CN103513527B - A kind of colored carbon powder and preparation method thereof - Google Patents
A kind of colored carbon powder and preparation method thereof Download PDFInfo
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- CN103513527B CN103513527B CN201210214546.8A CN201210214546A CN103513527B CN 103513527 B CN103513527 B CN 103513527B CN 201210214546 A CN201210214546 A CN 201210214546A CN 103513527 B CN103513527 B CN 103513527B
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Abstract
The invention provides a kind of colored carbon powder and preparation method thereof, this preparation method comprises the following steps: 1) preparation feedback component: colorant, wax, Charge controlled agent dispersing liquid and polymer emulsion; The ionic surfactant that in four kinds of components, at least one uses is made to have opposite-sign; Four kinds of components are divided into two groups by the electrical difference of used ionic surfactant, and each component often in group has electrically identical; 2) component of first group is made to mix in organic solvent, the component adding second group is again reacted, maintain stir and in detection reaction system, the change of size of particle reaches setting range time, add particle diameter accretion inhibitor stopped reaction, through thermal treatment, cooling, separation, drying, make toner particle; 3) in the above-mentioned toner particle made, add external additive, be uniformly mixed and make colored carbon powder.This colored carbon powder anti-sticking roller is good, stable storing, and printing, duplicating color and luster and resolution are high, and carbon dust reclaims with clean easy.
Description
Technical field
The present invention relates to a kind of colored carbon powder and preparation method thereof, particularly relate to a kind of particle size distribution and pattern easily controls, anti-sticking roller is good, stable storing, printed drawings be as the colored carbon powder and preparation method thereof of even concentration and excellent in stability.
Background technology
Xerography forms electrostatic latent image on photoreceptor or electrostatic recording medium, then sticking on described electrostatic latent image with colored carbon powder makes it develop, then hot-pressing roller is utilized under the action of heat and pressure, carbon powder image is transferred on paper and forms fixing image, so performance and the quality of colored carbon powder directly affects image quality.
The colored carbon powder being conventionally used to development of static charge adopts physical method to prepare usually, as melting pulverization, by resin, colorant (pigment or dyestuff), adjuvant (charge control agent etc.) through melting mixing, extrude, cool, fragmentation, ultra-fine grinding, classification, add the operations such as external additive, finally obtain colored carbon powder.But, this preparation method not only also exist toner not easily dispersed in resin, the colored carbon powder out-of-shape of preparation, particle diameter are comparatively large and the defect of wider distribution, thus cause printing, easy roll banding, resolution are low when duplicating, shade deviation, useless powder rate are higher, the method also deposits the complex process of classification process in process of production simultaneously, the shortcoming that cost is higher.
There is many defects owing to adopting physical method; so occurred adopting chemical method to prepare the technology of colored carbon powder; usual chemical method is prepared colored carbon powder and is mainly comprised suspension polymerization; as patent US65666028, US6740463, US6528222, US6177223 etc.; and emulsion polymerization, as the record of patent US4983488, US6531256, US5916725 etc.
The feature of suspension polymerization is the size that effectively can control colored carbon powder particle, make the mobility of toner, charging performance significantly improves, thus improve the fixing stability of toner, concreteness, effectively suppress print through phenomenon, but there is carbon dust broad particle distribution in the colored carbon powder adopting suspension polymerization to prepare, the defect that printing, the color and luster duplicated and resolution are not good enough, and the carbon powder particle obtained too circle, be unfavorable for that carbon dust reclaims and clean difficulty.
Emulsion polymerization prepare colored carbon powder also exist on the one hand polymer emulsion and colorant mixing, flocculation, thermal treatment time be difficult to make resin and colorant is dispersed and the defect that adheres to; On the other hand, when emulsion polymerization prepares carbon dust, also exist and partially print performance for improving the anti-of colored carbon powder, usually the consumption improving wax is needed, and now easily cause wax move to carbon powder particles surface and pollute carrier and development sleeve, and make pigment skewness in carbon dust, cause the defect printing, duplicate difficult quality raising.
Adopt chemical method to prepare above-mentioned defect in colored carbon powder technology and problem to overcome in the past, more and more for improving one's methods of colored carbon powder more in recent years, emulsion polymerization in situ is such as utilized to manufacture colored carbon powder technology disclosed in Chinese patent CN200910272568.8, its technical scheme comprise by anionic content of wax polymkeric substance complex emulsions (A) obtained through in-situ emulsion polymerization respectively and cationic be incorporated in percussion flow effect containing colorant polymkeric substance complex emulsions (B) is mixed under, by the moon, positive electricity interacts and makes emulsion particle aggegation and obtain carbon dust.Although the colored carbon powder prepared of the method prints, duplicate color and luster and resolution high, carbon dust reclaims with easily clean, but still there is preparation process complexity, reaction conditions shortcoming more rambunctious.
Summary of the invention
The object of the invention is to solve above-mentioned technical matters, provide a kind of chemical method preparing colored carbon powder, the colored carbon powder utilizing the method to prepare both had had domain size distribution and pattern easily controls, anti-sticking roller is good, stable storing, printed drawings as the feature of color and luster, resolution and excellent in stability, there is again technique simple, with low cost and reclaim and clean simple advantage.
Present invention also offers a kind of colored carbon powder utilizing said method to prepare.
