CN1168490A - Magnetic coated carrier, two-component type developer and developing method - Google Patents

Abstract

A magnetic coated carrier suitable for constituting a two-component type developer for use in electrophotography is composed of magnetic coated carrier particles comprising magnetic coated carrier particles comprising magnetic carrier core particles each comprising a binder resin and metal oxide particles, and a coating layer surface-coating each carrier core particle. The magnetic carrier core particles have a resistivity of at least 1x1010 ohm.cm, and the magnetic coated carrier has a resistivity of at least 1x1012 ohm.cm. The magnetic coated carrier has a particle size distribution such that it has a number-average particle size Dn of 5-100 mu m, it satisfies a relationship of Dn/ sigma >/=3.5, wherein sigma denotes a standard deviation of number-basis particle size distribution of the carrier, and it contains at most 25% by number of particles having particle sizes of at most Dnx2/3.

Description

Magnetic coated carrier, two-component developer and developing method

The present invention relates to a kind of magnetic carrier that is used to constitute developer, a kind of two-component developer and a kind of developing method that is used for for example electrofax and electrostatic recording structure imaging method.

Up to now in U.S. Pat 2297691, US3666363, US4071361 etc. disclose multiple accordance with electrophotographic process, in these methods, the light image that is equivalent to original image by irradiation forms electrostatic latent image on photoconductive layer, and on latent image adhering toner.Latent image is developed.Then, the toner image that obtains is transferred on the such transfer materials of paper for example, by or by intermediate transfer element, and then photographic fixing, for example, by heating, pressurization or heating and pressurizing or use solvent vapo(u)r are to obtain a the copy or photograph.

In the last few years, along with computing machine and multimedia development, the full-color image of the more high definition of the wide field that has had suitable method to produce to be applied to from the office to the family.The user that task is heavy is general, and requirement has high-durability or lasting imaging performance, even under the situation of duplicating continuously on a large amount of paper or printing, picture quality can variation yet.A small amount of office task user or domestic consumer, except requiring high-quality image, also require to reduce equipment size, to save space and energy consumption, toner is utilized again or reduce the system of toner consumption (or reduce detersive consumption) and more photographic fixing under the low temperature.Different researchers goes out to send to finish these purposes from different visual angles.

In static (latent image) development phase, by the electrostatic interaction of utilization, make charged toner-particle be attached to static (latent image), thereby form toner image with electrostatic latent image.Utilize toner to make in the known developing method of developing electrostatic latent image, using the method for the two-component developer of the potpourri comprise toner and carrier to be suitable for the full color duplicating machine and the full color printing machine of the special high image quality of requirement.

As the magnetic carrier that is used for two-component developer, commercially available have an iron powder carrier, ferrite carrier and disperse the resin carrier of magnetic material.The iron powder carrier is because its low-resistivity can cause by carrier from the electrostatic image leak charge, so that the interference electrostatic image produces defective image thus.Even have the ferrite carrier of suitable high resistivity, can not prevent that under certain conditions the electric charge of electrostatic image from leaking by carrier, particularly for comprising the developing method of using alternating electric field.And as the carrier with big saturation magnetization, it is hard that magnetic brush becomes easily, easily stays brush mark on product and toner image thus.

For fear of the problems referred to above, a kind of resin carrier that disperses magnetic material has been proposed, wherein the magnetic fine grained is dispersed in the adhesive resin.The resin carrier of this dispersion magnetic material is compared with ferrite carrier, has quite high resistivity, and little saturation magnetization and little true ratio make the carrier magnetic brush not really hard, and the good toner image that does not have brush mark can be provided.

But with regard to using the resin carrier that disperses magnetic material, because its low saturation magnetization, carrier easily causes carrier to adhere to.And if along with the more use of small grain size toner, the carrier granularity is also dwindled together, this carrier easily cause lower to toner give electric energy power, and produce the developer of lazy flow.

For fear of this problem, JP-A7-43951 has proposed a kind of resin carrier of dispersion magnetic material of the size-grade distribution with regulation.This Jap.P. discloses a kind of resin carrier production method, wherein magnetic material is mediated with adhesive resin and is made its dispersion, this kneading product is pulverized after cooling and is classified, and wherein improves disintegrating process so that size-grade distribution accurately to be provided, so that address the above problem.But, be difficult to sometimes from the vector product of classifying, eliminate the superfines part, thereby cause carrier to adhere to.The resin of the dispersion magnetic material by the preparation of this method is applied to forming monochrome image, but highly is still waiting when the full color duplicating machine of color reproducibility or full color printing machine further perfect when it is used for requirement.

General objects of the present invention provides a kind of magnetic coated carrier, a kind of two-component developer and the developing method that uses such two-component developer to address the above problem.

Purpose more specifically of the present invention provides and a kind ofly can show the charged ability of outstanding toner, particularly with the small grain size toner mixes and carrier-free is adhered to magnetic coated carrier, a kind of two-component developer and a kind of developing method that uses this two-component developer that includes such magnetic coated carrier.

Even another object of the present invention provides and a kind ofly can demonstrate outstanding flowability and can avoid continuing the magnetic coated carrier that image deterioration and metal oxide particle overflow in the imaging on a large amount of paper, a kind of two-component developer and a kind of developing method that uses this two-component developer that comprises such magnetic coated carrier.

A further object of the invention provides a kind of two-component developer and a kind of developing method that uses this two-component developer that can eliminate the generation of photographic fog and can adapt to the formation method that reduces detersive consumption.

Another object of the present invention provides a kind of two-component developer, it can adapt to the low-temperature fixing method and reduce detersive loss method, it has the reusable durability of having improved, and on photosensitive part no film forming phenomenon and a kind of developing method that uses this two-component developer.

Another object of the present invention provides a kind of stable developing method, and it can be applicable to the low-temperature fixing method and not have in long-time on developer bearing part melts the sticky hair life.

According to the present invention, a kind of magnetic coated carrier is provided, comprises: contain the magnetic coated carrier particle of magnetic carrier slug particle, each magnetic carrier slug particle comprises adhesive resin and metal oxide particle, with the coating of each carrier slug particle of surface-coated, wherein:

Metal oxide particle must be through surperficial lipophilization treatment,

The magnetic carrier slug particle has at least 1 * 10 ¹⁰The resistivity of ohm.cm,

Magnetic coated carrier has at least 1 * 10 ¹²The resistivity of ohm.cm, and

The size-grade distribution of magnetic coated carrier is such: (i) having number average particle size Dn is 5-100 μ m, (ii) satisfy relational expression: Dn/ σ 〉=3.5, wherein σ represents the standard deviation of carrier base size-grade distribution and (iii) contains 25% the granule number that maximum particle size is Dn * 2/3 that has at least.

According to the present invention, the limit provides a kind of two-component developer, is used for developing electrostatic image, comprising: toner and aforementioned magnetic coated carrier.

A kind of developing method also is provided according to the present invention, comprise: above-mentioned two-component developer is positioned over the bearing developer parts, seal a field generator for magnetic therein, on the bearing developer parts, form the magnetic brush of two-component developer, make magnetic brush contact with image bearing member, the bearing developer parts being applied alternating electric field simultaneously, on image bearing member, make electrostatic image development.

These purposes of the present invention and other purpose, characteristics and advantage.Consider the description and in conjunction with the accompanying drawings of the following preferred embodiments of the invention, it is clearer to become.

Fig. 1 is the development section synoptic diagram of imaging device that is suitable for implementing the specific embodiments of developing method of the present invention.

Fig. 2 is used to measure carrier, the diagram of the equipment of the resistivity of carrier core and nonmagnetic metal oxide.

Fig. 3 is the synoptic diagram of the uneven state of bearing developer parts surface.

Fig. 4 is the synoptic diagram of the full color imaging device that adopts of developing method of the present invention.

As our result of study, have been found that the magnetic coated carrier with wide size distribution optionally partly causes carrier to adhere to (namely the carrier granular on the electrostatic latent image load bearing component adheres to) with respect to small grain size easily in the situation that the particle mean size when carrier reduces. Also find also its toner load-carrying properties of shadow of carrier size distribution, have the carrier of wide size distribution because the reduction of developer flowability easily causes the unsettled triboelectrification of toner. Find that further the toner-particle surface configuration also affects the flowability of developer in ditty toner granularity situation. And, having core/shell structure and this core contains in the situation of low softening point material at toner-particle, this toner easily is damaged, and causes mobile the reduction. Based on these discoveries, have been found that and effectively be controlled at the magnetic coated carrier size distribution in the prescribed limit, minimize the granule content of (number average particle size) * 2/3 granularity that has Dn and reduce magnetic force by the magnetic coated carrier dispensing, solve the problems referred to above.

In order to prevent that toner from degenerating, the magnetic force of the coated carrier that effectively deperms dispensing, but find that also this will cause carrier to adhere to damaging preventing effectiveness with respect to toner being inverse proportion and increasing. But pass through the resistivity of the resistivity, particularly slug particle of increase magnetic coated carrier particle, and the size distribution of control magnetic coated carrier, such carrier adheres to growth trend can well be eliminated. And the magnetic coated carrier size distribution also is conducive to toner chargeding performance or toner band power (being the toner triboelectrification ability of carrier) more accurately.

Carrier production method commonly used comprises to be pulverized and classification, it is difficult to get rid of the fine powder part, on the other hand, the magnetic coated carrier with form factor 100-130SF-1 provides the developer flowability of having improved, and this developer further improved the toner chargeding performance.

The number average particle size that magnetic coated carrier of the present invention has (Dn) is 5-100 μ m, preferred 10-70 μ m. If Dn less than 5 μ m, just is difficult to prevent well that at no image section carrier from adhering to that this is because a certain amount of fine fraction is arranged in the carrier size distribution. Because its particle is big, Dn will cause irregular image greater than 100 μ m, and brush mark is owing to the Hard Magnetic brush can be avoided simultaneously.

According to the size distribution of magnetic coated carrier of the present invention, this carrier contain maximum 25% to have the granule number that maximum particle size is Dn * 2/3 (adding up) be very important. The quantity of this ratio preferred maximum 15%, more preferably maximum 10% quantity even like this in the situation that the developing bias voltage as the development conditions of imaging device fluctuates, can prevent better that also carrier from adhering to.

It also is very important satisfying Dn/ σ 〉=3.5. Dn/ σ 〉=4.0th, preferred. Be lower than 3.5, when with have average particle size (D₄) when the small grain size toner of 1-4 μ m mixed, the flowability of developer reduced, thereby but causes unsettled toner charging property.

It is crosslinked to be used for the support core particle preferred three-dimensional that is made of adhesive resin of the present invention. This is because control and the carrier production method of carrier size distribution are closely connected. The general production method of resin carrier of disperseing magnetic material is adhesive resin and blending ratio under heating condition the melt kneading of magnetic to stipulate, the product through mediating is after cooling, and pulverizing and classification obtain carrier. In this method, by being disclosed in the improvement method of JP-A7-43951 in pulverising step, size distribution can be too narrow to a certain degree. But because disintegrating apparatus, it partly is inevitable producing some fine powders. Particularly containing in the situation of a large amount of magnetics, easily taking place excessively to pulverize, by for example pneumatic classification or screening of progressive operation, the fine powder that obtains part can not be got rid of fully. And, in carrier, use thermoplastic resin as adhesive resin, on a large amount of paper, in the continuous imaging process, disperse the fine grain release of magnetic therebetween that problem can take place. Have been found that now by the use polymerisation process and can produce the support core particle that has accurate size distribution and almost do not have the dispersion magnetic material of fine powder part, wherein the support core particle of polymer beads formation is by comprising that monomer and solvent (polymerization reaction medium) the solution polymerization system as a kind of homogeneous solution makes, and be by metal oxide particle being dispersed in the support core particle, making through surperficial lipophilization treatment (being sometimes referred to as " lipophilic reaction " (or the particle " lipophilization " to processing)). The chances are because the mixture of polymerization carries out granulating when wherein adding metal oxide particle that monomer carries out polymerization with gelation for this, thereby obtained having the support core grain products that uniform particle size distributes and particularly almost do not have the fine powder part. And three-dimensional cross-linked by resin is carried out, disperse magnetic corpuscular therebetween more firmly to combine with it.

Using by average particle size (D₄) be that the preferred vector granularity also is reduced to the size that is equivalent to toner in the situation of the small grain size toner that represents of 1-10 μ m. Preceding method can make the carrier granular that does not almost have the fine powder part produce, and irrelevant with the average carrier granularity that reduces.

For the adhesive resin that consists of the support core particle that is obtained by pulverizing, the example of operable main polymerisable monomer comprises: styrene, styrene derivative, neighbour-methyl styrene for example, between methyl styrene, to methoxy styrene, to ethyl styrene, and p-tert-butylstyrene, acrylic acid, methacrylate; Acrylate, methyl acrylate for example, ethyl acrylate, n-butyl acrylate, acrylic acid n-propyl, isobutyl acrylate, 2-ethyl hexyl acrylate, dodecyl acrylate, acrylic acid 2 Octyl Nitrites, stearyl acrylate acyl ester, acrylic acid 2-chloro-ethyl ester and phenyl acrylate; Methacrylate, methylmethacrylate for example, ethyl methacrylate, methacrylate n-propyl, the positive butyl ester of methacrylate, the methacrylate isobutyl ester, methacrylate n-octyl, isobutene dodecyl gallate, methacrylate 2-Octyl Nitrite, methacrylate stearoyl ester, the methacrylate phenyl ester, methacrylate dimethylamino methyl esters, methacrylate lignocaine ethyl ester and isobutene acid benzyl ester; Acrylic acid 2-hydrogen ethyl ester, methacrylate 2-hydroxyl ethyl ester; Acrylonitrile, methacrylonitrile, acrylamide; Vinethene, ethylene methacrylic ether for example, ethyl vinyl ether, propyl vinyl ether, the normal-butyl vinethene, isobutylvinyl ether, β-chloroethyl vinyl ether, phenylvinyl ether, the p-methylphenyl vinethene, right-the chlorphenyl vinethene, to the bromophenyl vinethene, p-nitrophenyl vinethene and p-methoxyphenyl vinethene; And diolefin compound, for example butadiene.

These monomers can use separately or mix use, are used to provide a kind of polymeric components that shows preferred performance.

The adhesive resin of preferred vector slug particle is three-dimensional cross-linked. As crosslinking agent, the preferred use has the compound that has two polymerizable double bonds in the molecule at least. Such crosslinking agent example comprises: aromatic divinyl compound, for example divinylbenzene and divinyl naphthalene; Glycol diacrylate, glycol ester diisobutylene, TEG diisobutylene acid esters, 1,3-butanediol diisobutylene acid esters, 1,3-butanediol diisobutylene acid esters, trimethyl alcohol propane triacrylate, trimethyl alcohol propane TIB acid esters, 1, the 4-butanediol diacrylate, neopentylglycol diacrylate, 1, the 6-hexanediyl ester, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, pentaerythrite diisobutylene acid esters, pentaerythrite tetra methylacrylate, caprylic oxygen diisobutylene acid esters, N, N divinyl lanolin, divinyl sulfide, and divinylsulfone. Can be used with the form of mixtures of two or more in these compounds. These crosslinking agents can add in advance in the polymerizable mixture or after polymerisation during the suitable stage add.

Also can be made by other monomer as the adhesive resin of support core particle, these examples comprise: bis-phenol and as the raw-material chloropropylene oxide of epoxy resin; Phenol and aldehyde as phenolic resins; As the urea of urea resin and aldehyde with as melamine and the aldehyde of melamine resin.

Most preferred adhesive resin can be phenolic resins, and the raw material of preparation for example have: phenolic compounds, and for example phenol, metacresol, 3,5 dimethylbenzene are to alkylphenol, resorcinol and p-t-butyl phenol; And aldehyde compound, formalin for example, PARA FORMALDEHYDE PRILLS(91,95), furfural. The combination of phenol and formalin is especially preferred.

For such phenolic resins or melamine resin, can use base catalyst as vulcanization accelerator. The base catalyst that is fit to can be general base catalyst as producing phenolic resins. These examples comprise: ammoniacal liquor and amine, for example hexa, diethyl triamine and polymine.

According to the metal oxide of the carrier slug particle as carrier of the present invention, can comprise magnetite or by formula MO.Fe ₂O ₃(or MFe ₂O ₄) expression the magnetic oxysome, wherein M represents trivalent, divalence or valent metal ion.The example of M comprises: magnesium, aluminium, silicon, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, strontium, yttrium, zirconium, niobium, molybdenum, cadmium, tin, barium, lead and lithium.M represents one or more of metal.The magnetic metal oxide example that is fit to comprises: the iron-based oxide raw material, for example magnetite, Zn-Fe-based ferrite, Mn-Zn-Fe based ferrite, the Ni-Zn-Fe based ferrite, Mn-Mg-Fe based ferrite, Ca-Mn-Fe-based ferrite, Ca-Mg-Fe based ferrite, Li-Fe based ferrite and Cu-Zn-Fe-based ferrite.Also can use magnetic metal oxide and nonmagnetic metal hopcalite.The concrete example of nonmagnetic metal oxide comprises: Al ₂O ₃, SiO ₂, CaO, TiO ₂, V ₂O ₅, CrO ₂, MnO ₂, α-Fe ₂O ₃, CoO, NiO, CuO, ZnO, SrO, Y ₂O ₃And ZrO ₂

What need further specify is to disperse a kind of single metal oxide in resin, but particularly preferably in the potpourri that disperses at least two kinds of metal oxides in the resin.Under latter event, preferably use multiple particle, so that the adhesion and the high support strength of growth are provided with approximate proportion and/or shape.The type of the multiple metal oxide of preferred compositions comprises the combination of low-resistivity magnetic metal oxide and high resistivity magnetic or nonmagnetic metal oxide.The combination of low-resistivity magnetic metal oxide and high resistivity nonmagnetic metal oxide is particularly preferred.

