CN105372953A - Styrene-acrylic resin/polyester resin composite electrostatic image toner and preparation method thereof - Google Patents
Styrene-acrylic resin/polyester resin composite electrostatic image toner and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a styrene-acrylic resin/polyester resin composite electrostatic image toner and a preparation method thereof. A styrene-acrylic polymer composite emulsion A containing a coloring agent and a polyester composite emulsion B containing wax interact with each other by virtue of positive and negative charges under the action of a flocculant and a nonionic surfactant, so that emulsion particles are agglutinated to prepare nuclear particles; the nuclear particles are coated with a polymer emulsion C containing fluorine, so as to obtain toner matrix particles in a core-shell structure; the matrix particles are subjected to thermal treatment, filtration and drying; and an added assistant is added to prepare the composite electrostatic image toner. The core-shell styrene-acrylic resin/polyester resin composite toner prepared by the method is good in liquidity, excellent in environment resistance, good in storage stability, uniform surface charges, excellent image reproducibility and the like.
Description
Technical field
The present invention relates to a kind of toner for developing electrostatic latent image and preparation method thereof, concrete is compound electrostatic image toner of hud typed styrene-acrylic resin/vibrin and preparation method thereof.
Background technology
For the requirement such as high speed, energy-saving, miniaturization of printer, duplicating machine in recent years, need the low-temperature fixability improving toner further.The styrene-acrylic resin of widespread use is in the past used as binder resin toner, meeting energy-saving, the high glaze image quality of image formation, especially in low-temperature fixing, has significant limitation.Thus impel vibrin to be used as the fast development of the toner of binder resin, become the trend of a new generation's printing, used in copy machines toner.As the patent of the preparation method containing polyester toner, as CN200710166710.1, US8715897, CN201010531001.0 etc.
But, containing the styrene acrylic toner that polyesters toner is more traditional, because its polar group is more, water absorptivity is stronger, therefore the homogeneity of surface charge and stability to relative humidity and temperature very responsive, if if toner particle surf electric charge heterogeneity or instability may produce various problem, the repeatability comprising image is deteriorated, image quality is uneven, environment resistant low inferior problem.For reducing the problems referred to above, control toner surface situation, being coated on the surface of polyester-type toner by introducing fluorinated binder resin, effectively can reducing the susceptibility of toner particle surf to relative humidity, thus ensure that homogeneity and the stability of toner particle surf electric charge.
The mobility of toner ink powder is an important indicator of toner, when the poor fluidity of toner, can polluted membrane be formed to carrier and developing roller surface and hinder its frictional electrification, thus affect the life-span of carrier and developer roll, even cause toner itself to condense caking.The poor fluidity of toner also can cause the dispersion of toner in print procedure uneven, to cause on print paper the problems such as irregular colour.For head it off, developer is many reduces the interparticle Van der Waals force of powder by adding particle outward, by the hydrophobization process adjustment mobility of adding outward.But add particle outward and in use easily cause being buried by resin, mobility variations is very large, therefore has certain limitation in mating with resin.For solving the problem, by introducing fluorine-containing binder resin as shell structurre, make full use of the low-surface-energy of fluorine resin, the features such as high-weatherability, permanance are strong, hydrophobicity and intergranular Van der Waals force is reduced from toner, provide a kind of applicable area wide, the novel toner of good fluidity.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, providing that a kind of technique is simple, with low cost, the preparation method of the compound electrostatic image toner of the styrene-acrylic resin/vibrin of good reliability.
Present invention also offers a kind of weatherability adopting above-mentioned preparation method to prepare strong, moisture-proof is strong, good endurance, have excellent resistance to offset resistance, storage stability is strong, be suitable for area wide, good fluidity, does not pollute developer roll, can effectively reduce problems such as flying powder, under extreme conditions still maintain the compound electrostatic image toner of styrene-acrylic resin/vibrin of higher image quality.
Preparation method of the present invention is: by the polyester complex emulsions B containing the cinepazid polymer complex emulsions A of colorant and the content of wax under the effect of flocculating agent, non-ionic surfactant, rely on negative and positive charge interaction, emulsion particle aggegation is made to prepare nuclear particle, with fluoropolymer emulsion C, the toner mother particulate that outsourcing obtains having nucleocapsid structure is carried out to described nuclear particle again, then to parent particulate through thermal treatment, filtration, drying, add and outer add auxiliary agent and obtain compound electrostatic image toner.