The invention provides a kind of preparation method of colored carbon powder, comprise the following steps:
1) preparation feedback component:
Colorant, ionic surfactant and water are mixed with colorant dispersion;
Wax, ionic surfactant and water are mixed with wax dispersion;
Charge control agent, ionic surfactant and water are mixed with Charge controlled agent dispersing liquid;
Orqanics Monomer, ionic surfactant, chain-transferring agent, initiating agent and water is utilized to prepare polymer emulsion;
And the ionic surfactant that at least one in prepared colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid and polymer emulsion uses has opposite-sign;
Described colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid and polymer emulsion are divided into two groups according to the electrical difference of used ionic surfactant, and each reactive component often in group has electrically identical;
2) reactive component of described first group is mixed in organic solvent, the reactive component adding second group again reacts, maintain stir and in detection reaction system, the change of size of particle reaches setting range time, add particle diameter accretion inhibitor stopped reaction, through thermal treatment, cooling, separation, drying, make toner particle;
3) in the above-mentioned toner particle made, add external additive, be uniformly mixed and make colored carbon powder.
According to method of the present invention, colorant dispersion is comprised in preparation, wax dispersion, during the reactive component of Charge controlled agent dispersing liquid and polymer emulsion, by selecting to add, there is different electrical ionic surfactant, these reactive components for the preparation of colored carbon powder can be had and different be electrically divided into two groups, i.e. anionic or cationic reactive component, for above-mentioned four kinds of reactive components, be divided into when two groups and can have two kinds of modes, namely, described first group comprises three kinds and has identical electrical reactive component, described second group comprises the reactive component that a kind of and first group reactive component has opposite-sign.In the described colored carbon powder process of preparation, by controlling the reactive component containing opposite charges to react in organic solvent, achieve the control to carbon dust domain size distribution and pattern.
In method of the present invention, require electrically different reactive components to add in organic solvent in batches, such as, the operation that can adopt is, described first group comprise a kind of or two kinds there is identical electrical reactive component, correspondingly, described second group comprises three kinds or two kinds of reactive components, and they are electrically identical each other but electrically contrary with the reactive component of first group; When reacting, join again after first the reactive component of second group being mixed in the mixed liquor that the first group reaction component and organic solvent formed.Usually first group can be made to comprise two kinds or three kinds of electrical identical reactive components, and second group then comprises two kinds or a kind of electrically contrary reactive components.
The ionic surfactant used in the present invention is conventional anionic surface active agent and cationic surfactant.Anionic surface active agent can be selected from alkyl aryl sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl carboxylate, one or more combination in alkyl alkoxylated carboxylate etc., such as, lauryl sodium sulfate, sodium tetradecyl sulfate, pentadecyl sodium sulphate, neopelex, methyl stearate sodium sulfonate of ethoxylated, α sodium olefin sulfonate, Seconary Alkane Sulphonate Sodium, Di-phosphorus pentonide or lauryl alcohol phosphate etc., wherein, preferred alkyl sulfate, more preferably lauryl sodium sulfate, cationic surfactant can be selected from amine salt, one or more combination in quaternary ammonium salt, described amine salt cationic surfactant can be primary amine salt, secondary amine salt, tertiary ammonium salt, hydramine, diamines or polyamines, containing the amine salt cationic surfactant such as amine or guanidine derivatives of acyl group, described quaternary ammonium salt cationic surfactant can be alkyl phenyl alkyl dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, zephiran, alkyl trimethyl ammonium bromide, Alkyl dimethyl benzyl ammonium bromide, hexadecyldimethyl benzyl ammonium allyl ammonium chloride, Benzene Chloride diformazan hydrocarbon ammonium, brocide, the conventional quaternary ammonium salt cationic surfactants such as ten dimethylbenzene triethyl ammonium chlorides or dibenzyl two (stearamide ethyl) ammonium chloride, wherein, preferred use quaternary ammonium salt cationic surfactant, such as OTAC, hexadecyltrimethylammonium chloride etc.
The organic solvent that the present invention uses can be: methyl alcohol, ethanol, isopropyl alcohol, acetone, cyclohexanone, ether, glycol monoethyl ether, ethylene glycol monoethyl ether or ethylene glycol monobutyl ether etc.; Wherein, preferred alcohol, acetone, ethylene glycol monobutyl ether.
According to specific embodiment of the invention scheme, described organic solvent and polymer emulsion be (5-80) in mass ratio: 100 mix the carrying out more being conducive to reacting.
The particle diameter accretion inhibitor that the present invention uses can be aforementioned said ionic surfactant usually.
The external additive that the present invention uses can be the combination of inorganic external additive or inorganic external additive and organic external additive, inorganic external additive can be commonly use such as to comprise silicon dioxide, titania, aluminium oxide, zinc paste or magnesium oxide etc. oxide-based; Organic external additive can for comprising condensate pearl (as acrylate polymer) or metallic stearate (as zinc stearate) etc.The use of external additive is beneficial to the mobility that the present invention improves toner, the bonding cohesion suppressing between toner particle, even if make carbon dust also can steady in a long-termly store under hot and humid environment, generally can preferred inorganic external additive, such as silicon dioxide, titania or aluminium oxide etc., more preferably silicon dioxide.Can according to the character of the character of external additive and prepared toner particle, determine suitable external additive addition, usually, relative to toner particle 100 weight portion, the content of external additive is preferably 0.1 ~ 8 weight portion, is more preferably 0.2 ~ 5 weight portion.
