CN1126848A - A two-component type developer - Google Patents

Abstract

The present invention provides a binary system comprising a toner and a carrier. This toner contains tag grains which contain fixing resin and magnetic powder dispersed in this resin. this fixing resin is made up of a composition comprising a kind of resin with anionic polar group, and the magnetic powder is contained in the toner grains at a rate from 0.1 to 5 pt.wt to 100 pt.wt in the fixing resin. Carrier grains have a core grain and a covered layer cling this grain. The core grain consists of a magnetic material to be shown in an equation of MOFe2 O3 , and here M is at least a kind of metal to be selected out of a group consisting of Cu, Zn, Fe, Ba, Ni, Mg, Mn, Al and Co.

Description

Two-component developer

The present invention relates to a kind of two-component developer that is used for eletrophotography.More specifically, the present invention relates to a kind of two-component developer, it comprises carrier and does not contain the toner of charge control agent, is applicable to the eletrophotography imaging device, as Xerox and laser beam printer.

Two-component developer is used for the electrostatic latent image on the photoreceptor is developed in the eletrophotography imaging device as a kind of developer.This two-component developer comprises toner and magnetic carrier such as iron powder and the ferrite particle that contains adhesive resin and color agent such as carbon black.

Electrostatic latent image is developed through the following steps: developer forms the magnetic brush shape by its magnetic field on developer roll, and transfers on the photoreceptor.In this step, this toner is by being recharged with the carrier friction, to obtain desirable electric charge and charge polarity.Then, this developer contacts with photoreceptor by developer roll, and the result makes toner attached to top, forms electrostatic latent image.Usually, toner comprises charge control agent, and its control is also stablized the electric charge of toner, so that the toner of constant basis is attached on the electrostatic latent image, and provides good long developed image.Electronegative toner comprises negative charge controlling agent, metal complex dyes for example, comprise metallic ion such as chromium (III) (as, azo-compound-chromium (III) complex compound) and oxidation carboxylic acid one metal complex (as salicylic acid-metal complex) (Japanese Patent Application Publication No.3-67268).Positively charged toner comprises positive charge control agent, and for example oil-soluble dyes comprise Ni Ge and amine type charge control agent (Japanese Patent Application Publication No.56-106249).

A lot of metal complexs are used as conventional charge control agent, comprise heavy metal ion such as chromium ion.Consider for environmental protection, they are answered careful selection, thereby can only use those separately by strict toxicity test and safety test.Therefore, be safe although they self maybe ought be included in the toner, more preferably avoid using this metal complex of heavy metal that comprises as charge control agent.In addition, to divide former material to compare with color agent such as carbon black as bonding agent be expensive to its in charge control agent and the toner.Therefore, although the content of charge control agent only has a few percent, this increases prepared toner price.For this reason, wish the not charge control agent of containing metal complex compound of charge image developing toner.

Also have, when using conventional toner for a long time, this toner combination is tending towards attached on the carrier particle surface.The component that adheres to is called as waste material.Waste material makes the carrier electric charge have the level identical with toner, and the result produces following shortcoming, though the toner diffusion, and the transfer efficiency of reduction toner image.

Two-component type of the present invention develops and contains toner and carrier.This toner comprises toner-particle, and toner comprises adhesive resin and is dispersed in magnetic powder in the adhesive resin.This adhesive resin is to be made by the composition that comprises the resin with anionic group.The scope that is included in the magnetic in the toner-particle is that per 100 weight portion bonding agents are wanted fat 0.1-5 weight portion.Each carrier granular in the carrier all has slug particle and covers the coating of this slug particle, and slug particle is by using following formula (A):

Formula (A): MOFe ₂O ₃

The magnetic material of expression makes, and M represents the metal among at least a Cu of being selected from, Zn, Fe, Ba, Ni, Mg, Mn, Al and the Co in the formula.

In one embodiment, the extract that obtains with the methanol extraction toner does not have absorption peak substantially between 280-350nm, be substantially zero absorptivity between 400-700nm in the scope.

In one embodiment, the content range of magnetic is per 100 parts of weight adhesive resin 0.5-3 weight portions.

In one embodiment, toner-particle has the volume averaging particle diameter of 5-15 μ m, and having the volume averaging particle diameter is on the surface of separant particle attached to toner-particle of 0.05-1.0 μ m.

In one embodiment, coating is to make by containing the resin combination with cation group resin.

In one embodiment, coating is to be made by resin combination, and this resin combination comprises alkylated melamine resins and acryloyl group modified siloxane resin, and this alkanisation melamine resin has the weight average molecular weight M by following formula (B) expression:

C represents the carbon number in the contained alkyl in the alkanisation melamine resin in formula (B): M 〉=1000C-400 formula.

In one embodiment, coating is to be made by resin combination, and the pretty thing of this resin comprises methylsiloxane resin and methylated melamines resin, and this methylated melamines resin has 700 or bigger weight average molecular weight.

In one embodiment, coating is to be made by the resin combination that contains the methylsiloxane resin, and it is 70mol% or more T unit that this methylsiloxane resin contains content.

In one embodiment, coating is made by the resin combination that contains thermoset resin and thermoplastic resin, and this thermoplastic resin comprises that concentration is the quaternary ammonium group of per 100 gram resin combination 0.1-20mmol.

In one embodiment, coating comprises thermoset resin, has 85% or higher degree of cure.

In one embodiment, the content of coating is per 100 weight portion slug particle 0.001-2.5 weight portions.

In one embodiment, thermosetting resin is to be selected from least a in the following thing group; Modification or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acryl resin, phenol resin, epoxy resin and amino resins.

In one embodiment, the resin with cation group is to have the resin that contains the basic nitrogen group.

In one embodiment, the particle diameter of slug particle is 50-150 μ m.

Therefore, the present invention has following advantage: (1) provides and has contained the toner with excellent charged ability and the two-component developer that does not contain charge control agent fully; (2) provide a kind of two-component developer that contains toner, this toner or does not just spread in developer a little, to obtain high-quality copy image; (3) provide a kind of and contained the two-component developer of toner even when long-time the use, also do not produce waste material, therefore, can keep excellent picture quality, and transfer efficiency has been also stable.

Fig. 1 is the figure of the absorptivity of methanol extraction liquid in the 200-700nm scope of expression toner of the present invention.

Fig. 2 is that expression contains the figure of azo-compound-chromium complex dyes as the absorptivity of methanol extraction liquid in the 200-700nm scope of the toner of charge control agent.

Fig. 3 is that expression contains salicylic acid-metal complex as the methanol extraction liquid of the toner of the charge control agent figure in 200-700nm scope internal absorption factor.

Fig. 4 is the absorptivity of the methanol extraction liquid of carrier in the long-time two-component magnetic developing agent that uses of expression, wherein toner contains as being the dyestuff of the azo-compound-chromium complex of lotus controlling agent, and the charged ability of carrier is because waste material is unsettled in the 200-700nm scope.

Fig. 5 is the relation between expression time of vibration and the scrap rate, and this obtains with two kinds of two-component magnetic developing agents, a kind of toner and magnetic carrier that contains charge control agent, and another kind contains toner and the magnetic carrier that does not contain controlling agent.

Fig. 6 has shown the relation between time of vibration and the toner charge quantity, and this obtains with two kinds of bi-component magnetic developers, a kind of toner and magnetic carrier that contains charge control agent, and another kind contains toner and the magnetic carrier that does not contain charge control agent.

Fig. 7 shows the mutual relationship between the charge control agent content in carrier waste material amount and the toner-particle.

Fig. 8 has shown the mutual relationship between time of vibration and the waste material amount, this be in toner-particle each component mix individually with magnetic carrier and the condition vibrated under obtain.