Preferred examples of combinations comprises: magnetite and haematite stone (α-Fe2O3), magnetite and γ-Fe ₂O ₃, magnetite and SiO ₂, magnetite and Al ₂O ₃, magnetite and TiO ₂, magnetite and Ca-Mn-Fe based ferrite and magnetite and Ca-Mn-Fe-based ferrite.In the middle of them, the combination of magnetite and haematite stone is particularly preferred.

Disperse in resin under the situation of above-mentioned metal oxide with the preparation slug particle, it is 0.02-2 μ m that the metal oxide of demonstration magnetic preferably has number average particle size, and it changes along with the granularity of carrier slug particle simultaneously.Under the situation of disperseing two or more metal oxide compositions, show that it is 0.02-2 μ m that magnetic and metal oxide that have general low resistivity preferably has number average particle size ra, and another metal oxide preferably has the resistivity that is higher than magnetic metal oxide (it can be non magnetic), and preferably having number average particle size rb is 0.05-5 μ m.In this case, the ratio of rb/ra preferably surpasses 1.0 and mostly be 5.0 most.The ratio of rb/ra is that 1.2-5 is preferred.If this ratio is 1.0 or lower, just be difficult to form the state that the metal oxide particle with higher electric resistivity is exposed to the slug particle surface, make core resistivity be difficult to abundant growth, and be difficult to obtain the effect that prevents that carrier from adhering to.On the other hand, if this ratio surpasses 5.0, just be difficult to dispersing metal oxides particle in resin, thereby easily cause the release of lower physical strength of magnetic carrier and metal oxide.The measuring method of the metal oxide granularity that relates in addition will be described later.

About being dispersed in the metal oxide in the resin, the preferred resistivity of this magnetic-particle is 1 * 10 at least ³Ohm.cm, more preferably at least 1 * 10 ⁵Ohm.cm, under the situation of using two or more metal oxide mixtures, it is 1 * 10 at least that the magnetic metal oxide particle preferably has resistivity especially ³Ohm.cm, and preferred nonmagnetic other metal oxide particle preferably has the resistivity that resistivity is higher than the magnetic metal oxide particle.More preferably, other metal oxide particle has at least 10 ⁸The resistivity of ohm.cm, further preferably at least 1 * 10 ¹⁰Ohm.cm.

If the resistivity that the magnetic metal oxide particle has is lower than 1 * 10 ³Ohm.cm also is difficult to have suitable carriers resistivity even the amount of the metal oxide that disperses reduces, thereby easily causes electric charge to inject, and causes inferior picture quality and causes carrier and adhere to.Disperseing under the situation of two or more metal oxides, if the resistivity that has than the metal oxide of coarsegrain is lower than 1 * 10 ⁸Ohm.cm is difficult to finish purpose of the present invention thereby just be difficult to fully increase carrier core resistivity.The metal oxide resistor (MOX) rate measuring method that herein relates to will be described later.

The resin carrier core that is used for dispersing metal oxides of the present invention preferably contains the metal oxide of 50-99wt%.If the content of metal oxide is lower than 50wt%, it is unstable that the charged ability of the magnetic carrier that obtains becomes, and especially in the low temperature environment.Magnetic carrier is charged, easily produces residual charge, makes easily to adhere at the magnetic carrier particle surface toward the fine tuning toner particles and the outer doping of its adding.Surpassing under the situation of 99wt%, the carrier granular that causes obtaining does not have full intensity, and easily causes in continuous imaging process carrier granular to break and discharge the difficulty of metal oxide fine particles from carrier granular.

As the embodiment of present invention further optimization, contain in the resin core of two or more metal oxides dispersions dispersing metal oxides therebetween, magnetic metal oxide preferably contains the 30-95wt% that accounts for total metal oxide.Preferred content is lower than 30wt% so that the high resistivity core to be provided, but causes carrier to apply little magnetic force, thereby causes carrier to adhere under certain conditions.When being higher than 95wt%, be difficult to increase core resistivity.

The resin carrier core that further preferably contains the dispersing metal oxides of metal oxide must so that the slug particle of the magnetic carrier with accurate size-grade distribution is provided, and prevent to discharge metal oxide particle from carrier through lipophilization treatment.Under the carrier slug particle situation that forms the containing metal oxide particle, in the polyreaction liquid system of the homogeneous solution that contains monomer and solvent, carry out direct polyreaction, undissolved polymerizable particle carrying out along with polyreaction in system forms gradually, meanwhile absorbs metal oxide particle.In this case, it is believed that the lipophilization reaction can demonstrate the function that promotes that all even high density of metal oxide particle absorbs.Polymer beads and to the preventing of particles coalesce can provide goods support distribution of particles more accurately.

Lipophilization reaction is preferred as the surface treatment that has coupling agent to participate in, silane coupling agent for example, titanate esters coupling agent or aluminium coupling agent, or surfactant.Preferably have the surface treatment that coupling agent participates in especially, for example silane coupling agent or titanate esters coupling agent.

Silane coupling agent can be with a hydrophobic grouping, an amino or an epoxy radicals.

The example of hydrophobic group comprises alkyl, alkenyl, haloalkyl, halogenated alkenyl, phenyl, halogenophenyl or alkyl phenyl.The kind that preferably has the silane coupling agent of hydrophobic group can be represented by following formula: R _mS _iY _n, wherein R represents alkoxy, Y represents alkyl or ethene, and m and n are the integers of 1-3.

The example that preferably has the silane coupling agent of hydrophobic group comprises: vinyltrimethoxy silane, vinyltriethoxysilane, vinyl triacetic acid base silane, methyltrimethoxy silane, methyl triethoxysilane, the isobutyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, the trimethyl methoxy silane, the n-pro-pyl trimethoxy silane, phenyltrimethoxysila,e, the n-hexadecyl trimethoxy silane, n-octadecane base trimethoxy silane, with vinyl three ('beta '-methoxy) silane.

Silane coupling agent with hydrophobic group also can be selected from vinyl trichlorosilane, hexamethyldisilazane, trimethyl silane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, allyl phenyl dichlorosilane, benzyl dimethyl chlorosilane, bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane and CMDMCS chloromethyl dimethyl chlorosilane.

Example with amino silane coupling agent comprises: gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methoxyl diethoxy silane, N-beta-aminoethyl-gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyldiethoxysilane, N-beta-aminoethyl-gamma-amino propyl group methyl dimethoxysilane, γ-2-amino-ethyl-TSL 8330 and N-phenyl-TSL 8330.

Example with silane coupling agent of epoxy radicals can comprise: γ-epoxypropoxy methyldiethoxysilane, γ-epoxypropoxy triethoxysilane, and β-(3, the 4-epoxycyclohexyl) trimethoxy silane.

The example of titanate esters coupling agent comprises metatitanic acid isopropyl three isostearoyl esters, metatitanic acid isopropyl three (dodecyl) benzenesulfonyl, metatitanic acid isopropyl three (dioctylphyrophosphoric acid) ester, metatitanic acid isopropyl three (amino-ethyl-amino-ethyl) ester and metatitanic acid isopropyl-4-aminophenyl-sulphonyl-two (dodecyl benzene sulfonyl) ester.

The aluminium coupling agent can be an acetyl aluminum alkoxide diisopropyl hydrochlorate for example.

The magnetic carrier slug particle prepares by polyreaction, by with the dissolving of above-mentioned monomer and metal oxide particle or disperse to advance in the solvent and to wherein adding initiating agent or catalyzer and optionally adding surfactant or dispersion stabilizer has formed polymerization reaction system.In this case, solvent can comprise that wherein monomer is soluble material, but its polymkeric substance that constitutes adhesive resin is insoluble, along with precipitating of polyreaction.Such solvent object lesson can comprise: straight or branched aliphatic alcohol, for example methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, isobutyl alcohol, the tert-butyl alcohol, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, isoamylol, tert-pentyl alcohol, 1-hexanol, 2-methyl-1-pentene alcohol, 4-methyl-2-amylalcohol, 2-ethyl butanol, 1-enanthol, 2-enanthol, 3-enanthol, sec-n-octyl alcohol and 2-ethyl-1-hexanol; Aliphatic hydrocrbon, for example pentane, 2-methylbutane, normal hexane, thiacyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, normal octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methyl cyclopentane, methylcyclohexane, ethyl cyclohexane, to alkane in the Meng, and cyclohexyl; Aromatic hydrocarbon; Halogenated hydrocarbons; Ether compound; Aliphatic acid; Sulfocompound; And water.These solvents can use or mix use separately.

The example of operable dispersion stabilizer comprises: polystyrene, polyisobutylene acid methyl esters, phenol novolac resin, cresols novolac resin, styrene acrylic copolymer; Vinylic-ether polymer, for example polymethyl vinyl ether, poly-ethyl vinyl ether, poly-butyl vinyl ether and poly-IVE; Polyvinyl alcohol (PVA), polyvinyl acetate, Styrene-Butadiene, vinyl-vinyl acetate copolymer, polyvinylpyrrolidone, polycarboxylated styrene, Polyvinylchloride, polyvinyl acetal, cellulose, cellulose acetate, nitrocellulose, alkylated cellulose, hydroxyalkylation cellulose be Carboxymethyl Cellulose and hydroxypropyl cellulose for example, saturated alkyl vibrin, aromatic polyester resin, polyamide, polyacetal and polycarbonate resin.They can use separately or two or more mix use.

The polyreaction of above-mentioned monomer can be carried out in the presence of initiators for polymerization, and it can be the radical polymerization initiating agent.

Initiators for polymerization can comprise: the azo-type initiators for polymerization, for example 2,2 '-azo two-(2,2,2 the 4-methyl pentane nitrile), '-(azoisobutyronitrile), 1,1 '-azo two (cyclohexane-2-nitrile), 2,2 '-azo two-4-methoxyl-2,4-dimethyl-valeronitrile, azoisobutyronitrile; Amidine compound, for example 2,2 '-azo two (amino two propane of 2-)-dihydrochloride, 2,2 '-azo two (N, N '-dimethylene isobutyl amidine) and 2,2 '-azo two (N, N '-dimethylene isobutyl amidine); The peroxide type initiators for polymerization is benzoyl peroxide, methyl ethyl ketone peroxide, peroxide carbonic acid diisopropyl ester, cumene hydroperoxide, peroxidating 2 for example, 4-dichloro-benzoyl, and lauroyl peroxide; With persulfate type initiating agent, for example potassium persulfate, and ammonium persulfate, these initiating agents can use or mix use separately.

Comprise that the carrier slug particle that contains coagulating type phenolics can be by having under the base catalyst existence condition in containing metal oxide particle dispersion aqueous medium therebetween, polymerization phenol and aldehyde make.

The example of base catalyst comprises ammoniacal liquor, hexamethylene tetramine and diethyl triamine.

Can use chain-transferring agent in polyreaction, example comprises: halogenated hydrocarbons, as phenixin, carbon tetrabromide, acetate dibromo ethyl ester, acetate tribromo ethyl ester, dibromo ethylbenzene, ethylene dibromide and ethylene dichloride; The diazonium thioether; Hydrocarbon homolog, for example benzene, ethylbenzene, cumene; Mercaptan, for example uncle-dodecyl mercaptans and n-dodecane mercaptan; With disulfide, for example diisopropyl xanthogenic acid (diisopropylxanthogene) disulfide.

In the method for optimizing of preparation carrier slug particle, preferred monomers and solvent form homogeneous solution, and metal oxide particle has passed through lipophilization treatment.Further preferably above-mentioned composition was fully disperseed before polyreaction, then add catalyzer or initiators for polymerization, to cause this polyreaction, so that the accurate size-grade distribution of magnetic carrier slug particle is provided.After the polyreaction, the polymer beads that obtains for example, by vacuum drying with optionally through the classification processing, obtains narrower size-grade distribution with solvent cleaning, drying.Classification can be by using shaking screen or utilizing the multistage grader of inertial force, so that remove thin and thick powder part.

Can obtain by the magnetic carrier slug particle that applies aforementioned preparation with suitable coating according to magnetic coated carrier of the present invention.The preferred 0.1-10wt of coating rate, more preferably 0.3-5wt%.In the resin carrier of dispersion magnetic metal oxide of the present invention, this coating operation is preferably carried out like this, is 0.1-10 particle/μ m so that the metal oxide particle on carrier slug particle surface exposes density ², more preferably 0.5-5 particle/μ m is so that prevent that well carrier from adhering to and prevent that toner is excessive charged.

If coating rate is lower than 0.1wt%, the effect of coated carrier slug particle is low, thereby obtains the charged ability of low toner (that is, the lower ability that makes the toner electrification by friction), particularly after continuous imaging.If coating rate surpasses 10wt% on the other hand, the easy step-down of this flowability of carrier, thus obtain image inferior in the continuous imaging process on a large amount of paper.The method of determining carrier slug particle surface metal oxide particle exposure density will be described later.

The applicator material package is drawn together thermoplastic resin or thermosetting resin.The example of thermoplastic resin comprises: polystyrene resin, polyisobutylene acid methyl esters resin, copolymer in cinnamic acrylic ester, acryl resin, Styrene-Butadiene, the vinyl-vinyl-acetic ester multipolymer, vestolit, acetic acid vinyl ester resin, polyvinylidene fluoride resin, fluorocarbon resin, the perfluocarbon resin, the solvable perfluocarbon resin of solvent, polyvinyl alcohol (PVA), polyvinyl acetal, polyvinylpyrrolidone, petroleum resin, cellulose, cellulose acetate, nitrocellulose, methylcellulose, Carboxymethyl Cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, cellulose derivative, novolac resin, low molecular weight polyethylene, the saturated alkyl vibrin, polyethylene terephthalate, polybutylene terephthalate, the aromatic polyester resin is polyarylate for example, polyamide, polyacetal resin, polycarbonate resin, polyethersulfone resin, polysulfone resin, polyphenylens sulfide resin and polyether ketone resin.

The example of thermoset resin comprises: phenolics; phenol-formaldehyde resin modified; maleic resin; alkyd resin; epoxy resin; acryl resin; the unsaturated polyester (UP) that polycondensation reaction by maleic anhydride terephthalic acids-polyvalent alcohol forms; urea resin; melamine resin; urea-melamine resin; xylene resin; toluene resin; guanamine resin; melamine-guanamine resin; the acetylguanamine resin; glyptal resin; furane resin; silicone resin; the silicone resin of acryloyl group modification; epoxide modified silicone resin; the siloxane alkyd resin; polyimide; polyamide-imide resin; polyetherimide resin; and urethane resin.These resins can use or mix use separately.And thermoplastic resin can carry out vulcanizing treatment by mixing vulcanizing agent.

Magnetic coated carrier preferably by under floating or fluidized state to carrier slug particle spray coating resin solution so that form coat film on slug particle surface, or make by spray drying.This painting method is suitable for applying the resin slug particle that disperses magnetic carrier with thermoplastic resin.

Other painting method is included under the metal oxide existence condition, and under the shearing force effect, the solvent in the coated with resins solution evaporates gradually.

It is spherical basically that magnetic coated carrier according to the present invention is preferably designed to, and its shape is represented by the form factor SF-1 of 100-130 scope.If SF-1 surpasses 130, the developer that obtains has poor flowability, and the magnetic brush of shape inferior is provided, and makes to be difficult to obtain the high-quality toner image.The form factor SF-1 of carrier can measure, for example by amplify 300 times the field-emission scanning electron microscope (for example, " S-800 ", provide by Hitachikk) observe, at least 300 carrier granulars of random sampling, and by using image dissector (for example " Luzex3 " provided by Nireco K.k.) to measure the mean value of spheroid by following equation.

SF-1＝[(MXLNG) ²/AREA]×π/4×100

Wherein MX LNG represents the maximum gauge of carrier granular, and AREA represents the projected area of carrier granular.

For the magnetic that is used for magnetic carrier of the present invention, the preferred use applies 40-250emu/cm ³, more preferably 50-230emu/cm ³The magnetization, the low magnetic force magnetic carrier under 1 kilooersted condition respectively.Suitably select the magnetization of magnetic carrier according to the granularity of carrier.Though also be subjected to the influence of granularity, have the magnetization and surpass 250emu/cm ³Magnetic carrier easily on the developer sleeve, forms magnetic brush on the low-density development bar and comprise long and hard lug having, thereby easily cause on the toner image that obtains, scratch occurring, and developer damages in the continuous imaging process.Specifically, when mixing with the toner with core/shell structure that comprises the core that contains the low softening point material, the image shortcoming is coarse and real image irregular of medium tone image for example, because the deterioration of toner takes place especially easily.Be lower than 40emu/cm ³, magnetic carrier easily causes applying inadequate magnetic force, causes lower toner transportation performance, even and the fine powder of carrier partly be eliminated and toner also can take place adhere to.

Magnetic herein refers to the measured value that uses oscillating magnetic flux field pattern magnetic self recording apparatus (" BHV-30 " provided by Riken Denshi.k.k.).The actual conditions of measuring will be described later.

