CN103869645B - Carrier core material and preparation method thereof and carrier for electrostatic image developer - Google Patents
Carrier core material and preparation method thereof and carrier for electrostatic image developer Download PDFInfo
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- CN103869645B CN103869645B CN201410104936.9A CN201410104936A CN103869645B CN 103869645 B CN103869645 B CN 103869645B CN 201410104936 A CN201410104936 A CN 201410104936A CN 103869645 B CN103869645 B CN 103869645B
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- 239000011162 core material Substances 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 230000005415 magnetization Effects 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 238000000034 method Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 13
- 229910000859 α-Fe Inorganic materials 0.000 description 13
- 239000013078 crystal Substances 0.000 description 11
- 229910052712 strontium Inorganic materials 0.000 description 9
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000011859 microparticle Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 239000008187 granular material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- KLULSCKBRGQDOY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;toluene Chemical compound CC(=C)C(O)=O.CC1=CC=CC=C1 KLULSCKBRGQDOY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 fatty acyl amide Chemical class 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a kind of carrier for electrostatic image developer core material and preparation method thereof and carrier for electrostatic image developer, solve the problems, such as that surface differences are big existing for the carrier core material of existing small particle, resistivity is low.The preparation method of the carrier core material is：Using the mixture of metal oxide and rare earth oxide as raw material, it is made through crushing, granulation, calcining, sintering, wherein, at least contain metallic element Fe in metal oxide, rare earth oxide is at least containing a kind of rare earth element in La, Ce, Pr, Nd, Gd, and the content of rare earth oxide is no more than the 3% of raw material gross mass.The features such as carrier core material of the present invention has grain size small, and even grain size is moderate and high resistance.
Description
Technical field
The present invention relates to print field, specifically a kind of carrier for electrostatic image developer core material and its preparation side
Method and carrier for electrostatic image developer.
Background technology
Electrostatic image development technology has been applied to multiple fields, and in the art, image is prepared by the following：
Electrostatic latent image is formed on photoreceptor by charging and exposure process, then is shown electrostatic latent image with the toner containing colorant
Shadow is then transferred to transferring member, makes information visualization finally by heating fixing.Electrostatic charge image developer includes two big
Class：Two-component developing agent i.e. containing toner and carrier and the monocomponent toner for containing only toner.It is aobvious as bi-component
The carrier of shadow agent, now widely used is the carrier comprising carrier core material and the resin layer for being coated on carrier core material surface.
There are two basic functions for carrier tool, on the one hand, by the friction with toner, toner is made to have required electrification
Amount；On the other hand, carry the function that toner is transmitted to photoreceptor.In developer, carrier is due to by magneticaction
And it is attracted in magnetic roller.And on the surface of carrier particle, also it is attached with multiple toner particles, the i.e. catenulate magnetic brush knot of shape
Structure.When magnetic roller rotates, magnetic brush contacts photoreceptor, and toner is transferred to photosensitive surface and is developed, and carrier is filled in development
It is used repeatedly in setting.During use, it is desirable that the various functions of carrier keep stablizing.
In order to realize that the basic function of carrier, carrier core material should have good magnetism.If the magnetization of carrier core material
Intensity is less than specified value, and magnetic force is insufficiently resistant to centrifugal force, and carrier will disperse out from magnetic roller, causes image to occur different
Often, i.e., so-called carrier disperses phenomenon.If the intensity of magnetization of carrier core material is higher than specified value, and magnetic brush can be caused really up to the mark,
Good image cannot be obtained.
In recent years, in order to improve the quality of image, there is the demand for the grain size for reducing toner particle.It is corresponding, carrier
The grain size of particle also requires to further decrease.But with the small particle of carrier core material, and there is new problem to generate.One side
Face, diameter of carrier become smaller, and the intensity of magnetization of carrier may be caused to decline, and carrier occurs and disperses.On the other hand, the load of small particle
Body core material has the tendency for the surface differences for increasing carrier core material.Under normal circumstances, the step of preparing carrier core material includes raw material
Mixing, pulp, crush, be granulated, then carry out calcining and sintering make its Ferrite method.The carrier core material surface of small particle
Grain size distribution is wider, not of uniform size, is susceptible to coarse grain.This huge carrier core material of surface differences, and it is subsequent
Cladding process in cover coating resin between bad adhesion, cause under the carrier prepared and developer service life
Drop.
