CN1140267A - Toner for two-component developer - Google Patents

Abstract

The invention provides toner for a two-component type developer containing toner particles including a binder resin and magnetic powder dispersed in the binder resin. The binder resin is made of a component including a resin having an anionic polar group. The magnetic powder is included in the toner particles at a proportion of 0.1 through 5 parts by weight on the basis of 100 parts by weight of the binder resin. The toner particles have a volume-based average particle diameter of 5 through 15 mu m. Spacer particles having a volume-based average particle diameter of 0.05 through 1.0 mu m are attached onto the surfaces of the toner particles.

Description

The toner that is used for two-component developer

The present invention relates to a kind of toner that is used for the two-component developer of electrophotography.More particularly, the present invention relates to a kind of toner that does not contain charge control agent, is applicable to electrostatic printing imaging device such as Xerox and laser printer.

Two-component developer is to be used for making one of latent electrostatic image developing developer on photosensitive body at the electrostatic printing imaging device.Two-component developer comprises toner, and said toner contains colorant and magnetic carrier such as the iron powder and the ferrite particle of adhesive resin and carbon black and so on.

Electrostatic latent image develops by following step: developer forms the magnetic brush shape by magnetic field on developer roll, and is brought on the photosensitive body.In this step, toner is because charged with the carrier friction, and has desired electric charge and charge polarity therefrom.Then, developer contacts with photosensitive body by developer roll, makes toner attached on the formed electrostatic latent image on the photosensitive body.Usually, toner contains charge control agent, and this charge control agent plays control and stable toner charge, so that toner keeps a constant amount on electrostatic latent image, and developed image is remained intact over a long time.Electronegative toner contains negative charge controlling agent, as the metal complex that contains the metallic ion such as chromium (III) (for example, azo-compound-chromium (III) complex) and the dyestuff of hydroxycarboxylic acid-metal complex (for example, salicylic acid-metal complex) (JP special permission open 3-67268).Positively charged toner contains positive charge control agent, as comprises the oil-soluble dyes of Ni Ge, and amine type charge control agent (the open 56-106249 of JP special permission).

Many metal complexs, the metal complex that comprises heavy metal ion such as chromium ion all is the charge control agent of using always.But from environmental angle, need these metal complexs of careful selection, therefore have only those complexs that passed through various toxicity tests and safety testing to use.Although thereby metal complex itself or be safe when being contained in the toner, preferably do not use the metal complex charge control agent that comprises heavy metal.In addition, charge control agent is more expensive than other material in the toner such as adhesive resin and colorant such as carbon black, although therefore its consumption has only a few percent, has improved the price of gained toner.So require to develop a kind of toner of not metal-containing complex charge control agent.

In addition, when the toner of routine used for a long time, the toner component tended on the surface attached to carrier granular.This component that adheres to is called as waste material.This waste material can make electric charge identical with toner polarity on the carrier band, and the shortcoming that causes therefrom is that toner can spread, the transfer efficiency reduction of its image.

The toner that is used for two-component developer of the present invention contains toner-particle, and this particle includes adhesive resin and the magnetic that is dispersed in this resin.Adhesive resin is made by the resin with anionic polar group, magnetic is comprised in the toner-particle, its consumption is that per 100 weight portion adhesive resins are the 0.1-5 weight portion, the volume base mean grain size 5-15 μ m of toner-particle, and be on the surface of interval dose particle attached to toner-particle of 0.05-1.0 μ m with volume base mean grain size.

In one embodiment, the interval dose particle comprises: resistivity is 10 ¹With 10 ⁵First interval dose particle between the Ω cm and resistivity are 10 ⁸With 10 ¹³The second interval dose particle between the Ω cm.

In one embodiment, Metallic stearates is attached on the surface of an at least a interval dose material and toner-particle.

In one embodiment, Metallic stearates is be selected from zinc stearate and dolomol a kind of at least.

In one embodiment, Metallic stearates optionally is attached on the surface of interval dose.

In one embodiment, not having absorption peak with the resulting extract of methanol extraction toner basically at 280-350nm, is zero in the absorbance log of 400-700nm substantially.

In one embodiment, the consumption of the magnetic that is comprised is that per 100 weight portion adhesive resins are the 0.5-3 weight portion.

Therefore, invention described herein can have following advantage: (1) is provided at the chargeding performance of the toner excellence when at all not having charge control agent; (2) toner that is provided in the developing process that obtains the high-quality copy image does not almost spread, and (3) provide even using the toner that does not also produce waste material for a long time, by, the image of high-quality can be kept, and transfer efficiency can be stablized.

Fig. 1 is the methanol extraction liquid absorbance log curve map in 200-700nm that shows toner of the present invention.

Fig. 2 shows to contain the curve map of azo-compound-chromium complex dyes as methanol extraction liquid absorbance log in 200-700nm of the toner of charge control agent.

Fig. 3 shows the curve map contain as methanol extraction liquid absorbance log in 200-700nm of the toner of the salicylic acid-metal complex of charge control agent.

Fig. 4 is the curve map that is presented at the absorbance log of the methanol extraction liquid of the long-time carrier that uses in two component-type developers, wherein, toner has azo-compound-chromium complex dyes as charge control agent, carrier at the chargeding performance of 200-700nm because waste material and instability.

Fig. 5 be show time of vibration and the waste material ratio that obtains by the agent of two kinds of two-component magnetic shadows between the curve map that concerns; A kind of developer contains the toner that has charge control agent and magnetic carrier, and another kind of developer contains the toner of neutral controlling agent and magnetic carrier.

Fig. 6 be show time of vibration and the toner carried charge that obtains by two kinds of two-component magnetic developing agents between the curve map that concerns, a kind of developer contains the toner that has charge control agent and magnetic carrier, and another kind of developer contains the toner of neutral controlling agent and magnetic carrier.

Fig. 7 shows the curve map that concerns between the carrier waste material amount and charge control agent amount in the toner-particle.

Fig. 8 shows the curve map that concerns between time of vibration and the resulting waste material amount, in this occasion, mixes respectively and vibrates being included in each component in the toner-particle and magnetic carrier.

Fig. 9 has illustrated the mechanism of the charged failure that is caused by the waste material in the conventional two-component magnetic developing agent.

Figure 10 is in order to observe the synoptic diagram of white point used former figure in the replication performance test in the solid black part.

Figure 11 is the synoptic diagram that is used to measure the resistivity test device of the used interval dose of a present invention material resistivity.

The toner of two-component developer does not contain charge control agent according to the present invention, as the dyestuff of azo-compound-metal complex and hydroxycarboxylic acid-metal complex.Therefore, can produce hardly in the toner of the present invention and will narrate below, the waste material that causes by charge control agent, the high-quality duplicating image of the acquisition of time greatly thus.Because toner of the present invention does not contain charge control agent, therefore, by any chemistry or physical method, can not detect charge control agent from toner, i.e. the dye-type compound.For example also detect less than this compounds by any chemical reaction.In addition, in the organic solvent extraction liquid of toner of the present invention, also detect less than because this compounds produced absorbs.For example, when toner of the present invention extracted with organic solvent such as methyl alcohol, extract did not have absorption peak basically at 280-350nm, and was zero substantially in the 400-700nm absorbance log.At this, " not having absorption peak basically " refers to, with detected at all in the 50ml methanol extraction 0.1g toner of the present invention resulting extract less than absorption peak, even or detect, then absorption peak is 0.05 or littler.Similarly, " absorbance log be substantially zero " refers to, and is 0.05 or littler with the absorbance log value of the resulting extract of 50ml methanol extraction 0.1g toner of the present invention.

In toner of the present invention, compensate according to as described below owing to lack the electric charge instability of the toner that charge control agent causes.At first, use has the adhesive resin of the polymkeric substance of anionic group as toner-particle; Secondly, with predetermined ratio magnetic is included in the toner-particle.In order further to strengthen the effect of toner, two kinds of predetermined resistivities are arranged in the toner of the present invention and/or be attached with the interval dose particle of Metallic stearates.Therefore, stablize the chargeding performance of toner, and improved the density of image.

To describe the above-mentioned characteristic of toner of the present invention below in detail.