Average particle size (the D that is used for toner of the present invention ₄) be 1-10 μ m, preferred 3-8 μ m, and electrification by friction effect in order to produce, and do not have reversed charge to produce, with the repeatability that good latent image point is arranged, satisfactory preferred size distribute be toner particles contain at the most 20% have granularity at its number average particle size (D of half at most ₁) scope in the granule number that adds up, and contain at the most 10% have granularity at its average particle size (D of twice at least ₄) scope in the particle volume that adds up.In order to produce the toner that has improved frictional electrification ability and some repeatability, preferred toner-particle contains the 1/2D at the most that has of at least 15% quantity ₁The particle of granularity, further preferred 10% quantity at the most, and preferred 5% volume at the most has at least 2 times of D ₄The particle of granularity, further preferred 2% volume at the most.

If the average particle size (D that toner has ₄) surpass 10 μ m, make that the toner-particle that is used for developing electrostatic latent image is so big, even, can not realize the development of faithful to sub-image so that the magnetic force of magnetic carrier is lower.When through static printing, cause a large amount of toners to disperse.If D ₄Be lower than 1 μ m, toner causes the difficulty of powder-processed characteristic.

If have to number average particle size (D mostly ₁) the particle quantity that adds up surpass 20%, the electrification by friction of thin like this toner-particle can not produce satisfactorily, cause difficulty, for example wide frictional electrification toner distributes, make charged failure (reversed charge appearance), and because the location of toner granularity, granularity changes during continuous imaging.If the granularity that has is twice average particle size (D at least ₄) the particle quantity that adds up surpass 10% volume, with the metal oxide electrification by friction difficulty that becomes, it is difficult that the reproduction of sub-image loyalty becomes.The toner size-grade distribution can be measured, for example by using laser scanning type particle size distribution measurement device (for example, " CIS-100 " provided by GALIA company).

Be used for the granularity of toner granularity of the present invention and size-grade distribution and magnetic carrier and distribute closely related.When the number average particle size that has when magnetic carrier was 15-50 μ m, the average particle size of preferred toner was 3-8 μ m, and toner and carrier all have narrow size-grade distribution, but so that provided good charging property and high quality graphic.

Be used to simultaneously develop and cleaning systems or reduce under the situation of imaging system of clearer at developer of the present invention, the form factor SF-1 of preferred toner is 100-140, by direct polymerisation process, the remaining simultaneously residual monomer of 1000ppm content (Mres) at the most makes.

An example that reduces cleaner system like this can make an explanation.Use together can electronegative photosensitive part with can the situation of electronegative toner under, the transfer member by positively charged is transferred to the toner image that develops on transfer printing (reception) material.In this case, according to transfer materials and the relation between the characteristic (thickness, resistivity and specific inductive capacity) of the image area that forms on the transfer materials, the charged polarity of transfer printing residue toner does not wait from the positive pole to the negative pole.Even but transfer printing residue toner becomes positively charged, in the charged process of photosensitive part, the residue toner is even negative electricity on the area also by electronegative charging unit.Therefore, under the pattern situation of oppositely developing, allow remaining toner partly develop so that be retained in the there, but under the development field action, attracted to the parts of bearing developer, thereby be excluded at the residue toner of dark-part at light.

As our result to the big quantity research of different toners and carrier, development and cleaning systems or the performance that reduces the developer in the imaging system of clearer imaging characteristic continuously for example at the same time, with the magnetic force of carrier and in toner residual monomer content be closely connected.The effect of carrier was described in front.For toner, residual monomer content has following influence.For example, comprise mainly that at toner residual monomer is contained in the toner-particle under the situation of adhesive resin, pigment and charge control agent, and influence near the thermal characteristics the toner vitrifying point.This monomer is a LMWC, so that toner-particle is played plasticization.On the other hand, on its adhesive phase, receive photochemical action through the toner of discharge or the toner of handling through corona stream.For example the monomer chain in the resin can make it to produce resin degradation products and lower-molecular-weight component or on the contrary, this resin degradation products can promote polyreaction.On the other hand, the residual monomer in the toner is activated by the photochemical action of the charging unit of photosensitive part.

As mentioned above, toner contains active low-molecular-weight composition, antagonism mutually between them, and the charge control agent that contains in the toner-particle also is a kind of compound of emitting relatively strongly and absorbing electronic action that has.The combination for these factors is also clarified fully, but for example toner is mobile and the change gradually of charging property for the existence promotion toner-particle surface nature of residual monomer.

For all these reasons, this toner preferably has the low residual monomer content of 1000ppm at the most, more preferably 500ppm at the most, and further preferred 300ppm at the most is so that the continuous imaging characteristic and the qualitative picture that provide.The method of determining residual monomer content in the toner will be described later.

This toner preferably has the shape factor SF-1 of 100-140, more preferably 100-130.Effective especially in development and cleaning systems or the minimizing clearer imaging system so at the same time.The form factor SF-1 of toner can record, for example by field-emission scanning electron microscope (" S-800 ", provide by HitachiK.K.), the toner image of at least 300 amplifications of random sampling (amplifying 300 times), and, calculate according to following formula to image dissector (" Luzex3 " provided by Nireco K.K) input image data:

SF-1＝[(MXLNG) ²/AREA]×π/4×100

Wherein MX LNG represents the maximum gauge of toner-particle, and AREA represents the projected area of toner-particle.

Form factor SF-1 represents sphere, and SF-1 means and spherical different uncertain shapes above 140.If the SF-1 that toner has surpasses 140, toner produces by photosensitive part easily to the lower toner transfer efficiency of transfer materials and leave over a lot of residue toners on photosensitive part.About this point, the toner-particle by polymerisation process directly prepares can have the form factor SF-1 near 100, and has smooth surface.Because smooth surface, the phenomenon that occurs thick and fast at irregular toner-particle surface field can be alleviated, and the transfer efficiency and the transferring rate of growth are provided.

Be used for toner of the present invention and preferably have core/shell structure (or pseudo-gums capsule structure).The toner-particle with core/shell structure like this is endowed the antistick characteristic of high-quality and does not weaken the low-temperature fixing ability.Compare with the toner of bulk polymerization with coreless structure, the toner with core/shell structure that the shell of the core of a kind of low softening point material of its inner sealing that forms by polyreaction makes can easier post-processing stages after polyreaction be removed residual monomer from toner-particle.

Preferred this core mainly comprises the low softening point material.The low softening point material preferably includes a kind of compound, and on the thermal absorption curve that records according to ASTM D3418-8, its main peak is presented in the 40-90 ℃ of temperature range.If this thermal absorption main peak temperature is lower than 40 ℃, this low softening point material easily demonstrates low self-adhesion, causes weak departing from property of high temperature resistance.On the other hand, if the thermal absorption peak height in 90 ℃, the toner that obtains easily provides high fixing temperature.And, comprising by direct polymerisation process that particle forms and carry out polyreaction in aqueous medium prepares under the situation of toner-particle, if thermal absorption main peak temperature height, form in aqueous medium in the process of particle at the monomer composition that contains the low softening point material, the low softening point material easily precipitates.

The measurement of thermal absorption peak temperature realizes by using scanning calorimeter (" DSC-7 " provided by Perkin-Elmer company).To the correction of this equipment detector temperature, can be based on the fusing point of indium and zinc, and the correction of heat is based on the melting heat of indium.Sample is placed an aluminum dish, a blank panel also is set in contrast, being used at rate of temperature rise is measurement under the condition of 10 ℃/min.Under 30～160 ℃ of temperature ranges, measure.

The low softening point examples of substances can comprise: the derivant of wax, amide waxe, higher fatty acid, ester type waxes and these waxes that paraffin, polyolefin-wax, Fischer-Tropsch building-up process obtain and its grafting/or the segmented copolymer product.

The preferred addition of low softening point material is based on the 5-30wt% of toner-particle weight.

Toner-particle can suitably mix with outer doping, if toner-particle applies with so outer doping, cause the external application adjuvant to be present between the toner-particle and toner and carrier between, thereby the flowability and the life-span of the developer that has improved are provided.

Outer doping for example comprises the powder of following material: metal oxide, for example aluminium oxide, titanium dioxide, strontium titanates, cerium oxide, magnesium oxide, chromium oxide, tin oxide and zinc paste; Nitride, for example silicon nitrile, silicon nitride, carbonide, for example silit; Slaine is calcium sulphate, barium sulphate and calcium sulphate for example: aliphatic acid slaine, for example zinc stearate and calcium stearate; Carbon black, silica, teflon, Kynoar, polyisobutylene acid methyl esters, polystyrene and silicone resin.These powder preferably have number average particle size (D1) 0.2 μ m at the most.If particle mean size surpasses 0.2 μ m, cause toner to have lower flowability, because inferior the development and transferring properties caused lower picture quality.

Outer doping addition like this is the 0.01-10 weight portion, and preferred 0.05-5 weight portion is based on the toner-particle of per 100 weight portions.Outer doping like this can add separately or two or more mix adding.Preferred so outer doping has been carried out hydrophobization and has been handled (promptly must handle through hydrophobic property).

The BET method that absorbs according to nitrogen records, and outer doping preferably has 30m at least ²The specific surface area of/g, particularly 50-400m ²The specific surface area of/g.

Toner-particle and outer doping can by blender for example the Henschel mixer mix mutually.The toner that obtains can mix with carrier granular to form two-component developer.Though depend on the concrete developing method of use, this two-component developer preferably contains 1-20wt%, more preferably the toner of 1-10wt%.Toner in two-component developer preferably has the triboelectric charge of 5-100 μ c/g, more preferably 5-60 μ c/g.The method of measuring the toner triboelectric charge will be described later.

Toner-particle can cool off this melt kneading product by for example when adhesive resin, colorant and other internal additives carry out melt kneading, pulverizes and the method for classification prepares.The example of toner binder resin comprises polystyrene; The styrene polymer derivant, for example poly-to chlorostyrene and tygon toluene; Styrol copolymer, styrene-right-chloro-styrene copolymer for example, styrene-ethylene base toluene multipolymer, styrene-ethylene base naphthalenedicarboxylate copolymer, copolymer in cinnamic acrylic ester, styrene-methacrylate ester copolymer, styrene-α-chlorine methylmethacrylate multipolymer, styrene-acrylonitrile copolymer, styrene-ethylene ylmethyl ketone copolymers, Styrene-Butadiene, styrene-isoprene multipolymer and styrene-acrylonitrile indene copolymer; Polyvinylchloride, phenolics, phenol-formaldehyde resin modified, maleic acid resin, acryl resin, methacrylic resin, acryl resin, methacrylic resin, polyvinyl acetate, silicone resin, be selected from the vibrin that the monomer of aliphatic polyol, aliphatic dicarboxylic acid, aromatic dicarboxilic acid and aromatic diol and xenol constitutes; Urethane resin, polyamide, polyvinyl butyrate, terpene resin, coumarone-indene resin and petroleum resin.Styrene resin and vibrin are particularly preferred.

As another kind of method for optimizing, toner-particle can directly be produced toner-particle by for example suspension polymerization method, the dispersion polymerization method that is used for directly producing toner-particle is to carry out at the water-containing organic solvent medium, wherein monomer is solvable, but the product polymkeric substance is soluble, or the emulsion polymerization method, represents with the soap-free polymerization reaction method, by existing under the situation, directly prepare toner-particle at water-soluble polarity initiators for polymerization.

Suspension polymerization under normal pressure or condition of high voltage is particularly preferred for the present invention, because the SF-1 of the toner-particle that obtains can easily be controlled in the scope of 100-140, and to have accurate size-grade distribution and average particle size be that the fine tuning toner particles of 4-8 μ m can relatively easily obtain.

Can obtain to contain in the toner-particle hermetically-sealed construction of low softening point material by a kind of method.The low softening point material is chosen to have polarity in aqueous medium in this method, and its polarity is lower than the polarity of main monomer composition, and low amounts of resin or monomer with high polarity more add wherein, so that the toner-particle with core shell structure to be provided.By changing kind and the quantity almost do not have water miscible inorganic salts or to play the spreading agent of protective colloid action, by controlling mechanical appointed condition, rotor peripheral speed for example, the quantity of passage and stirring condition comprise the shape of stirring scratch board; And/or the shape of control container and in aqueous medium solids content, toner-particle granularity and its distribution can Be Controlled.

Toner-particle shell resin can comprise styrene-(methyl) acrylate copolymer or Styrene-Butadiene.The monomer of these resins can be used under the situation of the direct production toner-particle by polymerisation process.

The object lesson of such monomer comprises: styrene and its derivant be styrene for example, adjacent-,-or p-methylstyrene and or to ethyl styrene; (methyl) acrylate is (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl propionate, (methyl) butyl acrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) dodecyl acrylate, (methyl) 2-EHA, (methyl) stearyl acrylate acyl ester, (methyl) acrylic acid behenyl alcohol ester, (methyl) dimethylaminoethyl acrylate and (methyl) acrylic acid lignocaine ethyl ester for example; Butadiene; Isoprene; Cyclohexane; (methyl) vinyl cyanide and acrylamide.

These monomers can be separately or two or more mix and use so that theoretical vitrifying point (Tg) to be provided, be described in " polymer handbook " second edition, III-pp.139-192 is (by JohnWiley ﹠amp; Sons company provides) this theory vitrifying point is 40-75 ℃.If theoretical vitrifying point is lower than 40 ℃, easily cause the toner-particle that obtains to have lower storage-stable and permanance.On the other hand, if theoretical vitrifying point surpasses 75 ℃, the fixing temperature of toner-particle increases, thereby the color toner particle is easy to have inadequate color mixture characteristic separately, especially under the situation of full color imaging.

The molecular weight distribution of the solvable content of THF of shell resin can record by following gel permeation chromatography (GPC) in the present invention.Have under the toner-particle situation of core/shell structure, this toner-particle is by Soxhlet extractor, with toluene extracting 20 hours, then steams solvent toluene to obtain extract.Will be wherein low softening point substance dissolves and the undissolved organic solvent of shell resin (for example chloroform) join in the extract, fully clean and obtain the residue product with this.This residue product is dissolved in the tetrahydrofuran (THF), must have the filter of anti-solvent membrane of aperture 0.3 μ m to filter by apparatus, obtains sample solution (THF solution).This sample solution is injected into the GPC equipment (" GPC-150C " that has used post A801,802,803,804,805,806 and 807 (being made by Showa Denkok.k) combination, provide by Waters company), the calibration curve that uses the monodisperse polystyrene standard sample to obtain is determined molecular weight and its molecular weight distribution of sample.

The number-average molecular weight (Mn) of the solvable THF component of shell resin is preferably 5 among the present invention, 000-1, and 000,000, weight-average molecular weight (Mw) is preferably 2-100 with the ratio (Mw/Mn) of Mn.

Low softening point compound in the sealable outer resin (layer) especially preferably adds polar resin.The preferred embodiment of this polar resin comprises styrene-(methyl) acrylic copolymer, acrylic acid-maleic acid, saturated polyester resin and epoxy resin.Polar resin does not especially preferably contain and can or constitute the unsaturated group of the reactive vinyl monomer of outermost resin with the shell resin bed.This is because if polar resin contains unsaturated group, unsaturated group can with vinyl monomer generation cross-linking reaction, make that like this molecular weight of shell resin bed is very big because the blend of colors poor-performing, this is harmful to.

Can further carry out surface-coated by polymerization, thereby make it have outmost shell resin bed toner-particle with shell mechanism.

In order further to improve pick resistance, preferably outmost shell resin bed is designed to have the high glass transition temperature of glass transition temperature than the outermost resin under outmost shell resin bed, but and can not to its anchorage produce carry out in the dysgenic scope crosslinked.

The method that is used to prepare this shell resin bed be there is no special restriction, but example comprises:

(1) in the final stage of aforementioned polyreaction or finished aforementioned polyreaction, that selectivity is contained color resin, charge control agent or dissolving or decompose monomer component in wherein crosslinking chemical, make in the adding polymerization reaction system and under the initiation of initiators for polymerization, carry out polyreaction then by polymerizate particle absorption monomer component.

(2) will contain emulsion polymerized particles that the monomer component of polar resin, charge control agent or crosslinking chemical forms or soap-free polymerization particle by selectivity and add in the polymerization reaction system and be flocked on the existing aggregated particles, optionally make its firm attachment by heating.

(3) will be with mechanical means by the emulsion polymerized particles of appointing the monomer component contain polar resin, charge control agent or crosslinking chemical to form or soap-free polymerization particle securely attached on polymerizate that has formed in the drying system or the toner-particle.

The used colorant of the present invention comprises black colorant, yellow colorant, fuchsin colorant and ultramarine colorant.

The example of non magnetic black colorant comprises: carbon black and Huang/fuchsin/ultramarine colorant as follows mix, are the colorant of black.

The example of yellow colorant comprises: condense azo-compound, different three hydrogen oxindole compounds, anthraquinone compounds, azo-metal complex, methylidyne compound and aromatic radical amide compound.Concrete preferred embodiment comprises: C.I. pigment Yellow 12,13,14,15,17,62,74,83,93,94,95,109,110,111,128,147 and 168 and 180.