Carrier core material should also have resistivity appropriate.During long-time service, upper carrier point coating resin
Can be peeling-off, charge leakage phenomenon is generated, image deflects are caused.If carrier core material has preferable insulating properties, this phenomenon
It will be inhibited, it is very helpful for the service life for extending carrier.
Before this, it is disclosed the research that patent is dedicated to carrier core material small particle, such as is added in the feed micro
Strontium element（Sr）.Since strontium element can make the ferrite inner void that ferrite reacts and sintering is slowly carried out, therefore formed
It is few, particle surface crystal grain homogeneous.The carrier core material prepared using such method can make while realizing small particle
The crystallite dimension of particle surface is suitable, and can realize high intensity.Slow down the experimental results showed that the addition of strontium element can be played really
Reaction speed, refine ferrite crystal grains effect, but in process of production the addition of strontium be difficult to it is just right.If
The addition of strontium is on the low side, then ferritic crystallite dimension is unable to get effective control.If strontium element addition is on the high side, burning
More strontium ferrite is just will produce during knot.Strontium ferrite has higher residual induction, is unfavorable for the formation of magnetic brush.
Invention content
The purpose of the present invention is to solve above-mentioned technical problems, and granule is realized in electrophotographic developing carrier core material
While diameter, the even grain size of particle surface is moderate, and resistivity is high.
The present invention also provides a kind of preparation method of above-mentioned carrier core material, simple for process, flow controllability height, production
For carrier core material while with small particle, the even grain size of particle surface is moderate, and resistivity is high.
The present invention also provides a kind of use in developer developing electrostatic image that can form good image quality containing above-mentioned carrier core material
Carrier.
The preparation method of carrier for electrostatic image developer core material of the present invention, with the mixed of metal oxide and rare earth oxide
Conjunction object is raw material, is made through crushing, granulation, calcining, sintering, wherein at least contain metallic element Fe, rare earth in metal oxide
Oxide is at least containing a kind of rare earth element in La, Ce, Pr, Nd, Gd, and the content of rare earth oxide is total no more than raw material
The 3% of quality, preferably 0.25-1%.
The metal oxide also contains Mn and/or Mg.
The average grain diameter of material is in 0.5-3.0 μ ms after the pulverizing process, the average grain of the carrier core material of preparation
Diameter value is at 20 μm -30 μm.
The carrier for electrostatic image developer core material prepared by the above method, with chemical general formula MnxMgyFezO4(0≤x≤
1,0≤y≤1,2≤z≤3) shown in composition be used as main component, and also at least containing one kind in La, Ce, Pr, Nd, Gd
Rare earth element.
The average size of the carrier core material is in 20 μm or more 30 μm or less of range.
The volume resistivity of the carrier core material is 107-1012Ω·cm。
The carrier core material is under the magnetic field intensity effect of external 1000Oe, saturation magnetization σsFor 40-80Am2/ kg,
Remanent magnetization σrFor 10.0Am2/ kg is hereinafter, coercivity HCFor 5Am2/ kg or less.
Carrier for electrostatic image developer of the present invention, including the carrier core material and the tree that is coated in the carrier core material
Lipid layer.
The small particleization of carrier core material requires the raw material for preparing carrier core material also to realize small particle.This is because granule
The raw material of diameter helps to inhibit the growth of crystal when high temperature, can play the surface of control vector core material, crystallite dimension is made to close
Suitable effect.And when the grain size of raw material is larger, the filling rate of pelletizing reduces, and preparing carrier core material has emptying aperture generation.
But the method for merely reducing raw material particle size is also undesirable.This is because the raw material reactivity height that grain size is small, sintering process
Middle sintering velocity is very fast, it is difficult to the surface state of control vector core material.Therefore sintering must be controlled using additive simultaneously
Process.Rare earth oxide is added by in-depth study, selection in present inventor in the feed.The ionic radius of rare earth element
It is larger, it is difficult to enter in ferritic lattice dot matrix, can be only present in grain boundary sites.When ferrite crystal grains are grown, this
A little rare earth elements can play the role of hindering crystal growth, keep the ferrite crystal grains size uniform prepared moderate.At the same time,
Rare earth oxide in grain boundary sites also adds scattering of the crystal boundary to conduction electronics, improves the resistivity of carrier core material.