Fig. 1 shows the uv-vis spectra of the methanol extraction liquid of toner of the present invention at 200-700nm, and as can be seen, extract does not have the crest that forms owing to charge control agent from this spectrum.Specifically, this extract does not have absorption peak substantially at 280-350nm, is zero substantially in the absorbance log of 400-700nm.On the contrary, be shown in the containing in the absorption curve as the methanol extraction liquid of the toner of the azo-compound-chromium complex dyes of charge control agent of Fig. 2, at 400-700nm, particularly 550-570nm has found absorption peak.In addition, being shown in the containing in the uv-vis spectra as the methanol extraction liquid of the toner of the salicylic acid-metal complex of charge control agent of Fig. 3, found absorption peak at 280-350nm.

Just because of the charge control agent that suitable high concentration is arranged on the toner-particle surface, therefore, the methanol extraction liquid that contains the toner of charge control agent has because the absorption peak that charge control agent produced.

Be included in because the carrier in the developer of the chargeding performance deficiency that existence caused of waste material then, is measured the uv-vis spectra of extract with methanol extraction, finding has because the absorption peak that charge control agent produced at 400-700nm.For example, the long-time use contained the toner that has azo-compound-chromic compound, and its uv-vis spectra is shown in the developer of Fig. 2, to produce waste material therein.Then, measure the uv-vis spectra of the methanol extraction liquid of carrier in this developer, to obtain being shown in the spectrum of Fig. 4.As shown in Figure 4, finding absorption peak with the same position of Fig. 2 spectrum.It has been generally acknowledged that this is because the adhesive resin in the toner is attached to carrier surface with the formation resin molding, and has produced waste material.Yet from comparison shows that of the absorption curve of Fig. 2 and Fig. 4, the main cause that waste material produces is that charge control agent is from the transfer of toner-particle to carrier granular.

In order to find out relation other between charge control agent and the waste material, the present invention carries out following test: at first, the toner that will include the toner-particle of the azo-compound-chromium complex dyes that contains 1.5wt% mixes with carrier, thereby waits until a developer.With toner and carrier vibration-section preset time.Fig. 5 shows time of vibration and the relation between the adhesion amount on the carrier particle surface.In Fig. 5, adhesion amount represents with the waste material ratio, promptly based on the percentage of the carrying attachment of carrier granular general assembly (TW).In addition, Fig. 6 shows the relation between time of vibration and the toner carried charge.Developer for including the toning body that does not contain charge control agent and carrier repeats identical step.The test findings of this developer also is shown among Fig. 5 and Fig. 6, wherein, the resulting result of developer who includes the toner that contains charge control agent maps with black circle, and the resulting result of developer who includes the toner that does not contain charge control agent maps with circle.Be clear that from Fig. 5 and Fig. 6, attachment as waste material forms on carrier granular in a large number, and in the developer that includes the toner-particle that contains charge control agent, the quantity of electric charge of toner falls manyly than the quantity of electric charge of toner in the developer that includes the toner-particle that does not contain charge control agent.

Then, As time goes on measure the weight that is attached to the toner component on the carrier particle surface as waste material simultaneously.The results are shown in the curve of Fig. 7, wherein horizontal ordinate is represented the waste material amount that records, and ordinate is represented the amount of charge control agent in the toner-particle.Dotted line is represented among Fig. 7, suppose to adhere to identical with component in the toner-particle as the toner component of waste material and the charge control agent amount that calculates.Fig. 7 shows will have a large amount of charge control agents to be attached on the surface of carrier granular at initial period.In Fig. 7, along with the increase of waste material amount, measured value will be near calculated value.This is because they are the experimental results that obtain in not having the closed system of fresh toner supply.Thereby in changing to toner as duplicating machine, the difference between measured value and the calculated value is with much bigger.

In addition, the present inventor measures carrier and each toner component is a charge control agent, adhesive resin mixes as the carbon black of colorant and wax and causes adhesion amount on carrier particle surface, so that find out the relation between each toner component and the waste material.The results are shown in Fig. 8, attachment amount (being the waste material amount) time to time change.Wherein, resulting result maps with white circle with the potpourri of charge control agent, map with black circle with the resulting result of the potpourri of carbon black, resulting result maps with grid with the potpourri of adhesive resin, and resulting result maps with triangle with the potpourri of wax.Can find out clearly that from Fig. 8 charge control agent will produce because the maximum adhesion thing amount that waste material caused.

Based on the above-mentioned fact, come in the interpretation routine two-component magnetic developing agent by the caused charged failure of waste material below with reference to Fig. 9.Using the initial period of developer, carrier granular 1 positively charged and toner-particle 2 is electronegative is shown in Fig. 9 top.In this case, this toner-particle plays negative electricity toner 21.When this developer uses continuously, in toner-particle, include charge control agent and will be attached on the surface of carrier granular 1 as a kind of component of main component.Attachment 201 as waste material is electronegative.Electronegative attachment 201 will cause forming the toner-particle with positive lotus, i.e. the toner-particle 22 of oppositely charged.On the surface of carrier granular 1, form the toner-particle of oppositely charged, shown in the lower part of Fig. 9, will cause the diffusion of toner, and reduce the transfer efficiency of toner.

As mentioned above, preferred toner does not have charge control agent; This is not only because this agent has heavy metal, and because this agent is to produce waste material, the main cause that toner spreads and the toner transfer efficiency reduces.Therefore, toner of the present invention does not have charge control agent at all.

Owing to lack the instability, the particularly deficiency of toner charge amount of the toner charge that charge control agent causes, be compensated by using the aforesaid adhesive resin that has anionic group.Because adhesive resin itself owing to comprising anionic group negative charge is arranged, so can replenish the deficiency of the toner-particle quantity of electric charge.Because anionic group is connected on the main chain of adhesive resin, therefore, it can not moved on the surface of carrier granular by the image charge controlling agent like that, therefore, not can produce waste material.On the contrary, the electric charge that is produced by the anionic group of adhesive resin, be centered around around the toner-particle is very not many.Therefore, when toner-particle and carrier granular are transmitted as the magnetic brush that develops,, so can not produce electrostatic attraction between toner-particle and the carrier granular because the Coulomb force is not enough.Thereby, in quick copying operation,, therefore, be not enough to prevent the diffusion of toner owing to combine inadequately with carrier granular.The toner of diffusion stains the inwall of duplicating machine, and will produce so-called fuzzy on the image that duplicates.

In order to overcome this class defective, it is that per 100 weight portion adhesive resins are the magnetic of 0.1-5 weight portion that toner of the present invention includes predetermined ratio.So can compensate the deficiency of the toner-particle quantity of electric charge.The magnetic that is included in the toner-particle produces magnetic attraction between toner-particle and carrier granular.This magnetic attraction between toner-particle and carrier granular will prevent the diffusion of toner with electrostatic attraction.In addition, owing to hour also increased the quantity that is attached to the toner-particle on the electrostatic latent image, therefore, increased apparent development sensitivity at the quantity of electric charge of toner-particle.

As mentioned above, the content of magnetic is in toner-particle, and per 100 weight portion adhesive resins are the 0.1-5 weight portion.When this content during less than 0.1% weight, the quantity of electric charge of toner-particle is deficiency, cause not enough with combining of carrier granular, and the diffusion that therefore produces toner.In this case, will on the image that duplicates, be harmful formed fuzzy.In addition, because quantity of electric charge deficiency, so the density of duplicating image also will be very low.When this contained above 5% weight, the magnetic attraction between carrier granular and the toner-particle was too strong, and the result is that toner is not attached on the electrostatic latent image fully, has caused the density of duplicating image to reduce.

Some trials have been made by including (comprise and being added into) magnetic as a toner component, with resolution of improving copy image etc.For example, a day disclosure special permission communique 56-106249 has disclosed and has included the ferritic toner-particle of 10wt%, and a day disclosure special permission communique 59-162563 has disclosed the fine grain toner-particle of a kind of 5-35wt% of including magnetic.Yet in both cases, because magnetic is excessive, so the density of copy image is low.Day disclosure special permission communique 3-67268 has disclosed the toner that adds the 0.05-2wt% magnetic from the outside.In this case, because magnetic is not included in the toner-particle, so this magnetic will be attached on the surface of toner-particle equally unevenly, cause magnetic attraction not enough between toner-particle and carrier granular.In addition, in two kinds of above-mentioned toners,, therefore, will produce waste material nocuously owing to include charge control agent therein.

In the present invention, in order to increase the transfer efficiency of toner image, preferably be that the interval dose particle of 0.05-1.0 μ m is attached on the surface of toner-particle with particle diameter.This interval dose particle can play fluidity enhancers for toner-particle, and in addition, when toner was attached on the electrostatic latent image that forms on photosensitive body, this interval dose can also form a gap between photosensitive body and toner-particle.Thereby, even when obtaining a large amount of electric charge owing to long-term toner that copying operation makes, this toner also can easily be transferred on the copy paper from photosensitive body, thereby has caused high transfer efficiency.