Fig. 9 has shown that in conventional two-component magnetic developing agent it is the lotus Failure Mechanism that waste material makes.

Figure 10 has shown the alkylated melamine resins molecular weight.Carbon number and the mutual relationship of use alkylated melamine resins between the coating roughness that forms on the carrier granular in the alkyl that contains in the alkylated melamine resins.

Toner in the two-component developer of the present invention does not contain charge control agent, for example dyestuff of azo-compound-metal complex and carboxylic acid-metal complex fully.Therefore, the waste material by the charge control agent generation takes place hardly in toner of the present invention, this describes in detail below, and the result can obtain high technician's copy image in long-time.Because the toner that two-component developer of the present invention contains or not charge control agent, available any chemistry or physical method detect any charge control agent in the toner, i.e. dye-type compound.For example, all can not in the toner in the two-component developer of the present invention, detect this compound with any chemical reaction.In other words, in the organic solvent extraction solution of toner, can not detect the absorption peak of this compound.For example, when with organic solvent such as methanol extraction toner, this extract does not have absorption peak basically in the 280-350nm scope, and is substantially zero absorption in the 400-700nm scope.The connotation of here " not having absorption peak basically " is not detect absorption peak fully in the toner gained extraction solution in the 50ml methanol extraction 0.1 gram two-component developer of the present invention, if perhaps detect, this absorption peak also is 0.05 or littler.Similarly, the absorptivity that " being substantially zero absorption " means extraction solution is 0.05 or littler, and this extraction solution is with the toner gained in the 50ml methanol extraction 0.1 gram two-component developer of the present invention.

In the two-component developer of the present invention, owing to do not contain charge control agent, the instability of amount of charge compensates with following measure.At first, the adhesive resin in the toner-particle comprises and contains anionic group, secondly, comprises the magnetic that exists with predetermined ratio in the toner, the 3rd, and each carrier granular all has coating.Also have, if desired, have the surface of the separant particle of predetermined particle size, thereby improved the transfer efficiency of image on from the photosensitive body to transfer paper attached to toner-particle.

Preferably, the coating on the carrier granular contains the cation group in developer of the present invention, to strengthen the function of developer.The result is, makes the charged ability of carrier of gained constant.

In developer of the present invention, the coating on the preferred carrier granular contains the alkanisation melamine resin of molecular weight in preset range and the silicone resin of acryloyl group modification.As a result, make the charged ability of gained carrier further stable.Also have, because the coating of each independent carrier granular all prevents fusing and adhesion mutually each other, thereby each gained carrier granular all has smooth and uniform coating surface.This has reduced the generation of waste material, and has improved the permanance of carrier, has increased the life-span of developer.

In developer of the present invention, the coating on the carrier granular preferably contains the methylsiloxane resin and has the methylated melamines resin of molecular weight in the preset range.As a result, prevented that toner-particle from spreading in developing process, promptly prevented from duplicating figure shadow, to form so-called photographic fog.Also have, further suppress the generation that carrier granular and waste material condense, the result provides long-life developer, and has excellent flowability and permanance.

In developer of the present invention, the coating on the carrier granular preferably includes the methylsiloxane that contains 70mol% or more T unit, to strengthen the function of developer.As a result, advance to go up the step and suppressed the generation that carrier granular and waste material condense, therefore developer long-life and that have excellent flowability and permanance is provided.

In developer of the present invention, for strengthening the purpose of developer effect, the coating on the carrier granular preferably contains thermosetting and thermoplastic resin, and this thermoplastic resin can contain the quaternary ammonium group of predetermined content.

In developer of the present invention, in order to strengthen the purpose of developer function, the coating on the carrier preferably contains thermoset resin, and the degree of cure of coating is 85% or bigger.As a result, further suppressed the generation of waste material.In addition, make the gained developer have excellent picture steadiness, it does not cause the film forming of photoreceptor.

Describe the above-mentioned feature of the contained toner of two-component developer of the present invention below in detail.

Fig. 1 shows the uv-vis spectra of the methanol extraction liquid of contained toner in the interior two-component developer of the present invention of 200-700nm scope.Shown in this spectrum, this extract does not have the peak, and the peak is owing to charge control agent forms.Especially, this solution does not have absorption peak basically in the 280-350nm scope, and the absorptivity in the 400-700nm scope is substantially zero.On the contrary, Fig. 2 show contain in the absorbance curves of azo-compound-chromium complex as the methanol extraction liquid of the toner of charge control agent, in the 400-700nm scope, found absorption peak, especially in the 550-570nm scope.Also have, the salicylic acid-metal complex that contains shown in Figure 3 is done to have found absorption peak in the uv-vis spectra of methanol extraction liquid of toner of charge control agent in the 280-350nm scope.

Because charge control agent is present in the toner-particle surface with suitable high concentration, the methanol extraction liquid of toner that contains charge control agent is owing to charge control agent has absorption peak.

Contain carrier with methanol extraction developer of the present invention, this developer is not enough charged abilities owing to produce waste material, measures the uv-vis spectra of this extract then, has found the absorption peak that charge control agent produces in 400-700nm.For example, the long-time developer that contains toner that uses can produce waste material therein, and toner wherein contains the dyestuff of azo-compound-chromium complex, and the uv-vis spectra of this developer is shown in Fig. 2.Then, measure the uv-vis spectra of the methanol extraction liquid of carrier in this developer, obtain spectrum shown in Figure 4.As shown in Figure 4, with Fig. 2 in spectrum same position place found absorption peak.This is commonly referred to be and has produced waste material, this be because toner in adhesive resin attached to carrier particle surface formed resin molding.Yet,, illustrated that the main cause that waste material forms is that charge control agent has been transferred to carrier granular from toner-particle by the comparison between the absorption curve among Fig. 2 and Fig. 4.

The present invention carries out following experiment, and more to concern between discovery charge control agent and the waste material: at first, the toner that will contain toner-particle mixes the acquisition developer with carrier, and a toner material contains the dyestuff of 1.5wt% azo-compound-chromium complex.With toner and the carrier vibration schedule time, Fig. 5 shows time of vibration and attached to the relation between the attachment amount on the carrier particle surface.Among Fig. 5, the attachment amount represents with scrap rate, that is, and and based on the percentage of the carrier granular general assembly (TW) that has attachment.Also have, Fig. 6 has shown the relation between time of vibration and the toner charge.With comprising that the toner that do not contain electric charge control and the developer of carrier repeat identical processing.The experimental result of this developer also is shown in Fig. 5 and 6, and wherein the result who obtains with the developer that comprises the toner that contains charge control agent describes with bullet, and the result who obtains with the developer that comprises the toner that does not contain charge control agent represents with white circle.Can obviously find out by Fig. 5 and 6, comprise that containing electricity preserves the developer of the toner-particle of controlling agent to comprise the developer of the toner-particle that does not contain charge control agent, on carrier granular, form the more attachment that becomes waste material of volume, and the quantity of electric charge of toner reduces biglyyer.

Then, measured as the weight of waste material attached to the toner component on the carrier particle surface.The results are shown in Fig. 7, wherein horizontal ordinate is represented the quantity that records of waste material, and ordinate is illustrated in the content of charge control agent in the toner-particle.Dotted line among Fig. 7 is represented the charge control agent quantity that calculates, this hypothesis adhere to as the toner component of waste material and identical the calculating of component in the toner-particle.Fig. 7 shows in starting stage a large amount of charge control agent deposition and on attached to carrier particle surface.In Fig. 7, when the waste material amount increases, measured value is close with calculated value.This is because these data are not replenish the experimental result that obtains in the closed system of new toner.Therefore, when changing toner in duplicating machine, the difference between measured value and the calculated value will be very big.

