CN103513532A - Novel Mg-based ferrite carrier core material and double-component developer - Google Patents
Novel Mg-based ferrite carrier core material and double-component developer Download PDFInfo
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- CN103513532A CN103513532A CN201310442283.0A CN201310442283A CN103513532A CN 103513532 A CN103513532 A CN 103513532A CN 201310442283 A CN201310442283 A CN 201310442283A CN 103513532 A CN103513532 A CN 103513532A
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Abstract
The invention provides a magnesium-based ferrite carrier core material which is formed by a core shown in a general formula of MgXFe3-XO4, wherein x is less than or equal to 1 and more than or equal to 0. The carrier core material provided by the invention has excellent electrical characteristics and magnetic characteristics and low environmental dependency and can solve the problem of carrier dispersion.
Description
Technical field
The present invention relates to electrostatic image developing carrier, electrostatic image developing core, electrostatic image two-component developing agent.
Background technology
Electrofax is to be included on optical receiver, to form electrostatic latent image, deposit toner be transferred to the method on object to be formed into as pattern and by this toner on image.Electrofax comprises two main category: bi-component is developed and single component development.In bi-component is developed, developer comprises carrier and two components of toner, and magnetic carrier is commonly used for carrier.
In duplicating machine or MFP etc., as the dry method in electrofax, have and only using toner as the single component class developer of developer composition, and using toner and the carrier bi-component class developer as developer composition.In any one development method, all to photoreceptor, provide the toner with fixed charge amount.Then, by toner, make the electrostatic latent image that forms on photoreceptor visual, be transferred on paper.Afterwards, the visual image forming with toner is fixed on paper, obtains the image of expectation.
At this, the development of bi-component class developer is briefly described.In developer, take in the toner of ormal weight and the carrier of ormal weight.In developer, possess the rotatable magnetic roller that is arranged alternately in a circumferential direction a plurality of S utmost points and the N utmost point, and the agitating roller that toner and carrier are uniformly mixed in developer.By magnetic roller, take and hold the carrier being formed by magnetic.Magnetic force by this magnetic roller forms the straight chain shape magnetic brush being comprised of carrier particle.On the surface of carrier particle, by adhering to a plurality of toner particles because stirring the frictional electrification causing.By the rotation of magnetic roller, make this magnetic brush contact photoreceptor, to the surface of photoreceptor, provide toner.In bi-component class developer, develop as described so.
About toner, by paper is carried out to photographic fixing, consume gradually the toner in developer, therefore, from the toner hopper being arranged in developer, in developer, supply with the new toner that is equivalent to consumption at any time.On the other hand, about carrier, the consumption because developing and bringing, can directly not used to reaching its life-span.In the carrier of the constituent material as bi-component class developer, seek frictional electrification by being caused by stirring and make toner charged toner band Electricity Functional, insulativity or suitably transport and supply with the various functions such as toner transporting power of toner to photoreceptor effectively.For example, from improving the viewpoint of toner band power, require the resistance value (below also referred to as resistance) of carrier suitable, and insulativity is suitable.
Recently, above-mentioned carrier, the resinous coat of setting forms with being coated in this carrier core surface by its core, to form core carrier core partly.
At this, about carrier core, as its fundamental characteristics, wish that it has excellent magnetic characteristics.Simple declaration, in developer, as mentioned above, carrier is taken and is held on magnetic roller by magnetic force.Under this behaviour in service, if when the magnetic of carrier core self is concrete as low in the magnetization of carrier core self, a little less than the confining force for magnetic roller, may produce the problems such as so-called carrier disperses.Especially, recently, in order to tackle the requirement of higher image quality of the image of formation, trend towards reducing the particle diameter of toner particle, corresponding therewith, also trend towards reducing the particle diameter of carrier particle.If seek the small particle diameter of carrier, may cause the power of holding of taking of each carrier particle to reduce.Therefore,, for the above-mentioned carrier problem of dispersing, there is more effective solution countermeasure in expectation.