In addition, preferably with resistivity 10 ¹With 10 ⁵First interval dose particle between the Ω cm and resistivity are 10 ⁸With 10 ¹³The second interval dose particle between the Ω cm is added in the toner of the present invention as the interval dose particle.When these the two kinds of interval dose particles with different resistivity were attached on the surface of toner-particle, the transfer efficiency of toner from photosensitive body to copy paper was improved.In addition, the surface of toner-particle also is divided into two kinds of zones with different surfaces resistivity.Therefore, charge to toner respectively and discharge in these two kinds of zones.Therefore, can easily obtain the desirable quantity of electric charge.This will improve the charge stability of final toner, and stablize the density of copy image astoundingly.

Although also added the fine grained that is about 0.015 μ m as the particle diameter of fluidity enhancers in the toner of routine, such granule can not form enough big gap between photosensitive body and toner-particle.Therefore, for realizing above-mentioned purpose, they do not play the interval dose particle.

In the present invention, Metallic stearates can be attached on the surface of toner-particle and/or interval dose particle.This has increased the antistick characteristic between toner and the photosensitive body surface, and therefore, toner unlikely is attached on the surface of photosensitive body.Particularly, when Metallic stearates only optionally was attached on the surface of interval dose particle, this Metallic stearates will contact with the surface of photosensitive body effectively, whereby, will prevent more effectively that toner and interval dose particle are attached on the photosensitive body.

When Metallic stearates was attached on the surface of toner-particle, the resistance of toner suitably reduced, and this will produce highdensity image.In addition, owing to the melt viscosity that has reduced toner by Metallic stearates, therefore in passing through the thermal fixation process of warm-up mill, toner can infiltrate in the copy paper well, thereby obtains the fixation performance that copy image improves on copy paper.And because the melt temperature specific viscosity mixture resin of Metallic stearates is low, therefore, the surface of the copy image that forms by the set transferred image is more smooth, thereby has formed smooth copy image.

Now, will the preferred resin that be used as adhesive resin in the toner of the present invention be described.At this, " low-grade alkyl group " expression C _1-5Alkyl.

The adhesive resin that is included in the toner-particle of toner of the present invention comprises: the composition that comprises the polymkeric substance that has anionic group.Such adhesive resin is by the monomer that will have anionic group or has the monomer of anionic group and the potpourri of other monomer carries out polymerization and obtains.

The multipolymer that the adhesive resin that is used for toner of the present invention is preferably obtained by the monomer that contains anionic group and other monomer, as random copolymers, segmented copolymer and graft copolymers.

The example that has the monomer of anionic group comprises, has hydroxy-acid group, the monomer of sulfonic acid group or phosphate group; But use the monomer of band hydroxy-acid group usually.The example that has the monomer of hydroxy-acid group comprises, ethylenically unsaturated carboxylic acids, and as acrylic acid, methacrylic acid, butenoic acid, maleic acid and fumaric acid; Can form hydroxy-acid group monomer as maleic anhydride; And the low alkyl group half ester of dicarboxylic acid such as maleic acid and fumaric acid.The example that has the monomer of sulfonic acid group comprises styrene sulfonic acid and 2-acrylamido-2-methyl propane sulfonic acid.The example that has the monomer of phosphate group comprises 2-phosphono (oxygen) propyl methyl acid esters, 2-phosphono (oxygen) ethyl-methyl acrylate, 3-chloro-2-phosphono (oxygen) propyl methyl acid esters.

This class monomer that has anionic group can be a free acid, the salt of alkaline metal such as sodium and potassium, and the salt of earth alkali metal such as calcium and magnesium, and as zinc salt.

Selection is used for preparing adhesive resin, and with the monomer of anionic group, the result is not that final adhesive resin has required fixation performance of enough toners and chargeding performance, and this monomer is a kind of ethylenically unsaturated monomer or its potpourri.The example of such monomer comprises the ethylenically unsaturated carboxylic acids ester, monovinylarene, vinyl esters, vinyl ether, diolefin and mono-olefin.

The ethylenically unsaturated carboxylic acids ester is represented by following formula (I):

R in the formula ¹Be hydrogen atom or low alkyl group, R ²For being less than or equal to C ₁₁Alkyl or be less than or equal to C ₁₁Hydroxyalkyl.

The example of such ethylenically unsaturated carboxylic acids ester comprises, methyl acrylate, ethyl acrylate, butyl acrylate, 2-EHA, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, hexyl methacrylate, methacrylic acid 2-Octyl Nitrite, beta-hydroxyethyl acrylate, γ-hydroxypropyl acrylate, δ-hydroxyl butylacrylic acid ester and beta-hydroxyethyl methacrylate.

Monovinylarene is represented by the same form (II):

R in the formula ³Be hydrogen atom, low alkyl group or halogen atom; R ⁴Be hydrogen atom, low alkyl group halogen atom, alkoxy, amino or nitro; φ is a phenylene.

The example of such monovinylarene comprises, styrene, and α-Jia Jibenyixi, vinyltoluene, α-chlorostyrene, neighbour-chlorostyrene ,-chlorostyrene, right-chlorostyrene and right-ethyl styrene.

Vinyl esters is represented by following formula (III):

R in the formula ⁵Be hydrogen atom or low alkyl group.

The example of such vinyl esters comprises, vinyl formate, vinyl acetate and propionate.

Vinethene is represented by following formula (IV):

CH ₂=CH-O-R ⁶(IV) R in the formula ⁶For being less than or equal to C ₁₁The monovalence alkyl.

The example of such vinethene comprises, vinyl methyl ether, EVE, vinyl n-butyl ether, vinyl phenyl ether, and vinyl cyclohexyl ether.

Diolefin is represented by following formula (V): R in the formula ⁷, R ⁸And R ⁹Be hydrogen atom, low alkyl group or halogen atom independently.

The example of above-mentioned diolefin comprises, butadiene, isoprene and chlorbutadiene.

Mono-olefin is represented by following formula (VI): R in the formula ¹⁰And R ¹¹Be hydrogen atom or low alkyl group independently.

The example of above-mentioned mono-olefin comprises, ethene, propylene, isobutylene, 1-butylene, 1-amylene and 4-methyl-1-pentene.

The object lesson that has (being total to) polymers that the polymkeric substance of anionic group, i.e. polymerization by above-mentioned monomer obtain comprises styrene-propene acid copolymer, styrene-maleic acid copolymer and ionomer resin.In addition, also can use the vibrin that has anionic group.The polymkeric substance that has anionic group preferably includes the anionic group of following ratio: when anionic group existed with the form of free acid, resulting acid number was 2-30.When part or all of anionic group was neutralized, the ratio of preferred anionic group was: suppose that anionic group exists with the form of free acid, its acid number is in above-mentioned scope.When this acid number, be the anion concentration of polymkeric substance or composition when being lower than above-mentioned scope, the chargeding performance of final toner is with deficiency.When acid number surpasses this scope, final toner will have moisture pick-up properties nocuously.The preferred adhesive resin is, by monomer that has anionic group and the necessary composition of at least a conduct, by the ethylenically unsaturated carboxylic acids ester of structural formula (I) expression, and use as the selectivity composition if necessary, by the resulting multipolymer of any monomer of structural formula (II)-(VI) expression.Above-mentioned monomer a kind of, perhaps two or more combination can be used to prepare adhesive resin.

In addition, composition can also comprise the polymkeric substance that does not contain anionic group.In this case, in the whole composition content of anionic group preferably in above-mentioned scope

The magnetic that is included in (comprise and being added into) toner-particle can be any magnetic that uses in the conventional one-pack type developer.The example of magnetic comprises: tri-iron tetroxide (Fe ₃O ₄), maghemite (γ-Fe ₂O ₃), zinc-iron oxide (ZnFe ₂O ₄), oxidation yttrium iron (Y ₃Fe ₅O ₁₂), cadmium oxide iron (CdFe ₂O ₄), gadolinium oxide iron (Gd ₃Fe ₅O ₁₂), cupric oxide iron (CuFe ₂O ₄), oxidation galvanized iron (PbFe ₁₂O ₁₉), oxidation ferronickel (NiFe ₂O ₄), neodymia iron (NdFeO ₃), baryta iron (BaFe ₁₂O ₁₉), magnesium oxide iron (MgFe ₂O ₄), oxidation ferromanganese (MnFe ₂O ₄), lanthana iron (LaFeO ₃), iron (Fe), cobalt (Co) and nickel (Ni).Particularly preferred magnetic is made by the tri-iron tetroxide (magnetic iron ore) that fine powder closes.Preferred magnetite ore particles is the octahedron of the rule of diameter 0.05-1.0 μ m.Can carry out surface treatment to above-mentioned magnetite ore particles with silane coupling agent or titanium coupling agent.The particle diameter that is included in the magnetic in the toner-particle is generally 1.0 μ m or littler, preferably at 0.05-1.0 μ m.