Described fluoropolymer emulsion C is that raw material adopts emulsion polymerization to prepare with polymerizable monomer, and described polymerizable monomer is made up of fluorine-containing free radical polymerization monomer, styrene monomer and acrylic ester monomer.
Described fluorine-containing free radical polymerization monomer is perfluoroalkyl acrylate or perfluoroalkyl methacrylic ester.
Described fluorine-containing free radical polymerization monomer is at least one in Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, perfluoro decyl acrylate, perfluoro capryl acrylate, perfluoro hexyl ethyl propylene acid esters, perfluoro butyl ethyl propylene acid esters or perfluoro hexyl ethylmethyl acrylate.
Prepare in the described polymerizable monomer of described fluoropolymer emulsion C, the mole percentage that fluorine-containing free radical polymerization monomer accounts for polymerizable monomer total amount is 5-15%, the mole percentage that styrene monomer accounts for polymerizable monomer total amount is 60%-75%, and the mole percentage that acrylic ester monomer accounts for polymerizable monomer total amount is 20%-30% (three adds up to 100%).
Described have in the toner mother particle particulate of nucleocapsid structure, and the quality of shell accounts for the 15-25% of toner mother particle particulate gross mass.
The compound electrostatic image toner of styrene-acrylic resin/vibrin of the present invention, said method obtains.
The glass transition temperature range of described toner is 40 DEG C ~ 50 DEG C, and softening range is preferably 105 DEG C ~ 130 DEG C.
For Problems existing in background technology, inventor studies discovery, carry out outsourcing with fluoropolymer emulsion C to nuclear particle to obtain having in nucleocapsid structure, low as the polarizability of carbon-fluorine bond in the fluorine resin of shell structure, therefore the molecular force between air and solid interface is low, thus the surface free energy of fluoropolymer is low, be difficult to be spontaneously wet out by water or solid sticks together, the toner therefore with the shell structure containing fluorine resin shows good not viscosity, do not reunite, low-friction coefficient, the various features that mobility is strong.In addition; because in fluoropolymer emulsion C, the radius of fluorine atom is large; tight for atoms backbone can be encased; carbochain receives the good protection of fluorine atom; the simultaneously strong polarity of fluorine carbon bond in fluorine resin; make such polymer physics stable performance, therefore make toner of the present invention have good permanance, weatherability and chemical proof.
Described fluoropolymer emulsion C is that raw material adopts emulsion polymerization to prepare with polymerizable monomer, at least comprises fluorine-containing free radical polymerization monomer, styrene monomer and acrylic ester monomer in described polymerizable monomer.The mole percentage that preferred described fluorine-containing free radical polymerization monomer accounts for polymerizable monomer total amount is 5-15%.Fluorine-containing free radical polymerization monomer content lower than 5% time, then the specificity of shell resin embodies insufficient, and the anti-moisture stable of toner of follow-up preparation and mobility improve DeGrain; If fluorine-containing free radical polymerization monomer is higher than 15%, then easily cause emulsion polymerization activity to reduce, shell molecular resin amount is low, easily causes the problems such as toner fixing.
The polymerizable monomer phenylethylene used in described fluoropolymer emulsion C accounts for the 60%-75% of polymerizable monomer total amount, too high meeting causes prepared toner fixing poor performance, the problems such as printed drawings picture is matt, too low meeting causes prepared toner storage poor stability, prints the problems such as roll banding.
The polymerizable monomer butyl acrylate type monomer used in described fluoropolymer emulsion C accounts for the 20%-30% of polymerizable monomer total amount, too high meeting causes prepared toner storage poor stability, pollute carrier and printing device in print procedure, too low meeting causes printing the problems such as image fixing difference.
The described mixing quality containing the cinepazid polymer complex emulsions A of colorant and the polyester complex emulsions B of the content of wax is preferably (40-60): (60-40).
Described have in the toner mother particulate of nucleocapsid structure, and the quality of preferred shell accounts for the 15-25% of toner mother particle particulate gross mass.If the quality total amount of shell is lower than 15%, easily cause not exclusively coated, kernel exposes, and effectively can not improve humidity stability and the mobility of toner; If the quality of shell is too high, toner integral hardness can be caused higher, and charging effect is poor, causes the problems such as fixing.
The described cinepazid polymer complex emulsions A containing colorant is by colorant, phenylethylene and acrylic ester monomer under cationic surfactant effect, adopts emulsion polymerization to be prepared from.Optimization styrene class monomer accounts for 75-80%, and acrylic ester monomer accounts for 15-20%, and colorant accounts for 5-10%, and three adds up to 100% mass percent.