Summary of the invention
For overcoming above-mentioned technical matters, the object of this invention is to provide a kind of electrical characteristics and have excellent magnetic characteristics, electrophotographic developing carrier core that environment interdependence is little, more specifically, the present invention relates to comprise the carrier core of Mg based ferrite material, for the preparation of the method for Mg based ferrite core material, comprise the electrophotographic developing of this carrier.
For solving the problems of the technologies described above, the invention provides a kind of Mg-based ferrite carrier core, it is with formula M g
xfe
3-Xo
4shown core forms, wherein, and 0≤x≤1.
Wherein, the apparent density of described carrier core is 1.86g/cm
3above and at 2.45g/cm
3below.
Wherein, the value of the medium particle diameter in the volumetric particle size distribution of described carrier core is more than 25 μ m in the scope below 35 μ m, in volumetric particle size distribution, particle size values is that the particle ratio below 22 μ m is more than 1.0% below 1.5%, during number particle diameter distributes, particle size values is that the ratio of the particle below 22 μ m is below 5%, and external magnetic field is that the magnetization value in 10000e situation is below the above 80emu/g of 60emu/g.
Wherein, the preparation method of described carrier core is specially:
The first step, selects the raw material of iron content and containing the raw material of magnesium, according to the proportioning of final generation product, mixes in the proper ratio, and the described raw material containing magnesium is preferably MgO, and the raw material of described iron content is elected Fe as
2o
3;
Second step, in the raw material mixing in the first step, add reductive agent and water, carry out mix and blend pulp, make pulping raw material, described reductive agent can be carbon dust or polycarboxylic acid organism, polyacrylic acid type organic, maleic acid, acetic acid, polyvinyl alcohol (PVA) and composition thereof, and described solid component concentration accounts for the more than 50% of whole mixed slurry concentration;
The 3rd step, is used spray-dired mode to carry out granulation to the raw material after second step pulp, and spray-dired temperature is 100 ℃～200 ℃, and granulated particle diameter is 30～100 μ m;
The 4th step, the pelletizing that the 3rd step is obtained is sent in stove roast 10～20 hours, and the temperature in roast process in stove keeps 1000 ℃～1500 ℃;
The 5th step under the atmosphere of oxygen concentration 10～100%, keeps the product after roast 1～24 hour at 200～700 ℃, carries out oxidation processes and obtains carrier core;
The 6th step, to the carrier core after oxidation processes, with adjustment medium particle diameters such as vibratory screening apparatuss, the value that makes the medium particle diameter in volumetric particle size distribution is more than 25 μ m in the scope below 35 μ m, in volumetric particle size distribution, particle size values is that the particle ratio below 22 μ m is more than 1.0% below 1.5%, during number particle diameter distributes, particle size values is that the ratio of the particle below 22 μ m is below 5%, and external magnetic field is that the magnetization value in 10000e situation is below the above 80emu/g of 60emu/g.
The present invention also provides a kind of two-component developing agent, and it comprises toner and above-mentioned Mg-based ferrite carrier core.
Wherein, described toner comprises resin glue, colorant, release agent and band controling agent.
The present invention also provides the preparation method of above-mentioned double component developing, and above-mentioned toner and carrier core are mixed by mixer.
The present invention also provides a kind of image forming method, the image processing system by above-mentioned two-component developing agent for noncontact photographic fixing mode.
Beneficial effect of the present invention:
Carrier core electrical characteristics provided by the invention and have excellent magnetic characteristics, environment interdependence is little, can resolved vector scattering problem.
Embodiment
The invention provides two-component developing agent, it comprises toner and carrier core.
The apparent density of described carrier core is 1.86g/cm
3above and at 2.45g/cm
3below.
Described carrier core is with formula M g
xfe
3-Xo
4shown core forms, wherein, and 0≤x≤1.