The content of magnetic is in the toner: per 100 weight portion adhesive resin 0.1-5 weight portions, better at the 0.5-4 weight portion, the best is the 0.5-3 weight portion.When this content is too low, toner will spread during developing, and will reduce the transfer efficiency of aforesaid toner.

As mentioned above, toner-particle contains as the adhesive resin of necessary composition and magnetic, and comprises some internal additives that is generally used for toner if desired also not essentially.

The example of above-mentioned adjuvant comprises colorant and detackifier.

As colorant, can use following pigment:

Black pigment:

Carbon black, acetylene black, dim, nigrosine:

Extender:

Ground barium sulfate, barium carbonate, clay, silicon dioxide, white carbon black (whitecarlon), talcum, alumina white.

The consumption that is included in the above-mentioned pigment in the toner is per 100 weight portion adhesive resin 2-20 weight portions, preferred 5-15 weight portion.

As detackifier, can use the various waxes and the olefine resin that use in the conventional toner.

Can be by commonsense method such as the cracking and sorting method that is used for toner-particle, the fusion granulation, injection granulation and polymerization are come the toner-particle in the production toner of the present invention; But produce with the cracking and sorting method usually.

For example, at first the various components with toner-particle mix in mixer such as Henschel mixer, knead with the kneading machine as biaxial extruder so again, cool off then.Broken and the sorting with final product is to obtain toner-particle.The volume base mean grain size of toner-particle is generally 5-15 μ m, preferred 7-12 μ m (mean grain size that records with the Coulter meter).

In the toner of two-component developer of the present invention, the interval dose particle is attached on the surface of toner-particle, to improve the transfer efficiency of toner image.As the interval dose particle, can use particle diameter to be 0.05-1.0 μ m, more preferably any inorganic and organic inert particle of 0.07-0.5 μ m.The example of above-mentioned inert particle comprises silicon dioxide, aluminium oxide, titanium dioxide, magnesium carbonate, acryl resin, styrene and magnetic material.The interval dose particle can not only play fluidity enhancers, and can also improve aforesaid transfer efficiency.Be as the criterion with the toner general assembly (TW), the content of interval dose particle is 10wt% or still less, better at 0.1-10wt%, is preferably in 0.1-5wt%.When the interval dose particle was excessive, the density of duplicating image was not enough.

Particularly, preferably the interval dose particle of two kinds of different resistivity as described below is attached on the surface of toner-particle.

As the first interval dose particle, use volume base mean grain size to be 0.05-1.0 μ m, be preferably 0.07-0.5 μ m, resistivity is 10 ' and 10 ⁵Between the Ω cm, preferably 10 ³With 10 ⁵Organic or inorganic inert particle between the Ω cm.The example of this first interval dose particle comprises and carries out surface-treated titanium dioxide and magnetic iron ore with tin coating.

As the second interval dose particle, use volume base mean grain size to be 0.05-1.0 μ m, preferably at 0.07-0.5 μ m, resistivity is 10 ⁸With 10 ¹³Between the Ω cm, preferably 10 ⁹With 10 ¹²Organic or inorganic inert particle between the Ω cm.The example of this second interval dose particle comprises silicon dioxide, aluminium oxide, titanium dioxide, zinc paste, barium sulphate, magnesium carbonate, acryl resin, styrene resin and styrene-propene acid copolymer.

For example, can utilize the resistivity test device 4 of structure as shown in figure 11 to measure the resistivity of interval dose particle.The measuring method of resistivity test device 4 will be described now.At first, being placed on by internal diameter H1 as the interval dose particle of sample 8g is in the pipe 41 that makes of 1 inch vinyl chloride, and is clipped between the steel electricity level 421.The outside surface of electricity level 421 is equipped with the polyfluortetraethylene plate 43 that thickness is 2mm.With hydropress one of them polyfluortetraethylene plate 43 is being applied 200kg/cm ²Pressure P r the time, (Toa Electronics Ltd. makes, SM-5) measuring resistance r (Ω) with insulation resistance tester 42 at 500V.Then, the length H2 (cm) between measurement electricity level 421 two ends as shown in figure 11.Poor between the length H2 when promptly not containing sample in pipe 41 according to the H2 that records and 11.35cm calculates the thickness of sample.Then, calculate the resistivity R (Ω cm) of sample with following formula:

General assembly (TW) with final toner is as the criterion, and the total content of interval dose particle is 10wt% or lower, is preferably 0.1-10wt%, and the best is 0.1-5wt%.When they were excessive, the density of duplicating image was not enough.

Have no particular limits although be included in the first interval dose particle in the toner of the present invention and the ratio of the second interval dose particle, its weight ratio is preferably 1: 7-7: 1, more preferably 1: 4-4: 1.When these interval dose particles use with such ratio,, thus, increased the effect that obtains the desired quantity of electric charge with having the surface of the toner-particle that independently toner is charged and discharge.

The example that is added into the Metallic stearates in the toner-particle that is loaded with above-mentioned interval dose particle comprises, zinc stearate, dolomol, aluminium stearate, potassium stearate, chromium stearate, mercuric stearte, cerium stearate, ferric stearate (II), odium stearate, lead stearate, and barium stearate.Can use a kind of salt, the perhaps potpourri of two or more salt.The preferred use is selected from least a of zinc stearate and dolomol, more preferably uses zinc stearate.Above-mentioned Metallic stearates can substitute with stearic amide.

Be added into the Metallic stearates in the toner-particle that is loaded with the interval dose particle, be as the criterion with the toner general assembly (TW), its consumption is 0.001-3wt%, preferred 0.003-1wt%, best 0.005-0.2wt%.Metallic stearates not only can be attached on the surface of toner-particle, and can be attached on the surface of interval dose particle.Yet preferred Metallic stearates optionally is attached on the surface attached to the interval dose particle on the toner-particle." optionally be attached on the surface of interval dose particle " at this and refer to; Metallic stearates on the surface that only is attached to the interval dose particle; basically non-cohesive to the surface of toner-particle; in order optionally stearic acid metal pave floor with bricks, stones etc. to be attached on the surface of interval dose particle; in advance Metallic stearates is mixed with the interval dose particle, then the potpourri that obtains is added in the toner-particle as described below.

As mentioned above, it is lip-deep that toner of the present invention is included in toner-particle, the interval dose particle of predetermined particle diameter.If necessary, can use the interval dose particle of two kinds of different resistivity, or Metallic stearates is attached on the surface of toner-particle and/or interval dose particle.Except that Metallic stearates,, can further improve the flowability of final toner by adhering to the fluidity enhancers such as the silica dioxide granule hydrophobic, vapour deposition of particle diameter less than the interval dose grain diameter.

The primary particle diameter of fluidity enhancers such as silica dioxide granule is generally about 0.01 5 μ m.With the weight of whole toner is that the general assembly (TW) of toner-particle and adjuvant (as interval dose particle and fluidity enhancers) is as the criterion, and the amount that is added into the fluidity enhancers of toner is 0.1-2.0wt%.

Use following mode, with interval dose particle and Metallic stearates if necessary, fluidity enhancers etc. are added in the toner-particle that makes as mentioned above.For example, with interval dose particle (preferred two kinds of interval dose particles) and Metallic stearates if necessary, fluidity enhancers etc. are fully mixed.Then the potpourri that obtains is added in the toner-particle, final product is enough unconjugated.Therefore, the interval dose particle can be attached on the surface of toner-particle equably.When adding Metallic stearates in this mode, Metallic stearates will be attached on the surface of toner-particle and interval dose particle.

In addition, can in advance toner-particle be mixed with Metallic stearates fully.Make then the interval dose particle and if necessary fluidity enhancers be attached on the surface of the toner-particle that is loaded with Metallic stearates.Therefore, in final toner, Metallic stearates is not attached on the surface of interval dose, and only on the surface attached to toner-particle.