The polyester complex emulsions B of the described content of wax is wax, containing the unsaturated monomer of polyester structural units and acrylic ester monomer under anionic surfactant effect, adopt emulsion polymerization to be prepared from.Wherein, the unsaturated monomer of preferred polyester structural unit and acrylic ester monomer mass ratio are (40-80): (60-20), and wax accounts for 9% ~ 15% of above-mentioned two class monomer gross masses.
Described fluoropolymer emulsion C be phenylethylene, acrylic ester monomer and fluorine-containing free radical polymerization monomer under anionic surfactant effect, adopt emulsion polymerization be prepared from.
The described unsaturated monomer containing polyester structural units be can with the monomer containing unsaturated double-bond of styrene, acrylic ester monomer copolymerization, polyester structural units skeleton is epoxy resin structural; It can be acrylic modified bisphenol-A epoxy base vinyl esters, acrylic acid modified bisphenol-A epoxy base vinyl esters, methacrylic acid and phenolic aldehyde polyepoxy vinyl esters, acrylic acid and phenolic aldehyde multi-epoxy type vinyl esters, methacrylic acid, fumaric acid modified bisphenol-A epoxy base vinyl esters, at least one of isocyanate-modified vinyl ester monomers.Preferred monomers is bisphenol-A epoxy base vinyl esters, acrylic acid modified bisphenol-A epoxy base vinyl esters etc.
In described cinepazid polymer complex emulsions A containing colorant and fluoropolymer emulsion C preparation process, described styrene monomer is specially Styrene and its derivatives, as styrene, α-methyl styrene, and optimization styrene.
Described acrylic ester monomer is the just own ester of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylic ester, acrylic acid, 2-EHA, lauryl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, n-BMA, isobutyl methacrylate, tert-butyl methacrylate, the just own ester of methacrylic acid, 1,3-butadiene, 1, at least one in 2-butadiene, preferred butyl acrylate.
Described non-ionic surfactant, that can enumerate has AEO, APES, polyoxyethylene carboxylate, alkanolamide, polyethenoxy alkanolamide etc.Preferred alkyl phenol polyethenoxy ether, more preferably with the APES of 8 ~ 10 carbon atoms.
The described particle diameter containing the cinepazid polymer complex emulsions A of colorant and the polyester complex emulsions B of the content of wax and fluoropolymer emulsion C is all between 200nm ~ 300nm.
In the preparation process containing the cinepazid polymer complex emulsions A of colorant and the polyester complex emulsions B of the content of wax and fluoropolymer emulsion C, inventor can add chain-transferring agent as required, for adjusting the molecular weight of complex emulsions.Described chain-transferring agent can be the chain-transferring agent that analiphatic sulphur alcohol and alkyl sulfhydryl are commonly used for free radical polymerization, preferred lauryl mercaptan.
In toner prepared by the present invention, for adapting to the requirement of high-speed printer (HSP)/duplicating machine, reach the fixation performance of toner and the balance of elevated temperature excursions, the glass transition temperature preferable range of this toner is 40 DEG C ~ 50 DEG C, is more preferably 42 DEG C ~ 48 DEG C.The softening range of this toner is preferably 105 DEG C ~ 130 DEG C, is more preferably 105 DEG C ~ 120 DEG C.
Described containing in the cinepazid polymer complex emulsions A preparation process of colorant, the cationic surfactant used can be at least one in amine salt cationic surfactant or quaternary ammonium salt cationic surfactant, and amine salt cationic surfactant is as primary amine salt, secondary amine salt, tertiary amine salt form surfactant, hydramine, diamines or polyamines, the amine containing acyl group, guanidine derivatives; The quaternary ammonium salt cationic surfactant that can enumerate has: DTAC, hexadecyltrimethylammonium chloride, OTAC, dodecyl benzyl dimethyl ammonium chloride, DTAB, cetyl trimethyl ammonium bromide, Cetyltrimethylammonium bromide, cetyl dimethyl benzyl ammonium bromide, octadecyl dimethyl benzyl ammonium bromide.Preferred quaternary ammonium salt cationic surfactant, more preferably dodecyl benzyl dimethyl ammonium chloride.
