CN1129815A - Electrophotographic toner - Google Patents
Electrophotographic toner Download PDFInfo
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- CN1129815A CN1129815A CN95116869A CN95116869A CN1129815A CN 1129815 A CN1129815 A CN 1129815A CN 95116869 A CN95116869 A CN 95116869A CN 95116869 A CN95116869 A CN 95116869A CN 1129815 A CN1129815 A CN 1129815A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0821—Developers with toner particles characterised by physical parameters
- G03G9/0823—Electric parameters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09716—Inorganic compounds treated with organic compounds
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Abstract
This invention relates to a electrophotographic toner having an especially small particle diameter and excellent in electrostatic chargeability and stability of a charged state as well as flowability. It contains a sort of toner particle and an additive for treating a surface of a toner particle. The additive contains a hydrophobic fine silica particle treated with hexamethyldisilazane and at least one of the following: (a) fine titanium oxide particles treated with a polyhydric alcohol, (b) fine titanium oxide particles having a resistivity of 10<6> to 10<8> OMEGA .cm, and (c) fine titanium oxide particles wherein the absolute charged amount obtained when it is charged by mixing with a magnetic carrier is 5 to 80 mu C/g and the charging polarity is the same as that of the toner.
Description
The present invention relates to a kind of toner, concretely, relate to a kind of electrophotographic toner of small particle diameter, it is used to keep forming the high picture quality of image.
Except magnetic color tuner as the single component developing agent, comprise that the double component developing of toner and magnetic carrier is used to as Xerox, the development in the imaging device of laser printer etc.
Usually mixed colorant (as carbon black, etc.) in the photographic fixing resin, charge control material waits produces the toner that is used for double component developing, and sorting and the particle that this mixture pelleting is become a pre-sizing are pulverized in extruding then.And then, for this electrophotographic toner, will adhere on the surface of toner-particle, thereby improve its flowability, charging property and charged stability less than the particulate additives of toner-particle.
Recently, the toner that is no more than 9 μ m sizes is used to keep the high picture quality of image.Yet, because the toner of fine particle than conventional toner good fluidity, easily hinders formation toner agglomerate so problem is this toner.In addition, because of the toner of short grained toner and routine than charging property shakiness, so because undercharge, or image is unclear, (photographic fog that is caused in the clear area that is forming image by toner adhesion, etc.) occurs toner easily and spreads.
Therefore, in order to address the above problem, the inventor studies to unite and uses silicon dioxide microparticle and titanium dioxide fine particles as adjuvant, handles the surface of toner.
In surface treating additive, silicon dioxide microparticle mainly works the flowability of improving toner-particle, increases the effect of the carried charge of whole toners.On the other hand, titanium dioxide fine particles moves by helping the electric charge between toner-particle, make the carried charge of whole toner-particles even, surpass predetermined carried charge with what prevent highly charged amount toner for electric weight, the carried charge of weak charged toner is less than predetermined carried charge, oppositely charged toner is filled into opposite polarity, stablizes the charging property of toner.
Yet, find by the inventor's result of study, about handling the adjuvant of short grained toner surface, only unite and use silicon dioxide microparticle and titanium dioxide fine particles can not be enough to obtain above-mentioned effect.
As the silicon dioxide microparticle in the surface-treated adjuvant, be generally the hydrophobic silica particulate, it can produce moisture resistance and to the shelf stability effect of toner.The hydrophobic silica particulate be included in roasting and hydrolysis volatilization silicon compound in the vapour phase (as, silicon tetrachloride, Deng), use organosilane (as dichlorodimethylsilane then, Deng) or organosiloxane (as, dimethyl polysiloxane, etc.) silanol of silica particles of the steaming obtain handled and obtain have a high hydrophobicity silicon dioxide microparticle; The silicon monoxide that will volatilize from the electric arc furnaces roasting and the arc process silicon dioxide microparticle that obtains; Or the like.Yet, because, easy agglomeration of any conventional hydrophobic silica particulate and the difficult surface that adheres to toner-particle equably.Be necessary to add a large amount of silicon dioxide microparticles, to produce flowability to toner.
When adding so a large amount of particulates, the problem of generation is charged quantitative change too big of whole toners.Excessive hydrophobic silica particulate is bonded at the surface of titanium dioxide fine particles, prevents that titanium dioxide fine particles from anchoring at the surface of toner, thereby can not obtain to help the effect of moving of electric charge between toner-particle.The result is, the distribution that strengthens the toner-particle carried charge generates the toner of high-band electric weight, the toner of weak carried charge and reverse charged toner, and it is unclear image therefore to occur, disperses photographic fog or the like as toner.
In addition, when a large amount of titanium dioxide particulate of admiring adds when preventing this phenomenon, problem is that image concentration can reduce.
Fundamental purpose of the present invention provides a kind of novelty, short grained electrophotographic toner, and it has good flowability, charging property and charged stability.