According to method of the present invention, described colorant dispersion can obtain as follows: colorant, ionic surfactant and water mixed in proportion and make it form uniform dispersion, wherein colorant and ionic surfactant can account for 5-30% and 1-10% of colorant dispersion quality respectively, and all the other are water.Can adopt the dispersion homogenizer that this area is conventional, such as, above-mentioned mixed liquor is uniformly dispersed by high pressure homogenizer, rotational shear homogenizer, bowl mill, sand mill, muller or high pressure opposite direction collisions dispersion machine etc., obtains preparing colorant dispersion.
The colorant that the present invention uses can be dyestuff, pigment or both potpourris, but considers from the angle of water tolerance, photostability and gas resistance, and the present invention selects pigment colorant.The concrete selection of pigment colorant does not limit, and can comprise green pigment, such as C.I. alizarol saphirol 2, alizarol saphirol 3, pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3 or pigment blue 15: 4 etc.; Magenta pigment, such as C.I. pigment red 30, pigment red 31, pigment red 32, pigment red 37, pigment red 38, pigment red 4 8:1, paratonere 53:1, paratonere 57:1, pigment red 112, paratonere 114, pigment red 122 or paratonere 184 etc.; Yellow uitramarine, such as C.I. pigment yellow 74, pigment yellow 81, pigment yellow 83, pigment yellow 97, pigment yellow 110 or pigment yellow 13 8 etc.; Black pigment, such as nigrosine, carbon black, non magnetic ferrite, cupric oxide or activated charcoal etc.
The wax dispersion that the present invention uses can be prepared in accordance with the following methods: wax, ionic surfactant and water mixed in proportion and make it form uniform dispersion, wherein wax and ionic surfactant can account for 5 ~ 30% and 1-10% of wax dispersion quality respectively, and all the other are water.The wax of usual 5 ~ 30% can ensure the gloss of image in print procedure, can not impact equipment simultaneously.According to the difference of the fusing point of wax, reaction controlling carries out at different temperatures, is generally 50-100 DEG C.The dispersion homogenizing machine that dispersing apparatus adopts this area conventional usually, such as, above-mentioned mixed liquor is uniformly dispersed by high pressure homogenizer, rotational shear homogenizer, bowl mill, sand mill, muller or high pressure opposite direction collisions dispersion machine etc., prepares wax dispersion.
The wax that the present invention uses can be such as, petroleum wax and the derivants such as paraffin, microcrystalline wax, vaseline; The polyolefin-wax such as Tissuemat E, polypropylene wax and derivant; The synthetic waxs such as Fischer-Tropsch wax; Wax such as natural series such as rice wax, Brazil wax etc.; One or more combination in ester system wax, department of botany's wax, animal system wax, SOLID ORGANIC silicon wax, montan wax etc., be known in this field and conventional wax, considering detachment, fixation performance and storage stability that carbon powder particle shows when printing, preferably having used the wax that fusing point is 50-100 DEG C.
The Charge controlled agent dispersing liquid that the present invention uses can obtain as follows: charge control agent, ionic surfactant and water mixed in proportion and make it form uniform dispersion, wherein charge control agent and ionic surfactant account for 5-30% and 1%-10% of Charge controlled agent dispersing liquid quality, and all the other are water.The use of charge control agent can effectively improve carbon dust carried charge, and the blackness of printed drawings picture is effectively improved.The dispersion homogenizing machine that usual employing this area is conventional, such as, above-mentioned mixed liquor is uniformly dispersed by high pressure homogenizer, rotational shear homogenizer, bowl mill, sand mill, muller or high pressure opposite direction collisions dispersion machine etc., prepares Charge controlled agent dispersing liquid.
The charge control agent of the present invention's use can be one or more combination, can select positive charge control agent or negative charge controlling agent according to application target difference.Positive charge control agent can use such as, quaternary amine based compound (e.g., commodity BontronP-51, CopyChargePSYVP2038 etc.); quaternary alkylphosphonium salt based compound, triphenyl methane based compound, imidazole compound, pyrimidine compound, polyamino resin, aminopyrine or amino silane etc.; Negative charge controlling agent can use metal complex and slaine, alkylated salicylamide acid metal compound, fatty acid soaps or the chain alkyl carboxylate etc. of azo based dye, metal naphthenate, salicylic acid and derivant thereof such as containing metals such as Cr, Co, Al, Fe, wherein, the metal complex of preferred salicylic acid and derivant thereof, more preferably di-tert-butyl salicylic acid.
Present invention also offers a kind of preparation method of polymer emulsion: when preparing polymer emulsion, the mass ratio of Orqanics Monomer, ionic surfactant, chain-transferring agent, initiating agent and water is (80 ~ 120): (1 ~ 10): (0.1 ~ 5): (0.1 ~ 5): (50 ~ 300), stirs and prepares polymer emulsion.Consumption and suitable preparation condition (such as 70-100 DEG C, 2-10 hour) by controlling initiating agent and chain-transferring agent in this process control polymer emulsion and have suitable molecular weight.In the present invention, the weight-average molecular weight (Mw) of polymer emulsion is 5000 ~ 100000, is preferably 10000 ~ 70000.The polymer emulsion of this molecular weight has excellent gathering amalgamation, paper tack and sufficiently high glass temperature, and now its glass temperature (Tg) is correspondingly at 40-75 DEG C, is beneficial to as final carbon dust provides good stability and fixation performance.