It is required that average grain diameter of the material after pulverizing process is in 0.5-3.0 μ ms.It should be pointed out that crushed
The average grain diameter of Cheng Zhong, material can be reduced compared to raw material, that is to say, that the average grain diameter of raw material is not limited to this range
It is interior.
In the preparation process of carrier core material, adhesive, dispersant and antifoaming agent to be also added as needed（These ingredients
It can be removed in sintering process）.Starch, polyvinyl alcohol, carboxymethyl cellulose etc., preferably polyvinyl alcohol may be selected in adhesive；Point
Fat carboxylic acid, fatty acyl amide, polycarboxylic acid's ammonium salt class, esters etc., preferably polycarboxylic acid's ammonium salt class may be selected in powder；Defoaming
Agent selects n-octyl alcohol.With chemical general formula MnxMgyFezO4Composition shown in (0≤x≤1,0≤y≤1,2≤z≤3) is used as carrier
The main component of core material.Mn ferrite has ferromagnetism, therefore preferably x ＞ 0.7 are to ensure that carrier core material has higher saturation
The intensity of magnetization.Although magnesium ferrite is magnetic weaker, it is with higher resistivity.Both ferrites, which are used cooperatively, to incite somebody to action
The magnetic characteristic and resistivity of carrier core material are adjusted to desirable level.The content of raw material middle rare earth is no more than gross mass
3%.It is expensive to be not only because rare earth element, also as when its content is more than this range, the carrier core material prepared
Grain boundary sites can a large amount of enrichment of rare earth elements.Although this is conducive to the promotion of resistivity, answering suffered by these positions
Power is concentrated very much, thus when carrier is stirred continuously in developing trough, stress can by carrier core material occur it is broken in a manner of be released
It puts, the service life of carrier can significantly shorten.Therefore it is preferred that the content of rare earth element is 0.25-1%, to ensure having sufficient amount of rare earth
Element is evenly distributed on grain boundary sites, has the function that crystal grain thinning.
The volume resistivity of carrier core material of the present invention is 107-1012Ω·cm.Present invention applicant notices addition rare earth
After element, the volume resistivity of carrier core material obviously rises, and effectively reduces carrier during Reusability, and charge injection carries
The possibility of body, the phenomenon for preventing carrier itself developed occur.
The average size of carrier core material of the present invention is preferably 20-30 μm.Within this range, carrier can be conveyed steadily
Toner forms the image of fine.Carrier is made of carrier core material and the resin layer that is coated in carrier core material, resin layer compared with
It is thin, coating function is only played, therefore the grain size of carrier is decided by the grain size of carrier core material.When the average grain diameter of carrier core material is less than upper
When stating range, the magnetic characteristic of single carrier can decline, and easy to produce carrier attachment phenomenon.And when the average grain diameter mistake of carrier core material
When big, carrier cannot meet the requirement of small particle toner.The concrete component that the present invention is coated on the resin layer in carrier core material can
It according to the prior art and specifically needs to reasonably select, content is preferably the 0.1-30% of carrier core material weight, further preferably
0.5-10%.The electrically conductive microparticle that volume average particle size is 0.1-1 μm is preferably added in resin layer, additive amount accounts for resin layer
The 2-40% of gross mass, the addition of electrically conductive microparticle can significantly inhibit the decline of carrier resistivity.The electrically conductive microparticle can be
The inorganic particles such as carbon black fine particle, titanium oxide microparticle, tin oxide particles.
Advantageous effect：
The carrier for electrostatic image developer core material preparation method of the present invention is with the mixed of metal oxide and rare earth oxide
Conjunction object is raw material, and carrier core material is prepared through processes such as crushing, granulation, calcining, sintering, and the method is simple and reliable, controllability is good,
The features such as carrier core material of preparation has grain size small, and even grain size is moderate and high resistance；
The carrier for electrostatic image developer grain size of the present invention is small, therefore the electrostatic charge image developer produced can be formed
The image of high quality.
Description of the drawings
Fig. 1 is the electron scanning micrograph of 1 carrier core material of embodiment.
Fig. 2 is the electron scanning micrograph of 1 carrier core material of comparative example.
Fig. 3 is the electron scanning micrograph of 4 carrier core material of comparative example.