At first, the inventor has studied the hydrophobic silica particulate of handling toner surface widely, to finish purpose of the present invention.
The result, discovery might obtain a kind of hydrophobic silica particulate, it is difficult for the surface that agglomeration but adheres to toner-particle easily equably, its act as through handle silica particle surface with hexamethyl-disilazane (HEXAMETHYLDISILAZANE) the silanol group silylanizing it, improve the flowability of toner.And then, also find when adopting the hydrophobic silica particulate that the surface of toner-particle is handled, the amount of hydrophobic silica particulate that requirement obtains the predetermined charge amount is very little, the amount that adheres to the lip-deep hydrophobic silica particulate of titanium dioxide fine particles is also little, therefore, can not reach the effect that helps electric charge between toner, to move.
Yet the inventor has studied titanium dioxide fine particles widely and has been used in combination with the hydrophobic silica particulate of handling with hexamethyl-disilazane.As a result, suitable binding energy provides a kind of toner, and it has good flowability, charging property and charged stability, and finished the present invention.
Promptly, the present invention's electrophotographic toner comprises a kind of toner-particle and handles the adjuvant of this toner surface that this adjuvant comprises hydrophobic silica particulate and at least a following titanium dioxide fine particles of handling with hexamethyl-disilazane (a)-(c):
(a) titanium dioxide fine particles of handling with polyvalent alcohol,
(b) resistance is 10
6-10
8The titanium dioxide fine particles of Ω .cm and
(c) titanium dioxide fine particles mixes when charging to toner-particle with magnetic carrier when it, and its absolute carried charge is 5-80 μ C/g, and charged polarity is identical with the polarity of toner.
In electrophotographic toner, unite use with polyvalent alcohol titanium dioxide fine particles of handling and the hydrophobic silica particulate of handling with hexamethyl-disilazane, titanium dioxide fine particles is difficult for agglomeration, and can adhere to the toner-particle surface together equably with hydrophobic silica, so it has the effect that good help electric charge moves between toner.
In addition, because resistance is 10
6-10
8The titanium dioxide fine particles of Ω .cm has the ability that suitable electric charge is shifted to toner, and this to move be gently to carry out, and it has acts on whole toner carried charges uniformly.
Therefore, the present invention's the electrophotographic toner one of at least a above-mentioned three kinds of titanium dioxide fine particles and that be used in combination with above-mentioned hydrophobic silica particulate that contains has good flowability, charging property and charged stability.
The present invention's purpose and advantage will make those skilled in the art understand by following description.
Brief Description Of Drawings
Fig. 1 is the constitutional diagram of the device of assessment toner flowability.
The present invention's hydrophobic silica particulate can be that those use hexamethyl second silicon nitrogen Alkane is processed the hydrophobicity dioxy of the silanol (SILANOL) on the silica particle surface The SiClx particulate. Described hydrophobic silica particulate comprise AEROGYL R812 and RX200 (NIHON AEROGYL CO.LTD production).
Reality as the silicon dioxide microparticle of the raw material of above-mentioned hydrophobic silica particulate Example can suitably be used and aforesaidly close through roasting with in vapour phase hydrolysis volatilization silication (FUMED) silica of the steaming that thing (such as, silicon tetrachloride, etc.) obtains.
In order to process the silanol group of silica particle surface with hexamethyl-disilazane Group makes it silylanizing, can make silicon dioxide microparticle with in the reaction column in the fluid bed Hexamethyl-disilazane reaction.
The hydrophobic silica particulate has aforesaid good improvement toner Mobile effect, because it is compared with the hydrophobic silica of routine, it is not Easily agglomeration. And then it demonstrates high hydrophobicity, because silanol seldom exists In its surface, and, moisture resistance and the storage stability of toner improved widely
The present invention is to the no particular determination of hydrophobic silica fine-grained particles size, from adding Say on the worker that when using (FUMED) silica of above-mentioned steaming, but it is elementary Particle (PRIMARY PARTICLE) is preferably about 5-50nm. Further, preferred Be that its particle size distribution should be in above-mentioned scope, purpose is to obtain stable band Electrical property and flowability. When the particle size of hydrophobic silica particulate less than above-mentioned Scope, they might agglomeration. In addition, this size changes greater than above-mentioned scope Advance the mobile effect of toner-particle and will become empty verbiage. And then, hydrophobic silica The mean particle size of particulate (primary granule) is preferably 7-30nm, more preferably 10-20nm is to obtain the electrically mobile toner in tool stabilized zone. What add dredges The amount of water-based silicon dioxide microparticle is about 0.01-5 by 100 parts of toner weighing scales Weight portion is preferably the 0.05-2 weight portion, more preferably the 0.1-1 weight portion.
When the amount of hydrophobic silica particulate less than above-mentioned scope, it improves toning It is inadequate that the effect of agent mobility of particle can become, and can hinder like this to form the toner agglomeration Thing. Further, because do not increase the effect of whole toner carried charges, can produce Toner carried charge deficiency. Therefore, produce image blurringly, reduce such as image concentration.