The value of the medium particle diameter in the volumetric particle size distribution of described carrier core is more than 25 μ m in the scope below 35 μ m, in volumetric particle size distribution, particle size values is that the particle ratio below 22 μ m is more than 1.0% below 1.5%, during number particle diameter distributes, particle size values is that the ratio of the particle below 22 μ m is below 5%, and external magnetic field is that the magnetization value in 10000e situation is below the above 80emu/g of 60emu/g.
The preparation method of described carrier core is specially:
The first step, selects the raw material of iron content and containing the raw material of magnesium, according to the proportioning of final generation product, mixes in the proper ratio, and the described raw material containing magnesium is preferably MgO, and the raw material of described iron content is elected Fe as
2o
3;
Second step, in the raw material mixing in the first step, add reductive agent and water, carry out mix and blend pulp, make pulping raw material, described reductive agent can be carbon dust or polycarboxylic acid organism, polyacrylic acid type organic, maleic acid, acetic acid, polyvinyl alcohol (PVA) and composition thereof, and described solid component concentration accounts for the more than 50% of whole mixed slurry concentration;
The 3rd step, is used spray-dired mode to carry out granulation to the raw material after second step pulp, and spray-dired temperature is 100 ℃～200 ℃, and granulated particle diameter is 30～100 μ m;
The 4th step, the pelletizing that the 3rd step is obtained is sent in stove roast 10～20 hours, and the temperature in roast process in stove keeps 1000 ℃～1500 ℃;
The 5th step under the atmosphere of oxygen concentration 10～100%, keeps the product after roast 1～24 hour at 200～700 ℃, carries out oxidation processes and obtains carrier core;
The 6th step, to the carrier core after oxidation processes, with vibratory screening apparatus etc., adjust medium particle diameter etc., the value that makes medium particle diameter in volumetric particle size distribution is more than 30 μ m in the scope below 40 μ m, in volumetric particle size distribution, particle diameter is that the particle ratio below 22 μ m is more than 1.0% below 2.0%, during number particle diameter distributes, the ratio of the particle of the value of particle diameter below 22 μ m is below 10%, and external magnetic field is that 1000Oe magnetization value is below the above 75emu/g of 50emu/g.
The volume average particle size of carrier core is more than 25 μ m and below 90 μ m.By making the volume average particle size of carrier core, be more than 25 μ m and below 90 μ m, can stably to the electrostatic latent image that is formed at photoreceptor, carry toner, and can form for a long time the image of high definition.When the volume average particle size of carrier core is less than 25 μ m, is difficult to suppress resin-coated carrier the carrier of photoreceptor is adhered to.When the volume average particle size of carrier core is greater than 90 μ m, can not form the image of high definition.
Form the toner of two-component developing agent of the present invention, by add external additive in containing resin glue, colorant, release agent and the toner matrix particle with controling agent etc., form.
Resin glue
Toner matrix particle forms by containing binder resin.As resin glue, have no particular limits, can use known resin.For example, can enumerate: polystyrene, styrene-propene acid copolymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-propene acids-copolymer-maleic anhydride, Polyvinylchloride, polyolefin resin, epoxy resin, silicone resin, polyamide, urethane resin, urethane-modified vibrin and acryl resin etc.As above-mentioned multipolymer, can be that segmented copolymer can be also graft copolymer.In addition, resin glue can be used separately a kind of of above-mentioned resin, also can use potpourri of more than two kinds.
As thermal property, preferred glass transition temperature (Tg) is 40 to 70 ℃.During lower than 40 ℃, in the situation that the temperature in image processing system rises, toner melting, produces cohesion between toner.In addition, while surpassing 70 ℃, fixation performance is deteriorated, lacks practicality.
Colorant
Toner matrix particle forms by containing colorant.As colorant, have no particular limits, can use known colorant.For example, can enumerate: carbon black, iron oxide black, alloy azo dyes, oil-soluble dyes and pigment etc.The addition of colorant, with respect to resin glue 100 weight portions, is preferably 1 weight portion to 10 weight portion.While being less than 1 weight portion, can not guarantee sufficient image color, while being greater than 10 weight portion, colorant can not be evenly dispersed in resin, therefore can not get high-quality image.