In the polyester complex emulsions B of the described content of wax and the preparation process of fluoropolymer emulsion C, the described anionic surfactant used can be at least one in metal carboxylate, Sulfonates, sulfuric ester salt and structure mixed surfactant, also can be its combination.That can enumerate has: aliphatic alcohol polyethenoxy ether carboxylate, odium stearate, sodium n-alkylbenzenesulfonate, sodium branched alkyl benzene sulfonate, diisopropyl sodium naphthalene sulfonate, alkyl sodium sulfonate, straight-chain alkyl sulfate, branched alkyl sodium sulphate, fatty alcohol polyoxyethylene ether sulfate etc.Preferred straight-chain alkyl sulfate, fatty alcohol polyoxyethylene ether sulfate.
The flocculating agent used in described aggegation process can be the salt of 1 valency or multivalence.That can enumerate has sodium chloride, potassium chloride, magnesium chloride, magnesium sulfate, lime chloride, calcium sulphate, aluminium hydroxide, aluminium polychloride, aluminium sulphate, sodium phosphate, potassium phosphate etc., preferred polymeric aluminum chloride.
Described colorant 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 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 269 etc.; Black colorant has carbon black, magnetic iron ore etc.
Wax used in the present invention 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, Brazil wax, beeswax.
Beneficial effect:
The inventive method is simple and reliable, with low cost, the toner of preparation can reduce the susceptibility of toner particle surf to relative humidity effectively, thus ensure that homogeneity and the stability of toner particle surf electric charge, and be that a kind of permanance is strong, the novel toner of good weatherability.Prepared toner hydrophobic nature is strong and intergranular Van der Waals force is low, effectively solves by adding the problem such as easily to bury improving mobility method outward, is a kind ofly to be suitable for area extensively, the novel toner of good fluidity.Toner provided by the invention has not viscosity, does not reunite, low-friction coefficient, the feature that mobility is strong.
Embodiment
Containing colorant cinepazid polymer complex emulsions A preparation example:
The preparation of colorant dispersion: 1200g carbon black (Cabot company) and 60g dodecane trimethyl ammonium chloride and 8200g water are at room temperature carried out stirring pre-dispersed, then this dispersion liquid is joined in high speed dispersion agent and disperse, by the dispersion of 2h, obtain colorant dispersion, its particle diameter is 126nm.
Prepare containing colorant cinepazid polymer complex emulsions: 150g DTAC is dissolved in 3300g water, then added in reactor, above-mentioned colorant dispersion 880g is dropped in reactor, be warming up to 75 DEG C, 1600g persulfate aqueous solution (including 40g potassium persulfate) is added in reactor, then by 2800g styrene, 600g butyl acrylate, 80g methacrylic acid and 26g lauryl mercaptan potpourri add gradually in reactor in 2h, after adding, system temperature is risen to 80 DEG C, react 3h at this temperature, the cinepazid polymer complex emulsions containing colorant can be obtained, its particle diameter is recorded for 247nm with nano particle size instrument, be referred to as the cinepazid polymer complex emulsions A. containing colorant
The polyester complex emulsions B preparation example of the content of wax:
The preparation of wax dispersion: 600g wax (behenic acid 20 diester) and 280g lauryl sodium sulfate and 1300g water are carried out stirring and dissolving at 90 DEG C, then this potpourri is joined in high speed dispersion agent fast and disperse, by the dispersion of 2h, obtain milky white wax dispersion, its particle diameter is 130nm.This particle diameter is measured by BeckmanCoulterLS230.
240g lauryl sodium sulfate is dissolved in 3000g water, then by above-mentioned for 800g wax dispersion, the bisphenol-A epoxy base vinyl esters (trade mark DERAKANE411) that 1800g is acrylic acid modified, 450g butyl acrylate, 75g lauryl mercaptan potpourri adds reactor, stirred at ambient temperature prepares emulsion performed polymer, reactor is warming up to 75 DEG C, then in reactor, add 1500g persulfate aqueous solution (potassium persulfate content is 30g), then by temperature to 80 DEG C, and maintain this thermotonus 3h, obtain the polyester complex emulsions B of the content of wax.The particle diameter being recorded the polyester complex emulsions B1 of the content of wax by nano particle size instrument is 233nm.
Fluoropolymer emulsion preparation example C1:
The preparation of seed monomer pre-emulsion: take 40g styrene, 18g butyl acrylate, 1.7g methacrylic acid, 0.3g lauryl mercaptan, 150g distilled water and the mixing of 2g neopelex, and at room temperature high-speed stirred prepares pre-emulsion.
The preparation of fluoropolymer performed polymer: by 364.5g styrene, 164g n-butyl acrylate, 15.5g methacrylic acid, 71.3g Hexafluorobutyl mathacrylate, 2g lauryl mercaptan, 1270g distilled water and the mixing of 32g neopelex, and at room temperature high-speed stirred prepares polymkeric substance performed polymer.