Also have, the present invention measures the weight of the attachment on the carrier particle surface, the result that this attachment produces mixes every kind in carrier and the toner component, be charge control agent, adhesive resin, as the carbon black and the wax of color agent, to find toner component that each is independent and the relation between the waste material.The results are shown in Fig. 8, be time dependent attachment amount (being the waste material amount), wherein draw with empty circles by the potpourri gained result who contains charge control agent, represent with bullet by the potpourri gained result who contains carbon black, represent with square that by containing adhesive resin gained result the gained result of the content of wax represents with triangle.Can find out obviously that by Fig. 8 charge control agent produces the attachment that causes becoming waste material of maximum.

Based on the above-mentioned fact, with reference to figure 9, the description below electric charge that waste material causes in two-component type magnetic developer commonly used lost efficacy.Be negative charge with carrier granular as the positive charge toner-particle in the starting stage that developer uses, shown in the top of Fig. 9.This state is arranged, and toner-particle is as the severe toner-particle 21 of negative electricity.When this developer of continuous use, contain charge control agent as the component of the main component of toner-particle surface attached to carrier granular 1.The attachment 201 that becomes waste material is negative charges, and this negative charge attachment 201 causes forming positively charged toner-particle, promptly with the toner-particle 22 of the anti-electric charge of machine.Should form on carrier granular 1 surface by opposite electric severe toner-particle 22, as Fig. 9 bottom institute not, this makes the toner diffusion, and reduces the transfer efficiency of toner.

As mentioned above preferably, toner does not contain electric severe controlling agent, and this injustice is because this charge control agent contains heavy metal, also because electric severe controlling agent is the major reason that causes that waste material, toner diffusion and toner transfer efficiency reduce.Therefore, the toner in the two-component developer of the present invention does not contain electric severe controlling agent fully.

Owing to lack charge control agent, the amount of charge of the instability of toner charge, particularly toner is not enough, compensates by using anion-containing as mentioned above adhesive resin.The electric weight of toner-particle can be replenished inadequately, and itself is electronegative severe because contain anionic group in the adhesive resin.Because anionic group is combined on the main chain of adhesive resin,, therefore produce waste material never so the image charge controlling agent moves on to carrier particle surface like that never.On the contrary, the electric charge around the roasting toner-particle surface that produces of the anion base of bonding agent is insufficient, and when toner-particle and carrier granular are carried when developing as magnetic brush, the toner-particle and the electrostatic attraction between the carrier granular that are caused by the Coulomb force are not enough.Therefore, in quick copying operation, because toner is coupled together with carrier granular deficiently, toner can not prevent diffusion fully.The toner duplicating machine inwall of making dirty of diffusion, and in copy image, cause so-called photographic fog.

In order to overcome this shortcoming, the toner in two group clump type developers of the present invention contains the magnetic of scheduled volume, that is, the 0.1-5 weight portion is based on the adhesive resin of 100 weight portions.Compensated the deficiency of toner-particle electric weight thus.The magnetic that contains in the toner-particle causes magnetic pull between toner-particle and carrier granular.This magnetic pull and the electrostatic attraction diffusion that prevented toner of toner-particle between carrier granular.Also have, because the quantity of electric charge of single toner-particle is less, making attached to the toner-particle number on the electrostatic latent image increases, thereby visible development sensitivity is increased.

As mentioned above, the content of magnetic is per 100 weight portion adhesive resins 0 in the toner-particle, 1-5 weight portion scope.When content during less than 0.1% (weight), the quantity of electric charge of toner-particle is not enough, and the coupling of result and carrier granular is insufficient, causes the toner diffusion.In this situation, on copy image, form disadvantageous photographic fog.Also have, because the quantity of electric charge makes the concentration of copy image low inadequately.When content during greater than 5% (weight), the magnetic pull between toner-particle and the carrier granular is too strong, can not be to cause toner fully attached on the electrostatic latent image, and the result has reduced the concentration of copy image.

Attempted resolution by magnetic is improved (adding) copy image as the toner component compatiblely etc.For example, Japanese Patent Application Publication No.59-162563 discloses the toner-particle that contains the 5-35wt% magnetic powder particle.Yet, another kind of situation, the concentration of copy image is low.Japanese Patent Application Publication No.3-67268 discloses toner, has wherein externally added the magnetic of 0.05-2wt%.Because magnetic is not to be contained in the toner-particle, always unevenly attached to the surface of toner-particle, the result makes the magnetic pull between toner-particle and the carrier granular not enough to magnetic in this situation.Also have, any in above-mentioned two kinds of toners causes waste material unfriendly owing to wherein contain charge control agent.

In the present invention, carrier granular has coating, can further strengthen the function of gained developer.The coating of carrier can be stablized the band of toner by ability.Also have, coating forms smooth and uniform surface on carrier.Therefore, suppress the generation of waste material, increased the permanance of carrier, obtained having long-life developer.

In one aspect of the invention, be to strengthen the purpose of developer function, the coating that superior is on the carrier granular comprises the resin with cation group.Because cation group makes carrier have charged ability.Therefore, when this is worn this and mixes with the toner that does not contain charge control agent, improved the charged ability of toner significantly.As a result, the charged ability of gained toner is stable.Have, because this toner do not contain charge control agent, promptly contain charge control agent unlike conventional toner, thereby suppressed the generation of the waste material on carrier granular that caused by charge control agent effectively, the result has prolonged the life-span of developer.

Example with resin of cation group comprises having the resin that contains basic nitrogen group such as amido.For example, melamine resin, the preferred alkyl melamine resin can use.

In the present invention on the other hand; for strengthening the developer function; preferably, the coating on the carrier granular comprises acryloyl group modified siloxane resin and has the alkylated melamine resins of molecular weight in the preset range that described predetermined molecules weight range is by following formula (B) expression mean molecular weight M:

C represents the alkyl institute carbon atom quantity in the alkylated melamine resins in formula (B): M 〉=1100C-400 formula.

Because have a large amount of amine groups in the melamine resin molecule, promptly anionic group when it is contained in the coating, makes carrier granular positively charged.Especially, because following former thereby preferred alkyl melamine.In this resin, at least, a part of methylol that is produced by melamine and formaldehyde reaction is by the further alkylation (being the alkyl etherificate) with ethanol synthesis.As a result, the fusing point of resin reduces, and its solubility that is dissolved in solvent is improved.Also have, also improved compatibility with acryloyl group modified siloxane resin.Therefore, alkylated melamine resins has excellent coating formation performance and curing performance.Also have,, obtained high activity, and when with acryloyl group modified siloxane resin-bonded, present excellent curing performance because in base, contain methylol group and/or alkylation methylol group.As a result, can form densification and with hard coating.

Silicone resin has the water resisting property and the friction factor of water proofing property, excellence.Therefore, this resin can prevent well that waste material from producing.Also have, when acryloyl modified siloxane resin is used in the developer in the coating on the carrier granular, this acryloyl modified siloxane resin is silicone resin and acryl resin sex change and obtain, and makes the gained copy image have high concentration, and can prevent going up waste material effectively and produce.Have again, when with acryl resin modified siloxane resin, also can improve with the compatibility and the curing activity of alkylated melamine resins.

Also have, when alkylated melamine resins had the mean molecular weight of formula (B) expression, the coating on the carrier granular had level and smooth and uniform surface, and has not a particle of coarse.In formula (B), preferred C is the 1-4 scope.