The example of fuchsin colorant comprises: condense azo-compound, diketone pyrroles pyrroles (diketopyrr-olpyrrole) compound, anthraquinone compounds, quinacridine compound, basic dyestuff color lake compound, naphthol compound, benzimidazole compound, thioindigo compound are with the perylene compound.Concrete preferred embodiment comprises: C.I. paratonere 2,3,5,6,7,23,48: 2,48: 3,48: 4,57: 1,81: 1,144,146,166,169,177,184,185,202,206,220,221 and 254.

The example of ultramarine colorant comprises: copper phthalocyanine compound and derivant thereof, anthraquinone compounds and basic dyestuff color lake compound.Concrete preferred embodiment comprises: C.I. pigment blue 1,7,15,15: 1,15: 2,15: 3,15: 4,60,62 and 66.

These colorants can use separately, use or use with the solid solution form with the form of mixtures of two kinds or more of colorants.Consider the permanance of color and luster, color saturation, colour, permanance, product ohp film and the dispersiveness in toner-particle, can suitably select above-mentioned dyestuff.The consumption of above-mentioned dyestuff is 1-20 weight portion/100 weight portion adhesive resins.

Used charge control agent comprises known charge control agent among the present invention.Preferred charge control agent is a charge control agent colourless, that have higher charging rate and have the performance that can stablize the charge volume that keeps regulation.When utilizing direct polyreaction to prepare toner-particle of the present invention, charge control agent is preferred a kind of especially not to have polyreaction to cause performance and charge control agent that be not contained in soluble constituent in the aqueous medium.

Charge control agent can be those positive types or negative type.The instantiation of positive charge control agent comprises: the intermetallic compound organic acid, as salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid and these sour derivants; Have the polymkeric substance (borate compound, carbamide compound, silicon compound) and the calicene (calixarene) that comprise sulfonic acid or carboxylic acid side chain.The instantiation of positive charge control agent comprises: quaternary ammonium salt; Polymkeric substance with the side chain that contains quaternary ammonium salt; Guanidine compound and imidazolium compounds.

The consumption of charge control agent is preferably the adhesive resin of 0.5-10 weight portion/100 weight portions etc.But for the used toner-particle charge control agent of the present invention is not necessary component.

The example that can be used for the initiators for polymerization of direct polymerization comprises: the azo-type initiators for polymerization, as 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azobis isobutyronitrile, 1,1 ' azo two (cyclohexanes-2-nitrile), 2,2 '-azo two-4-methoxyl 2, the 4-methyl pentane nitrile, azobis isobutyronitrile; With the peroxide type initiators for polymerization, as benzoyl peroxide, methyl ethyl ketone peroxide; Peroxidating carbonic acid diisopropyl ester, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide.

The addition of initiators for polymerization changes according to the degree of finishing polyreaction.The general consumption of initiators for polymerization is the 0.5-20%wt of polymerisable monomer weight.According to the difference of used polymerization process, some variation of initiators for polymerization can be used initiators for polymerization separately, and perhaps when half life temperature was relevant with 10 hours, form that can potpourri is used.In order to control the molecular weight of mixture of reaction products resin, also can add crosslinking chemical, chain-transferring agent, polymerization inhibitor etc.

Preparing by the suspension polymerization that utilizes dispersion stabilizer in the process of toner-particle, preferably in aqueous dispersion medium, using inorganic or/or organic dispersion stabilizer.The example of inorganic dispersant stabilizing agent comprises: the example of tricalcium phosphate, magnesium phosphate, aluminum phosphate, trbasic zinc phosphate, lime carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminium hydroxide, calcium silicate, calcium sulphate, barium sulphate, bentonitic clay, silicon dioxide and aluminium oxide, organic dispersion stabilizer comprises: polyvinyl alcohol (PVA), gelatin, methylcellulose, methylhydroxypropylcellulose, ethyl cellulose, sanlose, polyacrylic acid and salt thereof and starch.The consumption of these dispersion stabilizers is preferably part not polymeric monomer intermixture of 0.2-10 weight portion/100 in aqueous dispersion medium.

When using the inorganic dispersant stabilizing agent, can directly use commercially available product, also can in dispersion medium, form stabilizing agent to obtain fine particle in the scene.For example under the situation with the tricalcium phosphate used as stabilizers, under vigorous stirring, sodium phosphate aqueous solution and calcium chloride water are fully mixed, in aqueous medium, generate the tricalcium phosphate that is applicable to suspension polymerization.In order to make dispersion stabilizer energy fine dispersion, can use the surfactant of 0.001-0.1%wt in the potpourri, thereby improve the predetermined function of stabilizing agent.The embodiment of surfactant comprises: neopelex, sodium tetradecyl sulfate, pentadecyl sodium sulphate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate and calcium oleate.

Direct polymerization below toner-particle of the present invention is also available is made.Low softening point material (releasing agent), colorant, charge control agent, polymerization initiator and other optional adjuvant are added in the polymerisable monomer, utilize homogenizer or super ion dispersing apparatus that its uniform dissolution or dispersion are formed polymerisable monomer component, in containing the dispersion medium of dispersion stabilizer, make its dispersion and form particle by stirrer, homo-mixer or homogenizer.Under this condition, by control stirring extent and/or mixing time, the desirable particle size of the particle diameter toner-particle of the droplet of polymerizable monomer component.Continue to stir in addition, make the particle of the polymerizable monomer component that formed keep graininess, and prevent that particle from depositing.The temperature of polymerization reaction take place is minimum to be 40 ℃, is generally 50-90 ℃.Last stages temperature in polymerization can be raised.Also can be or after finishing polyreaction one one of aqueous system is distilled in the last stages of polymerization, remove not polymerization (yet-polymerized) part in the polymerisable monomer and in the step of fusing toner, can produce the secondary product of stink.After reaction is finished, the toner-particle that makes is cleaned, filters, dry then.In suspension polymerization, be preferably 300-3000 weight portion/100 weight parts monomers components as the consumption of the water of dispersion medium.

Also toner resin can be classified in order to control size distribution.For example, the preferred multilayer separation classifier of having used wall attachment effect that utilizes is produced the toner particle with desired particle size distribution effectively.

For example, available developing apparatus is as shown in Figure 1 implemented developing method of the present invention.Preferably at magnetic brush made from developer and latent image bearing part, as be used for the photosensitive drum 3 of alternating electric field, develop on the position contacting.Preferably reagent bearing components (development sleeve) 1 is placed on such position, making has the gap B of a 100-1000 μ m between it and the photosensitive drum 3, adheres to prevent carrier, and improves the repeatability of picture point.If the gap is narrower than 100 μ m, just can not provide enough developers, make image color low.If 1000 μ m are wider than in the gap, the magnetic line of force that is sent by development utmost point S1 spreads apart and makes that the concentration of magnetic brush is low, cause picture point repeatability difference and the carrier both constrains power of adhering to for carrier a little less than.

The crest voltage of preferred alternating electric field is the 500-5000 volt, and frequency is 500-10000Hz, and preferred 500-3000Hz carries out suitable selection according to process.Therefore can suitably select waveform, as triangular wave, square wave, sine wave or the waveform that obtains by the adjustment duty factor.Especially when reducing the toner granularity, preferably reduce component of voltage (V forward) load, this voltage is used to make toner to be transferred to the image-bearing element.If the voltage that applies is lower than 500V; Be difficult to obtain enough image colors, the photographic fog toner under the certain situation in non-image areas just reclaims unsatisfactorily.If voltage is higher than 5000V, latent image can be disturbed by magnetic brush, causes the quality of image lower under some situation.

By using two component type developers of the present invention, can on light activated element, utilize lower elimination photographic fog voltage (V is reverse) and lower former charging voltage, the term of life that can prolong light activated element like this.V oppositely is preferably maximum 200V, most preferably is maximum 180V.

Preferably utilize the contrast potential of 200-500V to produce enough image colors.Frequency can influence developing process, and the frequency that is lower than 500Hz can cause electric charge to inject carrier, and so in some cases, interference just causes picture quality lower with sub-image because carrier adheres to.When frequency is higher than 10000Hz, toner just is difficult to along with the electric field motion, and this just causes poor image quality.

In developing method of the present invention, the magnetic brush on the sleeve that develops the color preferably has the contact width C (seam develops) of a 3-8mm with photosensitive drum 3, and this is to put repeatability in order to form enough image colors with good, and does not have carrier to adhere to.Seam C is between 3-8mm, just can produce enough image colors and good some repeatability if develop.If be wider than 8mm, then developer can fill up so that cause equipment out of service, is difficult to prevent that carrier from adhering to.Can regulate the seam C that develops by changing the distance A between development regulating element 2 and the development sleeve 1 and/or changing the gap B that develops between cover 1 and the photosensitive drum 3.

Coloration method of the present invention is particularly suitable for being used in the full-colour image formation method, productive capacity to shadow tone in this method is considered more, when developer of the present invention was used for digital latent image, the some latent image can true reappearance, and does not have the ill-effect of magnetic brush and can not upset electrostatic image.

The developer of the application of the invention can be found not only at initial period picture quality height, and also can prevent image quality decrease in the formation image continuously because the developer in the developing apparatus is applied the inhibition shearing force on volume copying paper.

The used reagent bearing components of the present invention preferably satisfies surface appearance condition as shown in Figure 3: 0.2 μ m≤center line mean roughness (Ra)≤0.5 μ m, 10 μ m≤average thickness inequality distance (Sm)≤80 μ m, 0.05≤Ra/Sm≤0.50

Parameter Ra and Sm refer to JIS B0601 (with ISO 468) definition and with following formula calculate center line mean roughness and average uneven thickness distance: $\mathrm{Ra}=(1/\underset{-}{1}){\∫}_0^{\underset{-}{1}}\left|f\left(x\right)\right|\mathrm{dx}$ $\mathrm{Sm}=(1/n)\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Smi}$

If Ra is lower than 0.2 μ m, the developer transfer capability of reagent bearing components is not enough, and this makes and particularly can cause image color inhomogeneous in the consecutive image forming process.If Ra surpasses 5 μ m, the developer transfer capability can be fine, but it is too big to the restraint that developer transmits the stable region to regulate scraper plate, because extra friction causes the toner particle surface to be damaged, this just causes picture quality to reduce in the consecutive image forming process.

If Sm surpasses 80 μ m, developer is painted difficulty on developer merit element, and result images concentration is low.This mechanism is not also understood fully, consider the phenomenon that developer slides on reagent bearing components takes place on the transmission stable region of reagent bearing components, suppose in the inhomogeneity gap too big and the power on the block of acting on surpasses and acts under the situation of the dyeing power between toner-reagent bearing components, developer is pressed into block densely, and the image color that is produced is low.Therefore if Sm is less than 10 μ m, then many inequalities become littler than the particle mean size of developer on reagent bearing components, will select to enter the granularity of the developer of concave surface, and this just causes the fusing of developer fine powder composition bonding.And and be not easy to prepare reagent bearing components.

Further consider aforementioned some, calculate in the convex height on the reagent bearing components and inequality gap the inequality slope (=f (Ra/Sm) preferably satisfies following relation: 0.5 〉=Ra/Sm 〉=0.05, more preferably satisfied 0.3 〉=Ra 〉=0.7.

If Ra/Sm is less than 0.05, the toner colouring power of reagent bearing components is too little, it is painted to make that toner is difficult on reagent bearing components, and can not control the transport process that is sent to the definite district of developer, therefore is easy to cause the image color inequality.If Ra/Sm surpasses 0.5, the toner that enters concave surface does not mix with other toner in cyclic process, and it is bonding therefore to be easy to take place the toner fusing.

Here the value of Ra of Jie Shaoing and Sm is by using contact-type surface roughness instruments (" SE3300 ", Kosaka Kenkyuaso k.k. manufacturing) JIS-B0601, in the measurement length of 2.5mm, optional several points are measured on the developer load-carrying unit.

Reagent bearing components (sleeve) can form predetermined surfaceness, as, with the sand grains sandblast that contains irregularly shaped or regular shape particulate, grind (promptly vertical direction) with sand paper along the direction parallel with the developer direction of transfer with axle, form surface irregularity at circumferencial direction, handle with chemical method, use resinous coat, formed the resin protrusion then.

The used reagent bearing components of the present invention is made up of known substance, and the example comprises: metal, as al stainless steel and nickel; With the coated metal of carbon, resin or resilient material; Resilient material, as natural rubber, silicon rubber, urine gastral cavity ameripol, neoprene, butadiene rubber and chloroprene rubber, their right and wrong are foamed, foamed or spongiform, also can use carbon, resin or resilient material coated again.

The used reagent bearing components of the present invention can be cylindrical or the plain film shape.

In order to form more clearly full-colour image, preferably use four developing apparatuses respectively for pinkish red, dark blue, yellow and black four kinds of colors, form black image at last.

The image forming apparatus that is suitable for implementing full-colour image formation method of the present invention with reference to 4 couples in figure describes.

Color electric photographic equipment among Fig. 4 is divided into biography printed material material (recording chart) parts I roughly, and it comprises transfer drum 315, and (the right of Fig. 4) extends to the partly middle of equipment critical piece 301 from the right; The latent image that is installed near transfer drum 315 places forms parts II and developing apparatus III (promptly rotating developing apparatus).

It is composed as follows to transmit transfer materials parts I.On the right wall of the critical piece 301 of equipment, an opening is arranged, demountable supply transfer materials pallet 302 and 303 is installed in opening part, form the part of an extended part.Paper feeding (transfer materials) roller 304 and 305 is contained in the upper right side of pallet 302 and 303.For make paper supply roller 304 and 305 and the transfer drum 315 of on the left side can rotate together by the direction of arrow A, paper feed roller 306 has been installed, paper supply guides 307 and paper supply guides 308.Along rotation direction, press butt joint roller 309 from top to bottom, brake block (glipper) 310, the order of transfer materials separating charger 311 and disengaging pawl 312 is positioned on it on position of contiguous transfer roll 315 peripheries.

Transfer printing charger 313 and transfer materials separating charger 314 are arranged in the transfer drum 315.A part of twining the transfer drum 315 of transfer materials has transfer paper (figure is provided with demonstration), also has transfer materials static close attachment in the above.In the upper right side of transmitting drum 315, with conveyor-belt apparatus 316 be contained in disengaging pawl 312 near, fixing device 318 is contained in end (the right) position of the direction of transfer of conveyor-belt apparatus 316.Be equipped with one one one in the bottom of fixing device and stretch out main equipment 301 and dismountable paper delivery pallet 317.

It is composed as follows that latent image forms parts II: the photosensitive drum as the latent image load-carrying unit that rotates of the direction of arrow (as, OPC photosensitive drum) is installed on its circumferential surface and the contacted position of transfer drum 315 circumferential surfaces as shown in the figure.Be generally on the top or position of photosensitive drum 319, by the rotation direction of photosensitive drum discharge charger 320, scavenge unit 321 and former charger 323 be installed in proper order from top to bottom near photosensitive drum 319.In addition, will comprise that the reflection unit exposure device as laser instrument 324 and mirror 325 is installed in and can forming on the position of electrostatic latent image on the external peripheral surface of photosensitive drum 319.

Rotation developing apparatus III is constructed as follows.Rotary shell (below be called " rotating element ") 326 is installed in the reverse direction of photosensitive drum 319.In rotating element 326, four developing apparatuss of equidistant installation on radial direction make the static developing as seen (promptly to develop) on the external peripheral surface of photosensitive drum 319.Four developing apparatuss comprise yellow developing apparatus 327Y, magenta developing apparatus 327M, mazarine developing apparatus 327C and black developing device 327BK.

Describe in proper order according to the whole operation of panchromatic mode aforesaid image forming apparatus.When photosensitive drum 319 rotates in the direction of arrows, with former charger 323 chargings of drum 319 usefulness.In Fig. 3 equipment, the peripheral speed of each element (below be called " operating speed "), particularly the speed of photosensitive drum 319 is at least 100mm/sec (as 130-250mm/sec).After 323 chargings of former charger, the laser sensitization that photosensitive drum 319 has been modulated by the yellow image signal of original paper 328 uses the yellow developing apparatus 327Y by rotating element 326 location to develop then, forms yellow toner image.

Transfer materials (as blank sheet of paper) is through paper feeding guides 307, and paper-feed roll 306 and paper feeding guides 308 are braked piece (glipper) 310 and regularly take out, and is wrapped on the transfer drum 315 by butt joint roller 309 with the electrode that docks the installation of roller subtend.Transfer drum 315 rotates synchronously in arrow A direction and photosensitive drum 319, and the yellow toner image that is formed by yellow developing apparatus is transferred on the transfer materials on the spherical surface that photosensitive drum 319 under the effect of transfer printing charger 313 and transfer roll 315 are in contact with one another.The transfer drum 315 that remains in operation comes a kind of color under the transfer printing (magenta among Fig. 4).

On the other hand, with discharge charger 320 photosensitive drum 319 is removed electric charge.With removing scraper plate or scavenge unit 321 cleanings, with main charger 323 chargings, carry out imaging exposure based on the pinkish red picture signal of back then and form corresponding electrostatic latent image again.When forming electrostatic latent image based on the imaging of product red signal exposure on photosensitive drum 319, rotation rotating element 326 makes pinkish red developing apparatus 327M be positioned at a developing location Bed linens red color tone toner that has pre-determined to develop.Dark blue and black are repeated aforesaid method, finish the transfer printing of four colour toners images.Then with charger 322 and 314 image discharges (removing electric charge) with the development of four looks on the transfer materials, discharge from brake block (glipper) 310, by disengaging pawl 312 with it by separating with transfer drum 315, deliver to fixing device 318 by travelling belt 316 then, heating and pressurizing is with four colour toners image fixing in 318.So just, finished a series of panchromatic duplicating or image and formed operation, formed set full-colour image on the surface of transfer materials.