On the other hand, when the amount of hydrophobic silica particulate surpasses above-mentioned scope, What all the carried charge of toner then became is too big. In addition, excessive hydrophobicity titanium dioxide Silicon particle easily adheres to the surface of toner-particle, and the electric charge that therefore can not get help exists The effect of moving between toner-particle. The problem that produces like this is that the distribution of carried charge is drawn together Greatly, produce high-band electric weight toner, weak carried charge toner and reverse carried charge (INVERSELY CHARGED) toner causes the diffusion of image diffusion such as toner, Photographic fog etc.
Among the present invention as the hydrophobicity titanium dioxide fine particles, available aforesaid dioxy Change titanium particulate (a)-(c).
Roasting is pulverized and the sorting titanium dioxide granule gets titanium dioxide fine particles, and then Process this titanium dioxide fine particles surface with polyalcohol and can get described titanium dioxide fine particles (a ).
Described polyalcohol includes the trimethylolpropane of general formula (1) expression: CH3-CH
2-C(CH
2OH)
3(1) with by the pentaerythrite of general formula (2) expression: C (CH2OH)
4 (2)
In order to process the titanium dioxide fine particles surface with polyalcohol, can be at titanium dioxide fine particles The final stage of pulverizing adds polyalcohol, stirs subsequently. This stirring can make polyalcohol Hydroxyl bond be incorporated on the hydrophilic radical through morcelling newly-generated titanium dioxide fine particles. From And, the agglomeration of destruction titanium dioxide fine particles.
Granular size the present invention of titanium dioxide fine particles (a) does not limit, but at the beginning of it The mean particle size of grade particles is preferably about 10-200nm.
When described titanium dioxide fine particles grain size less than above-mentioned scope, its easy agglomeration, and surpass above-mentioned scope when it is big or small, the optical conductor surface is easily by the titanium dioxide fine particles scratch, promptly use when toner that titania makes, can produce so-called produce " transfer drum scratch ".The titanium dioxide fine particles mean particle size is preferably 20-100nm, 30-80nm more preferably, and purpose is to obtain a kind of electrical and mobile toner in stabilized zone that has.
The addition of titanium dioxide fine particles is calculated by the toner-particle of 100 weight portions, is about the 0.01-10 weight portion, is preferably the 0.05-3 weight portion, more preferably the 0.1-2 weight portion.
When the amount of titanium dioxide fine particles less than above-mentioned scope, all the carried charge of toners then become too big.The effect that the electric charge that can not get help simultaneously moves between toner-particle.The problem of Chan Shenging is that the distribution of carried charge is drawn together greatly like this, produces high-band electric weight toner, and weak carried charge toner and reverse carried charge (INVERSELY CHARGED) toner cause the diffusion of image blurring such as toner, photographic fog etc.
In addition, when the amount of titanium dioxide fine particles greater than above-mentioned scope, all the toner carried charges reduce, therefore, produces image blurring, as above-mentioned image concentration reduction.
It is 10 that titanium dioxide fine particles (b) is restricted to resistance
6-10
8The titanium dioxide fine particles of Ω .cm.
When the resistance of titanium dioxide fine particles less than above-mentioned scope, all the toner carried charges reduce, therefore, produces image blurring, as above-mentioned image concentration reduction.Work as resistance on the other hand and surpass above-mentioned scope, it is too big that the carried charge of whole toners then becomes.The effect that the electric charge that then can not get help moves between toner-particle.Simultaneously, the distribution of carried charge is drawn together greatly, produces high-band electric weight toner, and weak carried charge toner and reverse carried charge (INVERSELY CHARGED) toner cause the diffusion of image blurring such as toner, photographic fog etc.
In order in above-mentioned scope, to regulate the resistance of titanium dioxide fine particles, can change the kind of the treating agent that gives the titanium dioxide fine particles surface hydrophobic, or the addition of scalable treating agent.Described treating agent comprise each a kind of coupling agent as, silane, titanate, aluminium and zircoaluminate coupling agent, or silicon (oxygen alkane) oil.
For handling the titanium dioxide fine particles surface with treating agent, can adopt seasoning, it comprises that it only is treating agent that dropping or spray add, or its dilution, stir titanium dioxide fine particles with mixer is powerful simultaneously, and in oven additional mixing, drying composite stirs with mixer and pulverizes it then.Also can use wet method, it is included in mixes titanium dioxide fine particles and treating agent in the suitable organic solution, and drying composite is pulverized then.
When in order to obtain hydrophobicity, behind titanium dioxide fine particles surface-coated one deck resin, the addition of antimony oxide and tin oxide also can be regulated the resistance of titanium dioxide fine particles in the change coating, to regulate its electric conductivity.