The Orqanics Monomer used in polyreaction of the present invention can be one or more combination, can be various Orqanics Monomer conventional during carbon dust manufactures, they exist in polymer form in polymer emulsion, infinite Orqanics Monomer example can be phenylethylene, such as: styrene, α-methyl styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, to methoxy styrene or p-ethyl-styrene etc., vinyl ester, such as: vinyl acetate, propionate, vinyl benzoate or vinyl butyrate etc., (methyl) esters of acrylic acid, such as: methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl, n-octyl, dodecylacrylate, acrylic acid-2-ethyl caproite, 2-hydroxyethyl acrylate, stearyl acrylate acyl ester or acrylic acid-2-chloroethene ester, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, n octyl methacrylate, lauryl methacrylate, methacrylic acid-2-hydroxy methacrylate, methacrylic acid-2-Octyl Nitrite, methacrylic acid stearoyl ester, phenyl methacrylate, dimethylaminoethyl methacrylate or diethyl aminoethyl methacrylate etc., unsaturated carboxylic acid or anhydrides, such as: acrylic acid, methacrylic acid, methacrylate, maleic acid, maleic anhydride, halogen-containing vinyl monomer, such as: vinyl chloride, nitro class monomer, such as: the multipolymer of nitrostyrolene etc., vinyl cyanide, maleic anhydride, vinethene, methacrylonitrile, acrylamide etc.Relatively more conventional can be styrene, acrylate or their combination, such as, generates the multipolymer of styrene and one or more (methyl) acrylate monomers in polymer emulsion.
The chain-transferring agent that the present invention uses is conventional lauryl mercaptan, phenixin, trichlorine methyl bromide etc.
The initiating agent that the present invention uses is conventional persulfate, the initiating agent etc. that hydrogen peroxide or persulfate, hydrogen peroxide and ferrous salt form.
According to method of the present invention, the mean grain size making described colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid and polymer emulsion is 100-800nm, is conducive to obtaining required carbon powder particle.
A kind of method preparing colored carbon powder provided by the invention makes reaction system breakdown of emulsion due to the interaction of cationic and anionic surfactant, dispersed phase particles is impelled to assemble under suitable conditions, the temperature such as controlling reaction system reaches 35 ~ 60 DEG C, be more conducive to dispersed phase particles is flocculated, Multisizer3 Ku Erte sreen analysis calculating instrument is used to measure its particle diameter, when reaching required particle diameter, add particle diameter accretion inhibitor stopped reaction, again through thermal treatment, cooling velocity is regulated to make it cool, be separated, dry, make toner particle, appropriate external additive can also be added as required, fully be uniformly mixed and make colored carbon powder of the present invention.The research display of applicant, the mean grain size of carbon dust is 4 ~ 15 μm, be especially 5 ~ 9 μm is preferred, so, suitable particle diameter can be risen to by monitoring dispersed phase particles in the preparation process of colored carbon powder, inhibitor stopped reaction can be added.
According to specific embodiment of the invention scheme, control in reaction system, the mass ratio of described colorant, wax, charge control agent and polymer emulsion is (1-20): (3-25): (0.5-20): 100, mixing is more conducive to the carrying out reacted, and provides performance and the good colored carbon powder particle of quality with follow-up.And to maintain also be one of condition realizing invention effect to the stirring of reaction system, be that to control stirring rate be 500-2000rpm in preferred scheme.
About colorant dispersion, wax dispersion, charge control agent are known technology to the major effect of printing colored carbon powder and effect, those skilled in the art can grope to determine according to needs.In such scheme, the colorant preferably controlling the polymer emulsion mixture of every 100 mass parts in this system is 5-15 mass parts; Appropriate wax then provides good anti-sticking roller and improves image fixing effect, and the wax preferably controlling the polymer emulsion mixture of every 100 mass parts in this system is 6-18 mass parts; Charge control agent can regulate the carried charge of carbon dust, promotes the quality of printed drawings picture, and the charge control agent preferably controlling the polymer emulsion mixture of every 100 mass parts in this system is 2-15 mass parts.
In embodiment of the present invention, regulate reaction cooling velocity effectively can control the pattern of carbon powder particles and prevent the particle such as wax, colorant from separating out on the surface of carbon dust, in a particular embodiment, the cooling velocity regulating reaction product is 2-4 DEG C/min.
Present invention also offers a kind of colored carbon powder, this colored carbon powder can be obtain according to the method described in the present invention.
Colored carbon powder of the present invention is micron order colored carbon powder, and especially mean grain size is 4 ~ 15 μm, preferably 5 ~ 9 μm.
Compared with prior art, technical scheme of the present invention has following beneficial effect:
1, the dispersion liquid of the surfactant containing opposite charges and/or emulsion react by adopting by the present invention in organic solvent, thus to make in system Homogeneous phase mixing between each particle, be conducive to the control of domain size distribution and pattern, prevent from causing the problems such as generated carbon dust quality instability and print image quality difference because domain size distribution is wide and chargeding performance fluctuation is too large.
2, the various raw material sources of the present invention program's use are extensive, cheap, are therefore beneficial to commercial application.
3, the technique preparing colored carbon powder provided by the invention is simple, and has and reclaim and clean simple feature.