Specific implementation mode
I, the preparation of carrier core material
（Embodiment 1）
It crushes, be granulated
By 704gFe2O3, 259gMn3O4, 37gMgO, 10gLa2O3It as the raw material of carrier core material, is distributed in water, then
It is 1.1 μm to be crushed to average grain diameter with wet ball mill, obtains the mixed slurry of above-mentioned substance.The solid content of slurry, i.e.,
The mass percent of solid constituent will be controlled in 50% or more, preferably 60% or more.Such slurry gained after mist projection granulating is made
Grain powder intensity is high, and inner void is few after sintering, therefore it is preferred that.The polyvinyl alcohol of 30g is additionally incorporated as adhesive, then adds 10g
Polyacrylic acid and 5g n-octyl alcohol respectively as dispersant and antifoaming agent.With centrifugal spray dryer by the slurry 200
DEG C hot wind in be granulated, obtain pelletizing of the particle size range at 10-100 μm.
Calcining
Gained pelletizing is put into electric furnace, is heated to 800-1000 DEG C, is calcined 2 hours in air.
Sintering
Powder after calcining is crushed again, is granulated（Process is same as above）, gained pelletizing puts into electric furnace, is heated to
It 1230 DEG C, is sintered 2 hours in air.Temperature-fall period is passed through high pure nitrogen into stove, is adjusted by controlling the flow of nitrogen
Oxygen content in electric furnace, it is ensured that carrier core material has good magnetic characteristic.Then sinter is crushed, then by sieving and being classified
Process removes excessive and too small particle, and the granularity of carrier core material is adjusted to 20-30 μm.
（Embodiment 2）
Except using 10gCe in raw material2O3Instead of 10gLa2O3In addition, with condition similarly to Example 1, embodiment 2 is obtained
Carrier core material.
（Embodiment 3）
Except using 10gPr in raw material2O3Instead of 10gLa2O3In addition, with condition similarly to Example 1, embodiment 3 is obtained
Carrier core material.
（Embodiment 4）
Except using 10gNd in raw material2O3Instead of 10gLa2O3In addition, with condition similarly to Example 1, embodiment 4 is obtained
Carrier core material.
（Embodiment 5）
Except using 10gGd in raw material2O3Instead of 10gLa2O3In addition, with condition similarly to Example 1, embodiment 5 is obtained
Carrier core material.
（Embodiment 6）
In addition to the average grain diameter of material after pulverizing process becomes 1.7 μm, with condition similarly to Example 1, reality is obtained
Apply the carrier core material of example 6.
（Embodiment 7）
In addition to the average grain diameter of material after pulverizing process becomes 2.8 μm, with condition similarly to Example 1, reality is obtained
Apply the carrier core material of example 7.
（Embodiment 8）
Except La2O3Quantitative change be 5g other than, with condition similarly to Example 1, obtain the carrier core material of embodiment 8.
（Embodiment 9）
Except La2O3Quantitative change be 22g other than, with condition similarly to Example 1, obtain the carrier core material of embodiment 9.
（Comparative example 1）
In addition to not adding rare earth oxide in raw material, with condition similarly to Example 1, the carrier of comparative example 1 is obtained
Core material.
（Comparative example 2）
Except replacing 10gLa with 10gSrO in raw material2O3, the average grain diameter of material becomes other than 1.5 μm after pulverizing process, uses
Condition similarly to Example 1 obtains the carrier core material of comparative example 2.
（Comparative example 3）
Except La2O3Quantitative change be 35g other than, with condition similarly to Example 1, obtain the carrier core material of comparative example 3.
（Comparative example 4）
In addition to the average grain diameter of material after pulverizing process becomes 3.6 μm, with condition similarly to Example 1, compared
Compared with the carrier core material of example 4.
II, the preparation of carrier
Styrene-methyl methacrylate resin and carbon black are dissolved respectively and are scattered in toluene, is stirred the mixture for
Dispersion liquid is obtained after ten minutes.At 50 DEG C with fluid-bed type coatings equipment, by dispersion to the embodiment of 100 parts by weight
Thus the carrier of embodiment 1-9 and comparative example 1-4 is made in the carrier core material surface of 1-9 and comparative example 1-4.
The dispensing of carrier is as follows：Styrene -3 parts by weight of toluene methacrylate resin；Carbon black（VXC72, Cabot
Corporation is manufactured）0.4 parts by weight；25 parts by weight of toluene；100 parts by weight of carrier core material.