Also can immediately each color toner image be transferred on the transition transferring member, be transferred to then on the transfer materials image fixing.

The fixation rate of fixing device is than the peripheral speed (as 160mm) low (as 90mm/sec) of photosensitive drum.This is to provide enough heats for the uncertain image of giving two to four toner layers melt-blended.Use like this than the low speed of developing and carry out photographic fixing the change the line map heat of picture of toner of increasing supply.

Introduce the method for testing [carrier granularity] of various performances below

From sample carrier, randomly draw at least 200 particles (diameter is 0.1 μ m or bigger), amplify 100-500 with scanning electron microscope and doubly take a picture.To (obtain) on the flat board that photo is placed on computing machine links to each other that amplify from Wacom Co., the manual operations palm is measured the horizontal FERE diameter of each particulate, with this as granularity, thereby obtained comprising the base size-grade distribution of standard error σ and number average particle size (Dn), can calculate half (base ratio of≤1/2Dn%) particulate that size mostly is number average particle size most with these data.[magnetic of magnetic carrier]

Measure with oscillating magnetic flux field pattern magnetic property self-recording device (" BHV-30 " buied by Riken Denshik.k.).Magnetic carrier is placed on measures its magnification in the external magnetic field of 1 kilooersted.The magnetic carrier powdered sample is contained in the round shaped grain shape plastic housing tightly prevents that carrier particles moves at the volley.Record magnetic moment in this state, and obtain magnetic induction density (emu/g) divided by actual example weight of packing into.Use dry type autochroma instrument (" Accupic 1330 " are buied by SimazuSeisakusho k.k.) to measure the real density of carrier particles then, multiply by the magnetic induction density (emu/cm that real density obtains each volume with magnetic induction density ³).[measurement of carrier resistivity]

Measure the resistivity of carrier or carrier core with equipment (battery) E of Fig. 2.Equipment E is equipped with lower electrode 21, upper electrode 22, insulator 23, amp gauge 24, voltage meter 25, voltage regulator device 26 and guide ring 28.With sample carrier 27 chargings of battery E with about 1g, electrode 21 and 22 is connected, form voltage betwixt, measure electric current at that time, the calculated resistance rate.If magnetic carrier is pulverous, will note avoiding being compacted the variation of the resistivity that causes owing to Powdered magnetic carrier.Here the resistivity of Jie Shaoing is to carry out under such condition, i.e. the about 2.3cm of contact area of carrier 27 and electrode 21 or 12 ², carrier thickness d is about 2mm, and the weight of upper electrode 22 is 180g, and applied voltage is 100V.[metal oxide granularity]

With the photo amplification 5 of transmission electron microscope (" H-800 " buied by Hitachi Seisakasho K.k.) with the sample metal oxide powder, 000-20,000 times.Randomly draw at least 300 particulates (diameter is 0.01 μ m or bigger) and analyze with image analyzer (" Luzex3 " buied by Nicecok.k.) in photo, the horizontal FERE diameter that records each particulate is as its granularity.By measuring the granularity of at least 300 sample particulates, just can calculate number average particle size.[resistivity of metal oxide]

Similar to the measuring method of the carrier resistivity of introducing previously.[exposure density of carrier surface metal oxide]

Under the alternating voltage of 1kv, measure the exposure density of the metal oxide on the carrier surface of surface coating magnetic carrier particle with scanning electron microscope (" S-800 " buied by Hitachi Seisakusho k.k.) amplification 5000-10000 photo doubly.Observe each semicircle through the front of coating magnetic carrier particulate, the number of the metal oxide microparticle that counting has exposed on the per unit area (that is, protrudes the number of the metal oxide microparticle on surface.The counting diameter is 0.01 μ m or bigger ridge.At least 300 coating metal oxide fine particles are repeated aforesaid operations, obtain the average of the exposed metal oxide fine particle of per unit area.[cross-linked resin content in the carrier]

The quantified sample carrier was calcined 2 hours down at 500 ℃, with this definite calcining loss in weight as total resin content.On the other hand, the sample carrier of same amount is immersed in the tetrahydrofuran 2 hours, makes its dissolving, can determine the dissolving loss in weight after the drying as non-crosslinked resin content.Determine cross-linked resin content (R according to following formula _CL):

Cross-linked resin content (%)=[((total amount of resin)-(non-crosslinked resin amount))/(total resin content 9] * 100 (%) [toner granularity]

In the 100-150ml electrolyte solution, add the surfactant (alkyl benzene sulfonate) of 0.1-5ml and the sample toner of 2-20mg in (1% Nacl aqueous solution).The sample dispersion that is suspended in the electrolytic solution was handled 1-3 minute.Use laser scanning particle size distribution analysis instrument (" CIS-100 " buied by GALAI Co.) to measure size-grade distribution then.Measuring particle diameter is the particulate of 0.5 μ m-60 μ m, obtains number average particle size (D1) and average particle size (D4) by Computer Processing.Distribute from base and can calculate size and be half the quantity percentage of particulate of number average particle size.Similarly, distribute from volume reference and can calculate the percent by volume of particulate that granularity is at least the twice of average particle size.[the resin monomer amount (Mres) in the toner]

0.2g sample toner is dissolved among the THF of 4ml, under the following conditions solution is carried out gas chromatographic analysis, measure content of monomer with standard method.

Equipment: Shimazu GC-15A

Carrier: N ₂, 2kg/cm ², 50ml/min, separation rate=1: 60, linear velocity=30mm/Sec

Chromatographic column: ULBON HR-1,50mm * 0.25mm

Heat up: 50 ℃ of insulation 5min down, rise to 100 ℃ with the speed of 5 ℃/min, rise to 200 ℃ with the speed of 10 ℃/min, 200 ℃ of insulations down

Sample volume: 2 μ l

Standard model: toluene [triboelectric charge]

The toner of 5 weight portions and the magnetic carrier of 95 weight portions are mixed, potpourri was stirred 60 seconds with the Turbual stirrer.The mixture of powders (developer) of gained is placed on the bottom to be had in the canister of conductive mesh of one 635 mesh sieves, under the axle suction pressure of 250mmHg toner is sucked out with aspirator by screen cloth.By following formula by the suction before and after weight difference and the voltage of the electric capacity that links to each other with container calculate triboelectric charge Q.

Q(μc/g)＝(C×V/(W1-W2))

Weight before wherein W1 represents to aspirate, the weight after W2 represents to aspirate, C represents the electric capacity of capacitor, V represents the voltage of capacitor.

With embodiment the present invention is specifically described below: embodiment 1

Phenol (phenol) 7.5 weight portions

Formalin (contain about 40wt% formaldehyde, about 10wt% methyl alcohol, surplus is a water)

11.25 weight portion

Magnetic iron ore (lipophilization, handled) 53 weight portions with the gamma-amino propyl trimethoxy silicane of 1.0wt%

(the magnetic metal oxide particle,

Dav, (mean grain size)=0.25 μ m,

Rs (resistivity)=5.1 * 10 ⁵Ohm.cm)

α-Fe ₂O ₃(with the gamma-amino propyl trimethoxy silicane lipophilization of 1.0 weight portions) 35 parts

(nonmagnetic metal oxide particle, Dav=0.60 μ m, Rs=7.8 * 10 ⁹Ohm.cm)

(to the magnetic iron ore of 99 weight portions or the α-Fe of 99 weight portions ₂O ₃Add in (haematite) that (the gamma-amino propyl trimethoxy silicane of 1.0 weight portions stirs each potpourri 30 minutes, thereby carries out magnetic iron ore magnetic iron ore and α-Fe under 100 ℃ in the Herschel mixer ₂O ₃Lipophilization.)

Above-mentioned substance was mixed under 40 ℃ 1 hour with the water of 11 weight portions.The ammoniacal liquor (base catalyst) of the 28wt% of adding 2.0 weight portions and the water of 11 weight portions in the slurry product in flask, when stirring mixes up, flask contents was heated to 85 ℃ in 40 minutes, be incubated 3 hours down at 85 ℃ then, to generate and the slaking phenolic resin.Content is cooled to 30 ℃ then, adds 100 parts of water, remove water washing and precipitating thing behind the supernatant liquor, at air inner drying sediment.With drying sediment under the reduced pressure of maximum 5mmHg 180 ℃ further dry down, thereby in the phenolic resin potpourri, obtained containing spherical magnetic iron ore and di-iron trioxide and spherical magnetic carrier slug particle.These particles are crossed 60 orders and 100 mesh sieves; remove coarse particle wherein; separate pneumatic classifier (from " the ElboWJet Labo EJ-L-3 " of Nittetsu kogyok.k. acquisition) with the multilayer of utilizing wall attachment effect then and remove fine powder and meal, isolate the carrier slug particle that number average particle size (Dn) is 31 μ m thus.The cross-linked resin amount (RCL)=99% of the magnetic carrier slug particle that obtains like this, resistivity (Rs)=2.2 * 10 ¹²Ohm.cm.

In the following method the carrier slug particle of 100 weight portions is carried out the surface coating for the silicon resin composition of the gamma-amino propyl group 3-methoxy silane of the straight chain silicones of methyl and 0.025 weight portion entirely with the substituting group that contains 0.5 weight portion.At first above-mentioned silicones composition is dissolved in the concentration of 10wt% and forms carrier coating solution in the toluene.Coating solution is mixed with the carrier slug particle, thereby and apply shearing force continuously and come evaporating solvent that coating is exerted an influence.Coated carrier particle with gained after the decomposition solidified 2 hours down at 180 ℃; and mistake 100 mesh sieves; remove the coarse particle of agglomeration selectively; obtaining multilayer then separates pneumatic classifier and removes fine powder and meal; obtained magnetic coated carrier No.1 thus; its Dn=31 μ m, the particle of particle 0.5% is 2/3.Dn (Dn%=0.5%N promptly≤2/3) and Dn/ σ=5.5 to the maximum in the size distribution.

Carrier No.1 also shows Rs=3.1 * 10 ¹³Ohm.cm.sF-1=104, the magnetization under 1 kilooersted (σ 1000) is 130emu/cm ³And 3.47g/cm ³Actual specific gravity.

With electron microscope observation with by the result that Flame Image Process is measured is that the average surface exposure density (representing with the Mo-exposure rate) of the metal oxide of carrier No.1 is 2.3 (particle)/μ m2.

The physical property of the physical property of carrier No.1 (magnetic coating body) and other carrier of introducing below is as shown in table 1.Embodiment 2

Prepare the magnetic carrier slug particle of Dn:35 μ m with the method among the embodiment 1, difference is that the consumption with lipophilic reagent (gamma-amino propyl group Ethoxysilane) is changed into the R of 0.5wt% magnetic carrier slug particle by 1.0wt% _CLBe 98%, Rs is 1.5 * 1012ohm.cm.

Generate silicone coatings with the method identical and obtain carrier No.2 (magnetic coating carrier) then with embodiment 1.The Dn=35 μ m of carrier No.1 ,≤2/3, the about 1.0%N of Dn%=, Dn/ σ=6.3, fine powder amount wherein has a little increase.The Rs=1.3 of carrier No.2 * 10 ¹³Ohm.cm, SF-1=104, σ ₁₀₀₀=131emu/cm ³, SG=3.49g/cm ³, the Mo-exposure rate is 4.1/ μ m ²Comparative Examples 1

Prepare the magnetic carrier core material of Dn=30 μ m with the method identical with embodiment 1, difference is the α-Fe with the less greaseization of particle mean size (Dav.) ₂O ₃(Dav.=0.20 μ m, Rs=2 * 10 ⁹Ohm.cm) change α-Fe ₂O ₃The Rcl=99% of magnetic carrier slug particle, Rs=5.8 * 10 ⁸Ohm.cm.

Generate silicone coatings with the method identical, obtain carrier No.3 (magnetic coating carrier) then with embodiment 1.The Dn=30 μ m of carrier No.3 ,≤2/3Dn%=0%N, Dn/ σ=5.5.The Rs=7.2 of carrier 12 0.2 * 10 ¹⁰Ohm.cm, SF-1=106, σ ₁₀₀₀=132emu/cm ³, SG=3.51g/cm3, the Mo-exposure rate is 11.6/ μ m ² Embodiment 3

Phenol 7.5 weight portions

Formalin (with embodiment 1) 11.25 weight portions

Magnetic iron ore (lipophilization with embodiment 1) 44 weight portions

α-Fe ₂O ₃(lipophilization, with embodiment 1) 44 weight portions are above-mentioned substance, 2.0 the water of the ammoniacal liquor of the 28wt% of weight portion (base catalyst) and 30 weight portions adds in the flask (not needing to be pre-mixed), mix, in 30 minutes, be heated to 85 ℃, be cured reaction in 3 hours 85 ℃ of insulations then.With the same procedure of embodiment 1 aggregated particles is carried out aftertreatment then, thereby obtain the magnetic carrier slug particle, its Dn=38 μ m, R _CL=99%, Rs=5.8 * 10 ¹²Ohm.cm.

As among the embodiment 1, the magnetic carrier slug particle is prepared carrier No.4 with the silicone coatings coating.

The Dn=38 μ m of the carrier No.4 that obtains thus, the about 9%N of≤2/3.Dn%=, Dn/ σ=3.9 show the size distribution broad.

The Rs=5.0 of carrier No.4 * 10 ¹³Ohm.cm, SF-1=104, σ ₁₀₀₀=103emu/cm ³, SG=3.53g/cm ³, the Mo-exposure rate is 4.5/ μ m ²Embodiment 4

Phenol 7.5 weight portions

Formalin (with embodiment 1) 11.25 weight portions

Magnetic iron ore (the gamma-amino propyl trimethoxy silicane lipophilization of usefulness 1.0wt%)

44 weight portions

(Dav.＝0.24μm，Rs＝5×10 ⁵ohm.cm)

α-Fe ₂O ₃(the gamma-amino propyl trimethoxy silicane lipophilization of usefulness 1.0wt%) 44 weight portions

(Dav.＝0.60μm，Rs＝2×10 ⁹ohm.cm)

Above-mentioned substance was mixed 1 hour at 40 ℃ with 9 weight parts waters.The 28wt% ammoniacal liquor (base catalyst) of 2.2 weight portions and 9 weight parts waters are added in the slurry in the flask, mix, between 40 minutes,, keep at 85 ℃ and to react and to solidify in 3 hours mixture heated to 85 ℃.Then the material in the flask is cooled to 30 ℃, adds the water of 100 weight portions, remove supernatant, the sediment water is cleaned, then at air drying.With drying sediment further dry under 180 ℃, the condition of decompression (maximum 5mmHg), thereby in the phenolic resin potpourri, obtained containing the spherical magnetic carrier of magnetic iron ore and di-iron trioxide.With the method identical with embodiment 1 with these particles classification, the Dn=20 μ m of the magnetic carrier slug particle that obtains, R _CL=100%, Rs=1.0 * 10 ¹²Ohm.cm.

Generate silicone coatings with the method identical, obtain carrier No.5 (magnetic coated carrier) then with embodiment 1, its Dn=20 μ m, the about 1%N of≤2/3.Dn%=, Dn/ σ=5.4 show that size distribution is very narrow, Rs=8.4 * 10 ¹²Ohm.cm, SF-1=104, σ ₁₀₀₀=140emu/cm ³, SG=3.48g/cm ³, Mo-exposure rate=6.6/ μ m ² Embodiment 5

Melamine 7.5 weight portions

Formalin (with embodiment 1) 11.25 weight portions

Magnetic iron ore is (with three (N-aminoethyl aminoethyl)-isopropyl titanates of 1.5wt%

Lipophilization) (Dav.=0.24 μ m, Rs=5 * 10 ⁵Ohm.cm) 44 weight portions

α-Fe ₂O ₃(three (N-aminoethyl aminoethyl)-isopropyl titanate lipophilization of usefulness 1.5wt%) (Dav.=0.30 μ m, Rs=3 * 10 ⁹Ohm.cm) 44 weight portions

Above-mentioned substance was mixed 1 hour with 15 weight parts waters down at 40 ℃.The water of the ammoniacal liquor (base catalyst) of the 28wt% of 2.5 weight portions and 20 weight portions is added in the slurry in the flask, carry out then with embodiment 1 in identical reaction and aftertreatment, in the melmac potpourri, obtain containing the spherical magnetic carrier center particle of magnetic iron ore and di-iron trioxide.Use method among the embodiment 1 with above-mentioned particle gradation then, obtain Dn=58 μ m, R _CL=98%, Rs=5.9 * 10 ¹¹The magnetic carrier slug particle of ohm.cm.