The grain size of titanium dioxide fine particles (b) does not have particular determination, and the about 10-200nm of single its primary granule size is preferably 20-100nm, 30-80nm more preferably, and its reason is identical with above-mentioned titanium dioxide fine particles (a).
In addition, the addition of above-mentioned titanium dioxide fine particles is calculated by the toner-particle of 100 weight portions, is about the 0.01-10 weight portion, is preferably the 0.05-3 weight portion, more preferably the 0.1-2 weight portion.Its reason is same as described above.
Above-mentioned titanium dioxide fine particles is defined as to mix when charging to toner-particle with magnetic carrier when it, and its absolute carried charge is 5-80 μ C/g, the titanium dioxide fine particles that charged polarity is identical with the polarity of toner.Be titanium dioxide fine particles when electronegative, its carried charge-5 in-80 μ/g scope.During the titanium dioxide fine particles positively charged, its carried charge arrives in+80 μ/g scope+5.
When absolute carried charge is opposite with the polarity of toner less than above-mentioned scope or charged polarity, all the carried charge of toners reduces, and it is unclear image to occur, reduces as imaging concentration.In addition, when absolute carried charge surpasses above-mentioned scope, all the carried charge of toners then become too big.Simultaneously, the distribution of carried charge is drawn together greatly, produces high-band electric weight toner, and weak carried charge toner and reverse carried charge (INVERSELY CHARGED) toner cause the diffusion of image blurring such as toner, photographic fog etc.
The absolute carried charge of titanium dioxide fine particles is preferably the 7-70 μ/g in the above-mentioned scope, more preferably 10-60 μ/g.Ding Yi carried charge is not the intrinsic absolute value of titanium particulate herein, but the relative value that changes with the kind of used magnetic carrier.Promptly can adopt a kind of like this titanium dioxide fine particles, wherein mix with magnetic carrier so that toner-particle is charged when it, described absolute carried charge changes in above-mentioned scope.Also can use conventional assay method to measure carried charge, as brush method.
As the method for regulating the titanium dioxide fine particles carried charge, the foundation of adoptable method changes for the resistance of carried charge along with titanium dioxide fine particles.Promptly when mixing with magnetic carrier, when toner was charged, the resistance that can regulate titanium dioxide fine particles can change carried charge in above-mentioned scope.
The grain size of titanium dioxide fine particles (C) does not have particular determination, but the about 10-200nm of its primary granule size is preferably 20-100nm, 30-80nm more preferably, and its reason is identical with above-mentioned titanium dioxide fine particles (a).
In addition, the addition of above-mentioned titanium dioxide fine particles is calculated by the toner-particle of 100 weight portions, is about the 0.01-10 weight portion, is preferably the 0.05-3 weight portion, more preferably the 0.1-2 weight portion.Its reason is same as described above.
Below will explain in detail the present invention's toner-particle.
The toner-particle that can use any known toner-particle that has been used in the dried development method to adopt as the present invention.This toner is usually through disperseing to make as adjuvants such as colorants in the photographic fixing resin.
The fixer resin comprises styrene polymer, acrylate copolymer, styrene-propene acid polymer, olefin polymer, (as chlorinated polyphenyl ethene, polypropylene, ionomer etc.), poly-(vinyl chloride), polyester, polyamide, Polyurethane, epoxy resin, diallyl phthalic resin (DIALLYL PHTHALATE RESIN), silicone resin, rosin modified phenolic resin, phenolics, acetone resin, poly-(vinyl butyral) resin, xylene resin, Abietyl modified maleic acid resin, rosin ester etc.Wherein, acrylate copolymer, or the preferred pulverizing easily of styrene-propene acid polymer are controlled the distribution of molecular weight easily.As use full-color toner, preferably use polyester with good color mixed characteristic.
The colorant that is pre-dispersed in the photographic fixing resin comprises acetylene black, carbon black, and second cyanogen is black etc.
Can adopt magenta, CYAN and yellow pigment are as panchromatic colorant.
Pinkish red colorant comprises C.I. dyestuff red 49, C.I. dyestuff is red 57, and the C.I. dyestuff is red 81, C.I. dyestuff red 122, C.I. molten both red 19, C.I. solvent red 49, C.I. solvent red 52, C.I. basis red 10, C.I. disperse Disper red 15, Deng, they are suitable for as pinkish red colorant as C.I. dyestuff red 122 by the color index classification.
Cyan (CYAN) colorant comprises C.I. dyestuff orchid 15, C.I. dyestuff orchid 16, and C.I. solvent orchid 55, C.I. solvent orchid 70, C.I. is orchid 86 directly, etc., its door is pressed the color index classification.Wherein, Tongran material such as phthalein such as C.I. dyestuff orchid 15 are suitable for as cyan colorant.