Release agent
Toner matrix particle forms as release agent and anti-offset dose by containing wax.Wax has no particular limits, and can use known wax, for example, can enumerate: by least one wax forming being selected from tygon, polypropylene, ethylene-propylene copolymer and polyolefin etc.The addition of wax, with respect to resin glue 100 weight portions, is preferably 1 weight portion to 10 weight portion.While being less than 1 weight portion, easily produce skew, while being greater than 10 weight portion, easily produce film forming.
Band controling agent
Toner matrix particle forms by containing band controling agent.Band controling agent has is just with electric control to control with two kinds of band controling agents with band controling agent and negative charging, can enumerate: azo dyes, carboxylic acid metal complex, quaternary ammonium compound and nigrosine class dyestuff etc.With the addition of controling agent, with respect to resin glue 100 weight portions, be preferably 0.1 weight portion to 5 weight portion.While being less than 0.1 weight portion, can not give sufficient charging property, while surpassing 5 weight portion, band controling agent can not evenly mix in binder resin.
External additive
Toner forms by add external additive in toner matrix particle.As external additive, have no particular limits, can use known external additive, for example, can enumerate: the attritive powder of the metal nitride particulates such as the metal oxide particles such as monox, titanium dioxide, aluminium oxide, magnetic iron ore and ferrite and silicon nitride and boron nitride etc.In addition, hydrophobization processing is preferably carried out on the surface of these attritive powders.As hydrophobization, process, can enumerate that silane coupling agents such as: dimethyldichlorosilane and amino silane is processed, silicone oil is processed and fluorine-containingly become divisional processing etc.External additive can be used separately a kind of of said external adjuvant, also can be used in combination two or more.In addition, as external additive, more preferably monox.Even if the outside particulate adding beyond monox only, exists in the contacting of toner and carrier and chargedly give inadequate situation, and monox also plays the effect as toner flowable, so can stablize the quantity delivered of toner.
The addition of external additive, with respect to toner matrix particle 100 weight portions, is preferably 0.1 weight portion to 5.0 weight portion.
Two-component developing agent of the present invention, can manufacture by mix above-mentioned toner and carrier with mixer.As mixer, can use knownly, can enumerate nauta mixer, V-Mixer etc.
Two-component developing agent of the present invention, owing to containing the good carrier of the present invention of permanance and environmental stability, thereby in the image processing system of high speed and miniaturization, even for a long time in hot and humid lower use, also stable charging property can be obtained, high-quality image can be obtained.
The present invention also provides a kind of image forming method, the image processing system by above-mentioned two-component developing agent for noncontact photographic fixing mode.
The carrier core of the present application is dissolved in acid solution, with ICP, carries out quantitative test.The amount of the Mg of the carrier core of recording in the present application is that the Mg that uses the quantitative test by this ICP to obtain measures.
About the mensuration of volumetric particle size distribution and the distribution of number particle diameter, the micro-trace device Model9320-X100 that uses Nikkiso Company Limited to manufacture.
The mensuration of resistance.First, at the insulcrete of horizontal positioned, for example, use on the acrylic board of teflon (registered trademark) coating the SUS(JIS that is 2mm through electrolytic polishings and thickness of slab as two surfaces of electrode configuration) 304 plates, making interelectrode distance is 2mm.Now, make the normal direction of two battery lead plates become horizontal direction.In space between two battery lead plates, pack into after powder 200 ± 1mg to be measured, in the behind of each battery lead plate, configure the magnet that sectional area is 240mm2, between electrode, form the electric bridge of powder to be measured.Under this state, between electrode, apply DC voltage, by two-terminal method, measure the current value that flows through powder to be measured, calculated resistance rate.In addition the teraohmmeter SM-8215 that, uses Zhi Electric Co., Ltd to manufacture here.In addition, the calculating formula of resistivity is resistivity (Ω cm)=actual measurement resistance (Ω) * sectional area (2.4cm2) ÷ electrode separation (0.2cm).Then, measure the resistivity (Ω cm) having applied while applying in the situation of voltage in table.In addition, the magnet of use, as long as powder can form electric bridge, can be used various magnet, but in the present embodiment, using surface magnetic flux density is permanent magnets more than 1000 Gausses, for example ferrite lattice.