Drop in the glass reactor of the jacketed of 2 liters by above-mentioned seed monomer pre-polymerization emulsion, control stirring rate is 200rpm, and this glass reactor contains stainless steel 45 ° of gradient half aial flow impellers, thermocouple thermometer feeler lever, water cooled condenser device.Reactor is warming up to 75 DEG C, in reactor, then adds 100g persulfate aqueous solution (potassium persulfate massfraction is 6%), maintain this thermotonus 30min, form seed emulsion.Within the 120min time, slowly drip above-mentioned fluoropolymer performed polymer subsequently in reactor, after fluoropolymer performed polymer dropwises, be warming up to 80 DEG C and maintain this temperature 3 hours.Namely prepare fluoropolymer emulsion C1, recording fluoropolymer emulsion C1 particle diameter by nano particle size instrument is 281nm.。
Fluoropolymer emulsion preparation example C2
In fluoropolymer emulsion preparation example C1, remove 164g n-butyl acrylate, 71.3g Hexafluorobutyl mathacrylate changes 109g n-butyl acrylate into, outside 220.6g Hexafluorobutyl mathacrylate, other conditions are constant, obtain fluoropolymer emulsion C2, recording fluoropolymer emulsion C2 particle diameter by nano particle size instrument is 274nm.
Fluoropolymer emulsion preparation example C3
In fluoropolymer emulsion preparation example C1, remove 164g n-butyl acrylate, 71.3g Hexafluorobutyl mathacrylate changes 224g n-butyl acrylate into, outside 124g dodecafluoroheptyl methacrylate, other conditions are constant, obtain fluoropolymer emulsion C3, recording fluoropolymer emulsion C3 particle diameter by nano particle size instrument is 292nm.
Fluoropolymer emulsion preparation example C4
In fluoropolymer emulsion preparation example C3, change into except 240.8g dodecafluoroheptyl methacrylate except by 71.3g Hexafluorobutyl mathacrylate, other conditions are constant, obtain fluoropolymer emulsion C4, record fluoropolymer emulsion C4 particle diameter 265nm by nano particle size instrument.
Fluoropolymer emulsion preparation example C5
In fluoropolymer emulsion preparation example C2, except 71.3g Hexafluorobutyl mathacrylate being changed into except 129.5g perfluoro capryl acrylate, other conditions are constant, obtain fluoropolymer emulsion C5, and recording fluoropolymer emulsion C5 particle diameter by nano particle size instrument is 279nm.Fluoropolymer emulsion preparation example C6
In fluoropolymer emulsion preparation example C2, except 142.5g dodecafluoroheptyl methacrylate being changed into 90.73g perfluoro butyl ethyl propylene acid esters, other conditions are constant, obtain fluoropolymer emulsion C6, and recording fluoropolymer emulsion C6 particle diameter by nano particle size instrument is 204nm.
Fluoropolymer emulsion does not prepare comparative example C7
In fluoropolymer emulsion preparation example C1, except not adding 71.3g Hexafluorobutyl mathacrylate, other conditions are constant, obtain not fluoropolymer emulsion comparative example C7, and recording fluoropolymer emulsion C7 particle diameter by nano particle size instrument is 214nm.
Toner preparation example 1
150g latex A is joined in reactor, the speed stirred is regulated to be 500rpm, then 150g emulsion B was under agitation joined gradually in reactor in 20 minutes, then in reactor, add the aluminium polychloride of 20g1%, the pH of regulation system is 3, start after stirring 30min to heat up, by 30min, the temperature of system is raised to 65 DEG C, monitoring agglutination particle particle diameter is about 4-5um scope, stop heating up, outer for 48.08g fluoropolymer emulsion C1 packet emulsion is added in reactor, then the stirring rate of system is reduced to 200rpm, then the change of the particle diameter of detection system is started, when the particle diameter of agglutination particle increases to 7 μm, non-ionic surfactant X-405 (DOW Chemical) is added in system, then stirring rate is increased to 350rpm, then be warmed up to 95 DEG C and carry out spheroidization, when the sphericity of particle arrives more than 0.96 (using FPIA-3000 to measure), cooling, use centrifugal separator filters, wash, heating drying under reduced pressure, ultimate size is about 6.5um.Add additive process to particle after drying and namely obtain toner, the toner obtained is toner (T-1).The softening point of toner uses the CFT-500D capillary rheometry of Japanese SHIMADZU, and the softening point temperature recording toner T-1 is 116.9 DEG C.