Yellow colorants comprises azo dyes, as C.I. dyestuff Huang 1, and C.I. dyestuff Huang 5, C.I. dyestuff Huang 12, C.I. dyestuff Huang 17 etc., they press the color index classification; Inorganic dyestuff such as yellow iron oxide, yellow ochre or the like.Dyestuff (DYE) comprises nitro dye, as C.I. acid Huang 1, etc.; Lipid-soluble dye such as C.I. solvent yellow 2, C.I. solvent yellow 6, C.I. solvent yellow 14, C.I. solvent yellow 15, C.I. solvent yellow 16, C.I. solvent yellow 19, C.I. solvent yellow 21 or the like.Wherein, benzidine dye such as C.I. dyestuff Huang 12 are suitable for as yellow colorants.
The amount according to the .2 toner that adds is preferably the photographic fixing resin by 100 weight portions, 1-30 weight powder, more preferably 2-20 weight portion.Typical adjuvant but not colorant comprises charge control material passes seal inhibitor or the like.
For the control frictional electrification character of toner, hybrid charge control material, and the charged feature of pressing toner are divided into two classes, that is, and and for controlling positive and negative charge control material.
The charge control material of control negative charge comprises lipid-soluble dye (as oil black nigrosine (C.I.5-45), glossy black (C.I.26150), SPIRON is black etc.), metallic azo dyes, metal naphthenate, alkyl salicylic acid slaine, fatty acid soaps, resin acid soaps or the like.
The addition of charge control material by 100 weight portion photographic fixing resins, is preferably the 0.1-10 weight portion, more preferably the 0.5-8 weight portion.Mix and pass seal inhibitor (OFFSET INHIBITOR) to give toner to compensate the effect of pressing down.Pass the seal inhibitor and comprise aliphatic hydrocrbon, aliphatic slaine, high molecular weight fatty acid, fatty acid ester or its partly-hydrolysed material, silicone oil, various waxes.Wherein, be preferably mean molecular weight and be about 1,000-10,000 aliphatic hydrocrbon.For example, also can only use low-molecular-weight polypropylene, low molecular weight polyethylene, paraffin, low-molecular-weight has 4 or the olefin polymer of a plurality of carbon atom olefin units, silicone oil etc., or their potpourri.
Pass the addition that seal presses down agent,, be preferably the 0.1-10 weight portion, more preferably the 0.5-8 weight portion by 100 weight portion photographic fixing resins.
When the magnetisable material powder adds the present invention's electrophotographic toner, can obtain magnetic carrier as monocomponent toner.
Described magnetisable material is a kind of material in its magnetic direction hard magnetization.Magnetisable material that the present invention uses is preferably and is no more than 1 μ m size, particularly about 0.01-1 μ m particulate.Its chemical is stable.Typical magnetisable material comprises iron oxide, as magnetic iron ore, and haematite, tri-iron tetroxide, or the like; Metal, as iron, cobalt, nickel, etc.; The same aluminium of these metals, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, the alloy of tungsten and vanadium; Or its potpourri.
The addition of magnetisable material by 100 weight portion photographic fixing resins, is preferably the 20-300 weight portion, more preferably the 50-150 weight portion.
In addition, also can sneak into the various compounds of right quantity, as stabilizing agent.
The present invention does not limit especially to the toner-particle size.Yet, preferably use mean grain size to be no more than the granule toner of 9 μ m, purpose is to obtain the above-mentioned image with high picture quality.The average particle size particle size of described granule toner from the improvement of image quality, is preferably the 4-9 μ m in the above-mentioned scope, more preferably 6-8 μ m.
Simultaneously, the present invention also can be applied to common toner, but not the granule toner, therefore, the average-size of toner-particle can surpass above-mentioned scope.
Prepare electrophotographic toner of the present invention by handling described toner with above-mentioned hydrophobic silica particulate.Mix above-mentioned each component with above-mentioned addition and carry out surface treatment.Therefore, hydrophobicity silicon dioxide and titania can be adhered on the surface of each toner-particle equably.For example, can adopt various well known devices in the practice as mixing arrangement, as the HENSCHEL mixer, or the V-type mixer or the like.
Also can hydrophobic silica particulate and titanium dioxide fine particles and toner-particle be mixed simultaneously.Yet, for these two kinds of uniform particles adhere on the surface of toner-particle, preferably a kind of particulate is mixed with toner-particle; so that it anchors on the surface of toner; then, another kind of particulate is mixed with toner-particle, make it anchor at its surface.
The electrophotographic toner that obtains like this can be used as one-component or double component developing.
When as single component developing agent, can use electrophotographic toner of the present invention, this toner is to carry out above-mentioned surface treatment through containing magnetisable material (or nonmagnetic thing), and the toner-particle that obtains.
In addition, in order to obtain double component developing, can mix with carrier through above-mentioned surface-treated electrophotographic toner of the present invention.