III, the preparation of developer
It is stirred 30 minutes using the carrier that mixing machine obtains 5 parts of toners and 95 parts of embodiment 1-9 and comparative example 1-4,
Products therefrom obtains the developer of embodiment 1-9 and comparative example 1-4 by screening.
IV, every physical property values determination method
The assay method of embodiment 1-9 and every physics value of comparative example 1-4 carrier core materials is given below：
Volume resistivity
Volume resistivity uses GEST-121 Instrument Measuring Resistivity of Carbon Products（Instrument Ltd.'s manufacture is tested in Beijing hat test）It measures.
Magnetic characteristic
Magnetic characteristic uses HH-10 vibrating specimen magnetometers（Nanjing Nanda Instrument Plant manufactures）It measures.Measure external magnetic field
Saturation magnetization σ under 1000Oes, remanent magnetization σrWith coercivity HC。
Volume average particle size
Volume average particle size, which uses, uses laser diffraction granularity tester（Such as COULTER LS230）It measures.
Intensity
In KER-1/100A sealed type sample pulverizers（Ke Rui sample making apparatus Co., Ltd of Zhengjiang City manufactures）Middle addition
The carrier core material of 100g is simultaneously 60 seconds broken, is compared to the particle diameter distribution of broken front and back carrier core material.The present application is with broken
For the volume incrementss of broken front and back 22 μm of particles below as the index for weighing carrier core material intensity, this numerical value is smaller, shows to carry
The intensity of body core material is bigger.
The preparation condition transitivity value of each embodiment and comparative example carrier core material is as shown in table 1.
[table 1]
Fig. 1 is the electron scanning micrograph of 1 carrier core material of embodiment.Fig. 2 is the scanning electricity of 1 carrier core material of comparative example
Sub- microscope photo.Fig. 3 is the electron scanning micrograph of 4 carrier core material of comparative example.
As shown in Figure 1, the carrier core material even grain size that rare earth oxide is added is moderate, illustrate that rare earth element presses down really
The fast-growth for having made crystal grain plays the role of controlling grain surface state.And the carrier core material of rare earth oxide is not added
（Such as comparative example 1, Fig. 2）, in sintering process grain growth be not effectively controlled, size differs, wider distribution.This table
Bad adhesion between the huge carrier core material of face difference, with coating resin, there is not the service life of carrier and developer
Profit influences.
With reference to table 1 it can be found that high an order of magnitude of resistivity of the resistivity and comparative example 1 of embodiment 1-9, this shows
The rare earth oxide of addition is effectively distributed at grain boundary sites, scattering of the crystal boundary to conduction electronics is increased, to improve
The resistivity of carrier core material.Continue the content of raising rare earth oxide（Such as comparative example 3）, resistivity can also be further up.
By comparing magnetic characteristic data, it can be found that each embodiment all has saturation magnetization appropriate with comparative example
Value.But the remanent magnetization of comparative example 2 is high, coercivity is big, this is because the additive amount of Sr is higher, the shape in sintering process
At the reason of more strontium ferrite.Present invention applicant is also noted that when the average grain diameter of material is excessive（Such as comparative example
4）, remanent magnetization and coercivity can also increase extremely.After being observed carrier core material surface with scanning electron microscope
It was found that the even grain size of carrier core material is moderate in Fig. 1, and there are more emptying apertures on carrier core material surface in Fig. 3.This is because
The average grain diameter of material is excessive before being granulated, and pelletizing can not achieve fine and close filling, and there are a large amount of gaps, therefore load after sintering
Body core surfaces and inside leave emptying aperture.Emptying aperture inhibits the normal growth of ferrite crystal grains, and sintered crystallite dimension is too small,
Therefore the remanent magnetization of carrier core material and coercivity increase.
When the too high levels of rare earth oxide（Such as comparative example 3）, since rare earth element is largely gathered in grain boundary sites, answer
Power is excessively concentrated, and the intensity of carrier core material is caused to decline.In addition, when the average grain diameter of material is excessive（Such as comparative example 4）, carrier
There is emptying aperture in core material, and Fragmentation Phenomena easily occurs in whipping process, and intensity is also decreased obviously.