Coating forms coarse reason and thinks that the coating on the carrier granular melts, and has therefore formed the attachment of carrier granular.When coating is solidified or when coating is solidified the back cooling, the coating fusing is also adhered to mutually.When the resin of this fusing breaks, on coating surface, form coarse owing to breaking of interlaminar resin melt portions.When toner-particle during attached to this irregular carrier particle surface, cause waste material, the result has reduced the life-span of carrier.When coating is formed by alkylated melamine resins, find to be correlated with between the carbon number of alkyl in coarse formation, alkylated melamine resins molecular weight and the alkylated melamine resins.Figure 10 has shown the relation between the carbon number of groups in the molecular weight of coating roughness formation, alkylated melamine resins and the alkylated melamine resins.In the figure, horizontal ordinate is represented carbon number in the alkyl (C), and ordinate is represented the mean molecular weight (M) of alkylated melamine resins.Forming coarse usefulness " * " on coating draws, do not form coarse usefulness " zero " and draw, as shown in figure 10, when using molecular weight to satisfy the alkylated melamine resins of formula (B), promptly when specifying used alkylated melamine resins molecular weight, prevented that coating from adhering to each other greater than predetermined value.As a result, do not form coarsely at coating surface, make the gained carrier granular have smooth coating surface.When carrier granular has thisly when sliding and uniformly during coating surface, suppressed the generation of waste material significantly.

Aspect another, is the purpose that strengthens the developer function of the present invention, and the coating on the preferred carrier granular comprises alkylated melamine resins and silicone resin.For example, preferably have the methylated melamines resin of molecular weight (being that molecular weight is 700 or bigger) in the preset range and the bond of methylsiloxane resin.In this situation, because comprising, the coating on the carrier granular has cationic resin, also obviously improved the charged ability of the toner that does not contain charge control agent.Also have,, also suppressed condensing of carrier granular, Gu this has improved the flowability of toner because silicone resin has suppressed the generation of waste material.For these purposes, the methylsiloxane resin is effective especially, and the methylsiloxane resin that does not contain phenyl is preferred.When using this methylsiloxane resin, suppress waste material and the effect of condensing further strengthens.

In aforementioned developer, by melamine resin being defined as the methylated melamines resin, and the molecular weight of resin is defined as predetermined value or bigger, obtained following advantage.Because the compatibility between silicone resin and melamine resin is very poor usually, the melamine resin particle agglomerate is dispersed in the silicone resin in the coating that is formed by these resins.Yet, the curing materials tool of this specific methylated melamines resin not with the same high hardness of curing materials of methylsiloxane resin.Therefore, be dispersed in the silicone resin although carve polyimide resin particle agglomerate, when carrier vibrated in developing apparatus repeatedly, this agglomerate did not come off from coating yet.Therefore, the anti-system because of vibration in the surface of coating loses its homogeneity.As a result, further suppressed condensing and the generation of waste material of carrier granular, therefore a kind of long-life developer with permanance of superior fluidity is provided.

In one side more of the present invention, in order to increase the function of developer, the coating on the preferred carrier particle comprises the methylsiloxane resin that contains 70mol% or more T unit, and the T unit i.e. three functional unit (RSO _1.5, wherein R is a methyl).As mentioned above, methylsiloxane prevent that carrier granular from condensing and the waste material generation aspect be excellent.T content is defined as 70mol% or more for a long time in the methylsiloxane resin, make the three-dimensional net structure that solidifies the formation of methylsiloxane resin obtain finer and close structure, the result has improved the hardness and the homogeneity of carrier granular coating surface, and has further increased the effect that prevents that carrier granular from condensing and waste material produces.Therefore, when using this methylsiloxane to form coating, the gained developer has obtained more long-life and high flowability and permanance.When T content during, increased respectively that to be helpless to crosslinked D unit (be difunctional unit R less than 70mol% ₂SiO) and the M unit that reduces molecular weight (be single functional unit R ₃SiO _0.5), thereby reduced the hardness of coating a little.

Of the present invention for strengthening the developer function, the coating of preferred carrier granular comprises thermoset resin and thermoplastic resin more on the one hand, and thermoplastic resin contains the quaternary ammonium group of predetermined content.When this resin is included in the coating, in curing process, induced thermoplastic resin with quaternary ammonium group and the phase separation between the thermoset resin, therefore, thermoplasticity moves the surface of coating.Therefore, when the carrier with this coating when having the toner that contains charge control agent to mix, can stablize the charged ability of gained developer.Also have,, suppressed the generation of waste material on the carrier granular effectively, thereby improved the developer life-span because toner does not contain the contained charge control agent of conventional developer.Usually, the resin that contains quaternary ammonium group is thermosetting resin or thermoplastic resin.But in the present invention, quaternary ammonium group is contained in the thermoplastic resin in the resin combination that forms coating.Therefore, can use it and stable charged ability be arranged and the toner that do not reduce the coating permanance.Can further stabilized zone electric energy power by in the 100g resin combination, containing 0.1-20 mM (mmol) quaternary ammonium group.

In another aspect of the present invention, for increasing the developer function, preferred carrier granular coating contains thermoset resin, and preferred coating degree of cure is 85% or more.This thermoset resin is preferably used for forming coating on carrier granular, this carrier is wear-resistant mill, hard, non-adhesion, heat-resisting and durable carrier.By degree of cure being restricted to 85% or more, this curing materials has obtained high density, has improved the homogeneity of gained coating surface, prevents having gone up peeling off of coating, and has further strengthened the effect that prevents to produce waste material.When using this resin,, produce the film forming and the waste material of photoreceptor hardly because coating hardness has increased.

Following this degree of cure that obtains.On slug particle, form coating and curing with the preparation carrier granular.With this gained carrier granular of solvent cleaning, this can dissolve or disperse to be used to form the resin combination that solidify at end that coating is.The ratio of will be not washed off by solvent that still is retained in the coating on the slug particle is as degree of cure.This ratio can calculate with following formula:

C represents the quantity of the C that records by ultimate analysis etc. in the formula.

Now, developer of the present invention is described, " low alkyl group " here refers to have the alkyl of 1-5 carbon atom.(adhesive resin of toner-particle is included in the developer of the present invention)

The adhesive resin of the toner-particle that developer of the present invention contains contains the composition that comprises the polymkeric substance with anionic group.The polymerization of the potpourri of the monomer by having anionic group or the precious monomer that anionic group arranged and other monomers obtains this adhesive resin.The gained resin can be homopolymer or multipolymer.

The used adhesive resin of agent is preferably by the multipolymer of the monomer with anionic group and other monomers in the two-component developer of the present invention, for example random copolymers, segmented copolymer and graft copolymer.

Example with monomer of anionic group comprise have hydroxy-acid group, the monomer of sulfonic acid group or phosphate group, and use monomer usually with hydroxy-acid group.Example with monomer of hydroxy-acid group comprises olefinic unsaturation carboxylic acid, as acrylic acid, methacrylic acid, butenoic acid, maleic acid autumn fumaric acid; Can form the monomer of hydroxy-acid group, as maleic anhydride; Low alkyl group half ester with dicarboxylic acid such as maleic acid and fumaric acid.Example with monomer of sulfonic acid group comprises styrene sulfonic acid and 2-acryloyl group amino-2-methyl propane sulfonic acid.Example with monomer of phosphate group comprises 2-phosphono (oxo) propyl group methacrylate, 2-phosphono (oxo) ethyl methacrylate, 2-chloro-2-phosphono (oxo) propyl group methacrylate.

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

The monomer of selecting not contain anionic group is used to prepare adhesive resin, makes the gained adhesive resin have toner required enough photographic fixing abilities and charged ability, and this monomer can be a kind of of olefinic unsaturation monomer or their bond.This examples of monomers comprises olefinic unsaturation carboxylate monovinylarene, vinyl esters, vinyl ether, diolefin and mono-olefin.

This olefinic unsaturation carboxylate is represented by following formula (I): formula: (I) R in the formula ¹Be hydrogen atom or low alkyl group; R ²Be have 11 or still less carbon atom hydrocarbon or have 11 or the alkyl alkyl of carbon atom still less.