Can use beaded glass, oxidation or unoxidized iron powder, the particle of the magnetisable material of iron oxide or cobalt etc., its surface-coated synthetic resin (as, acryl resin, styrene acrylic resin, fluororesin, silicone resin, vibrin etc.) or the like the material that obtains do carrier.Under the normal condition, the average particle size particle size of this carrier is 50-2000 μ m.When using double component developing, toner concentration is preferably 2-15% (weight).
Embodiment
Following examples and comparative example are further explained in detail the present invention, singly not delimit the scope of the invention.
Embodiment 1 and comparative example 1-7
The preparation of＜toner-particle 〉
Alkyd resin with 100 weight portions as the photographic fixing resin, 5 weight portions as the quinoline bifurcation pyridine dyestuff of colorant and 2 weight portions, charge control material as the control negative charge, the melting of zinc salicylate compound, extruding, pulverize, the toner-particle that a kind of average particle size particle size is 8 μ m is produced in sorting respectively.
The preparation of＜electrophotographic toner 〉
The toner by above-mentioned production of 100 weight portions is mixed with the particulate of hydrophobic silica shown in the table 1, and wherein consumption such as table 1 are identical, stir with the HENSCHEL mixer.Titanium dioxide fine particles with shown in the amount adding table 1 shown in the table 1 stirs the mixture then, prepares electronegative electrophotographic toner.
In the table 1, " silicon dioxide " one blocks the represented symbol that goes out and represents following hydrophobic silica particulate respectively.
I: with the hydrophobic silica particulate that hexamethyl-disilazane was handled, average primary particle size: 12nm
II: with the hydrophobic silica particulate that dimethyl dichloro silazane was handled, average primary particle size: 16nm
III: with the hydrophobic silica particulate that dimethyl polysiloxane was handled, equal primary particle size: 16nm
In the table 1, " titania " one blocks the represented symbol that goes out and represents following titanium dioxide fine particles respectively.
I: with the titanium dioxide fine particles that trimethylolpropane was handled, average primary particle size: 50nm.
Ii: with the titanium dioxide fine particles that alumina treatment is crossed, average primary particle size: 50nm.
Iii: with the titanium dioxide fine particles that octyl group trimethoxy silane (OCTYLTRIMETHOXYSILANE) was handled, average primary particle size: 50nm.
The toner that obtains in the various embodiments described above and the comparative example is carried out following experiment respectively, assess its characteristic.
＜mobile experiment 〉
Measure the flowability of the toner that obtains in the various embodiments described above and the comparative example with device shown in Figure 1.
This device comprises a hopper 1, and the sample toner is housed on it, a toner feeding roller 2, and it is contained on the bottom outlet 11 of hopper 1 and a square position 3 that is placed in below them.Toner feeding roller 2 is that a kind of diameter is the 20mm metal cylinder, its surface imperfection.Roller 2 is designed to when roller 2 rotates, and the sample toner can be fallen on the square position from hopper 1.The toner of scheduled volume is put into hopper 1, the toner feeding roller is rotated by the speed rule of reserving in advance, in the preset time section, measure the quantity of the toner that falls into dish 3, thereby estimate the flowability of toner.In this mensuration, the velocity of rotation furnishing 3rpm of toner feeding roller 2 measured the amount that falls into dish 3 toners in 5 minutes.The result represents that it is many more that toner falls, and the flowability of toner is just big more.
The mensuration of＜fog density 〉
The same coated carrier of each toner (through using the styrene-propene acid resin, mean grain size: 65 μ m coating magnetic iron ore surface makes) with obtaining in the foregoing description and the comparative example prepares the double component developing that its toner concentration is 4% weight.With Xerox (DC-4585 MITA INDUSTRIAL CO.LTD makes), 20,000 time, use the developer imaging, reflective concentration determination instrument (REFLECTION DENSITOMETER) RD-918 that makes with MACBECH CO. measures the image concentration of the clear area of last imaging.
The diffusion of＜observation toner 〉
After imaging 20,000 times, the internal state of visual inspection duplicating machine, according to following standard evaluation it.
Zero: no toner diffusion
△: toner slight spread
*: the toner diffusion
The results are shown in Table 1.
Table 1
The mobile fog density toner of silicon dioxide and titanium dioxide
Kind quantity
The diffusion of kind quantity (amount of falling)
(weight portion), (weight portion) [restraining/5 minutes] embodiment 1 I 0.5 i 0.7 7.1 0.001 0 comparative examples 1 II 0.5 i 0.7 3.8 0.009 * comparative example 2 III 0.5 i 0.7 3.2 0.010 * comparative example 3 I 0.5 ii 0.7 6.8 0.009 * comparative example 4 I 0.5 iii 0.7 7.5 0.011 * comparative example 5 II 1.0 i 0.7 4.7 0.010 * comparative example 6 II 0.3 i 0.7 2.8 0.009 △ comparative examples 7 I 0.5 ii 1.0 7.0 0.008 △
From table 1, can obviously see, the toner of the embodiment of the invention 1, it is the hydrophobic silica particulate of handling with hexamethyl-disilazane, carry out surface treatment with the titanium dioxide fine particles of handling with polyvalent alcohol (front three hydroxy propane), this toner has good flowability, clear image (disperse as no toner, photographic fog produces).