" adhere to " at this and to refer to, two particle surfaces keep in touch and partly embed in the particle.

Use this mode, made toner of the present invention.

In the present invention, can use magnetic iron ore or ferrite usually, as the carrier of double component developing.As time goes on or by changing environment, its resistance is stable and changes hardly that therefore, it provide stable chargeding performance can for final developer in above-claimed cpd.In addition, when applying magnetic field, above-mentioned compound will form the shape (soft spicatedshape) that soft spike is arranged in developing apparatus.This will stop the disturbance of the toner image that forms on photosensitive body, suppressed to form in duplicating image white stripes thus.The preferred ferrite that uses.

The carrier granular that is used for carrier of the present invention more preferably is made of the double-deck particle that comprises the coating on core granule and the core granule.This core granule contains the magnetic material by following formula (A) expression:

MOFe ₂O ₃(A) M is at least a Cu that is selected from the formula, Zn, Fe, Ba, Ni, Mg, Mn, the metal of Al and Co.

Compound by formula (A) expression is that M is preferably Cu, Zn, Mn, the ferrite of Ni or Mg in magnetic iron ore (M is Fe in the formula) or ferrite (M is a kind of metal except that Fe in the formula) and the formula.Above-mentioned magnetic iron ore and ferrite its resistance after a very long time is almost constant, and when applying magnetic field, in developing apparatus, this magnetic iron ore and ferrite will form the shape that soft spike is arranged.The particle diameter that comprises the core granule of above-mentioned magnetic material is 30-200 μ m, preferred 50-150 μ m.Core granule is by air prilling etc. fine grain magnetic material to be carried out granulation, and the particle that obtains of heating obtains then, and the specific volume resistance of core granule is 10 ⁵-10 ⁹Ω, cm is preferably 10 ⁶-10 ⁸Ω cm.The saturation magnetization of core granule is 30-70 electromagnetic unit/g, is preferably 45-65 electromagnetic unit/g.

Be used for forming the carrier granular coating, be included in resin in the resin combination, the band cation group, can be thermoplastic resin and thermoset resin.With regard to thermotolerance and permanance, preferred thermoset resin or thermoset resin and thermoplastic resin potpourri.The example of cation group comprises, as contain primary, the second month in a season and uncle's amino, quaternary ammonium group, amide group group, imido grpup group, imide group, hydrazide group group, the basic nitrogen of guanidino group and amidino groups group; Wherein particularly preferably be amino group and quaternary ammonium group.

The example that has the thermoplastic resin of cation group comprises, thermoplastic acrylic resin, and thermoplastic styrene-acryl resin, vibrin, polyamide and olefin copolymer, each above-mentioned material has included cation group.The example of thermoset resin comprises silicone resin, thermosetting acrylic resin, and thermosetting styrene-acryl resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy resin and amino resins, above-mentioned each material has included cation group.Monomer by the condensation zone cation group or the potpourri that contains the monomer that has cation group have obtained including the above-mentioned resin of cation group.In addition, compound that can be by having cation group obtains above-mentioned resin with the resin-bonded of cation group not.Also have a kind of method to be, the monomer and/or the another kind of monomer that will have cation group carry out (being total to) polymerization by the polymerization initiator that has cation group, whereby, cation group are introduced final resin.

When using the resin that makes by alkoxy silane or alkoxytitanium, during the preparation of this resin or afterwards,, can produce the resin that has cation group by making silane coupling agent and this resin reaction that has cation group.The example of silane coupling agent comprises N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, γ-An Jibingjisanyiyangjiguiwan and N-phenyl-3-TSL 8330.By being present in the lip-deep hydroxyl of core granule usually, this one type of silane coupling agent is bonded on the surface of core granule, therefore, itself just can form coating above-mentioned silane coupling agent.The example of the polymerization initiator of band cation group comprises amidine compound, for example azo two compounds.

Be used to form separately resin coating, that be with cation group, or use, or use with another resin of cation group not with above-mentioned other resin.

In the resin of band cation group, the content of cation group is: every 100g resin is 0.1-2000mmole, is preferably 0.5-1500mmole.When the resin that will have cation group when not using with the resin of cation group, be included in the ratio of the cation group in the whole resin that forms the carrier granular coating, preferably drop in the above-mentioned scope.

The resin combination that forms the carrier granular coating comprises at least a above-mentioned resin that has cation group, and another kind of if necessary not with the resin of cation group.The resin of band cation group and not comprising with the example of the potpourri of the resin of cation group, the potpourri of alkylated melamine resins and styrene-propene acid copolymer, and the potpourri of alkylated melamine resins and acrylic acid modified silicone resin.This resin combination also can comprise adjuvant, as silicon dioxide, and aluminium oxide, carbon black, fatty acid metal salts, silane coupling agent and silicone oil.These adjuvants are used for regulating the physical property of coating.

The resin combination that will include cation group by known method is applied on the surface of core granule, thereby forms coating.For example,, and carry out drying, form coating thus with the solution or the dispersion liquid coating core granule of resin combination.In addition, when using thermoset resin or reactant resin oligomer, with uncured resin, or the solution of oligomer or dispersion liquid coating core granule, heat then to solidify this resin.Can be by any method commonly used such as infusion process, spray-on process, fluidized bed process, moving bed method and rotary drum coating form coating, as being used for dissolving or the solvent of dissipating resin composition, can use any common organic solvent.The example of solvent comprises, aromatic hydrocarbon such as toluene and dimethylbenzene; Ketone, as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Cyclic ethers is as tetrahydrofuran and dioxan; Alcohols such as ethanol, propyl alcohol and butanols; Molten brazing flux class is as molten brazing flux of ethyl and the molten brazing flux of butyl; Ester class such as ethyl acetate and butyl acetate; Amide solvent such as dimethyl formamide and dimethyl acetamide.According to the chemical property such as the dissolubility of resin, suitably selective solvent.

The particle diameter of the carrier granular that so obtains is 30-200 μ m, is preferably 50-150 μ m.Weight ratio in the coating of carrier granular is that per 100 weight portion core granules are the 0.001-2.5 weight portion, preferred 0.005-2.0 weight portion.The specific volume resistance of the carrier granular that obtains is 10 ⁵-10 ¹³Ω cm is preferably 10 ⁷-10 ¹²Ω cm, saturated electromagnetism intensity is 30-70 electromagnetic unit/g, is preferably 45-65 electromagnetic unit/g.

Make two-component developer by mixing above-mentioned toner and carrier.The weight mixing ratio of carrier and toning body is generally 98: 2-90: 10, be preferably 97: 3-94: 6.

By common electrophotographic image forming method, use toner of the present invention to carry out copying operation.Specifically, for example, the photosensitive layer on the photosensitive body is carried out uniform charging, carry out exposure then on photosensitive layer, to form electrostatic latent image.The magnetic brush of being made by two-component magnetic developing agent is contacted with photosensitive body, make developing electrostatic latent image become toner image thus easily.The toner image that so obtains is transferred on the copy paper,, by warm-up mill transferred image is heated and pressurization then, thereby this image is anchored on the copy paper to form transferred image.

Embodiment

To the present invention be described by embodiment now.Be pointed out that the present invention is not limited to these embodiment.

Embodiment 1.1

Toner component parts by weight

Adhesive resin a) 100

Colorant: carbon black 7

Magnetic: magnetic iron ore 2

A) have the styrene-propene acid copolymer (wherein, styrene, butyl methacrylate, acrylic acid weight ratio is 80: 15: 5) of carboxyl.

Utilize the component melt kneading that biaxial extruder will list above, the product that obtains jet mill fragmentation, and carry out sorting with the pneumatic separating device, to obtain the toner-particle that mean grain size is 10.0 μ m.

In the toner-particle that obtains, add with 100 weight portion toner-particles be as the criterion 03 weight portion, mean grain size be 0.015 μ m, as the hydrophobic silica powder of fluidity enhancers and 0.5 weight portion, mean grain size be 0.15 μ m, as the acrylic resin particle of interval dose particle.

The ferrite carrier that the toner that so obtains and mean grain size are 100 μ m evenly mixes, thereby obtains the two-component developer that toner concentration is 3.5wt%.

Embodiment 1.2

Repeat the step of example 1.1, different is, is 0.4 μ m as the mean grain size of the magnetite ore particles that interval dose added, and makes developer thus.

Comparative Examples 1

Repeat the step of example 1.1, different is, does not use the interval dose particle, makes developer thus.