Embodiment
the preparation of anionic polymer emulsion
75g styrene, 5g methacrylic acid-2-hydroxy methacrylate and 20g n-butyl acrylate organic monomer potpourri are mixed with 1g lauryl mercaptan, after fully stirring 15min, forms organic monomer solution;
3g lauryl sodium sulfate and the mixing of 150g deionized water are warming up to 75 DEG C, add the 0.5g ammonium persulfate dissolved in advance, slowly add organic monomer solution again, control feed time and be no more than 4h, afterwards reaction mixture is continued reaction 4h, reaction terminates slowly to be down to room temperature afterwards, adopting American-European gram laser particle analyzer LS300 to measure emulsion particle diameter is 180nm, adopting differential scanning calorimeter DSC to measure glass temperature Tg is 55 DEG C, and adopting gel permeation chromatography GPC to measure emulsion weight-average molecular weight MW is 43000.
the preparation of cation type polymer emulsion
Change above-mentioned anionic into cationic surfactant OTAC, other conditions are constant, final emulsion particle diameter is 190nm, glass temperature Tg is 56 DEG C, and adopting gel permeation chromatography GPC to measure emulsion weight-average molecular weight MW is 45000.
the preparation of anionic Charge controlled agent dispersing liquid
20g di-tert-butyl salicylic acid, 3g lauryl sodium sulfate and 77g deionized water are carried out stirring at normal temperatures pre-dispersed, then being joined by dispersion liquid in high pressure homogenizer with working pressure is that 1000 atmospheric pressure carry out homogenous disperse, obtain the Charge controlled agent dispersing liquid containing anionic surface active agent, its particle diameter is 200nm.
the preparation of cationic Charge controlled agent dispersing liquid
Change anionic in above-mentioned anionic Charge controlled agent dispersing liquid into cationic surfactant OTAC, charge control agent di-tert-butyl salicylic acid changes BontronP-51 into, other conditions are constant, obtain the Charge controlled agent dispersing liquid of cationic surfactant, its particle diameter is 180nm.
the preparation of anionic wax dispersion
20g paraffin, 3g lauryl sodium sulfate and 77g deionized water are carried out stirring at 85 DEG C pre-dispersed, then being joined by this dispersion liquid in high pressure homogenizer with working pressure is that 1000 atmospheric pressure carry out homogenous disperse, obtain the wax dispersion containing anionic surface active agent, its particle diameter is 350nm.
the preparation of cationic wax dispersion
Change above-mentioned anionic into cationic surfactant OTAC, other conditions are constant, obtain the wax dispersion of cationic surfactant, and its particle diameter is 370nm.
the preparation of cationic colorant dispersion
Embodiment 1
By 20gC.I. pigment blue 15: 3, at room temperature to carry out stirring pre-dispersed for 3g OTAC and 77g deionized water, then being joined by this dispersion liquid in high pressure homogenizer with working pressure is that 1000 atmospheric pressure carry out homogenous disperse, obtain cationic cyan colorant dispersion liquid, its particle diameter is 200nm.
Embodiment 2
In embodiment 1, by colorant C.I. pigment blue 15: 3 make C.I. pigment red 122 into, and other conditions are identical, obtain cationic red colored agent dispersing liquid, its particle diameter is 250nm.
Embodiment 3
In embodiment 1, by colorant C.I. pigment blue 15: 3 make C.I. pigment yellow 74 into, and other conditions are identical, obtain cationic yellow coloring agent dispersing liquid, its particle diameter is 260nm.
Embodiment 4
In embodiment 1, by colorant C.I. pigment blue 15: 3 make carbon black into, other conditions are identical, obtain cationic black colorant agent dispersing liquid, and its particle diameter is 150nm.
the preparation of anionic colorant dispersion
Embodiment 5
By 20gC.I. pigment blue 15: 3, at room temperature to carry out stirring pre-dispersed for 3g lauryl sodium sulfate and 77g deionized water, then being joined by this dispersion liquid in high pressure homogenizer with working pressure is that 1000 atmospheric pressure carry out homogenous disperse, obtain anionic cyan colorant dispersion liquid, its particle diameter is 210nm.
Embodiment 6
In embodiment 5, by colorant C.I. pigment blue 15: 3 make C.I. pigment red 122 into, and other conditions are identical, obtain the red colored agent dispersing liquid of anionic, its particle diameter is 240nm.
Embodiment 7
In preparation example 5, by colorant C.I. pigment blue 15: 3 make C.I. pigment yellow 74 into, and other conditions are identical, obtain anionic yellow coloring agent dispersing liquid, its particle diameter is 260nm.
Embodiment 8
In embodiment 5, by colorant C.I. pigment blue 15: 3 make carbon black into, other conditions are identical, obtain anionic black colorant agent dispersing liquid, and its particle diameter is 170nm.
the preparation of colored carbon powder
Embodiment 9
By the cationic wax dispersion of 72g obtained in cationic for the 95g obtained in embodiment 1 cyan colorant dispersion liquid and specific embodiment, join in reactor as the first group reaction component, add 50g deionized water and 50g ethanol again, at room temperature, be that 600rpm stirs 20min with stirring rate, make it fully mix;
Using the 250g anionic polymer emulsion that obtains in specific embodiment and 47g anionic Charge controlled agent dispersing liquid as the second group reaction component, abundant mixing, then this anionic mixed liquor is slowly joined aforementioned containing in the cationic mixed liquor of organic solvent;
After adding, warming while stirring, its stirring rate is 600rpm, and be warming up to 50 DEG C with the speed of 1 DEG C/min, stirring reaction at such a temperature, adopt the change of size of Multisizer3 Ku Erte sreen analysis calculating instrument detection system, when particle diameter reaches 5.5 ~ 6.0 μm, anionic is added in system, suppress the growth of particle, continue to stir 30min, then 85 DEG C are slowly warming up to, heat 2h at this temperature, by the cooling velocity of 3 DEG C/min, system temperature is dropped to room temperature, through being separated and drying, obtain toner particle,
The toner particle obtained is added external additive hydrophobic silica, uses Henschel mixer mixing, obtain blue carbon powder.Measured by Multisizer3 Ku Erte sreen analysis calculating instrument, the mean grain size of this carbon dust is 5.9 μm.