Embodiment 2 and 3, comparative example 8-12
Undertaken by the method that the foregoing description 1 is identical with comparative example 1-7, different is with the titanium dioxide fine particles with the quantity shown in the table 2 and resistance (Ω .cm), prepares electronegative electrophotographic toner.
The toner that is obtained by the foregoing description and comparative example carries out above-mentioned experiment, and as the flowability experiment, the mensuration of fog density is observed the diffusion experiment of toner etc., estimates its characteristic.The result is as shown in table 2.
Table 2
The mobile fog density toner of silicon dioxide and titanium dioxide
The diffusion of kind quantity resistance quantity (amount of falling)
(weight portion) (weight portion) [restraining/5 minutes] embodiment 2 I 0.5 108 0.7 7.1 0.000 0 embodiment 3 I 0.5 106 0.7 6.9 0.001 0 comparative examples 8 I 0.5 109 0.7 7.2 0.011 * comparative example 9 I 0.5 105 0.7 7.0 0.010 * comparative example 10 II 0.5 108 0.7 3.5 0.009 △ comparative examples 11 III 0.5 108 0.7 3.1 0.008 △ comparative examples 12 II 1.0 108 0.7 4.7 0.010 *
Obviously as seen, the hydrophobic silica particulate of handling with hexamethyl-disilazane is 10 with having resistance in the table 2
6-10
8The titanium dioxide fine particles of Ω .cm carries out surface treatment, and embodiment 2 and 3 has good flowability, clear image (disperse as no toner, photographic fog produces).
Embodiment 4-6 and comparative example 13-16
Undertaken by the method that the foregoing description 1 is identical with comparative example 1-7, different is to obtain after quantity shown in the table 3 and coated carrier mix with having, and has the titanium dioxide fine particles of carried charge (μ C/g), prepares electronegative electrophotographic toner.
The toner that is obtained by the foregoing description and comparative example carries out above-mentioned experiment, and as the flowability experiment, the mensuration of fog density is observed the diffusion experiment of toner etc., estimates its characteristic.The result is as shown in table 3.
Table 3
The mobile fog density toner of silicon dioxide and titanium dioxide
The diffusion of kind quantity resistance quantity (amount of falling)
(weight portion) (weight portion) [restraining/5 minutes] embodiment 4 I 0.5-78 0.7 7.5 0.000 0 embodiment 5 I 0.5-31 0.7 7.2 0.000 0 embodiment 6 I 0.5-5 0.7 7.4 0.001 zero comparative examples 13 II 0.5-31 0.7 3.2 0.008 △ comparative examples 14 III 0.5-31 0.7 3.3 0.009 △ comparative examples 15 I 0.5+5 0.7 6.8 0.015 * comparative example, 16 I 0.5-100 0.7 7.1 0.012 *
From table 3 obviously as seen, hydrophobic silica particulate and the titanium dioxide fine particles handled with hexamethyl-disilazane carry out surface treatment to it, wherein the absolute carried charge of titanium dioxide fine particles is that it mixes with coated carrier, so that charging obtains to toner, its quantity is 5-80 μ C/g, and its charged polarity is identical with the polarity of toner, and the toner of embodiment 4-6 has good flowability, clear image (disperse as no toner, photographic fog produces).
As mentioned above, the present invention's electrophotographic toner has good flowability, and charging property and charged stability use special hydrophobic silica particulate and special titanium dioxide fine particles as adjuvant, to the toner surface treatment because unite.Therefore, the present invention can be used as and make short grained electrophotographic toner, to keep high image quality.
Claims (4)
1. an electrophotographic toner comprises a kind of toner-particle and adds adjuvant in the described toner-particle, so that toner is carried out surface treatment, and
Described adjuvant comprises hydrophobic silica particulate of handling with hexamethyl-disilazane and the titanium dioxide fine particles of handling with polyvalent alcohol.
2. electrophotographic toner as claimed in claim 1, wherein said polyvalent alcohol are the trimethylolpropane (TRIMETHYLOLPROPANE) of general formula (1) expression: CH
3-CH
2-C (CH
2OH)
3(1) or by pentaerythrite: C (CH by general formula (2) expression
2OH)
4(2)
3. an electrophotographic toner comprises a kind of toner-particle and adds adjuvant in the described toner-particle, so that toner is carried out surface treatment, and
Described adjuvant comprises the hydrophobic silica particulate of handling with hexamethyl-disilazane and has resistance is 10
6-10
8The titanium dioxide fine particles of Ω .cm.