Embodiment 2.1

Toner component parts by weight

Adhesive resin a) 100

Colorant: carbon black 10

Magnetic: magnetic iron ore 2

A) have the styrene-propene acid copolymer (in the base, styrene, butyl methacrylate and acrylic acid weight ratio are 70: 28: 2) of carboxyl.

The component of listing is above carried out melt kneading with biaxial extruder, and the product that obtains carries out fragmentation with jet mill, and carries out sorting with the pneumatic separating device, to obtain the toner-particle that mean grain size is 10.0 μ m.

In the toner-particle that obtains, add with 100 weight portion toners be as the criterion 0.3 weight portion, mean grain size be 0.015 μ m, as the hydrophobic silica powder of fluidity enhancers.Add with 100 weight portion toner-particles again and be as the criterion 0.5 weight portion as the titan oxide particles of the first interval dose particle, this particle carried out surface treatment with tin coating, and its volume base mean grain size is 0.3 μ m, and resistivity is 2 * 10 ³Ω cm; And be the alumina particle of 0.5 weight portion as the second interval dose particle, the volume base mean grain size of this particle is 0.3 μ m, resistivity is 10 ¹⁰Ω cm.The potpourri that obtains was mixed 2 minutes with the Henschel mixer,, on described toner-particle, be attached with above-mentioned particle to obtain including the toner of toner-particle.

The ferrite carrier that the toner that so obtains and mean grain size are 100 μ m evenly mixes, to obtain the two-component developer that toner concentration is 3.5wt%.

Embodiment 2.2

Repeat the step of embodiment 2.1, different is, adds with the be as the criterion first interval dose particle of 1 weight portion of 100 weight portion toner-particles, does not add the second interval dose particle, prepares developer thus.

Embodiment 2.3

Repeat the step of example 2.1, different is, adds with the be as the criterion second interval dose particle of 1 weight portion of 100 weight portion toner-particles, does not add the first interval dose particle, prepares developer thus.

Embodiment 2.4

Repeat the step of example 2.1, different is, does not add the first and second interval dose particles, is that 0.3 μ m, resistivity are 10 and add be as the criterion 1 weight portion, volume base mean grain size of 100 weight portion toner-particles ⁶The titan oxide particles of Ω cm prepares developer thus.

Embodiment 3.1

Use the method identical to prepare toner with example 2.1.

With mean grain size is that the spherical ferrite particle of 100 μ m is as the magnetic core granule.Be added into smears in the ferrite particle of 100 weight portions, and the product that obtains is mixed with the thermal agitation device as the listed component of table 1.From final potpourri, remove and desolvate, and with residue 200 ℃ of thermal treatments 1 hour, to obtain all cated carrier granular of each particle.

The toner and the carrier that so obtain are evenly mixed, to obtain the two-component developer that toner concentration is 3.5wt%.

Embodiment 3.2

Repeat the step of example 3.1, different is that the component of employed smears is listed in table 1, prepares developer thus.

Embodiment 3.3

Repeat the step of example 3.1, different is that the component of employed smears is listed in table 1, prepares developer thus.

Embodiment 3.4

Repeat the step of example 3.1, different is, does not use any smears and does not form coating, prepares developer thus.

Table 1, smears component example 3.1 examples 3.2 examples 3.3 examples 3.4 resins 1 acrylic acid modified aminomethyl phenyl polystyrene-acrylic acid of routine 3.1-3.4 does not have (weight portion) polysiloxane siloxane polymer

2.5 4.8 3.5 resins, 2 methylated melamines gamma-amino propyl group methylated melamines do not have (weight portion) triethoxysilane

2.5 0.2 1.5 solvents: toluene 200 200 200 does not have (weight portion)

Embodiment 4.1

Toner component weight portion

Adhesive resin ^A)100

Colorant: carbon black 10

Magnetic: magnetic iron ore 2

A) the styrene-propene acid copolymer (wherein, styrene, butyl methacrylate and acrylic acid weight ratio are 70: 28: 2) of band carboxylic group.

Utilize biaxial extruder that above-listed component fusion is kneaded, with the product fragmentation that obtains, and carry out sorting with airslide disintegrating mill, to obtain the toner-particle that mean grain size is 10.0 μ m with airflow separator.

In the toner-particle that obtains, add with 100 weight portion toner-particles be as the criterion 0.3 weight portion, mean grain size be 0.015 μ m, as the hydrophobic silica powder of fluidity enhancers, and 0.5 weight portion, mean grain size be 0.15 μ m, as the magnesium carbonate of interval dose particle. in addition, add again with 100 weight portion toner-particles be as the criterion 0.05 weight portion, as the zinc stearate of Metallic stearates.Utilize the Henschel mixer that final potpourri was mixed 2 minutes, to obtain toner.

The ferrite carrier that the toner that so obtains and mean grain size are 100 μ m evenly mixes, to obtain the two-component developer that toner concentration is 3.5wt%.

Embodiment 4.2

At first, be the MgCO of 0.15 μ m with the Henschel mixer with 10 weight portion mean grain sizes ₃Mixed 10 minutes with the zinc stearate of 1 weight portion as Metallic stearates.

The potpourri that obtains is added into 100 weight portion toner-particles, 0.55 weight portion (the i.e. 0.5 weight portion MgCO that is as the criterion ₃With 0.05 weight portion zinc stearate) in example 4.1 preparation toner-particle in.In addition, add again with 100 weight portion toners be 0.3 weight portion, mean grain size be 0.015 μ m, as the hydrophobic silica fine grained of fluidity enhancers.Utilize the Henschel mixer that the potpourri that obtains was mixed 2 minutes, to obtain toner.

The ferrite carrier that the toner that so obtains and mean grain size are 100 μ m evenly mixes, to obtain the double component developing that toner concentration is 3.5wt%.

Embodiment 4.3

Repeat the step of example 4.2, different is, replaces 1 weight portion zinc stearate with 2 weight portion dolomols, and with 0.52 weight portion, MgCO ₃Potpourri (that is 0.5 weight portion MgCO, with dolomol ₃With 0.02 weight portion dolomol) add in the toner-particle, prepare toner thus.

The ferrite carrier that the toner that so obtains and mean grain size are 100 μ m evenly mixes, to obtain two-component developer.

Embodiment 4.4

Repeat the step of example 4.1, different is, does not add stearic acid zinc, prepares developer thus.

Embodiment 5.1

Prepare toner with the mode identical with example 4.1.

Using mean grain size is that the spherical ferrite particle of 100 μ m is as the magnetic core granule.The smears of the listed component of table 2 is added in the 100 weight portion ferrite particles, and mix resulting product with the thermal agitation device.From final potpourri, remove and desolvate, and with residue 200 ℃ of thermal treatments 1 hour, to obtain all cated carrier granular of each particle.

The toner and the carrier that so obtain are evenly mixed, to obtain the two-component developer that toner concentration is 3.5wt%.

Embodiment 5.2

Repeat the step of example 5.1, different is that the component of used smears is as shown in table 2, prepares developer thus.

Embodiment 5.3

Repeat the step of example 5.1, different is that the component of used smears is as shown in table 2, prepares developer thus.

Embodiment 5.4

Repeat the step of example 5.1, different is, does not use any smears and does not form coating, prepares developer thus.

The smears of the routine 5.1-5.4 of table 2

Component	Example 5.1	Example 5.2	Example 5.3	Example 5.4
					Resin 1 (weight portion)	The polysiloxane 2.5 of acrylic acid-modification	Methyl phenyl silicone 4.8	Styrene-acrylate copolymer 3.5	Do not have
Resin 2 (weight portion)	Methylated melamines 2.5	The Ethoxysilane 0.2 of gamma-amino propyl group	Methylated melamines 1.5	Do not have
					Solvent: toluene (weight portion)	?????200	??????200	????200	Do not have

Embodiment 6.1

Prepare toner with the mode identical with example 4.2.

Using mean grain size is that the spherical ferrite particle of 100 μ m is as the magnetic core granule.The smears of component as shown in table 3 is added in the 100 weight portion ferrite particles, and mix resulting product with the thermal agitation device.From potpourri remove and to desolvate, and with residue 200 ℃ of thermal treatments 1 hour, to obtain all cated carrier granular of each particle.

The toner and the carrier that so obtain are evenly mixed, to obtain the two-component developer that toner concentration is 3.5wt%.