Embodiment 10
Change the cationic cyan colorant dispersion liquid in embodiment 9 and cationic wax dispersion into the anionic cyan colorant dispersion liquid in embodiment 5 and the anionic wax dispersion in specific embodiment respectively, change organic solvent ethanol into acetone, anionic polymer emulsion and anionic Charge controlled agent dispersing liquid are changed respectively into the cation type polymer emulsion in specific embodiment and cationic Charge controlled agent dispersing liquid, change particle diameter accretion inhibitor anionic into cationic surfactant OTAC, other conditions are constant, measured by Multisizer3 Ku Erte sreen analysis calculating instrument, the mean grain size of this carbon dust is 5.8 μm.
Embodiment 11
The cationic wax dispersion of 72g obtained in cationic for the 95g obtained in embodiment 1 cyan colorant dispersion liquid, specific embodiment and the cationic Charge controlled agent dispersing liquid of 47g are joined in reactor, add 50g deionized water and 50g ethylene glycol monobutyl ether again, at room temperature, be that 600rpm stirs 20min with stirring rate, make it fully mix.The 250g anionic polymer emulsion obtained in embodiment is slowly added aforementioned containing in the cationic mixed liquor of organic solvent, other conditions are constant, measured by Multisizer3 Ku Erte sreen analysis calculating instrument, the mean grain size of this carbon dust is 5.9 μm.
Embodiment 12
Cationic cyan colorant dispersion liquid in embodiment 9 is changed into the cationic red colored agent dispersing liquid in embodiment 2, other conditions are constant, and final obtained red carbon powder mean grain size is 5.8 μm.
Embodiment 13
Cationic cyan colorant dispersion liquid in embodiment 9 is changed into the cationic yellow coloring agent dispersing liquid in embodiment 3, other conditions are constant, and final obtained Yellow carbon powder mean grain size is 5.9 μm.
Embodiment 14
Cationic cyan colorant dispersion liquid in embodiment 9 is changed into the cationic black colorant agent dispersing liquid in embodiment 4, other conditions are constant, and final obtained black carbon powder mean grain size is 5.8 μm.
Comparative example 1
The cationic wax dispersion of 72g obtained in cationic for the 95g obtained in embodiment 1 cyan colorant dispersion liquid and specific embodiment is joined in reactor, adds the mixing of 50g deionized water, be called mixed liquor A;
The 250g anionic polymer emulsion obtained in specific embodiment and 47g anionic Charge controlled agent dispersing liquid are fully mixed, is called mixed liquid B, mixed liquid B is slowly added in mixed liquor A;
After adding, warming while stirring, its stirring rate is 2500rpm, and be warming up to 65 DEG C with the speed of 1 DEG C/min, stirring reaction at such a temperature, adopt the change of size of Multisizer3 Ku Erte sreen analysis calculating instrument detection system, when particle diameter reaches 5.0 ~ 7.0 μm, anionic is added in system, suppress the growth of particle, continue to stir 50min, then 95 DEG C are slowly warming up to, heat 2.5h at this temperature, cooling, be separated and drying, obtain blue carbon powder, measured by Multisizer3 Ku Erte sreen analysis calculating instrument, this carbon dust mean grain size is 5.9 μm.
Comparative example 2
Cationic cyan colorant dispersion liquid in comparative example 1 is changed into the cationic red colored agent dispersing liquid in embodiment 2, other conditions are constant, and final obtained red carbon powder mean grain size is 5.7 μm.
Comparative example 3
Cationic cyan colorant dispersion liquid in comparative example 1 is changed into the cationic yellow coloring agent dispersing liquid in embodiment 3, other conditions are constant, and final obtained Yellow carbon powder mean grain size is 5.6 μm.
Comparative example 4
Cationic cyan colorant dispersion liquid in comparative example 1 is changed into the cationic black colorant agent dispersing liquid in embodiment 4, other conditions are constant, and final obtained black carbon powder mean grain size is 5.8 μm.
target product is both pick, ambient storage stability, printed drawings be as even concentration and estimation of stability
The present invention uses the carbon dust obtained in above-described embodiment to carry out both pick, ambient storage stability, printed drawings as even concentration and estimation of stability.
One, both pick evaluation method
The pixel rate using this printer to carry out Huang/magenta/green grass or young crops/black colors under low temperature and low humidity (10 DEG C/10%RH environment) is dot pattern (half tone image of the both full-pixel rate=40%) continuous printing 1000 of 10%, then under power down state, a night is stopped, morning prints on a blank sheet of paper, by the carbon dust of visual valuation fixing section with or without spuing.
Two, ambient storage method for estimating stability
Huang/magenta/green grass or young crops/black assorted packing carbon powder is entered in the corresponding handle box of printer, places 10 days under hot and humid (40 DEG C/95%RH environment) and low temperature and low humidity (10 DEG C/10%RH environment), see that carbon dust assembles caking with or without generation by range estimation.