ER1000V as electrical characteristics in table, is illustrated between two battery lead plates the numerical value while applying 1000V voltage.In addition,, in table, BD is for puncturing the situation of (can not measure).
The apparent density of carrier core be take JIS Z25042000 as benchmark mensuration.
Below adopt embodiment to describe embodiments of the present invention in detail, to the present invention, how application technology means solve technical matters whereby, and the implementation procedure of reaching technique effect can fully understand and implement according to this.
The preparation of embodiment 1 toner
In binder resin polystyrene 100 weight portions, add colorant carbon black 7.5 weight portions, tygon 2.0 weight portions and band controling agent 1.0 weight portions, with high-speed mixer, fully mix, by the potpourri obtaining Dual-screw kneader melt kneading.Gained kneaded material is pulverized by jet-propelled comminutor, then carried out classification, obtain the toner matrix particle of volume average particle size 7.0 μ m.With respect to these toner matrix particle 100 weight portions, add 1.2 weight portion silicon oxide particles as external additive, obtain thus toner.
The preparation of embodiment 2 carrier cores 1
In 7.5kg water, disperse 13.7kg Fe
2o
3(mean grain size: 1 μ m), 6.5kgMgO(mean grain size: 1 μ m), add 135g poly carboxylic acid ammonium class spreading agent as spreading agent, add 68g carbon black as reductive agent, make potpourri.Measure solid component concentration now, result is 75 % by weight.By wet ball mill (medium diameter 2mm) this potpourri of pulverization process, obtain mixing slurry.By spray dryer, in the hot blast of approximately 130 ℃, this slurry is sprayed, obtain drying-granulating powder.And, now with screening out targeted particle size distribution pelletizing in addition.This pelletizing is dropped in electric furnace, and at 1130 ℃, roasting is 3 hours.Now, flow into adjusting atmosphere makes in electric furnace that the oxygen concentration in electric furnace is 0.8%.Screen sizing after the calcining matter obtaining is pulverized, making mean grain size is 35 μ m.And then for the carrier core obtaining, by 470 ℃, under air, keep 1 hour, the carrier core obtaining is implemented to oxidation processes.Then with vibratory screening apparatus etc., adjust medium particle diameter etc., obtain the carrier core 1 of embodiment 2, the apparent density of carrier core is 1.93g/cm
3.In addition, about embodiment 4～5 and comparative example 1～4, also adopt identical method to prepare carrier core, magnetic characteristic and the electrical characteristics of the carrier core obtaining are as shown in table 1.
The preparation of embodiment 3 two-component developing agents 1
With the toner of bowl mill mix embodiment 1 preparation at the appointed time and the carrier core 1 of embodiment 2 preparations, obtain two component electron-like photographic developers.
Use and adopt 60 machines of digital discharged-area development mode as evaluation machine, carrier dispersion and the image quality of embodiment and comparative example are evaluated.
The evaluation that carrier disperses:
Using above-mentioned 60 machines as evaluation machine, the carrier about two component electron-like photographic developers is disperseed to evaluate.Particularly, the carrier on image the is dispersed grade of (hickie) is evaluated by following three ranks.Result is as shown in table 1.
◎: do not have albomaculatus grade completely in 10 A3 paper.
Zero: in 10 A3 paper, each has the grade of 1～10 hickie on opening.
*: in 10 A3 paper, each has the grade of more than 11 hickie on opening.
Image quality:
Using above-mentioned 60 machines as evaluation machine, the image quality grade about bi-component amount electrophotographic developing is evaluated by following three ranks.Result is as shown in table 1.