Embodiment 6.2

Repeat the step of example 6.1, different is that the component of used smears is as shown in table 3, prepares developer thus.

Embodiment 6.3

Repeat the step of example 6.1, different is that the component of used smears is as shown in table 3, prepares developer thus.

Embodiment 6.4

Repeat the step of example 6.1, different is, does not use any smears and does not form coating, prepares developer thus.

The smears of the routine 6.1-6.4 of table 3

Component	Example 6.1	Example 6.2	Example 6.3	Example 6.4
					Resin 1 (weight portion)	The polysiloxane 2.5 of acrylic acid-modification	Methyl phenyl silicone 4.8	Styrene-acrylate copolymer 3.5	Do not have
Resin 2 (weight portion)	Methylated melamines 2.5	The Ethoxysilane 0.2 of gamma-amino propyl group	Methylated melamines 1.5	Do not have
					Solvent: toluene (weight portion)	????200	????200	????200	Do not have

According to following items the developer that obtains in the foregoing description and Comparative Examples is assessed.In order to make the assessment sample easier, with electrically driven duplicator (electriccopying machine) (Mita Industrial Co., Itd. manufacturing; Trade (brand) name: DC-4685) improve, and with improved used in copy machines in assessment.

(a) transfer efficiency:

At first measure the dosage of mixing colours in the toner distributing device in the duplicating machine, and copy the copy of predetermined quantity.Measure the toning dosage of staying in the toner distributing device then.According to the poor of dosage of mixing colours before and after the copying operation, calculate the consumption of toner.Meanwhile, also measure the toning dosage in copying operation, in cleaning process, collected as collecting amount.According to this tittle, calculate the transfer efficiency of toner by using following formula (i).The original paper that uses in copying operation has 8% black region.Carry out the assessment of transfer efficiency, thereby carry out the described various assessment tests of following project (b)-(i).

(b) image color (I.D.):

There is the original paper of 8% black region to carry out copying operation by use, with regard to embodiment 1.1,1.2 and the developer of Comparative Examples 1, until duplicating 100, till 000 copy, with regard to the developer of embodiment 2.1-2.4 and 4.1-4.4, until duplicating 50, till 000 copy, and main other developer is lower than 70% until transfer efficiency.By reflected light densimeter (Tokyo Denshoku Co., Itd. manufacturing; TC-6D) measure the concentration of black part of the printing image of per 5000 copies, and to be averaged concentration be image concentration (I.D.).By example 1.1 and 1.2 and the developer of Comparative Examples 1 obtain the results are shown in table 4, example 2.1-2.4 the results are shown in table 5, and routine 3.1-3.4 the results are shown in table 6, and 4.1-4.4 the results are shown in table 7, example 5.1-5.4 the results are shown in table 8, and routine 6.1-6.4 the results are shown in table 9.

(c) fog density (F.D.):

Have the original paper of 8% black region to carry out copying operation by use, with regard to embodiment 1.1 and 1.2 and Comparative Examples 1 with regard to, till duplicating 100,000 copies; With regard to embodiment 2.1-2.4 and 4.1-4.4, till duplicating 50,000 copies; And with regard to other toner, be lower than till 70% until transfer efficiency.By reflected light densimeter (Tokyo Denghoku Co., Ltd. manufacturing; TC-6D) concentration of white portion in the printing image of per 5000 copies of measurement.Poor between the concentration of the paper that will be used for copying operation (body paper) that calculating is measured by the reflected light densimeter and the concentration of so measurement, and to get maximum difference be fog density (F.D.).According to embodiment 1.1 and 1.2 and Comparative Examples 1 obtain the results are shown in table 4, embodiment 2.1-2.4 the results are shown in table 5, embodiment 3.1-3.4 the results are shown in table 6, embodiment 4.1-4.4 the results are shown in table 7, embodiment 5.1-5.4 the results are shown in table 8, and embodiment 6.1-6.4 the results are shown in table 9.

(d) resolution

There is the original paper of 8% black region to carry out copying operation by use.When for example 1.1 and 1.2 and the developer of Comparative Examples 1 duplicate 40, during 000 copy, and when duplicating 50,000 copies, (in this case, duplicating 40 for other developer, 000 or 50, during 000 copy, transfer efficiency has been lower than 70%), the copy standard chart original paper (original paper that many patterns are arranged, in each pattern, be decorated with the many predetermined parallel lines that are spaced apart 1mm), and with the naked eye assess the printing image that obtains.By example 1.1 and 1.2 and the developer of Comparative Examples 1 obtain the results are shown in table 4, example 2.1-2.4 the results are shown in table 5, and example 3.1 and 3.4 the results are shown in table 6, and routine 4.1-4.4 the results are shown in table 7, example 5.1-5.4 the results are shown in table 8, and routine 6.1-6.4 the results are shown in table 9.

(e) quantity of electric charge:

There is the original paper of 8% black region to carry out copying operation by use, for example 1.1 and 1.2 and the developer of Comparative Examples 1, until copy 100, till 000 copy, developer for routine 2.1-2.4 and 4.1-4.4, till 50,000 copies of copy, be lower than till 70% until transfer efficiency for other developer.During this copying operation, behind 5000 copies of every duplicating, by discharging quantity of electric charge measurement mechanism (blowoff powder charge amount measuring device) (the Tosh-iba Chemical Co. of powder, Ltd. make) measure the quantity of electric charge of 200mg developer, and be the quantity of electric charge mean value of the every 1g toner of basic calculation with this measured value.By example 1.1 and 1.2 and Comparative Examples 1 obtain the results are shown in table 4, routine 2.1-2.4 the results are shown in table 5, example 3.1 and 3.4 the results are shown in table 6, routine 4.1-4.4 the results are shown in table 7, routine 5.1-5.4 the results are shown in table 8, and routine 6.1-6.4 the results are shown in table 9.

(f) toner diffusion:

There is the original paper of 8% black region to carry out copying operation by use, for example 1.1 and 1.2 and the developer of Comparative Examples 1, until copy 100, till 000 copy, for the developer of routine 2.1-2.4 and 4.1-4.4, till 50,000 copies of copy, and, be lower than till 70% until duplicating efficient for other developer.Then, detect by an unaided eye and assess the disperse state of toner in the duplicating machine.By example 1.1 and 1.2 and the developer of Comparative Examples 1 obtain the results are shown in table 4, example 2.1-2.4 the results are shown in table 5, and example 3.1 and 3.4 the results are shown in table 6, and routine 4.1-4.4 the results are shown in table 7, example 5.1-5.4 the results are shown in table 8, and routine 6.1-6.4 the results are shown in table 9.In these tables, zero expression toner indiffusion, the diffusion of * expression toner.

(g) permanance:

After whenever duplicating 10,000 copies, calculate transfer efficiency with the consumption and the collecting amount of toner, be lower than copy number before 70% to find out transfer efficiency.Get the mark of this copy number as the developer permanance.The results are shown in table 6 by what the developer of routine 3.1-3.4 obtained, routine 5.1-5.4 the results are shown in table 8, and routine 6.1-6.4 the results are shown in table 9.

(h) because waste material and attachment amount on carrier particle surface:

There is the original paper of 8% black region to carry out copying operation by use.For example 1.1 and 1.2 and the developer of Comparative Examples 1 after duplicating 40,000 copies, duplicating 50 for other developer, (, duplicating 40,000 or 50 behind 000 copy in this occasion, before 000 copy, transfer efficiency has been lower than 70%), following developer is tested.Developer is placed on the 400 purposes sieves, and with fan blower from following suction, whereby toner is separated with carrier.Get the 5g carrier of staying on the sieve, and in the burning bar that is added with toluene of packing into.So, dissolved owing to waste material is attached to toner component on the carrier particle surface.Then, discharge toluene solution, and with magnet from beaker bottom sucking-off carrier.Repeat this step for several times, till final toluene solution bleach.Then, with the final carrier of baking oven for heating, evaporating the toluene of staying on the carrier, and the weight of the residue that measures.Get the weight of (that is, being 5g) beaker carrier of packing into for the first time and evaporating poor between the weight of residue behind the toluene, as because waste material and attached to the amount (being the waste material amount) of the toner component on the carrier particle surface in this occasion.The waste material amount is represented with the mg number that is attached to the toner component on the 1g carrier.By example 1.1 and 1.2 and the developer of Comparative Examples 1 obtain the results are shown in table 4, example 2.1 to 2.4 the results are shown in table 5, routine 3.1-3.4 the results are shown in table 6, routine 4.1-4.4 the results are shown in table 7, example 5.1-5.4 the results are shown in table 8, and routine 5.1-5.4 the results are shown in table 9.

