deionized water 6 times, 55 degree of lower vacuum drying, namely add additive process to dried particle obtains black carbon powder, the particle diameter of this carbon dust is 6.7 μm, distribution of particles is 2.92, and sphericity is 0.973, in carbon dust containing the resin of 87%, the carbon black of 5% and 8% wax.
Carbon dust prepares comparative example 2
In reactor, drop into 66 parts of styrene, 16 parts of butyl acrylates and 10 parts of Masterbatch 2 stirring at room temperature be uniformly dissolved; Then in still, drop into 8.5 parts of stearic acid octadecyl esters (Japanese grease, NOF), be heated to 70 degree and stir fusing evenly, then in still, drop into 1.64 parts of ABVN stirring and dissolving, obtain organic phase.
In reactor, drop into the deionized water of 200 parts successively, the concentration of 150 parts is the Na of 0.1mol/L
3pO
4aqueous solution, stirs and is warming up to 40 degree, and with HOMOMIXER (spectrum Lai Mikesi, PRIMIX) circulation homogeneous under 6000rpm rotating speed, in still, drip 23 parts of concentration is the CaCl of 1mol/L
2aqueous solution, time for adding is 30 minutes, obtains Ca
3(PO4)
2inorganic colloid spreading agent.In 50 degree of condition downhill reaction stills, drop into organic phase, homogeneous speed is brought up to 15000rpm, homogeneous 50 minutes; 67 degree are warming up to after homogeneous, stir polymerization to cool after 8 hours, use hydro-extractor filters, spend deionized water 6 times, 55 degree of lower vacuum drying, namely add additive process to dried particle obtains red carbon powder, the particle diameter of this carbon dust is 8.4m, distribution of particles is 3.13, and sphericity is 0.978, in carbon dust containing the resin of 87.7%, the pigment red 146 of 4.3% and 8% wax.
The carbon dust of carbon dust in the embodiment of the present invention 1,2,3,4 and comparative example 1,2 in fraternal printer HL-3040CN and embodiment 5,6,7,8 is carried out printing test (normal temperature 25 degree at Hewlett-Packard printer HP1215, normal wet 60%), its result is as follows:
Test data shows, carbon dust fine grained of the present invention is few, and domain size distribution is narrower, and bottom ash, useless powder rate, consumption are lower, and Recipe is stablized, wider to the selectivity of raw material.
Claims (8)
1. adopt suspension polymerization to prepare a method for colored carbon powder, it is characterized in that, comprise the following steps:
1) colorant and resin through melting mixing, extrude, pulverize and obtain Masterbatch;
2) in monomer, add Masterbatch, wax and initiating agent, heating stirring and dissolving, obtains the organic phase containing colorant, resin, initiating agent, wax, monomer;
3) add step 2 to containing in the aqueous solution of suspension stabilizer) organic phase first carry out low velocity shear dispersion, and then by high speed shear dispersion obtain suspension;
4) by step 3) described suspension intensification polymerization obtains colored carbon powder parent, then through filtering washing, dry, mixing additive obtains colored carbon powder.
2. the method adopting suspension polymerization to prepare colored carbon powder as claimed in claim 1, is characterized in that, described step 1) in, in control Masterbatch, colorant particle size dispersion is to 50-600nm.
3. the method adopting suspension polymerization to prepare colored carbon powder as claimed in claim 1, is characterized in that, described step 2) in, the heating-up temperature in described heating stirring and dissolving is 40-80 DEG C.
4. the method adopting suspension polymerization to prepare colored carbon powder as claimed in claim 1, is characterized in that, described step 3) in, described suspension stabilizer is surfactant.
5. the method adopting suspension polymerization to prepare colored carbon powder as claimed in claim 1, it is characterized in that, described step 3) in, described surfactant is at least one in anionic surfactant, cationic surfactant, non-ionic surfactant, synthetic polymer spreading agent or natural polymer spreading agent.
6. the employing suspension polymerization as described in claim 4 or 5 prepares the method for colored carbon powder, it is characterized in that, described step 3) in, the described surfactant addition as suspension stabilizer is 0.5 weight portion ~ 5 weight portion relative to monomer 100 weight portion.
7. the method adopting suspension polymerization to prepare colored carbon powder as claimed in claim 1, it is characterized in that, in described step (3), the rotating speed of low velocity shear dispersion is 2000rpm ~ 8000rpm, and the rotating speed of described high speed shear dispersion is 10000rpm ~ 20000rpm.
8. the method adopting suspension polymerization to prepare colored carbon powder as claimed in claim 1, is characterized in that, in described step (4), the temperature of suspension intensification polymerization is 50 DEG C ~ 98 DEG C.
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