◎: very well reproduced trial image.
Zero: substantially reproduced trial image.
*: do not reproduce trial image completely.
Table 1
As can be seen from Table 1, when the value of the medium particle diameter of carrier core is more than 25 μ m in the scope below 35 μ m, in volumetric particle size distribution, particle size values is that the particle ratio below 22 μ m is more than 1.0% below 1.5%, during number particle diameter distributes, particle size values is that the ratio of the particle below 22 μ m is 5% when following, its practical characteristic in the early stage and 10K(K:1000) durable printing after all do not have carrier to disperse, image quality is also good.
And comparative example 1～comparative example 4, after the durable printing that the initial stage in its practical characteristic or 10K open, carrier disperse and image quality at least one for in-problem grade.
All above-mentioned these intellecture properties of primary enforcement, do not set restriction this new product of other forms of enforcement and/or new method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. a Mg-based ferrite carrier core, it is with formula M g
xfe
3-Xo
4shown core forms, wherein, and 0≤x≤1.
2. carrier core as claimed in claim 1, is characterized in that: the apparent density of described carrier core is 1.86g/cm
3above and at 2.45g/cm
3below.
3. carrier core as claimed in claim 1 or 2, it is characterized in that: the value of the medium particle diameter in the volumetric particle size distribution of described carrier core is more than 25 μ m in the scope below 35 μ m, in volumetric particle size distribution, particle size values is that the particle ratio below 22 μ m is more than 1.0% below 1.5%, during number particle diameter distributes, particle size values is that the ratio of the particle below 22 μ m is below 5%, and external magnetic field is that the magnetization value in 10000e situation is below the above 80emu/g of 60emu/g.
4. the carrier core as described in claims 1 to 3, is characterized in that: the preparation method of described carrier core is specially:
The first step, selects the raw material of iron content and containing the raw material of magnesium, according to the proportioning of final generation product, mixes in the proper ratio, and the described raw material containing magnesium is preferably MgO, and the raw material of described iron content is elected Fe as
2o
3;
Second step, in the raw material mixing in the first step, add reductive agent and water, carry out mix and blend pulp, make pulping raw material, described reductive agent can be carbon dust or polycarboxylic acid organism, polyacrylic acid type organic, maleic acid, acetic acid, polyvinyl alcohol (PVA) and composition thereof, and described solid component concentration accounts for the more than 50% of whole mixed slurry concentration;
The 3rd step, is used spray-dired mode to carry out granulation to the raw material after second step pulp, and spray-dired temperature is 100 ℃～200 ℃, and granulated particle diameter is 30～100 μ m;
The 4th step, the pelletizing that the 3rd step is obtained is sent in stove roast 10～20 hours, and the temperature in roast process in stove keeps 1000 ℃～1500 ℃;
The 5th step under the atmosphere of oxygen concentration 10～100%, keeps the product after roast 1～24 hour at 200～700 ℃, carries out oxidation processes and obtains carrier core;
The 6th step, to the carrier core after oxidation processes, with adjustment medium particle diameters such as vibratory screening apparatuss, the value that makes the medium particle diameter in volumetric particle size distribution is more than 25 μ m in the scope below 35 μ m, in volumetric particle size distribution, particle size values is that the particle ratio below 22 μ m is more than 1.0% below 1.5%, during number particle diameter distributes, particle size values is that the ratio of the particle below 22 μ m is below 5%, and external magnetic field is that the magnetization value in 10000e situation is below the above 80emu/g of 60emu/g.
5. a double component developing, is characterized in that: comprise the carrier core described in toner and claim 1 to 4.
6. two-component developing agent as claimed in claim 5, is characterized in that: described toner comprises resin glue, colorant, release agent and band controling agent.
7. the preparation method of double component developing described in claim 5 or 6, is characterized in that: described toner and carrier core are mixed by mixer.
8. an image forming method, is characterized in that: the image processing system by the two-component developing agent described in claim 5 or 6 for noncontact photographic fixing mode.
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