(i) white point that in the solid black part, exists:

By use three solid black parts 31, wherein the size of each part be 50mm * 50mm, size is the original paper of 210mm * 297mm, as shown in figure 10.Duplicate 500 copies continuously, and make the copy image set with warm-up mill.Direction Pa shown in the white arrow of Figure 10 delivers to warm-up mill with each copy image.With the interior copy image of observing when surveying 50000 pages, to determine in three solid black parts, whether white point being arranged.The results are shown in table 7.

Table 4 example 1.1, the assessment of example 1.2 and Comparative Examples 1 and toner component

Adhesive resin 100 100 100 carbon blacks 777 magnetics 222 external additives of example 1.1 examples 1.2 Comparative Examples 1 toner component (weight portion) band carboxyl

Silicon dioxide 0.3 0.3 0.3

Acroleic acid polymerization composition granule 0.5 does not have

Magnetic iron ore does not have 0.5 nothing assessment I.D. 1.369 1.379 1.342 F.D. 0.002 0.001 0.003 resolving power, 5.6 5.0 5.6 transfer efficiencies (%), 85.2 86.5 81.5 quantities of electric charge (μ C/g)-18.6-17.6-22.5 waste material amounts (mg), 0.22 0.19 0.28 toner and spreads 000

Toner component and the assessment of the routine 2.1-2.4 of table 5

Example 2.1 examples 2.2 examples 2.3 examples 2.4 toner component (weight portion) adhesive resins 100 100 100 100 carbon blacks 10 10 10 10 magnetics 2222 charge control agents do not have no external additive 0.3 0.3 0.3 0.3

Silicon dioxide (0.015 μ m) interval dose particle 1 0.5 1.0 does not have 1.0

Kind titanium dioxide titanium dioxide titanium dioxide

Diameter (μ m) 0.3 0.3 0.3

Resistivity (Ω cm) 2E1 2E1 1E6 interval dose particle 20.5 does not have 1.0 and does not have

Kind aluminium dioxide aluminium dioxide

Diameter (μ m) 0.3 0.3

Resistivity (Ω cm) 1E10 1E10 assessment I.D. 1.395 1.405 1.352 1.362 F.D. 0.001 0.005 0.003 0.003 resolving power 5 4.5 55 waste material amounts (mg) 0.63 0.69 0.67 0.65 toner spreads 0000 transfer efficiencies (%), 84.2 73.1 78.5 74.4 quantities of electric charge (μ C/g)

1 part of copy time-21.5-22.2-21.6-21.4

10000 parts of copy time-21.8-20.5-23.2-18.5

30000 parts of copy time-22.1-18.3-24.3-22.1

50000 parts of copy time-22.0-16.2-26.4-23.2

The assessment of the routine 3.1-3.4 of table 6

Example 3.1 examples 3.2 examples 3.3 routine 3.4I.D. 1.402 1.362 1.401 1.388F.D., 0.003 0.003 0.003 0.004 resolving power, 5555 quantities of electric charge (μ C/g)-23.1-24.4-24.5-22.5 toners spread 0000 durability (number of pages), 140,000 140,000 130,000 70000 waste material amounts (mg) 0.31 0.31 0.34 0.57 (during 50000 parts of special shellfishes)

Table 7, toner component and the assessment of routine 4.1-4.4

Example 4.1 examples 4.2 examples 4.3 examples 4.4 toner component (weight portion) adhesive resins 100 100 100 100 carbon blacks 10 10 10 10 magnetics 2222 charge control agents do not have no Metallic stearates 0.05 0.05 0.02 and do not have

The metallic zinc zinc-magnesium

Adding method and toning and MgCO ₃With MgCO ₃

Agent mixes external additive

Silicon dioxide (0.015 μ m) 0.3 0.3 0.3 0.3

MgCO ₃The white point nothing that (0.15 μ m) 0.5 0.5 0.5 0.5 assessment I.D. 1.420 1.409 1.401 1.368 F.D., 0.003 0.002 0.002 0.003 resolving power, 5555 quantities of electric charge (μ C/g)-18.6-19.3-19.8-23.2 toners spread 0000 waste material amounts (mg), 0.64 0.63 0.65 0.65 black part has

The assessment of the routine 5.1-5.4 of table 8

Example 5.1 examples 5.2 examples 5.3 routine 5.4I.D. 1.404 1.358 1.409 1.398F.D., 0.003 0.002 0.003 0.004 resolving power, 5555 quantities of electric charge (μ C/g)-20.3-22.7-22.0-19.5 toners spread 0000 permanance (number of pages) 140,000 140,000 130,000 70,000 waste material amount 0.32 0.32 0.34 0.57 (during 50000 parts of copies)

The assessment of the routine 6.1-6.4 of table 9

Example 6.1 examples 6.2 examples 6.3 routine 6.4I.D. 1.405 1.355 1.411 1.393F.D., 0.002 0.002 0.003 0.004 resolving power, 5555 quantities of electric charge (μ C/g)-20.6-23.2-21.4-18.7 toners spread 0000 permanance (number of pages) 150,000 150,000 140,000 70,000 waste material amount 0.29 0.30 0.33 0.56 (during 50,000 parts of copies)

Compare with the developer that does not have the interval dose particle that Comparative Examples 1 is produced, the quantity of electric charge of the developer that example 1.1 and 1.2 is produced is more stable, the waste material amount still less, fog density is lower and transfer efficiency is higher.

The developer that contains the toner that includes a kind of desirable interval dose particle that example 2.2 is produced prevents the toner diffusion in fog density, and transfer efficiency and charge stability aspect are excellent.The developer that contains the toner that includes two kinds of interval dose particles that example 2.1 is produced has further improved transfer efficiency and charge stability.

Although what example 3.4 was produced comprises the developer that does not have coated carrier in fog density, the quantity of electric charge and prevent that toner diffusion aspect from being excellent, the developer that includes coated carrier that routine 3.1-3.3 produces has littler waste material amount and longer permanance.

Although the developer that comprises the toner that does not have Metallic stearates that example 4.4 is produced is in fog density, prevent the toner diffusion, the quantity of electric charge and anti-waste material aspect of performance are excellent, but the developer that comprises the toner that contains Metallic stearates that routine 4.1-4.3 produces has further improved the rejection that partly occurs white point in solid black.

Although example 5.4 is produced contain do not have coated carrier developer in fog density, the quantity of electric charge and to stop toner diffusion aspect be excellent, the developer of the carrier that contains coating that routine 5.1-5.3 produces has further improved waste material amount and permanance.

Under the spirit that does not depart from the scope of the present invention, various improvement will be conspicuous, and can be easy to make these improvement by those skilled in the art.Therefore, the scope of claims of the present invention is not limited to explanation described herein, but is briefly explained.

Claims (7)

1. the toner of a two-component developer contains the toner-particle that comprises adhesive resin and be dispersed in the magnetic in the described adhesive resin,

Wherein said adhesive resin contains the resin that has the anionic polar group,

Described magnetic is included in the described toner-particle, and its consumption is as the criterion with the described adhesive resin of 100 weight portions and is the 0.1-5 weight portion,

The volume base mean grain size of described toner-particle is 5-15 μ m,

Volume base mean grain size is that the interval dose particle of 0.05-1.0 μ m is attached on the surface of described toner-particle.

2. according to the toner of the two-component developer of claim 1, wherein said interval dose particle comprises that resistivity is 10 ¹-10 ⁵The first interval dose particle and the resistivity of Ω cm are 10 ⁸-10 ¹³The second interval dose particle of Ω cm.

3. according to the toner of the two-component developer of claim 1, wherein, Metallic stearates is attached on described interval dose particle and the described toner-particle surface one of at least.

4. according to the toner of the two-component developer of claim 3, wherein said Metallic stearates is at least and is selected from a kind of of zinc stearate and dolomol.

5. according to the toner of the two-component developer of claim 3, wherein said Metallic stearates is optionally on the surface attached to described interval dose particle.

6. according to the toner of the two-component developer of claim 1, wherein the extract that described toner extraction obtains is not had absorption peak basically at 280-350nm, do not absorb basically at 400-700nm with methyl alcohol.

7. according to the toner of the two-component developer of claim 1, the consumption of wherein said magnetic is as the criterion with the described adhesive resin of 100 weight portions and is the 0.5-3 weight portion.

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