Evaluation criterion is as follows:
A: do not find that carbon dust assembles caking;
B: carbon dust slightly assembles caking;
C: carbon dust more obviously assembles caking;
D: carbon dust significantly assembles caking.
Three, printed drawings is as even concentration evaluation method
Huang/magenta/green grass or young crops/black assorted packing carbon powder is entered in the corresponding handle box of printer, first 1 page of region-wide solid-printed image is exported under ambient temperature and moisture (23 DEG C/50%RH environment), then exporting 500 pages of printing rates is continuously the image of 1%, export 1 page of region-wide solid-printed image again, printing before repetition, until exporting 4000 pages of printing rates is the image of 1%, evaluate the homogeneity of the image density that paper is observed.
Evaluation criterion is as follows:
A: after exporting 4000 pages, its region-wide solid-printed image can observe good homogeneity on paper;
B: in the sample obtained after exporting 4000 pages, printer paper is observed the slight homogeneity of region-wide solid-printed image and declines;
C: in the sample obtained after exporting 500 pages and output 4000 pages, printer paper is observed the slight homogeneity of region-wide solid-printed image and declines;
D: in the sample obtained after exporting 500 pages and output 4000 pages, printer paper is observed region-wide solid-printed image homogeneity and declines.
Four, printed drawings is as stability of concentration evaluation method
Huang/magenta/green grass or young crops/black assorted packing carbon powder is entered in the corresponding handle box of printer, first 1 page of region-wide solid-printed image is exported under ambient temperature and moisture (23 DEG C/50%RH environment), then exporting 500 pages of printing rates is continuously the image of 1%, export 1 page of region-wide solid-printed image again, printing before repetition, until exporting 4000 pages of printing rates is the image of 1%, the average color density of region-wide solid-printed image is measured by color density instrument, to the image color after homepage and 4000 pages and bottom ash concentration, by being { 0 } with paper reflection concentration, relative reflection concentration compares.
Evaluation result:
Table one anti-sticking roller evaluation result
| With or without spuing after 1000 | |
| Embodiment 9,12,13,14 | Nothing |
| Embodiment 10,12,13,14 | Nothing |
| Embodiment 11,12,13,14 | Nothing |
| Comparative example 1,2,3,4 | Slight generation |
Table two ambient storage estimation of stability result
| Hot and humid (40 DEG C/95%RH environment) | Low temperature and low humidity (10 DEG C/10%RH environment) |
| Embodiment 9,12,13,14 | A | A |
| Embodiment 10,12,13,14 | A | A |
| Embodiment 11,12,13,14 | A | A |
| Comparative example 1,2,3,4 | B | A |
Table three printed drawings is as even concentration evaluation result
| Homepage | 500 pages | 4000 pages | |
| Embodiment 9,12,13,14 | A | A | A |
| Embodiment 10,12,13,14 | A | A | A |
| Embodiment 11,12,13,14 | A | A | A |
| Comparative example 1,2,3,4 | B | B | C |
Table four printed drawings is as stability of concentration evaluation result
Known by above-mentioned contrast test: colored carbon powder anti-sticking roller of the present invention is good, storage stability, printed drawings be as even concentration, excellent in stability.Compared to comparative example, the present invention have manufacturing process simple, be easy to the advantage that controls, production efficiency is high.
Claims (25)
1. a preparation method for colored carbon powder, comprises the following steps:
1) preparation feedback component:
Colorant, ionic surfactant and water are mixed with colorant dispersion;
Wax, ionic surfactant and water are mixed with wax dispersion;
Charge control agent, ionic surfactant and water are mixed with Charge controlled agent dispersing liquid;
Orqanics Monomer, ionic surfactant, chain-transferring agent, initiating agent and water is utilized to prepare polymer emulsion;
Further, the ionic surfactant that at least one in prepared colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid and polymer emulsion uses has opposite-sign;
Described colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid and polymer emulsion are divided into two groups according to the electrical difference of used ionic surfactant, and each reactive component often in group has electrically identical;
2) reactive component of first group is made to mix in organic solvent, the reactive component adding second group again reacts, maintain stir and in detection reaction system, the change of size of particle reaches setting range time, add particle diameter accretion inhibitor stopped reaction, through thermal treatment, cooling, separation, drying, make toner particle;
3) in the above-mentioned toner particle made, add external additive, be uniformly mixed and make colored carbon powder.
2. preparation method according to claim 1, is characterized in that, described first group comprises three kinds and have identical electrical reactive component, and described second group comprises the reactive component that a kind of and first group reactive component has opposite-sign.
3. preparation method according to claim 1, it is characterized in that, described first group comprise a kind of or two kinds there is identical electrical reactive component, correspondingly, described second group comprises three kinds or two kinds of reactive components, and they are electrically identical each other but electrically contrary with the reactive component of first group;
When reacting, join again after first the reactive component of second group being mixed in the mixed liquor that the first group reaction component and organic solvent formed.
4. preparation method according to claim 1, is characterized in that, the mean grain size of described colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid and polymer emulsion is 100-800nm.
5. preparation method according to claim 1, is characterized in that, described particle diameter accretion inhibitor is ionic surfactant.
6. preparation method according to claim 1, is characterized in that, described ionic surfactant is anionic surface active agent or cationic surfactant, wherein,
Described anionic surface active agent is one or more the combination in alkyl aryl sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl carboxylate, alkyl alkoxylated carboxylate;
Described cationic surfactant is one or more the combination in amine salt, quaternary ammonium salt.