Claims (8)
1. a kind of preparation method of carrier for electrostatic image developer core material, which is characterized in that with metal oxide and rare earth oxygen
The mixture of compound is raw material, is made through crushing, granulation, calcining, sintering, wherein metal oxide Fe2O3, Mn3O4With
A kind of oxide of rare earth element in MgO, rare earth oxide La, Ce, Pr, Nd, Gd, and the content of rare earth oxide is not
More than the 3% of raw material gross mass.
2. the preparation method of carrier for electrostatic image developer core material as described in claim 1, which is characterized in that rare-earth oxidation
The content of object accounts for the 0.25-1% of raw material gross mass.
3. the preparation method of carrier for electrostatic image developer core material as claimed in claim 1 or 2, which is characterized in that described
The average grain diameter of material is in 0.5-3.0 μ ms after pulverizing process, and the average size of the carrier core material of preparation is at 20 μm -30
μm。
4. a kind of carrier for electrostatic image developer core material prepared by any one of claim 1-3 preparation methods, feature exist
In with chemical general formula MnxMgyFezO4, 0≤x≤1 in formula, 0≤y≤1, composition shown in 2≤z≤3 is used as main component, and
And the oxide also at least containing a kind of rare earth element in La, Ce, Pr, Nd, Gd.
5. carrier for electrostatic image developer core material as claimed in claim 4, which is characterized in that the carrier core material is averaged
Particle size values are in 20 μm or more 30 μm or less of range.
6. carrier for electrostatic image developer core material as claimed in claim 4, which is characterized in that the volume of the carrier core material
Resistivity is 107-1012Ω·cm。
7. the carrier for electrostatic image developer core material as described in claim 4 or 6, which is characterized in that the carrier core material exists
Under the magnetic field intensity effect of external 1000Oe, saturation magnetization σsFor 40-80Am2/ kg, remanent magnetization σrFor
10.0Am2/ kg is hereinafter, coercivity HCFor 5Am2/ kg or less.
8. a carrier for electrostatic image developer, which is characterized in that the carrier includes any one of claim 4-7 carriers
Core material and the resin layer being coated in the carrier core material.
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| CN105652616B (en) * | 2016-03-15 | 2020-06-05 | 湖北鼎龙控股股份有限公司 | Carrier core material for two-component electrostatic image developer and carrier |
| JP6757284B2 (en) * | 2017-03-31 | 2020-09-16 | Ｄｏｗａエレクトロニクス株式会社 | Carrier core material, carrier for electrophotographic using it, and developer for electrophotographic |
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| CN1550932A (en) * | 2003-05-02 | 2004-12-01 | ������������ʽ���� | Image forming apparatus with a toner supply device |
| CN102411271A (en) * | 2010-09-21 | 2012-04-11 | 富士施乐株式会社 | Toner for developing electrostatic image, method for producing the same, developer, and image forming method |
| CN102540787A (en) * | 2010-12-13 | 2012-07-04 | 富士施乐株式会社 | Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, image forming method, and image forming apparatus |
| CN102608886A (en) * | 2012-03-02 | 2012-07-25 | 湖北鼎龙化学股份有限公司 | Low-density carrier core material for electrostatic image developer and preparation method thereof and carrier and application thereof |
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| JPS6217756A (en) * | 1985-07-16 | 1987-01-26 | Canon Inc | Electrophotographic magnetic toner |
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|---|---|---|---|---|
| CN1550932A (en) * | 2003-05-02 | 2004-12-01 | ������������ʽ���� | Image forming apparatus with a toner supply device |
| CN102411271A (en) * | 2010-09-21 | 2012-04-11 | 富士施乐株式会社 | Toner for developing electrostatic image, method for producing the same, developer, and image forming method |
| CN102540787A (en) * | 2010-12-13 | 2012-07-04 | 富士施乐株式会社 | Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, image forming method, and image forming apparatus |
| CN102608886A (en) * | 2012-03-02 | 2012-07-25 | 湖北鼎龙化学股份有限公司 | Low-density carrier core material for electrostatic image developer and preparation method thereof and carrier and application thereof |
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Inventor after: Zhu Shunquan Inventor after: Li Bo Inventor after: Liu Min Inventor after: Lan Zeguan Inventor after: Zhang Ping Inventor before: Zhu Shunquan Inventor before: Li Bo Inventor before: Liu Min Inventor before: Lan Zeguan |
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