The example of this olefinic end saturated carboxylic acid ester comprises methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methylmethacrylate, the own ester of methacrylate, 2-ethylhexyl methacrylate, beta-hydroxy ethyl propylene acid esters, γ-hydroxypropyl acrylate, δ-hydroxybutyl acrylate and beta-hydroxy ethyl methacrylate.

This monovinylarene is represented by following formula (II): formula (II)

R wherein ₃Be hydrogen atom, halogen atom, R ⁴Be oxygen atom low alkyl group halogen atom alkoxy, amino or nitrogen base, Φ is a phenylene.

This monovinylarene comprises styrene, α-Jia Jibenyixi, vinyltoluene, 2-chlorostyrene, O-chlorostyrene, m-chlorostyrene, P-chlorostyrene and P-ethyl styrene.This vinyl esters is represented by following formula (III): formula (III)

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

The example of vinyl esters comprises vinylformic acid ester, vinylacetate and vinyl propionic ester like this.

This vinyl ether is represented by following formula (IV):

Formula (IV) CH ₂=CH-O-R ⁶R in the formula ⁶Be to have 11 or the monovalence alkyl of carbon atom still less.

The example of this vinyl ether comprises methoxy ethylene, ethyl vinyl ether, vinyl n-butyl ether, vinyl phenyl ether and vinyl hexamethylene ether.

This diolefin is represented by following formula (V): formula (V)

R in the formula ⁷, R ⁸And R ₉Be hydrogen atom, low alkyl group or halogen atom individually.

The example of this diolefin comprises butadiene, isoprene, chlorbutadiene.

This mono-olefin is represented by following formula (VI): formula (VI)

R in the formula ¹⁰And R ¹¹Be hydrogen atom or low alkyl group individually.

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

Special example with polymkeric substance of anionic group, promptly (being total to) polymkeric substance that obtains by the above-mentioned monomer of polymerization comprises styrene-propene acid copolymer, styrene-maleic acid copolymer and ionomer resin.Also have, cutter can use the vibrin with anionic group.When anionic group existed as free acid, the polymkeric substance with anionic group preferably contained the anionic group of the proportional quantities that can obtain 2-30, preferred 5-15 acid number.When part or whole anionic group when being neutralized, suppose that it exists with free acid, then preferably contain the negative ion of such proportional quantities, promptly acid number is in above-mentioned scope.When the acid number of polymkeric substance or composition, promptly anion concentration is lower than above-mentioned scope, and then the charged energy of gained toner is not enough.When surpassing this scope, the gained toner has disadvantageous hydroscopicity.The preferred adhesive resin is the multipolymer that is obtained by the ethylization unsaturation carboxylate of formula (I) expression that the monomer that contains anionic group and at least a conduct must components, if desired, can use by represented any monomer of formula (II) to (VI) as the selectivity component.One or both of available above-mentioned monomer or more kinds of bonds prepare adhesive resin.

In the present invention, low-molecular weight polymer is preferably the multipolymer that contains the styrene component.In the preparation low-molecular weight polymer, the weight ratio of styrene and whole used monomer is 70% or still less, is preferably 20%-65%.When crossing 70%, the gained toner is easy to cause that electric charge lost efficacy.As a result, reduced the permanance of toner.

Obtain containing the multipolymer of styrene component by the monomer copolymerization that contains aromatics list ethene, monomer.The preferred adhesive resin is a styrene acrylic resin.

In the present invention, preferably, the acid number of low-molecular weight polymer is less than the acid number of heavy polymer in the adhesive resin.Especially, when negative ion existed with free acid, the acid number of low-molecular weight polymer was 3-15.The acid number of preferred heavy polymer is 6-25, and the ratio of high molecular weight polymeric acid value and low-molecular-weight acid number is 1: 1.2-1: in 8 scopes.When the acid number of low-molecular weight polymer greater than above-mentioned scope, and when the ratio of acid number during less than above-mentioned scope, the gained toner is easy to cause that electric charge lost efficacy.

As described below, by at first preparing low-molecular weight polymer, then to the monomer together polymerization of its adding as the heavy polymer raw material, can obtain the resin of pbz polymer weight polymers and low-molecular weight polymer, in other words, this preparation that independently polymkeric substance can be independent and mixing.When anionic group existed with free acid, preferred resin contained the ratio value negative ion that the acid number that makes whole resin is the 20-30 scope, and preferred acid number is 4-20, and preferred acid number is 5-15.When part or all of anionic group was neutralized, the preferred anionic surfactants group supposed that it exists with free acid so that the proportional quantities of acid number in above-mentioned scope exists.When the acid number of polymkeric substance or composition, i.e. the concentration of anionic group, during less than above-mentioned scope, the charged ability of gained toner is not enough.When greater than above-mentioned scope, the gained toner has disadvantageous hydroscopicity.

The used adhesive resin of the present invention is to be made by the composition that contains above-mentioned polymkeric substance, and said composition also can contain the polymkeric substance that does not have anionic group.In this situation, the proportional quantities of anionic group is preferably in above-mentioned scope in the whole composition.(magnetic)

Toner contained magnetic (comprising adding) can be the used any magnetic of conventional one-pack type developer.The example of magnetic powder material comprises tri-iron tetroxide (Fe ₃O ₄), maghemite (γ-Fe ₂O ₃), iron oxide zinc (ZnFe ₂O ₄), iron oxide yttrium (YaFe ₅O ₁₂), iron oxide cadmium (CdFe ₂O ₄), iron oxide gallium (Gd ₃Fe ₅O ₁₂), iron oxide copper (CuFe ₂O ₄), iron oxide lead (PbFe ₁₂O ₁₉), iron oxide nickel (NiFe ₂O ₄), iron oxide neodymium (NdF _eO ₃), barium ferric oxide (BaFe ₁₂O ₁₉), iron oxide magnesium (MgFe ₂O ₄), iron-manganese oxide (MnFe ₂O ₄), iron oxide lanthanum (LaFeO ₃), iron (Fe), cobalt (Co) and nickel (Ni).Particularly preferred magnetic is made by tri-iron tetroxide (magnetic iron ore) fine powder.Preferred magnetic iron ore is that particle diameter is the symmetrical octahedral bodily form of 0.05-1.0 μ m.This magnetite ore particles can carry out surface treatment with silane coupling agent or titanium coupling agent.Be contained in that the particle diameter of magnetic is generally 1.0 μ m or littler in the toner-particle, preferable range is 0.05-1.0 μ m.

The content of magnetic is per 100 weight portion adhesive resin 0.1-5 weight portions in the toner-particle, is preferably the 0.5-4 weight portion, more preferably the 0.5-3 weight portion.When content too hour, toner diffusion in developing process, and the toner transfer efficiency reduces, as mentioned above.(internal additives of toner-particle)

As mentioned above, toner-particle contains as the adhesive resin of necessary component and magnetic, if desired, can comprise at random that some are generally used for the internal additives of toner.

The example of this adjuvant comprises color and detackifier.

As the color agent, following pigment can use:

-black pigment:

Carbon black, acetylene black, dim, nigrosine;

-replenishers:

Barite, barium carbonate, clay, silica, hard charcoal, talcum, alumina white.

The content of this pigment is per 100 parts of (weight) adhesive resin 2-20 weight ranges in toner-particle, is preferably the 5-15 weight portion.

As detackifier, resemble conventional toner, can use various waxes and olefin resin.(preparation of toner)

The toner-particle of toner can prepare with any toner-particle preparation method commonly used in the two-component developer of the present invention, for example grinds and classification, and fusing granulation, mist projection granulating and polymerization prepare with grinding with stage division usually.