Toner preparation example 2
In toner preparation example 1, except being changed into outside 73.37g fluoropolymer emulsion C2 by packet emulsion except 48.08g fluoropolymer emulsion C1, other conditions are constant, obtain toner (T-2), and the softening point temperature recording this toner T-2 is 119.4 DEG C.
Toner preparation example 3
In toner preparation example 1, except packet emulsion except 48.08g fluoropolymer emulsion C1 is changed into outside 57.69g fluoropolymer emulsion C3, other conditions are constant, obtain toner (T-3), the toner obtained is called toner (T-3), and the softening point temperature recording this toner T-3 is 105.3 DEG C.
Toner preparation example 4
In toner preparation example 3, except packet emulsion except 48.08g fluoropolymer emulsion C1 is changed into outside 52.7g fluoropolymer emulsion C4, other conditions are constant, and the toner obtained is called toner (T-4), and the softening point temperature recording this toner T-4 is 110.2 DEG C.
Toner preparation example 5
In toner preparation example 1, except packet emulsion except 48.08g fluoropolymer emulsion C1 is changed into outside 64.1g fluoropolymer emulsion C5, other conditions are constant, and the toner obtained is called toner (T-5), and the softening point temperature recording this toner T-5 is 112.5 DEG C.
Toner preparation example 6
In toner preparation example 1, except packet emulsion except 48.08g fluoropolymer emulsion C1 is changed into outside 66.16g fluoropolymer emulsions C6, other conditions are constant, and the toner obtained is called toner (T-6), and the softening point temperature recording this toner T-6 is 107.9 DEG C.
Toner preparation example 7
In toner preparation example 1, except 48.08g fluoropolymer emulsion C1 is changed into except 64.1g fluoropolymer emulsion C1, other conditions are constant, and the toner obtained is called toner (T-7), and the softening point temperature recording this toner T-7 is 115.7 DEG C.
Not fluorine-containing hud typed toner preparation example 8
150g latex A is joined in reactor, the speed stirred is regulated to be 500rpm, then 150g emulsion B was under agitation joined gradually in reactor in 20 minutes, then in reactor, add the aluminium polychloride of 20g1%, the pH of regulation system is 3, start after stirring 30min to heat up, by 30min, the temperature of system is raised to 65 DEG C, monitoring agglutination particle particle diameter is about 4-5um scope, stop heating up, packet emulsion outside 52.14g not fluoropolymer emulsion C7 is added in reactor, then the stirring rate of system is reduced to 200rpm, then the change of the particle diameter of detection system is started, when the particle diameter of agglutination particle increases to 7 μm, non-ionic surfactant X-405 (DOW Chemical) is added in system, then stirring rate is increased to 350rpm, then be warmed up to 95 DEG C and carry out spheroidization, when the sphericity of particle arrives more than 0.96 (using FPIA-3000 to measure), cooling, use centrifugal separator filters, wash, heating drying under reduced pressure, ultimate size is about 6.5um.Add additive process to particle after drying and namely obtain toner, the toner obtained is toner (T-1).The softening point of toner uses the CFT-500D capillary rheometry of Japanese SHIMADZU, and the softening point temperature recording toner T-1 is 115.6 DEG C.
Not fluorine-containing non-nucleocapsid structure toner preparation example 9
150g latex A is joined in reactor, the speed stirred is regulated to be 500rpm, then 150g emulsion B was under agitation joined gradually in reactor in 20 minutes, then in reactor, add the aluminium polychloride of 20g1%, the pH of regulation system is 3, start after stirring 30min to heat up, by 30min, the temperature of system is raised to 65 DEG C, monitoring agglutination particle particle diameter is about 4-5um scope, stop heating up, , then the stirring rate of system is reduced to 200rpm, then the change of the particle diameter of detection system is started, when the particle diameter of agglutination particle increases to 7 μm, non-ionic surfactant X-405 (DOW Chemical) is added in system, then stirring rate is increased to 350rpm, then be warmed up to 95 DEG C and carry out spheroidization, when the sphericity of particle arrives more than 0.96 (using FPIA-3000 to measure), cooling, use centrifugal separator filters, wash, heating drying under reduced pressure, ultimate size is about 6.5um.Add additive process to particle after drying and namely obtain toner, the toner obtained is toner (T-1).The softening point of toner uses the CFT-500D capillary rheometry of Japanese SHIMADZU, and the softening point temperature recording toner T-1 is 116.3 DEG C.