4. an electrophotographic toner comprises a kind of toner-particle and adds adjuvant in the described toner-particle, so that toner is carried out surface treatment, and
Described adjuvant comprises the hydrophobic silica particulate of handling with hexamethyl-disilazane, and titanium dioxide fine particles, when this titanium dioxide fine particles mixes when charging to toner-particle with magnetic carrier, its absolute carried charge is 5-80 μ C/g, and charged polarity is identical with the polarity of toner.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6228068A JPH0895285A (en) | 1994-09-22 | 1994-09-22 | Electrophotographic toner |
| JP228068/94 | 1994-09-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1129815A true CN1129815A (en) | 1996-08-28 |
Family
ID=16870697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95116869A Pending CN1129815A (en) | 1994-09-22 | 1995-09-22 | Electrophotographic toner |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0704769A1 (en) |
| JP (1) | JPH0895285A (en) |
| KR (1) | KR960011576A (en) |
| CN (1) | CN1129815A (en) |
| TW (1) | TW335461B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388126C (en) * | 2002-10-02 | 2008-05-14 | 松下电器产业株式会社 | Carrier for electrophotography |
| CN101344736B (en) * | 2007-07-09 | 2012-01-25 | 夏普株式会社 | External toner additive, toner and image forming apparatus using the same |
| CN108698852A (en) * | 2016-01-20 | 2018-10-23 | 国立大学法人东京大学 | Magnetic material, magnetic color tuner and Magnaglo |
| CN109031904A (en) * | 2015-05-28 | 2018-12-18 | 湖北鼎龙控股股份有限公司 | The test method of toner-particle mobility |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3595631B2 (en) * | 1996-07-31 | 2004-12-02 | キヤノン株式会社 | Toner for developing electrostatic images |
| EP0844536B1 (en) * | 1996-11-26 | 2004-05-06 | Canon Kabushiki Kaisha | Image forming method |
| JPH11119463A (en) * | 1997-08-04 | 1999-04-30 | Ricoh Co Ltd | Electrostatic charge image developing toner and image forming method |
| KR100409079B1 (en) * | 2001-01-17 | 2003-12-11 | 주식회사 엘지화학 | Toner composition having high transcription efficiency and a method for preparing the same |
| JP2004109898A (en) * | 2002-09-20 | 2004-04-08 | Ricoh Co Ltd | Negative charge type toner |
| US20080070146A1 (en) | 2006-09-15 | 2008-03-20 | Cabot Corporation | Hydrophobic-treated metal oxide |
| US8435474B2 (en) | 2006-09-15 | 2013-05-07 | Cabot Corporation | Surface-treated metal oxide particles |
| US8455165B2 (en) | 2006-09-15 | 2013-06-04 | Cabot Corporation | Cyclic-treated metal oxide |
| US8202502B2 (en) | 2006-09-15 | 2012-06-19 | Cabot Corporation | Method of preparing hydrophobic silica |
| TWI349701B (en) * | 2007-07-26 | 2011-10-01 | Ind Tech Res Inst | Superhydrophobic self-cleaning powders and fabrication method thereof |
| JP5102125B2 (en) * | 2008-06-27 | 2012-12-19 | 株式会社リコー | White toner for developing electrostatic image, two-component developer, image forming method, image forming apparatus, process cartridge |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6346469A (en) * | 1986-08-14 | 1988-02-27 | Fuji Xerox Co Ltd | Developer composition |
| US4904558A (en) * | 1988-03-08 | 1990-02-27 | Canon Kabushiki Kaisha | Magnetic, two-component developer containing fluidity improver and image forming method |
| US5272040A (en) * | 1991-04-09 | 1993-12-21 | Minolta Camera Kabushiki Kaisha | Toner for developing electrostatic latent images |
-
1994
- 1994-09-22 JP JP6228068A patent/JPH0895285A/en active Pending
-
1995
- 1995-09-05 EP EP95306186A patent/EP0704769A1/en not_active Withdrawn
- 1995-09-15 KR KR1019950030169A patent/KR960011576A/en not_active Application Discontinuation
- 1995-09-18 TW TW084109762A patent/TW335461B/en active
- 1995-09-22 CN CN95116869A patent/CN1129815A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388126C (en) * | 2002-10-02 | 2008-05-14 | 松下电器产业株式会社 | Carrier for electrophotography |
| CN101344736B (en) * | 2007-07-09 | 2012-01-25 | 夏普株式会社 | External toner additive, toner and image forming apparatus using the same |
| CN109031904A (en) * | 2015-05-28 | 2018-12-18 | 湖北鼎龙控股股份有限公司 | The test method of toner-particle mobility |
| CN108698852A (en) * | 2016-01-20 | 2018-10-23 | 国立大学法人东京大学 | Magnetic material, magnetic color tuner and Magnaglo |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960011576A (en) | 1996-04-20 |
| JPH0895285A (en) | 1996-04-12 |
| TW335461B (en) | 1998-07-01 |
| EP0704769A1 (en) | 1996-04-03 |
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