For example, the component of toner-particle is pre-mixed in mixer such as Henschel mixer, kneads with kneading machine such as twin shaft extruding force, then cooling.Grinding products therefrom also, classification obtains toner-particle.The particle diameter of toner-particle is 5-15 μ m, preferred 7-12 μ m, volume averaging particle diameter (intermediate sizes that records with the Coulter counter).

If desired, by will can further improving the flowability of toner as the mobile dose of external additive such as hydrophobicity vapor deposition silica dioxide granule surface attached to toner-particle.The primary particles of this flowability dose such as a silicon dioxide tears typically has a diameter from about 0.015 μ m, join mobile dose in the toner in 0.1-2.0 weight portion scope, with whole toner weight is base, and promptly the general assembly (TW) with toner-particle and mobile dose is a base.

Also have, the present invention preferably adds and has the separant of particle diameter greater than mobile dose particle diameter.As the separant particle, available particle diameter is 0.05-1.0 μ m, any organic and inorganic inert particle of preferred 0.07-0.5 μ m.The example of this inert particle material comprises silicon dioxide, alumina, titanium dioxide, magnesium carbonate, acryl resin, styrene resin and magnetic material.As mentioned above, separant can not only also increase transfer efficiency as the flowable dose.As the separant particle, preferably use fine particulate with toner-particle in identical magnetic, particularly tri-iron tetroxide (magnetic iron ore).When being used as the separant particle, can suppress magnetic the diffusion of toner effectively, as mentioned above.The content of separant is 10 weight portions or still less, more preferably the 0.1-10 weight portion most preferably is the 0.1-5 weight portion, is base with the toner general assembly (TW).When the separant particle excessively was contained in the toner, the concentration of copy image was not enough.When magnetic when the separant particle, in toner-particle, contain the magnetic total amount be preferably 10% (weight) or still less, be base with the adhesive resin.When excessive containing, the concentration of copy image reduces.

When mobile dose and separant particle join in the toner-particle, preferred following preparation method: at first mobile dose and separant particle are fully mixed each other, then the gained potpourri is joined in the toner-particle, open this toner-particle is loose fully again.Therefore, the separant particle is attached on the toner-particle surface.Here " adhering to " means with toner-particle and keeps in touch, and is partially submerged into toner-particle simultaneously again.In this mode, prepared toner-particle of the present invention.(carrier granular)

Each particle all preferably is made up of the particle with double-layer structure in the developer used carrier of the present invention, and this double-layer structure comprises slug particle and covers the coating of this slug particle.Because coating, the resistance of carrier granular is stable, and in time or by the influence of environment electricity He is to change considerably lessly.As a result, the charged ability of particle is stable.Also have,, prevented the waste material that friction causes between carrier granular and the toner-particle because that carrier particle surface is made with coating is smooth.As a result, improve the permanance of carrier, therefore, prolonged the life-span of gained developer.

This slug particle is made by the magnetic material of following formula (A) expression:

Formula (A): MOFe ₂O ₃M represents to be selected from least a among Cu, Zn, Fe, Ba, Ni, Mg, Mn, Al and the Co in the formula.

The compound of formula (A) expression is magnetic iron ore (wherein M represents Fe) or ferrite (wherein M represents a kind of metal except that Fe), and preferably using wherein, M is the ferrite of Cu, Zn, Mn, Ni or Mg.This magnetic iron ore and ferritic resistance change in time tinily, and when applying magnetic field in developing apparatus, they can form soft spike spread geometry.The slug particle that contains this magnetic material has 30-200 μ m, the particle diameter of preferred 50-150 μ m.By method granulation magnetic material fine graineds such as spraying granulations, and heating gained particle makes slug particle.It is 10 that this slug particle has volume resistivity ⁵-10 ⁹Ω cm is preferably 10 ⁶-10 ⁸Ω cm.The saturation magnetization of slug particle is 30-70emu/g, preferred 45-65emu/g.

In one aspect of the invention, the resin combination that is used for formation coating on carrier granular preferably has the resin of cation group, and this resin can be thermoplastic resin or thermoset resin.Thermoset resin or to contain the potpourri of thermoset resin preferably heat-resisting and durable.The example of cation group comprises and contains the basic nitrogen group, as primary, the second month in a season and uncle's amino, quaternary ammonium group, amide group, imino group, diazanyl, guanidine radicals and amidino groups, and wherein preferred especially amino and quaternary ammonium group.

Example with cation thermoplastic resin comprises thermoplastic acrylic resin, thermoplastic styrene-acryl resin, vibrin, polyamide and olefin copolymer, and each in them is the cation group all.The example of thermoset resin comprises modification and unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acryl resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy resin and amino resins, and each in them is the cation group all.The potpourri of the monomer by having cation group or the monomer of cation group and this resin that other monomer polymerizations prepare the cation group.In other words, make this resin by the compound of cation group and the resin crosslinks of cation group not.Call by name and talk about, therefore the polymerization initiator by using the cation group, is introduced monomer and/or other monomers (being total to) polymerization of cation group in the gained resin with cation group.

When the resin that uses by alkoxy silane or alkoxytitanium preparation, in the preparation resin process or afterwards, the resin that silane coupling agent by following the cation group and resin reaction make the 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.This silane coupling agent is attached on the slug particle surface by the hydroxyl that exists usually on the slug particle surface.Therefore, this silane coupling agent self can form coating.The example of the polymerization initiator of cation group comprises amidine compound, as azo-compound.

The resin that is used to form the cation group of coating can use separately, or uses with any other above-mentioned resin, or uses with other resin of cation not.

The content of cation group in the resin of cation group is in every 100g resin 0.1-2000mmol scope, preferred 0.5-1500mmol.When the resin of cation group when the resin of cation group does not use, form the cation group that preferably contains ratio in the above-mentioned scope in all resins of carrier granular coating.

The resin that forms the carrier granular coating comprises at least a above-mentioned resin that contains cation group, if desired, with other resin-bonded of cation group not together.The fat of cation group and not the example of the potpourri of the resin of cation group comprise the potpourri of alkylated melamine resins and styrene-propene acid copolymer and the potpourri of alkylated melamine resins and propenyl modified siloxane resin.

In another aspect of the present invention, the resin combination that forms coating on carrier granular preferably includes alkylated melamine resins (being the thermoset resin of cation) and propenyl modified siloxane resin.

This alkylated melamine resins is obtained by the alkylation of methylol melamine, and this alkylation is to react between the part methylol groups in any alcohol and the methylol melamine, and methylol melamine is that the addition polymerization by any melamine and formaldehyde obtains.

This melamine comprises melamine and melamine derivative such as benzoguanamine and acetylguanamine.Melamine contains three amino and a guanamines that contains two amino.Use any these compounds as melamine to prepare in the above-mentioned resin, in melamine and formaldehyde reaction, (promptly form in the reaction) at methylol melamine, every 1mol melamine uses 1.0-8.0mol, preferably the formaldehyde of 2.0-7.0mol.It is effective that this methylol melamine formation is reflected under oxyhydroxide such as alkaline metal or earth alkali metal or base catalyst such as the ammonia existence.Form in the reaction at methylol melamine, the condensation reaction in the methylol melamine makes the cured methylene group that helps of methylol melamine and bonding mutually each other simultaneously, and the result has increased molecular weight.

When methylol melamine and alcohol reaction, formed ehter bond by condensation.The example that is fit to alcohol comprises methyl alcohol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanols and isobutyl alcohol.By using this alcohol, the alkyl group with carbon number of hope is introduced in the melamine molecules, has therefore formed alkylated melamine resins.The alkylation degree, promptly ehter bond forms the extent of reaction, is 10-85%, is preferably 20-80%, adds up to base with methylol group in the melamine.