Toner is evaluated
1 fluidity evaluating
Carbon dust in the embodiment of the present invention is naturally trickled down after toner is sieved by 250um by ambient temperature and moisture environment (25 DEG C/humidity 65%) the A3 xerox cardboard upper end (adhering to cardboard by smooth for A3 paper) to 45 degree of pitch angle, toner has certain initial accumulated, unrestrained toner further, toner-particle glides in snowball mode and tumbles, record toner-particle tumbles speed downwards at panel, the rolling speed of toner-particle reflects the flowing property of toner, and the faster then toner fluidity of rolling speed is better.When the speed that tumbles of toner is lower than 8cm/s, the poor fluidity of toner, easily causes printing unequal problem.
2 hot and humid condition fluidity evaluatings
By the carbon dust in the embodiment of the present invention in hot and humid environment (30 DEG C/humidity 85%), by toner by naturally trickling down the A3 xerox cardboard upper end (adhering to cardboard by smooth for A3 paper) to 45 degree of pitch angle after 250um sieve, toner has certain initial accumulated, unrestrained toner further, toner-particle glides in snowball mode and tumbles, record toner-particle tumbles speed downwards at panel, the faster then toner fluidity of rolling speed is better, and flowing velocity when contrasting ambient temperature and moisture.When the speed that tumbles of toner is lower than 8cm/s, the poor fluidity of toner, easily causes printing unequal problem.
2 keeping quality evaluations
10g toner is loaded in the flexible container of an open system, as 50 DEG C, place 72h under 80% humidity environment, then transfer to gently and hold in the container of toner, visual toner is with or without condensing.Do not observe toner surface cohesion, then represent keeping quality excellent; If toner surface has cohesion, but can eliminate without the need to vibrations during transfer, not affect actual printing effect, be then represented as good; If toner surface has cohesion, during transfer, vibrations can not be eliminated, then represent that keeping quality is poor.Evaluation result is in table 1.
3 stain resistance evaluations
By completing printing, whether visual developer roll and photoreceptor exists toner contamination.
The evaluation of toner stain resistance is carried out according to Recording criteria below:
Excellent: not observe on developer roll and photoreceptor and there is toner contamination, no problem in practical; Good: to observe on developer roll and photoreceptor and there is extremely slight toner contamination, no problem in practicality; In: observe on developer roll and photoreceptor and there is slight toner contamination, no problem in practicality; Difference: observe on developer roll and photoreceptor and there is obvious toner contamination, have problems in practicality.
On 4, machine prints and evaluates
Examination with computer, print originally other for the toner in inventive embodiments under ambient temperature and moisture and hot and humid condition, evaluate its printing effect, evaluation result is in table 1.
Toner prepared by the inventive method can reduce the susceptibility of toner particle surf to relative humidity effectively, thus ensure that the stability of toner-particle, is that a kind of permanance is strong, good weatherability, the novel toner that stain resistance is strong.Prepared toner hydrophobic nature is strong and intergranular Van der Waals force is low, good fluidity and under extreme conditions still keep the novel toner of good fluidity.
Claims (9)
1. the compound electrostatic image toner preparation processes of styrene-acrylic resin/vibrin, it is characterized in that, by the polyester complex emulsions B containing the cinepazid polymer complex emulsions A of colorant and the content of wax at flocculating agent, under the effect of non-ionic surfactant, rely on negative and positive charge interaction, emulsion particle aggegation is made to prepare nuclear particle, with fluoropolymer emulsion C, the toner mother particulate that outsourcing obtains having nucleocapsid structure is carried out to described nuclear particle again, then to parent particulate through thermal treatment, filter, dry, add auxiliary agent outside adding and obtain compound electrostatic image toner.
2. the compound electrostatic image toner preparation processes of styrene-acrylic resin/vibrin as claimed in claim 1, it is characterized in that, described fluoropolymer emulsion C is that raw material adopts emulsion polymerization to prepare with polymerizable monomer, and described polymerizable monomer is made up of fluorine-containing free radical polymerization monomer, styrene monomer and acrylic ester monomer.
3. the compound electrostatic image toner preparation processes of styrene-acrylic resin/vibrin as claimed in claim 2, it is characterized in that, described fluorine-containing free radical polymerization monomer is perfluoroalkyl acrylate or perfluoroalkyl methacrylic ester.
4. the compound electrostatic image toner preparation processes of styrene-acrylic resin/vibrin as claimed in claim 3, it is characterized in that, described fluorine-containing free radical polymerization monomer is at least one in Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, perfluoro decyl acrylate, perfluoro capryl acrylate, perfluoro hexyl ethyl propylene acid esters, perfluoro butyl ethyl propylene acid esters or perfluoro hexyl ethylmethyl acrylate.