7. preparation method according to claim 5, is characterized in that, described ionic surfactant is anionic surface active agent or cationic surfactant, wherein,
Described anionic surface active agent is one or more the combination in alkyl aryl sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl carboxylate, alkyl alkoxylated carboxylate;
Described cationic surfactant is one or more the combination in amine salt, quaternary ammonium salt.
8. preparation method according to claim 1, is characterized in that, described organic solvent is alcohols, ethers or ketone.
9. preparation method according to claim 1, is characterized in that, makes in described reaction system,
The mass ratio of organic solvent and polymer emulsion is (5-80): 100;
The mass ratio of colorant, wax, charge control agent and polymer emulsion is (1-20): (3-25): (0.5-20): 100.
10. preparation method according to claim 1, is characterized in that, described external additive is the combination of inorganic external additive or inorganic external additive and organic external additive, wherein,
Described inorganic external additive comprises silicon dioxide, titania, aluminium oxide, zinc paste or magnesium oxide;
Described organic external additive comprises condensate pearl or metallic stearate.
11. preparation methods according to claim 1, is characterized in that, described colorant is dyestuff, pigment or the potpourri for both;
Described wax comprise in synthetic wax, natural series wax one or more; Described charge control agent is selected from positive charge control agent or negative charge controlling agent.
12. preparation methods according to claim 11, is characterized in that, described synthetic wax comprise in polyolefin-wax and derivant thereof, ester system wax, SOLID ORGANIC silicon wax one or more.
13. preparation methods according to claim 11, is characterized in that, described natural series wax comprise in petroleum wax and derivant, department of botany's wax, animal system wax, montan wax one or more.
14. preparation methods according to claim 11, it is characterized in that, described positive charge control agent comprises quaternary ammonium salt based compound, quaternary alkylphosphonium salt based compound, triphenyl methane based compound, imidazole compound, pyrimidine compound, aminopyrine or amino silane;
Described negative charge controlling agent comprises metal complex or slaine, alkyl salicylate or its metallic compound, fatty acid soaps or the chain alkyl carboxylate of azo based dye, metal naphthenate, salicylic acid and derivant thereof containing Cr, Co, Al, Fe metal.
15. preparation methods according to any one of claim 1-14, it is characterized in that, described colorant, wax, charge control agent account for the 5-30% of colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid quality respectively, and described ionic surfactant accounts for the 1-10% of colorant dispersion, wax dispersion, Charge controlled agent dispersing liquid quality respectively.
16. preparation methods according to claim 1, it is characterized in that, when preparing polymer emulsion, the mass ratio of described Orqanics Monomer, ionic surfactant, chain-transferring agent, initiating agent and water is (80 ~ 120): (1 ~ 10): (0.1 ~ 5): (0.1 ~ 5): (50 ~ 300), and making the weight-average molecular weight of formed polymkeric substance be 5000-100000, glass temperature is 40-75 DEG C.
17. preparation methods according to claim 1 or 16, is characterized in that, described Orqanics Monomer is one or more combinations in styrene monomer, vinyl ester monomer, unsaturated carboxylic acid monomer, halogen-containing vinyl monomer or nitro class monomer;
Described chain-transferring agent is lauryl mercaptan, phenixin or trichlorine methyl bromide;
Described initiating agent is persulfate, the initiating agent that hydrogen peroxide or persulfate, hydrogen peroxide and ferrous salt form.
18. preparation methods according to claim 1 or 16, is characterized in that, described Orqanics Monomer is one or more combinations in styrene monomer, acrylic ester monomer, unsaturated carboxylic acid monomer, halogen-containing vinyl monomer or nitro class monomer;
Described chain-transferring agent is lauryl mercaptan, phenixin or trichlorine methyl bromide;
Described initiating agent is persulfate, the initiating agent that hydrogen peroxide or persulfate, hydrogen peroxide and ferrous salt form.
19. preparation methods according to claim 18, is characterized in that, described acrylic ester monomer is methacrylate-based monomer.
20. preparation methods according to claim 1, is characterized in that, control the temperature 35-60 DEG C of reaction system, to realize the flocculation of dispersed phase particles.
21. preparation methods according to claim 1, is characterized in that, the stirring rate maintaining reaction system is 500-2000rpm.
22. preparation methods according to claim 1, is characterized in that, controlled cooling model speed is 2-4 DEG C/min.
23. 1 kinds of colored carbon powders prepared according to preparation method described in any one of claim 1-22.
24. colored carbon powders according to claim 23, wherein, described colored carbon powder is micron order.
25. colored carbon powders according to claim 23 or 24, wherein, the mean grain size of described colored carbon powder is 4-15 μm.
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| CN101676807A (en) * | 2008-09-19 | 2010-03-24 | 富士施乐株式会社 | Toner, preparing process, developer, image forming method and device |
| CN101840181A (en) * | 2009-03-19 | 2010-09-22 | 富士施乐株式会社 | Container for the storage of toner, container for the storage of developer and image-forming apparatus using these containers |
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| CN101676807A (en) * | 2008-09-19 | 2010-03-24 | 富士施乐株式会社 | Toner, preparing process, developer, image forming method and device |
| CN101840181A (en) * | 2009-03-19 | 2010-09-22 | 富士施乐株式会社 | Container for the storage of toner, container for the storage of developer and image-forming apparatus using these containers |
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