Propenyl modified siloxane resin can be segmented copolymer or the graft copolymer that contains siloxane resin component and acryl resin component, perhaps has the potpourri of these multipolymers of silicone resin and/or acryl resin.Here " propenyl modified siloxane resin " is to have the multipolymer of silicone resin and/or acryl resin and the potpourri of these multipolymers.

The silicone resin that use contains organic polysiloxane unit and has an active functional group group is as the silicone resin component, described organopolysiloxane example is dimethyl polysiloxane, diphenyl polysiloxane and tolyl polysiloxane, and described active functional group cumularsharolith is in the terminal of strand or in strand.The example of this reactive group comprises hydroxyl, monoalkoxy silicyl, bis-alkoxy silicyl, trialkoxysilyl, alkoxy silicane oxygen base, vinyl silicyl and vinyl siloxy.

Use by a large amount of acrylate or methacrylate monomer and the multipolymer of olefinic unsaturation monomer gained that contains alkoxysilyl on a small quantity as the acryl resin component.The example of acrylate and methacrylate comprises methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, the methacrylate propyl ester, butyl acrylate, butyl isocrotonate, the 2-hydroxy ethyl methacrylate, the 2-hydroxyethyl methacrylic ester, the 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-amino-ethyl acrylate, 2-amino-ethyl methacrylate, N-ethyl-2-amino-ethyl acrylate and N-ethyl-2-amino-ethyl methacrylate.The example that contains the olefinic unsaturation monomer of alkoxysilyl comprises vinyltriethoxysilane, 3-triethoxysilylpropyltetrasulfide acrylate and 3-triethoxysilylpropyltetrasulfide methacrylate.

When silicone resin component and acryl resin component react to each other, cause the reaction between the active alkoxy grp in the active function groups and acryl resin in the silicone resin, therefore, prepared the multipolymer that contains siloxane resin component and acryl resin component.Especially, with acryl resin the silicone resin modification is obtained propenyl modified siloxane resin.

Weight ratio in the propenyl modified siloxane resin between acryl resin component and the silicone resin component is preferably 80: 20 to 20: 80, more preferably is 70: 30 to 30: 70.The acryl resin component here comprises two kinds, a kind of is acryl resin itself, and another kind is to be contained in thing acryl resin in the multipolymer during as propenyl modified siloxane resin when the potpourri that uses acrylic acid-silicone copolymers and acryl resin and/or siloxane.Similarly, the silicone resin component comprises two kinds of the contained silicone resin components of silicone resin self and multipolymer.

This propenyl modified siloxane has the group with methylol or the reaction of etherificate methylol, as hydroxyl and alkoxy.The concentration of this reactive group is generally per 100 gram resin 1-400mmol, preferred 3-200mmol.

The resin combination that forms coating on carrier granular comprises the propenyl modified siloxane resin of alkylated melamine resins and any content.The mixture ratio of preferred alkylated melamine resins and propenyl modified siloxane resin is 5: 95 to 70: 30.When mixture ratio is in this scope, can further improve the charged ability of gained carrier granular, also can further improve the smoothness of coating surface.In addition, can reduce the generation of waste material.

Aspect another, the resin combination that forms coating on carrier particle surface contains methylsiloxane resin and methylated melamines resin of the present invention.

For example, the methylsiloxane resin can be prepared by methyl chlorosilane.This methylsiloxane resin is added in the slug particle as the methylsiloxane resin oligomers usually, then as following curing.

This methylated melamines resin has 700 or bigger weight average molecular weight.Here unqualified to the upper limit of methylated melamines molecular resin amount, but be preferably 2,000.Here unqualified to the content of methylsiloxane resin and methylated melamines resin, but the content of this methylated melamines resin in coating is preferably in the 5wt%-70wt% scope.When the content of methylated melamines resin was in this scope, the charged ability of gained carrier granular can further be stablized.Also have, in this case, the self-crosslinking degree of methylated melamines resin is most suitable, makes the activity of solidifying the methylmelamine resin in the processing procedure very excellent, and the filming performance that makes the methylated melamines resin is satisfied.Therefore, further improved cohesive between gained coating and the slug particle.

Of the present invention also aspect one in, preferably, the resin combination that forms coating on carrier granular contains the methylsiloxane resin that ratio is 70mol% or more T unit.In order to solidify this methylsiloxane resin, use the methylsiloxane resin oligomers that contains 70mol% or more T unit to comprise the more T of 70mil% unit.For T unit content in the oligomer is adjusted to 70mol% or more, make methyl trichlorosilane (CH ₃SiCl ₃) mixture ratio be 70mol% or more, this methyl trichlorosilane is the source as T unit in the methyl chlorosilane of methylsiloxane oligomer raw material.

In another aspect of the present invention, the resin combination that forms coating on carrier granular preferably includes the thermoplastic resin of thermoset resin and particular type.This thermoset resin is selected from least a in the following thing group: modification or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acryl resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy resin and amino resins.Suitable thermoplastic resin has quaternary ammonium group, and the example of this thermoplastic resin comprises acryl resin, styrene-propene acid resin, vibrin, polyamide and olefin resin, and all these comprises quaternary ammonium group.This thermoplastic resin with quaternary ammonium group can obtain by the monomer with quaternary ammonium group or the monomer mixture with quaternary ammonium group and other monomer polymerization.In other words, it can obtain with being connected of the compound that contains quaternary ammonium group by the thermoplastic resin that does not contain quaternary ammonium group.

The concentration that this thermoplastic resin that contains quaternary ammonium group contains quaternary ammonium group is per 100 gram resin combination 0.1-20mmol.When this thermoplastic resin is contained in the coating, the further charged ability of stable carrier.

In another aspect of the present invention, the resin combination of formation coating preferably includes thermoset resin on carrier granular.The example of this thermoset resin comprises modification or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acryl resin, phenol resin, urethane resin, thermosetting polyester resin, epoxy resin and amino resins.When heat curing, the molecular weight of this thermoset resin increases, and becomes unsettled in solvent.For obtaining above-mentioned 85% or bigger degree of cure, need to adjust heating-up temperature and time.In the present invention, thermoplastic resin can be contained in the coating, does not reduce the characteristic of coating up to it.This thermoplastic resin comprises acryl resin, styrene-propene acid resin, vibrin, polyamide and olefin copolymer resin.In them one or both or above bond can use.

The resin combination that forms coating on carrier granular also can contain adjuvant such as silicon dioxide, alumina, carbon black, fatty acid metal salts, silane coupling agent and silicone oil, if necessary.These adjuvants play the effect of adjusting coating characteristic.(preparation of carrier)

With the method for known formation coating, the resin combination of cation group is applied to the surface of slug particle.For example, slug particle is applied with the solution or the dispersion liquid of resin combination, and dry, form coating thus.In other words, when using thermoset resin or reactant resin oligomer, solution or dispersion liquid coating core particle with uncured resin or this oligomer heat then to solidify this resin.This coating can form as dipping, spraying, bed process, moving bed process and tumbling barrel process with any common method.Can use the solvent of any conventional organic solvent as dissolving or dissipating resin composition.The example of solvent comprises aromatic hydrocarbons such as toluene and dimethylbenzene; Ketone such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Cyclic ethers such as tetrahydrofuran are with diox; Alcohol is as ethanol, propyl alcohol and butanols; Cellulose such as ethyl cellulose and butyl cellulose; Ester such as ethyl acetate and butyl acetate; Amide type solvent such as dimethyl formamide and dimethyl acetamide.Selective solvent according to the chemical property of resin such as dissolubility and suitably.