With the silicones of 0.4 weight portion or with the same procedure coating magnetic carrier slug particle among the embodiment 1, obtain carrier No.6 then, its Dn=58 μ m, the about 0.8%N of≤2/3.D n%=, Dn/ σ=6.6 show that size distribution is very narrow, fine powder is less in the particle, Rs=6.0 * 10 ¹²Ohm/cm, SF-1=103, σ ₁₀₀₀=100emu/cm ³, SG=3.50g/cm ³, MO-exposure rate=9.8/ μ m ² Embodiment 6

Styrene 17 weight portions

Divinylbenzene 3 weight portions

Magnetic iron ore (the gamma-amino propyl trimethoxy silicane lipophilization of usefulness 2.0wt%) (Dav.=0.24 μ m, Rs=5 * 10 ⁵Ohm.cm)

62 weight portions

α-Fe ₂O ₃(the gamma-amino propyl group three TMOS lipophilization of usefulness 2.0wt%)

(Dav.＝0.60μm，Rs＝2×10 ⁹ohm.cm)

18 weight portions

Above-mentioned substance was mixed 1 hour with the water of 5 weight portions with the methyl alcohol of 20 weight portions down at 30 ℃.With the methyl alcohol of 20 weight portions, 2,2 of 5 weight parts waters and 1.2 weight portions '-azoisobutyronitrile adds in the slurry in the flask, mix, in 20 minutes with mixture heated to 64 ℃, 64 ℃ down insulation reacted and solidified in 10 hours.Flask contents is cooled to 30 ℃ then, adds 200 weight portion methanol/water mixture, remove supernatant liquor, the water washing and precipitating thing is at the air drying sediment.Under 120 ℃ of decompressions (maximum 5mmHg) condition with drying sediment further dry, in the cross-linked polystyrene resin potpourri, obtain containing the spherical magnetic carrier slug particle of magnetic iron ore and di-iron trioxide then.Method with embodiment 1 obtains Dn=32 μ m, R with above-mentioned particle separation then _CL=86%, Rs=3.3 * 10 ¹¹The magnetic carrier slug particle of ohm.cm.

Press the method for embodiment 1, obtain carrier No.7 (magnetic carrier), its Dn=32 μ m ,≤2/3, the about 14%N of Dn%=, Dn/ σ=5.4, Rs=9.9 * 10 with silicone coatings magnetic carrier slug particle ¹²Ohm.cm, SF-1=105, σ ₁₀₀₀=112emu/cm ³, SG=2.78g/cm ², Mo-exposure rate=7.4/ μ m ²Comparative Examples 2

In the pressurization mixer with the vibrin of 100 weight portions, tetrahydro three iron powder of 500 weight portions, the abundant fusion of silicon dioxide of 2 parts by weight of carbon black and 1.5 weight portions is also melt-blended.After the cooling melt-blended product being carried out coarse crushing with grinding along slurry, is 2.5kgf/cm pulverizing air pressure ²Following with the jet mill of impingement plate that includes truncated ordinary cone (removed 120 ° drift angle, formed a trapezoid cross section) with the meticulous pulverizing of melt-blended product, then with mutliplexer with the product gradation, obtain carrier No.8, its Dn=31 μ m, R _CL=1%, Rs=2.2 * 10 ⁸Ohm.cm, the about 23.6%N of≤2/3.Dn%=, Dn/ σ=2.3, SF-1=145, δ ₁₀₀₀=162emu/cm ³, SG=3.02g/cm ³, Mo-exposure rate=20.4 μ m ²Comparative Examples 3

The shared molar ratio of metal oxide is Fe ₂O ₃=50mol%, CuO=25mol%, ZnO-25mol% mixes above-mentioned metal oxide with ball milling.With the potpourri calcining, grind with ball milling, make it form particulate by spray dryer.After cooling,, carry out the air-flow gradation then, obtain magnetic carrier core particulate, its Dn=30 μ m, Rs=4.0 * 10 the particulate clinkering ⁸Ohm/cmo.

With the method among the embodiment 1 with carrier core particulate with clean silicones component coating, obtain carrier N0.9 (magnetic coated carrier), its Dn=30 μ m, the about 22.7%N of≤2/3.Dn%=, Dn/ σ=2.38, Rs=1.1 * 10 ¹⁰Ohm.cm, SF-1=116, σ ₁₀₀₀=289emu/cm ³, SG=5.02g/cm ³With reference to embodiment

Method with embodiment 1 prepares magnetic carrier core particulate, and difference has been to use magnetite ore particles and the α-Fe that does not pass through lipophilization treatment ₂O ₃Particle, and multilayer of no use separation classifier carries out gradation.With the method among the embodiment 1 the carrier slug particle is carried out surface coating with clean silicones and prepare carrier No.10 (magnetic coating carrier).

The performance of carrier No.1-10 is summed up as shown in table 1:

Table 1: carrier character

			Dn (μm)	Size distribution			The R of bonding mixture CL	?SF-1	MO-exposure rate (/ μ m 2)	σ1000 (emu/cm 3)	??SG ??(g/cm 3)
												Slug particle (ohm.cm)	Coated carrier (ohm.cm)	≤2/3.Dn％ (％by ?number)	σ	Dn/σ
	1 (embodiment)	2.2×10 12		3.1×10 13	31.14	????0.5											??5.65	????5.51	????99	?104	????2.3	????130	????3.47
2 (embodiment)			1.5×10 12				1.3×10 13	35.01	????0	??5.52	????6.34	????98	?104	????4.1	????131	????3.49
	3 (embodiment)	5.8×10 8		7.2×10 10	30.14	????0											??5.45	????5.53	????99	?106	????11.6	????132	????3.51
4 (embodiment)			5.8×10 12				5.0×10 13	38.40	????9	??9.80	????3.91	????99	?104	????4.5	????103	????3.53
	5 (embodiment)	1.0×10 12		8.4×10 12	20.00	????1											??3.70	????5.41	???100	?104	????6.6	????140	????3.48
6 (embodiment)			5.9×10 11				6.0×10 12	58.20	????0.8	??8.75	????6.65	????98	?103	????9.9	????100	????3.50
	7 (embodiment)	3.3×10 11		9.9×10 12	32.79	????1.4											??6.03	????5.44	????86	?105	????7.4	????112	????2.78
8 (Comparative Examples)			2.2×10 8				????-	31.75	????23.6	?13.58	????2.34	????1	?145	????20.4	????162	????3.02
	9 (Comparative Examples)	4.0×10 8		1.1×10 10	30.22	????22.7											?12.72	????2.38	????-	?116	?????-	????289	????5.02
10 (reference examples)			2.2×10 12				3.1×10 13	31.0	????13.0	?13.0	????2.4	????99	?105	????2.3	????130	????3.47

Toner prepares embodiment 1

0.1M Na with 450 weight portions ₃PO ₄Aqueous solution adds in the deionized water of 710 weight portions, and down 12,000rpm stirs down with high speed agitator (" TK-Homomixer is available from Tokushukika dogyok.k) at 60 ℃.Then with the 1.0M CaCl of 68 weight portions ₂Aqueous solution adds in the above-mentioned system gradually, obtains containing Ca ₃(PO ₄) ₂Aqueous medium.Monomer component is preparation respectively with the following method:

Styrene 165 weight portions

Butyl acrylate 35 weight portions

C.I. pigment blue 15: 3 (colorants), 15 weight portions

Dialkyl group metal salicylate compound (charging control agent) 5 weight portions

Saturated polyester 10 weight portions

Ester type waxes (fusing point m.p:70 ℃) 50 weight portions

Said components 60 ℃ of heating down, 11, (is used TK-Homoixen) under the 000rpm and stirred said components, make its uniform dissolution, dispersion.Dissolve in then 2,2 of 10 weight portions '-azo two (2,4-dimethyl-valeronitrile) (polymerization initiators) forms polymerizable monomer component.

Polymerizable monomer component is added in the aqueous medium for preparing previously, filling N ₂Situation under at 60 ℃ down 11,000rpm stirred 10 minutes, was dispersed into the component in the system microgranular.(this step is called " particlized " hereinafter.) with paddle agitator system is stirred then, being heated to 80 ℃, polymerization 10 hours after the polyreaction, distills residual monomer under reduced pressure, and cooling adds dissolving with hydrochloric acid calcium phosphate, filters, washing, drying obtains the mazarine toner particle.

With 1.6 weight portions, the specific surface area (SBET) that records with the BET method is 200m ²The hydrophobic silica powder of/g adds in the mazarine toner particle of 100 weight portions and prepares mazarine toner A (suspension polymerization toner).The average particle size (D4) of mazarine toner A is 6.0 μ m, number average particle size (D1) is 4.7 μ m, the granule amount percentage (cumulative percentage) that granularity is D1 half (hereinafter with "≤1/2.D1% represents ") to the maximum is 6.9%N (" %N " expression number percentage), the percent by volume of particulate that granularity is at least the twice (hereinafter with "≤2.D4% " expression) of D4 is 0%V (" %V " represents percent by volume), form factor SF-1 is 103, and residual monomer content (Mres) is 400ppm.Toner particle has the core/shell structure of the core that ester is sealed.Toner prepares embodiment 2

Except the stirring rate with granulation step becomes 13, outside the 000rpm (using TK-Homomixer), use the same materials and the method that prepare embodiment 1 with toner to prepare the mazarine toner particle.Then with the hydrophobic titanium dioxide fine powder (S of toner particle and 2.5 weight portions _BET=200m ²/ g) mixing obtains mazarine toner B.

The D4 of mazarine toner is about 4.9 μ m, D1=3.8 μ m, and≤1/2D1%=6.3%N ,≤2D4=0%V, SF-1=104, encloses ester and forms core/shell structure in the toner particle Mres=620ppm.Toner prepares embodiment 3

Styrene 165 weight portions

Butyl acrylate 35 weight portions

C.I. pigment blue 15: 3 15 weight portions

Dialkyl group metal salicylate compound 3 weight portions

Saturated polyester (acid number (AV)=14, peak molecular weight (Mp)=8000)

10 weight portions

Ester type waxes (Tmp=70 ℃) 10 weight portions

60 ℃ of down heating, 12,000rpm (use TK-Homomixer) stirs and makes the said components uniform dissolution disperse with said components, dissolve in 2,2 of 10 weight portions '-azo two (2, the 4-methyl pentane nitrile) but formation aggressiveness monomer component.

The polymerizable monomer component that in the aqueous medium identical, adds aforementioned preparation with prepare the aqueous medium that makes among the embodiment 1 at toner, under the condition of inflated with nitrogen, under 60 ℃, with 11,000rpm stirs (using TH-Homomixer) and finished particlized (particulation) in 10 minutes.60 ℃ of heating, stir polymerization 6 hours with paddle agitator then.After the polyreaction,, add dissolving with hydrochloric acid calcium phosphate, filter the system cooling, washing, drying obtains the mazarine toner particle.Then with 100 weight portion toner particles and 1.5 weight portion hydrophobic peptide oxide fine powder (S _BET=200m ²/ g) mix, obtain mazarine toner C, its D4 is about 6.4 μ m, D1=5.0 μ m ,≤1/2D1%=8.1%N ,≤2D4%=0%V, SF-1=105, Mres=2400ppm.Toner prepares embodiment 4

The C.I. pigment blue 15 that adds 5 weight portions in the vibrin of 100 weight portions: the dialkyl group metal salicylate compound of 3,5 weight portions, the low-molecular-weight polypropylene of 5 weight portions mixes in the Henschel mixer then.Undertaken melt-blended by the double screw extrusion machine that the gas outlet links to each other with suction pump potpourri.Behind cooling curing,, reclaim meal by the 1mm-mesh screen with the melt-blended product hammer-mill coarse crushing of gained.So use meal is pulverized with jet mill, separate classifier (" Elbow Jet ") with multilayer again and carry out gradation to obtain the mazarine toner particle.With the toner particle of 100 weight portions and the hydrophobic titanium oxide fine powder (SBET=200m of 1.2 weight portions ²/ g) mix, obtain mazarine toner D, its D4 is about 7.8 μ m, D1=5.6 μ m ,≤1/2D1%=10.2%N ,≤2D4%=0.3V, SF-1=145, Mres=440ppm.Toner prepares embodiment 5

Prepare the Yellow toner particulate with preparation method identical among the embodiment 1 with toner, difference is with alternative blue lake (the C.I. pigment blue 15: 3) wherein of the C.I. pigment yellow 17 of 4.5 weight portions.To prepare embodiment 1 identical with toner then, with the hydrophobic titanium oxide fine powder (SBET=200m of the Yellow toner particulate and 1.6 weight portions of 100 weight portions ²/ g) be mixed with Yellow toner E, its D4=5.9 μ m, D1=4.7 μ m ,≤1/2D1%=6.2%N ,≤2D4%=0%V, SF-1=102, Mres=440ppm.This toner particle has the core/shell structure that ester type waxes is encapsulated in in-core.Toner prepares embodiment 6

(C.I. alizarol saphirol (5: 3) is used and is prepared the identical method of embodiment 1 with toner and prepare pinkish red toner particle to substitute the toner pigment with the C.I. paratonere 202 of 5 weight portions.Then with the pinkish red toner particle of 100 weight portions and the hydrophobic titanium oxide fine powder (SBET=200m of 1.6 weight portions ²/ g) mixing prepares pinkish red toner F, its D4=6.2 μ m, D1=4.9 μ m ,≤1/2D1%=6.5%N ,≤2.D4%=0%V, SF-1=103, Mres=390ppm.This toner particle has core/shell structure that ester type waxes is encapsulated in in-core.Toner prepares embodiment 7

Substitute dark blue pigment (C.I. pigment blue 15: 3), prepare the non magnetic black toner particle with 4 parts by weight of carbon black to prepare the identical method of embodiment 1 with toner.Then with the hydrophobic titanium oxide powder (S of the black toner particulate and 1.6 weight portions of 100 weight portions _BET=200m ²/ g) mixing prepares black toner G, its D4=6.1 μ m, D1=4.7 μ m ,≤1/2D1%=8.3%N ,≤2D4%=0%V, SF-1=103, Mres=480ppm.This toner particle shows core shell structure, and wherein ester type waxes is encapsulated in this structure.

The character of toner A-G is as shown in table 2.

Toner	????D4 ??(μm)	????D1 ??(μm)	≤ 1/2D1% (% number)	≤ 2D4% (% volume)	????SF-1	Residual monomer Mres (ppm)
							Dark blue A	????6.0	????4.7	????6.9	????0	????103	????400
Dark blue B	????4.9	????3.8	????6.3	????0	????104	????620
							Dark blue C	????6.4	????5.0	????8.1	????0	????105	????2400
Dark blue D	????7.8	????5.6	????10.2	????0.3	????145	????440
							Yellow E	????5.9	????4.7	????6.2	????0	????102	????440
Pinkish red F	????6.2	????4.9	????6.5	????0	????103	????390
							Black G	????6.1	????4.7	????8.3	????0	????103	????480

Embodiment 7

With carrier No.1 (magnetic coating carrier) respectively with mazarine toner A, Yellow toner E, magenta toner F and black toner G are mixed with the developer of four kind of two component, the result makes concentration and is respectively 8.0% toner.

Four look developers are added (" CLC-500 " is available from Canon K.K.) in the panchromatic laser copier with a kind of form of having transformed, and each developing apparatus wherein as shown in Figure 1.With reference to figure 1, each developing apparatus is designed to have the space of-550 μ m between developer delivery element (development sleeve) 1 and developer regulating element (magnetic scraper plate) 2, at development sleeve 1 with the space that-500 μ m are arranged between the electrostatic latent image load-carrying unit (photosensitive drum) 3 of the surface protecting layer that gathers tetrafluoroethylene of being scattered here and there is arranged.Developing gap is 5.5mm at that time.Development sleeve 1 and photosensitive drum 3 drive with 2.0: 1 circumferential speed.The top S1 of development sleeve is designed to provide the magnetic field of one 1 kilooersted, development conditions comprises that a crest voltage is 2000V, frequency is the shape ripple alternating electric field of 2200Hz, development bias voltage-450V, toner development is to voltage (Vcont) 330V (absolute value), and 80V (absolute value) removes photographic fog voltage (V _{The back to}) and on photosensitive tube-the former charging voltage of 530V.The developer tube comprises the SUS cylindrical roller (being made by Hitachi kinzoku) of a diameter 25mm, surface sandblast (using " Pneumablaster " sandblast) available from FujiSeisakusho K.K, Ra=2.1 μ m, Sm=29.7 μ m (Ra/Sm=0.07).Under above-mentioned development conditions, utilize the developing apparatus of the development sleeve that comprises sandblast, on photosensitive drum 3, form digital sub-image (spot diameter=64 μ m) by reverse visualization mode.Developing apparatus comprises the heat fixing roll of a surface coating fluorine resin, and it need not used release oil and can use.

As a result, the image ultramarine of gained, Huang, magenta, black high-purity part (high solid-part) image color are respectively 1.51,1.56,1.53,1.52, and show versicolor good middle colourity repeatability.In addition, do not observe because the image confusion that carrier adheres to or photographic fog causes in non-image part.

On 40,000 paper, form continuous images.After this, as initial step image is tested.Consequently dark blue, yellow, the pinkish red and black pure parts of images concentration of image is respectively 1.52,1.55, and 1.52 and 1.50, the same with initial period, pure parts of images concentration height, separate room colourity repeatability is good.Also can't see the carrier attachment phenomenon.Observe mazarine two component type developers with SEM (sweep electron microscope) and can see the basic identical of the surface appearance of carrier particles and initial period.Also not observing metal oxide particle in addition is released and is dispersed in the carrier.

Then, even removing photographic fog voltage (V _Oppositely) also can't see the carrier attachment phenomenon when being risen to 180V.

Then, low temperature/low temperature (L/L=15 ℃/10%RH), normal temperature/normal humidity (N/N=23.5 ℃/60%RH) and high temperature/high humidity (the charged rate of triboelectricity of measuring the mazarine developer under H/H=30 ℃/80%RH) the environment is respectively-30.1 μ c/g,-29.0 μ c/g and-27.8 μ c/g, this shows that dark blue developer has good environmental stability.