5. the compound electrostatic image toner preparation processes of styrene-acrylic resin/vibrin as claimed in claim 2, it is characterized in that, in described polymerizable monomer, the mole percentage that fluorine-containing free radical polymerization monomer accounts for polymerizable monomer total amount is 5-15%, the mole percentage that styrene monomer accounts for polymerizable monomer total amount is 60%-75%, and the mole percentage that acrylic ester monomer accounts for polymerizable monomer total amount is 20%-30%.
6. the compound electrostatic image toner preparation processes of styrene-acrylic resin/vibrin as claimed in claim 1, it is characterized in that, the described cinepazid polymer complex emulsions A containing colorant is by colorant, styrene monomer and acrylic ester monomer under cationic surfactant effect, adopts emulsion polymerization to be prepared from; The polyester complex emulsions B of the described content of wax be by wax, containing the unsaturated monomer of polyester structural units and acrylic ester monomer under anionic surfactant effect, adopt emulsion polymerization to be prepared from.
7. the compound electrostatic image toner preparation processes of the styrene-acrylic resin/vibrin as described in any one of claim 1-6, it is characterized in that, described have in the toner mother particle particulate of nucleocapsid structure, and the quality of shell accounts for the 15-25% of toner mother particle particulate gross mass.
8. the compound electrostatic image toner of styrene-acrylic resin/vibrin, is characterized in that, adopts any one of claim 1-7 method to obtain.
9. the compound electrostatic image toner of styrene-acrylic resin/vibrin as claimed in claim 8, it is characterized in that, the glass transition temperature range of described toner is 40 DEG C ~ 50 DEG C, and softening range is preferably 105 DEG C ~ 130 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112764331A (en) * | 2021-01-18 | 2021-05-07 | 湖北鼎龙控股股份有限公司 | Styrene-acrylic resin type toner and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59181358A (en) * | 1983-03-31 | 1984-10-15 | Fuji Photo Film Co Ltd | Capsule toner |
| JPS60126657A (en) * | 1983-12-13 | 1985-07-06 | Fuji Photo Film Co Ltd | Encapsulated toner enhanced in triboelectrifiability and its manufacture |
| US20080057431A1 (en) * | 2006-09-05 | 2008-03-06 | Xerox Corporation | Toner compositions |
| CN102354088A (en) * | 2011-07-19 | 2012-02-15 | 湖北鼎龙化学股份有限公司 | Toner for developing electrostatic charge image and manufacturing method for toner |
| CN103576478A (en) * | 2012-07-26 | 2014-02-12 | 京瓷办公信息系统株式会社 | Toner for electrostatic latent image development |
| 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 |
| CN105005183A (en) * | 2015-08-11 | 2015-10-28 | 湖北鼎龙化学股份有限公司 | Preparing method for styrene-acrylic resin/polyester resin compound type static charge image color matching agent |
-
2015
- 2015-11-17 CN CN201510790685.9A patent/CN105372953B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59181358A (en) * | 1983-03-31 | 1984-10-15 | Fuji Photo Film Co Ltd | Capsule toner |
| JPS60126657A (en) * | 1983-12-13 | 1985-07-06 | Fuji Photo Film Co Ltd | Encapsulated toner enhanced in triboelectrifiability and its manufacture |
| US20080057431A1 (en) * | 2006-09-05 | 2008-03-06 | Xerox Corporation | Toner compositions |
| CN102354088A (en) * | 2011-07-19 | 2012-02-15 | 湖北鼎龙化学股份有限公司 | Toner for developing electrostatic charge image and manufacturing method for toner |
| CN103576478A (en) * | 2012-07-26 | 2014-02-12 | 京瓷办公信息系统株式会社 | Toner for electrostatic latent image development |
| 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 |
| CN105005183A (en) * | 2015-08-11 | 2015-10-28 | 湖北鼎龙化学股份有限公司 | Preparing method for styrene-acrylic resin/polyester resin compound type static charge image color matching agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112764331A (en) * | 2021-01-18 | 2021-05-07 | 湖北鼎龙控股股份有限公司 | Styrene-acrylic resin type toner and preparation method and application thereof |
| CN112764331B (en) * | 2021-01-18 | 2024-02-23 | 湖北鼎龙控股股份有限公司 | Styrene-acrylic resin type toner and preparation method and application thereof |
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