The result of the result of present embodiment and the following examples and Comparative Examples together sums up shown in table 3 and table 4.Embodiment 8

Substitute carrier No.1 with carrier No.2 and use with embodiment 7 similar methods and prepare versicolor two component type developers, use the method identical to measure with embodiment 1.

As a result, the navy blue high-purity parts of images concentration of gained image is 1.47, and yellow is 1.49, magenta be 1.47, black be 1.47; The gained image shows good shadow tone repeatability for shades of colour.In addition, do not observe because the image confusion that carrier adheres to or photographic fog causes in non-image part.

Then, consecutive image is 40, after forming on 000 paper, carry out image measurement, consequently dark blue, yellow, pinkish red and black high-purity parts of images colourity of image is respectively 1.50,1.49,1.52 and 1.48, and show good shadow tone repeatability for shades of colour at the similar gained image of initial period.Also can't see the carrier attachment phenomenon.Shown in the result who observes dark blue two component type developers with SEM, the surface appearance of carrier particles wherein basic identical with at initial period.Not observing metal oxide in addition is released and is dispersed in the carrier.

The mazarine developer is at low temperature/low humidity (L/L), the charged rate of triboelectricity under normal temperature/normal humidity (N/N) and the high temperature/high humidity (H/H) is respectively-30.3 μ c/g,-28.8 μ c/g and-27.4 μ c/g, this shows that the mazarine developer has good environmental stability.Comparative Examples 3

Substitute carrier No.1 with carrier No.3 (magnetic coating carrier, contrast is used), use with embodiment 7 similar methods to prepare versicolor two component type developers.Same procedure with embodiment 7 is measured.

As a result, dark blue, yellow, pinkish red and black high-purity parts of images concentration of gained image is respectively 1.45,1.44, and 1.45 and 1.46, but some is poor to versicolor shadow tone repeatability.Can be observed carrier attachment phenomenon and small photographic fog on this external non-image part.

Consecutive image is 40, after forming on 000 paper, carry out image measurement, consequently high-purity parts of images concentration of dark blue, yellow, the magenta of gained image and black is respectively 1.50,1.48,1.47 and 1.47, to similar at initial period, but the shadow tone repeatability is poor, and the similar carrier that occurred of the initial period that coexists adheres to.At low temperature/low humidity (L/L), the charged rate of triboelectricity of mazarine developer is respectively-31.6 μ c/g under normal temperature/normal humidity (N/N) and high temperature/high humidity (H/H) environment ,-30.3 μ c/g and-27.7 μ c/g.Embodiment 9

Substitute carrier No.1 with carrier No.4, use with embodiment 7 similar methods to prepare versicolor two component type developers (toner concentration wherein is 7.5%wt%), and measure with the method for embodiment 7.

As a result, dark blue, yellow, the magenta of gained image and high-purity parts of images concentration of black are respectively 1.48,1.51, and 1.48 and 1.52, the gained image shows good shadow tone repeatability to shades of colour.In addition, do not observe because the image confusion that carrier adheres to or photographic fog causes in non-image part.

Consecutive image is 40, after forming on 000 paper, carry out image measurement, its result very similar at initial period, dark blue, yellow, the magenta of gained image and the solid constituent image chroma of black are respectively 1.50,1.53,1.47 and 1.49, the gained image table reveals good shadow tone repeatability.Do not observe the carrier attachment phenomenon yet.Result with SEM observation mazarine two component type developers is, the surface appearance of carrier particles wherein basic identical with at initial period.Also not observing metal oxide microparticle is released and is dispersed in the carrier.

At low temperature/low humidity (L/L), the charged rate of triboelectricity of mazarine developer is respectively-31.6 μ c/g under the environment of normal temperature/normal humidity (N/N) and high temperature/high humidity (H/H),-29.6 μ c/g and-27.5 μ c/g, in fact and no problem the environmental factor dependence that shows the mazarine developer is bigger, but this result.Embodiment 10

Substitute carrier No.1 with carrier No.5, use with embodiment 7 similar methods to prepare versicolor two component type developers (toner concentration wherein is 9.5wt%), and measure with the same procedure of embodiment 7.

High-purity parts of images concentration of dark blue, yellow, the magenta of gained image and black is respectively 1.53,1.55 as a result, and 1.53 and 1.56, the gained image all shows good shadow tone repeatability to shades of colour.And do not observe the carrier attachment phenomenon.

Consecutive image is 40, after forming on 000 paper, carry out image measurement, its result very similar at initial period, dark blue, yellow, the magenta of gained image and the solid constituent image chroma of black are respectively 1.52,1.54,1.53 and 1.52, the gained image shows good shadow tone repeatability to shades of colour.The SEM observed result of mazarine two component type developers is, the surface appearance of carrier particles wherein basic identical with at initial period.And do not observe metal oxide microparticle and discharge and be dispersed in the carrier.

In addition, the mazarine developer is at low temperature/low humidity (L/L), the charged rate of triboelectricity under the environment of normal temperature/normal humidity (N/N) and high temperature/high humidity (H/H) is-28.8 μ c/g,-27.8 μ/g and-26.0 μ c/g, this shows similar among mazarine developer and the embodiment 7 to have good environmental stability.Embodiment 11

Substitute carrier No.1 with carrier No.6, use with embodiment 7 similar methods to prepare versicolor two component type developers (toner concentration wherein is 5wt%), and measure with the same procedure among the embodiment 7.

As a result, high-purity parts of images concentration dark blue, yellow, pinkish red, black of gained image is respectively 1.54,1.47, and 1.44 and 1.46, the gained image all has good shadow tone repeatability for shades of colour, but is not so good as the good of embodiment 7.In addition, do not observe that carrier adheres to or photographic fog.

Consecutive image is 40, carry out image measurement after forming on 000 paper, its result very similar at initial period, dark blue, yellow, the magenta of gained image and the solid constituent image chroma of black are respectively 1.45,1.48,1.46 with 1.49, the gained image shows good shadow tone repeatability to shades of colour.Do not observe that carrier adheres to or photographic fog yet.Result with SEM observation mazarine two component type developers is, the surface appearance of carrier particles wherein basic identical with at initial period.Also not observing metal oxide microparticle is released and is dispersed in the carrier.

In addition, the mazarine developer is at low temperature/low humidity (L/L), the charged rate of triboelectricity under normal temperature/normal humidity (N/N) and high temperature/high humidity (H/H) environment is respectively at-32.5 μ c/g,-31.3 μ c/g and-29.9 μ c/g, identical with embodiment 7, this shows dark blue developer having good stability to environment.Embodiment 12

Substitute carrier No.1 with carrier No.7, use with embodiment 7 similar methods to prepare versicolor two component type developers, and measure with the same procedure of embodiment 7.Measurement result is similar to embodiment 7, and dark blue, pinkish red, yellow and black high-purity parts of images concentration of gained image is respectively 1.49,1.52, and 1.47 and 1.47, the gained image has good shadow tone repeatability to shades of colour.And do not observe that carrier adheres to or photographic fog.

After forming consecutive image on 40,000 paper, carrying out image measurement, its result similar at initial period, dark blue, yellow, the magenta of gained image and the solid constituent image color of black are respectively 1.50,1.51,1.49 and 1.50, the gained image has good shadow tone repeatability.Do not observe that carrier adheres to or photographic fog yet.Observe the result of dark blue two groups of type developers be with SEM, the surface appearance of carrier particles wherein basic identical with at initial period do not observe metal oxide microparticle yet and is released and is dispersed in the carrier.

In addition, the mazarine developer is at low temperature/low humidity (L/L), the charged rate of triboelectricity under normal temperature/normal humidity (N/N) and high temperature/high humidity (H/H) environment is respectively-30.5 μ c/g ,-28.9 μ c/g and-27.0 μ c/g, and this shows the good stability of mazarine developer to environment.The comparative example 4

Substitute carrier No.1 with carrier No.8 (relatively thing), use with embodiment 7 similar methods to prepare versicolor two component type developers, and measure with the same procedure of embodiment 1.

The measurement result of gained image is, high-purity parts of images concentration of dark blue, yellow, magenta and black is respectively 1.44,1.46,1.45 and 1.46, and image is to versicolor shadow tone repeatability relatively poor (having the point-like confusion).Can be observed in addition that carrier adheres to and photographic fog.

In addition, carry out image measurement form consecutive image on 40,000 paper after, its result is respectively 1.50,1.51,1.49 and 1.51 for the solid constituent image color of dark blue, yellow, magenta and black, compared with the value height in stage that begins.The same with initial period, shadow tone repeatability and carrier attachment phenomenon are all relatively poor.

The mazarine developer is at low temperature/low humidity (L/L), the charged rate of triboelectricity under normal temperature/normal humidity (N/N) and high temperature/high-temperature (H/H) environment is respectively-35.2 μ/g,-31.7 μ c/g and-27.7 μ c/g, this shows that the mazarine developer is bigger to environment dependence property.The comparative example 5

Substitute carrier No.1 with carrier No.9 (relatively thing), use with embodiment 7 same procedure to prepare versicolor two component type developers, and measure with the same procedure among the embodiment 7.

Test result is that the image color of high-purity part of pitch black, yellow, the magenta of gained image and black is respectively 1.45,1.46,1.44 and 1.45, and the gained image is to versicolor shadow tone repeatability relatively poor (having the point-like confusion).Also have carrier to adhere to and photographic fog in addition.

Carry out image measurement form consecutive image on 40,000 paper after, its result is respectively 1.49,1.49,1.47 and 1.48 for the solid constituent image color of dark blue, yellow, magenta and black, compared with the value height in stage that begins.Do not have the carrier attachment phenomenon, but shadow tone repeatability and photographic fog become poorer compared with initial period.The mazarine developer is at low temperature/low humidity (L/L), the charged rate of triboelectricity under normal temperature/normal humidity (N/N) and high temperature/high humidity (H/H) environment is respectively-33.6 μ c/g,-31.5 μ c/g and-27.2 μ c/g, this shows that the mazarine developer is bigger to the dependence of environment.Embodiment 13

Substitute mazarine toner A with mazarine toner B, prepare two component type mazarine developers with the method for embodiment 7.

The mazarine developer that makes is added in the panchromatic laser copier of modified identical with embodiment 7, carry out monochromatic type image formation mensuration with the same procedure among the embodiment 7.

High-purity parts of images concentration of gained image is 1.49, and has good especially shadow tone repeatability.Do not observe that carrier adheres to or photographic fog yet.Embodiment 14

Substitute mazarine toner B with mazarine toner C, prepare and test two component type mazarine developers with the same procedure among the embodiment 13.Embodiment 15

Substitute mazarine developer B with mazarine developer D, prepare and test two component type mazarine developers with the same procedure among the embodiment 13.Comparative examples

Substitute carrier No.1 with carrier No.10, prepare and measure versicolor two component type developers with the same procedure among the embodiment 7.

The result of the foregoing description is shown in table 3 and table 4.After the illustrated in table 4 of table 3 and table 4.

Table 3

	The starting stage image forms performance
					The solid constituent image color	The shadow tone repeatability	Photographic fog	Carrier adheres to
	Toner	Toner	Toner	V oppositely=80V V180V
						??Cy????Y?????M?????BK	?Cy?Y??M??BK	?Cy??Y??M??BK
7 real 89 execute 10 11 examples 12 13 14 15	?1.51??1.56??1.53??1.52 ?1.47??1.49??1.47??1.47 ?1.48??1.51??1.48??1.52 ?1.53??1.55??1.53??1.56 ?1.45??1.47??1.44??1.46 ?1.49??1.52??1.47??1.47 ?1.49????-????-?????- ?1.46????-????-?????- ?1.45????-????-?????-	?A??A??A??A ?A??A??A??A ?B??B??B??B ?A??A??A??A ?B??B??B??B ?A??A??A??A ?A??-??-??- ?B??-??-??- ?B??-??-??-	?A???A???A??A ?A???A???A??A ?B???B???B??B ?A???A???A??A ?A???A???A??A ?B???B???B??B ?B???-???-??- ?B???-???-??- ?B???-???-??-						????A????A ????A????A ????B????B ????B????B ????A????A ????B????B ????A????A ????A????A ????A????A
				To 3 to 4 examples 5	?1.45??1.44??1.45??1.46 ?1.44??1.46??1.45??1.46 ?1.45??1.46??1.44??1.45	?C??C??C??C ?C??C??C??C ?D??D??D??D	?C???D???D??D ?D???E???E??E ?E???C???C??C	????E????E ????E????E ????C????C
The contrast row	?1.50???-????-??????-	?A??-??-??-	?A???-???-??-						????A????C

(evaluation) A: fine, B: good, C: better, and D: relatively poor, F: poor.

Table 4

	Image forms performance				The charged rate of triboelectricity (μ c/g)
								The solid constituent image color	The shadow tone repeatability	Photographic fog	Carrier adheres to	L/L	?N/N	?H/H
	Toner	Toner	Toner
					??Cy?????Y?????M????BK	?Cy????Y????M????BK	?Cy?Y??M?BK
7 real 89 execute 10 11 examples 12 13 14 15	?1.52??1.55??1.52??1.50 ?1.50??1.49??1.52??1.48 ?1.50??1.53??1.47??1.49 ?1.52??1.54??1.53??1.52 ?1.45??1.48??1.46??1.49 ?1.59??1.51??1.49??1.50 ?1.51????-????-?????- ?1.50????-????-?????- ?1.50????-????-?????-	?A?????A????A????A ?A?????A????A????A ?B?????B????B????B ?A?????A????A????A ?B?????B????B????B ?A?????A????A????A ?A?????-????-????- ?B?????-????-????- ?B?????-????-????-	?A??A??A??A ?A??A??A??A ?B??B??B??B ?A??A??A??A ?A??A??A??A ?B??B??B??A ?B??-??-??- ?C??-??-??- ?C??-??-??-					?A ?A ?B ?B ?A ?B ?A ?A ?A	-30.1 -30.3 -31.6 -28.8 -32?5 -30.5 -35.6 -31.5 -30.9	??-29.0 ??-28.8 ??-29.6 ??-27.8 ??-31.3 ??-28.9 ??-34.6 ??-30.0 ??-29.8					??-27.8 ??-27.4 ??-27.5 ??-26.0 ??-29.9 ??-27.0 ??-32.7 ??-28.2 ??-27.6
				To 3 to 4 examples 5	?1.50??1.48??1.47??1.47 ?1.50??1.51??1.49??1.51 ?1.49??1.49??1.47??1.48	??C????C????C?????C ??D????D????D?????D ??E????E????E?????E	?D??D??D??D ?E??E??E??E ?E??E??E??E				?E ?E ?C	-31.6 -35.2 -33.6	??-30.3 ??-31.7 ??-31.5	??-27.7 ??-27.7 ??-27.2
Reference examples 5	?1.51????-????-??????-	??A????-????-?????-	?A??-??-??-					?A	-30.0	??-28.8					??-27.6

(evaluation) A: fine, B: good, C: better, and D: relatively poor, F: the explanation of difference his-and-hers watches 3 and table 4

The gauge outfit of table 3 and table 4 comprises the following symbol that is used to illustrate toner:

Cy: dark blue toner Y: Yellow toner

M: magenta toner BK: black toner

Represent situation with the test result of symbol A-E in table 3 and the table 4 with the test of following aspect:

A: fine, B: good, C: better, D, relatively poor, E: difference assay method and standard (1) image color

The image color of real image part that is determined at the image that forms on the blank sheet of paper with the reflection photometry density instrument that the SPI filtrator is housed (" Machbeth Color Checker is available from Macbeth Co.) is as relative concentration.(2) shadow tone repeatability

To compare with intrinsic half tone image in the roughness of the half tone image of reproduced image part by naked eyes, estimate the half tone image roughness partly of reproduced image thus.(3) carrier adheres to

End the reproduction of solid white image, adhesive tape is attached on the photosensitive drum that develops between part and the removing part, make magnetic carrier attached on the photosensitive drum.Add up the adhesion amount of magnetic carrier particulate in 5cm * 5cm then, calculate every square centimeter of number that adheres to magnetic carrier.Carry out result evaluation according to following benchmark:

A: less than 10 particles/cm ²

B:10-is less than 20 particles/cm ²

C:20-is less than 50 particles/cm ²

D:50-is less than 100 particles/cm ²

E:100 particle/cm ²Or it is more.(4) photographic fog

Before forming image, measure the average reflectance Or (%) of blank sheet of paper with photometry density instrument (" TC-6MC " is available from TokyoDenshoku K.K).On identical blank sheet of paper, form the solid white pattern then, measure the average reflectance Ds (%) of solid white image with identical method.Calculate photographic fog rate (%) with following formula then: photographic fog rate (%)=Dr (%)-Ds (%).Carry out result evaluation according to following benchmark:

A: be lower than 1.0%D:2.0-and be lower than 3.0%

B:1.0-is lower than 1.5% E:3.0% or higher

C:1.5-is lower than 2.0%

Claims (89)

1 one kinds of magnetic coated carriers comprise: contain the magnetic coated carrier particle of magnetic carrier slug particle, each magnetic carrier slug particle comprises adhesive resin and metal oxide particle, and the coat of each carrier slug particle of surface-coated, wherein:

Metal oxide particle is through surperficial lipophilization treatment,

The magnetic carrier slug particle has the resistivity of at least 1 * 1010ohm.cm,

Magnetic coated carrier has the resistivity of at least 1 * 1012ohm.cm, and

The size-grade distribution that magnetic coated carrier has should have (i), and to have number average particle size Dn be 5-100 μ m, (ii) satisfy relational expression: Dn/ σ 〉=3.5, wherein σ represent carrier the base size-grade distribution standard deviation and (iii) contain 25% the granule number that maximum particle size is DnX2/3 that has at least.

2 magnetic coated carriers according to claim 1, wherein adhesive resin is crosslinked.

3 magnetic coated carriers according to claim 1, wherein adhesive resin comprises thermoset resin.

4 magnetic coated carriers according to claim 1, wherein coat comprises resin.

5 magnetic coated carriers according to claim 1, wherein the magnetic carrier slug particle prepares by polymerisation process, and the form factor SF-1 that this carrier has is 100-130.

6 magnetic coated carriers according to claim 1, metal oxide particle wherein is by being selected from least a lipophilization treatment of having carried out of silane coupling agent, titanate esters coupling agent and aluminium coupling agent and surfactant.

7 magnetic coated carriers according to claim 1, magnetic carrier slug particle wherein comprises that at least two kinds of total amounts are the metal oxide particle of 50-99wt%, and this metal oxide particle comprises that at least a feeromagnetic metal oxide particle and another kind have the nonmagnetic metal oxide particle that resistivity is higher than the feeromagnetic metal oxide particle; The number average particle size that described another kind of metal oxide particle has is greater than 5 times at the most of feeromagnetic metal oxide particles, and the magnetization that magnetic coated carrier has is 40-250emu/g under 1 kilooersted condition.

8 magnetic coated carriers according to claim 1, wherein the adhesive resin of magnetic carrier slug particle comprises phenolics.

9 magnetic coated carriers according to claim 7, wherein said feeromagnetic metal oxide particle comprise that ferromagnetic ore deposit and described another kind of metal oxide particle comprise haematite stone.

10 magnetic coated carriers according to claim 7, wherein metal oxide particle is exposed to the magnetic coated carrier particle surface, and average exposure is 0.1-10 particle/nm ²

11 magnetic coated carriers according to claim 1, wherein the number average particle size (Dn) that has of magnetic coated carrier is 10-70 μ m.

12 magnetic coated carriers according to claim 1, wherein the form factor SF-1 that has of magnetic coated carrier is 100-130.

13 magnetic coated carriers according to claim 1, wherein magnetic coated carrier contain at the most 15% have a granularity granule number of Dn * 2/3 at the most.

14 magnetic coated carriers according to claim 1, wherein magnetic coated carrier contain at the most 10% have a granularity granule number of Dn * 2/3 at the most.

15 magnetic coated carriers according to claim 1, wherein magnetic coated carrier satisfies Dn/ σ 〉=4.0.

16 magnetic coated carriers according to claim 7, the number average particle size that wherein said feeromagnetic metal oxide particle has are 0.02-2 μ m.

17 magnetic coated carriers according to claim 7, the number average particle size that wherein said nonmagnetic metal oxide particle has are 0.05-5 μ m.

18 magnetic coated carriers according to claim 7, wherein said feeromagnetic metal oxide particle has at least 1 * 10 ³The resistivity of ohm.cm.

19 magnetic coated carriers according to claim 7, wherein said nonmagnetic metal oxide particle has at least 1 * 10 ⁸The resistivity of ohm.cm.

20 magnetic coated carriers according to claim 7, wherein said nonmagnetic metal oxide particle has at least 1 * 10 ¹⁰The resistivity of ohm.cm.

21 magnetic coated carriers according to claim 7, wherein the feeromagnetic metal oxide particle accounts for the 30-95wt% of total metal oxide particle in the magnetic carrier slug particle.

22 magnetic coated carriers according to claim 1, metal oxide particle is wherein handled with having amino silane coupling agent.

23 magnetic coated carriers according to claim 22, wherein said silane coupling agent with amino is the compound that is selected from gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methoxyl diethoxy silane, N-beta-aminoethyl-gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyldiethoxysilane, N-beta-aminoethyl-gamma-amino propyl group methyl dimethoxysilane, γ-2-amino-ethyl-TSL 8330 and N-phenyl-gamma-amino propyl trimethoxy silicane.

24 magnetic coated carriers according to claim 1, wherein metal oxide particle is handled with the silane coupling agent with hydrophobic group.

25 magnetic coated carriers according to claim 24, wherein said silane coupling agent with hydrophobic group is the silane coupling agent with alkyl, alkenyl, haloalkyl, halogenated alkenyl, phenyl, halogenophenyl or alkyl phenyl.

26 magnetic coated carriers according to claim 24, wherein said silane coupling agent with hydrophobic group comprises uses following formula: the alkoxy silane that RmSiYn represents, wherein R represents alkoxy, Y represents alkyl or vinyl, and m and n are the integers of 1-3.

27 magnetic coated carriers according to claim 24, wherein said silane coupling agent with hydrophobic group is to be selected from vinyltrimethoxy silane, vinyltriethoxysilane, vinyl triacetic acid base silane, methyltrimethoxy silane, methyl triethoxysilane, the isobutyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, the trimethyl methoxy silane, the n-pro-pyl trimethoxy silane, phenyltrimethoxysila,e, the n-hexadecyl trimethoxy silane, n-octadecane base trimethoxy silane, compound with vinyl three ('beta '-methoxy) silane.

28 magnetic coated carriers according to claim 24, wherein said silane coupling agent with hydrophobic group are to be selected from vinyl trichlorosilane, hexamethyldisilazane, trimethyl silane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, allyl phenyl dichlorosilane, benzyl dimethyl chlorosilane, bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane and CMDMCS chloromethyl dimethyl chlorosilane.

29 magnetic coated carriers according to claim 1, wherein metal oxide particle is handled with the silane coupling agent with epoxy radicals.

30 magnetic coated carriers according to claim 29, wherein said coupling agent are to be selected from γ-epoxypropoxy methyldiethoxysilane, γ-epoxypropoxy triethoxysilane and β-(3,4-epoxycyclohexyl) trimethoxy silane.

31 magnetic coated carriers according to claim 1 wherein carry out lipophilization treatment with silane coupling agent or titanate esters coupling agent to metal oxide particle, and the consumption of coupling agent is per 100 weight portions of 0.1-10 weight portion.

32 magnetic coated carriers according to claim 1 wherein carry out lipophilization treatment with silane coupling agent or titanate esters coupling agent to metal oxide particle, and the coupling agent consumption is per 100 weight portions of 0.2-6 weight portion.

33 magnetic coated carriers according to claim 1, wherein the magnetization that has under 1 kilooersted condition of magnetic coated carrier is 40-250emu/g.

34 magnetic coated carriers according to claim 1, wherein the magnetization that has under 1 kilooersted condition of magnetic coated carrier is 50-230emu/g.

35 1 kinds of two-component developers that are used for developing electrostatic image comprise toner and magnetic coated carrier; Wherein magnetic coated carrier comprises the magnetic coated carrier particle that contains the magnetic carrier slug particle and the coat of each carrier slug particle of surface-coated, and each slug particle comprises adhesive resin and metal oxide particle, wherein

Metal oxide particle is through surperficial lipophilization treatment,

The magnetic carrier slug particle has at least 1 * 10 ¹⁰The resistivity of ohm.cm,

Magnetic coated carrier has at least 1 * 10 ¹²The resistivity of ohm.cm, and

The size-grade distribution that magnetic coated carrier has should have (i), and to have number average particle size Dn be 5-100 μ m, (ii) satisfy relational expression Dn/ σ 〉=3.5, wherein σ represents the standard deviation of carrier base size-grade distribution and (iii) contains 25% the granule number that maximum particle size is DnX2/3 that has at least.

36 developers according to claim 35, wherein the average particle size (D4) that has of toner is 1-10 μ m.

37 developers according to claim 35, wherein the average particle size that has of toner is 3-8 μ m.

38 developers according to claim 35, wherein to contain at the most 20% the granularity that has be at most half toner-particle quantity of its number average particle size (D1) to toner, and contain at the most 10% the toner-particle volume that granularity is its average particle size (D4) twice at least that has.

39 developers according to claim 35, wherein the number average particle size (Dn) that has of magnetic coated carrier is 15-50 μ m, and the average particle size (D4) that this toner has is 3-8 μ m.

40 developers according to claim 38, wherein the shape factor SF-1 that has of toner is 100-140, and residual monomer content is 1000ppm at the most.

41 developers according to claim 40, the residual monomer content that toner wherein has is 500ppm at the most.

42 developers according to claim 35, the form factor SF-1 that toner wherein has is 100-130, and residual monomer content is 300ppm at the most.

43 developers according to claim 35, toner wherein comprises the toner-particle that respectively has core/shell structure.

44 developers according to claim 43, wherein each toner-particle has the core that includes the low softening point material, and its fusing point that has is 40-90 ℃.

45 developers according to claim 44, wherein toner-particle contains the low softening point material of its 5-30wt%.

46 developers according to claim 35, wherein toner comprises the outer doping that number average particle size mostly is 0.2 μ m most that has of toner-particle and powdery.

47 developers according to claim 46 wherein add the toner-particle that content of additive is per 100 weight portions of 0.01-10 weight portion.

48 developers according to claim 46 wherein add the toner-particle that content of additive is per 100 weight portions of 0.05-5 weight portion.

49 developers according to claim 35, wherein the absolute value of the frictional electrification that has of toner is 5-100 μ c/g.

50 developers according to claim 35, wherein the friction that has of toner can charged ability absolute value be 5-60 μ c/g.

51 developers according to claim 35, wherein adhesive resin is crosslinked.

52 developers according to claim 35, wherein adhesive resin comprises thermoset resin.

53 developers according to claim 35, wherein coat comprises resin.

54 developers according to claim 35, wherein the magnetic carrier slug particle prepares by polyreaction, and the shape factor SF-1 of this carrier is 100-130.

55 developers according to claim 35, wherein metal oxide is by being selected from least a lipophilization treatment of having carried out of silane coupling agent, titanate esters coupling agent, aluminium coupling agent and surfactant.

56 developers according to claim 35, wherein the magnetic carrier slug particle comprises that at least two kinds of total amounts are the metal oxide particle of 50-99wt%, and this metal oxide particle comprises that at least a ferromagnetic metal oxide particle and the another kind of resistivity that has are higher than the nonmagnetic metal oxide grain of ferromagnetic metal oxide particle; The number average particle size that described another kind of metal oxide particle has is greater than 5 times at the most of ferromagnetic metal oxide particles; And the magnetization that magnetic coated carrier has is 40-250emu/g under 1 kilooersted condition.

57 developers according to claim 35, wherein the adhesive resin of magnetic carrier slug particle comprises phenolics.

58 developers according to claim 35, wherein said ferromagnetic metal oxide particle comprise that magnetic iron ore and described another kind of metal oxide particle comprise haematite.

59 developers according to claim 56, wherein metal oxide particle is exposed to the magnetic coated carrier particle surface, and on average exposing speed is 0.1-10 particle/μ m2.

It is 10-70 μ m that 60 developers according to claim 35, magnetic coated carrier wherein have number average particle size (Dn).

61 developers according to claim 35, wherein the form factor SF-1 that has of magnetic coated carrier is 100-130.

62 developers according to claim 35, wherein magnetic coated carrier contains at the most 15% the granule number that granularity is Dn * 2/3 at the most that has.

63 developers according to claim 35, wherein magnetic coated carrier contains at the most 10% the granule number that granularity is Dn * 2/3 at the most that has.

64 developers according to claim 35, wherein magnetic coated carrier satisfies Dn/ σ 〉=4.0.

65 developers according to claim 56, the number average particle size that wherein said ferromagnetic metal oxide particle has are 0.02-2 μ m.

66 developers according to claim 56, the number average particle size that wherein said nonmagnetic metal oxide particle has are 0.05-5 μ m.

67 developers according to claim 56, wherein said ferromagnetic metal oxide particle has at least 1 * 10 ³The resistivity of ohm.cm.

68 developers according to claim 56, wherein said nonmagnetic metal oxide particle has at least 1 * 10 ⁸The resistivity of ohm.cm.

69 developers according to claim 56, wherein said nonmagnetic metal oxide particle has at least 1 * 10 ¹⁰The resistivity of ohm.cm.

70 developers according to claim 56, wherein the ferromagnetic metal oxide particle accounts for the 30-95wt% of total metal oxide particle in the magnetic carrier slug particle.

71 developers according to claim 35, wherein metal oxide particle is handled with having amino silane coupling agent.

72 developers according to claim 71, wherein said silane coupling agent with amino is selected from gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methoxyl diethoxy silane, N-beta-aminoethyl-gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyldiethoxysilane, N-beta-aminoethyl-gamma-amino propyl group methyl dimethoxysilane, γ-2-aminoethylamino propyl trimethoxy silicane and N-phenyl-gamma-amino propyl trimethoxy silicane.

73 developers according to claim 35, wherein metal oxide particle is handled with the silane coupling agent with hydrophobic group.

74 developers according to claim 73, wherein said silane coupling agent with hydrophobic group is the silane coupling agent with alkyl, alkenyl, haloalkyl, halogenated alkenyl, phenyl, halogenophenyl or alkyl phenyl.

75 developers according to claim 73, wherein said silane coupling agent with hydrophobic group comprises uses following formula: the alkoxy silane that RmSiYn represents, wherein R represents that alkoxy, Y represent alkyl or vinyl, and m and n are the integers of 1-3.

76 developers according to claim 73, the silane coupling agent that wherein has hydrophobic group is to be selected from vinyltrimethoxy silane, vinyltriethoxysilane, vinyl triacetic acid base silane, methyltrimethoxy silane, methyl triethoxysilane, the isobutyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, the trimethyl methoxy silane, the n-pro-pyl trimethoxy silane, phenyltrimethoxysila,e, the n-hexadecyl trimethoxy silane, the compound of n-octadecane base trimethoxy silane and vinyl three ('beta '-methoxy) silane.

77 developers according to claim 73, wherein said silane coupling agent with hydrophobic group are to be selected from vinyl trichlorosilane, hexamethyldisilazane, trimethyl silane, dimethyldichlorosilane, methyl trichlorosilane, allyldimethylcholrosilane, allyl phenyl dichlorosilane, benzyl dimethyl chlorosilane, bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane and CMDMCS chloromethyl dimethyl chlorosilane.

78 developers according to claim 35, wherein metal oxide particle is handled with the silane coupling agent with epoxy radicals.

79 developers according to claim 78, wherein said coupling agent are to be selected from γ-epoxypropoxy methyldiethoxysilane, γ-epoxypropoxy triethoxysilane and β-(3, the 4-epoxycyclohexyl) trimethoxy silane.

80 developers according to claim 35, wherein metal oxide particle carries out lipophilization treatment with silane coupling agent or titanate esters coupling agent, and its amount is per 100 weight portions of 0.1-10 weight portion.

81 developers according to claim 35, wherein metal oxide particle carries out lipophilization treatment with silane coupling agent or titanate esters coupling agent, and its amount is per 100 weight portions of 0.2-6 weight portion.

82 developers according to claim 35, wherein the magnetization that has under 1 kilooersted condition of magnetic coated carrier is 40-250emu/g.

83 developers according to claim 35, the magnetization that magnetic coated carrier wherein has under 1 kilooersted condition is 50-230emu/g.

84 1 kinds of developing methods, comprise: two-component developer is positioned on the parts of bearing developer, the field generator for magnetic of packing into therein, on the carrying developing parts, form the magnetic brush of two-component developer, make magnetic brush contact with the parts of load image, apply alternating electric field simultaneously at parts, electrostatic image development on the parts of load image to bearing developer;

Wherein two-component developer comprises toner and magnetic coated carrier; Wherein magnetic coated carrier comprises the magnetic coated carrier particle, and this particle comprises the magnetic carrier slug particle, and each slug particle comprises the coat of adhesive resin and metal oxide particle and surface coating carrier slug particle, wherein

Metal oxide particle is through surperficial lipophilization treatment,

The magnetic carrier slug particle has at least 1 * 10 ¹⁰The resistivity of ohm.cm,

Magnetic coated carrier has at least 1 * 10 ¹²The resistivity of ohm.cm, and

The size-grade distribution that magnetic coated carrier has should have (i), and to have number average particle size Dn be 5-100 μ m, (ii) satisfy relational expression Dn/ σ 〉=3.5, wherein σ represents the standard deviation of carrier base size-grade distribution and (iii) contains at least 25% the granule number that maximum particle size is DnX2/3 that has.

85 4 methods according to Claim 8, wherein alternating electric field has the frequency of peak-to-peak voltage and the 500-10000Hz of 500-5000V.

86 5 methods according to Claim 8, wherein alternating electric field has the frequency of 500-3000Hz.

87 4 methods are according to Claim 8 arranged out the minimum space of 100-1000 μ m between the parts of wherein said bearing developer and the parts of described load image.

88 4 methods according to Claim 8, wherein said two-component developer is the developer according to any one claim among the claim 32-66.

89 4 methods according to Claim 8, the parts of bearing developer wherein have the uneven surface that satisfies following condition: 0.2 μ m≤center line, one mean roughness (Ra)≤5.0 μ m, 10 μ m≤average irregular spacing (Sm)≤80 μ m and 0.05≤Ra/Sm≤0.5.

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