The carrier granular particle diameter that obtains thus is the 30-200 mu m range, is preferably 50-150 μ m.The weight ratio of coating is per 100 weight portion slug particle 0.001-2.5 weight portions on the carrier granular, is preferably the 0.005-2.0 weight portion.The specific insulation of gained carrier granular is 10 ⁵-10 ¹³Ω cm scope, preferred 10 ⁷-10 ¹²Ω cm, saturation magnetization is 30-70emu/g, preferred 45-65emu/g.(preparation of developer):

Prepare two-component developer by mixing above-mentioned toner and carrier.The mixture ratio of carrier and toner is generally 98: 2 to 90: 10, is preferably 93: 7-94: 6, by weight.

Carry out copying operation with the developer of the present invention that contains toner, reprography method is routinely carried out.For example, photoconductive coating uniform charging that particularly will be on photoreceptor forms electrostatic latent image thereon with image exposure.Then, will contact with photoreceptor by the magnetic brush that the two-component type magnetic developer is made, thereby easily latent electrostatic image developing is become toner image, then by hot-rolling with the heating of this image and pressurization with this image fixing.

Embodiment

The present invention is illustrated by embodiment.It should be noted that the present invention is not limited to these embodiment.

(embodiment 1.1)

(preparation of toner)

The composition parts by weight of toner

Adhesive resin a) 100

Color agent: carbon black 7

Magnetic: ferrite 2

A) adhesive resin that is used for present embodiment is the styrene-propene acid copolymer (wherein styrene, butyl isocrotonate, acrylic acid ratio are 70: 28: 2) with carboxyl.

Knead with above-mentioned component fusing and with two-axis extruder, gains are ground with jet mill, and use the pneumatic classifier classification, obtain having the toner-particle that mean grain size is 10.0 μ m.

The mean grain size that in the gained toner-particle, adds 0.3 weight portion be the hydrophobic silica powder of 0.015 μ m as mobile dose, be base with 100 weight toner-particles.With the Henschel mixer mixing of gained potpourri is obtained toner.

(preparation of carrier)

Mean grain size is that the spherical ferrite particle of 100 μ m is as the magnetic core particle.In 1000 weight portion ferrite particles, add the coating of the listed component of table 1, mix this gains with the thermal agitation device.Solvent is removed from this gained potpourri, and with residue in 200 ℃ of thermal treatments 1 hour, to obtain the carrier granular that each all has coating.

(preparation of developer)

Gained toner and carrier are evenly mixed, obtain having the two-component type toner that toner concentration is 3.5wt%.

(embodiment 1.2)

Except with having the coating agent of the listed component of table 1, repeat the step alternate with embodiment 1.1, prepare developer thus.

(embodiment 1.3)

Except with having the coating agent of the listed component of table 1, repeat the step identical with embodiment 1.1, make developer thus.

(comparative example 1.1)

Except not using any coating agent, promptly do not forming on the carrier outside the coating, repeat the step identical with embodiment 1.1, make developer thus.

The coating agent of table 1. embodiment 1.1-1.3

Component embodiment 1.1 embodiment 1.2 embodiment 1.3 resins 1 propylene modified methyl styryl phenyl-propylene (weight portion) siloxane oxyalkylene acid polymer

2.5 4.8 3.5 resins, 2 methylated melamines gamma-amino propyl group methylated melamines (weight portion) triethoxysilanes

2.5 0.2 1.5 solvents: toluene 200 200 200 (weight portion)

(embodiment 2.1)

(preparation of carrier)

Mean grain size is that the spherical ferrite particle of 100 μ m is used as the magnetic core particle, add coating agent with the listed component of table 2 to 1000 weight portion ferrite particles, with thermal agitation device mixing gains, from the gained potpourri, remove solvent, residue in 200 ℃ of heat treatment 1 hour, is obtained each all cated carrier granular.

(preparation developer)

The toner of embodiment 1.1 preparation is evenly mixed with gained carrier thus, obtain having the two-component developer that toner concentration is 3.5wt%.

The coating agent of table 2 embodiment 2.1

Component embodiment 2.1

Resin 1 acryloyl group modified siloxane

(weight portion) 2.5

Resin 2, methylated melamines

Molecular weight 700

(weight portion) 2.5

Solvent: toluene 200

(weight portion)

(embodiment 3.1)

(preparation of carrier)

Mean grain size is that the spherical ferrite particle of 100 μ m is used as the magnetic core particle, add coating agent with the listed component of table 3 to 1000 weight portion ferrite particles, with thermal agitation device mixing gains, from the gained potpourri, remove solvent, residue in 200 ℃ of heat treatment 1 hour, is obtained each all cated carrier granular.

(preparation of developer)

The toner of embodiment 1.1 preparation is evenly mixed with gained carrier thus, obtain having the two-component developer that toner concentration is 3.5wt%.

(embodiment 3.2)

Prepare developer with coating agent by embodiment 3.1 same way as with the listed component of table 3.

Table 3. embodiment 3.1 and 3.2 coating agent component embodiment 3.1 embodiment 3.2 resins 1 methylsiloxane methylsiloxane T unit (mol%) 87 87 weight portions, 3.5 5 resins, 2 methylated melamines do not have molecular weight 700 weight portions 1.5 solvents: toluene 200 200 weight portions

(embodiment 4.1)

(preparation of carrier)

The spherical ferrite particle of mean grain size 100 μ m is as the magnetic core particle, add coating agent with the listed component of table 4 to 1000 weight portion ferrite particles, with thermal agitation device mixing gains, from the gained potpourri, remove solvent, residue in 200 ℃ of heat treatment 1 hour, is obtained each all cated carrier granular.

(preparation of developer)

The toner of embodiment 1.1 preparation is evenly mixed with gained carrier thus, obtain having the two-component developer that toner concentration is 3.5wt%.

(embodiment 4.2)

Except that the content of quaternary ammonium group be table 4 listed, by preparing developer with embodiment 4.1 same way as.

(embodiment 4.3)

Except not using the styrene-propene acid resin that contains quaternary ammonium group, prepare developer with the method identical with embodiment 4.1.

(embodiment 4.4)

Except the content of quaternary ammonium group is as shown in table 4, prepare developer by the method identical with embodiment 4.1.

The coating agent of table 4. embodiment 4.1-4.4

Component embodiment 4.1 embodiment 4.2 embodiment 4.3 embodiment 4.4 resins 1 acryloyl group changes acryloyl group and changes acryloyl group and change acryloyl group and change

Property siloxane siloxane siloxane siloxane, (weight portion) 4.9 4.0 5.0 3.5 resin 2*, (weight portion) 0.1 1.0/1.5 amine contents 1.5 15.0 22.3, (mmol/100 restrains resin) solvent: toluene, (weight portion) 200 200 200 200

* the styrene-propene acid copolymer that has quaternary ammonium group.

(embodiment 5.1)

(preparation of carrier)

Mean grain size is that the spherical ferrite particle of 100 μ m is made the magnetic core particle, add coating agent with the listed component of table 5 to 1000 weight portion ferrite particles, with thermal agitation device mixing gains, from the gained potpourri, remove solvent, residue in 180 ℃ of heat treatment 1 hour, is obtained the carrier granular that each all has coating.

Then, the carrier that obtains is thus packed in the glass container, to wherein adding toluene, with uncured resin dissolves.Then, attract toluene solvant to be poured out with magnet illness carrier in the glass container bottom.This step repeats several times, then with baking box with the gained carrier drying.Survey the carbon number amount in O for toluene (washing) carrier thus with magnetic analyzer (by Horiba Co., LTD. company produces).Based on the carbon number amount that records thus with the carbon number amount that records before the O for toluene, can calculate degree of cure, the results are shown in table 5.

(preparation of developer)

The evenly toner of mix embodiment 1.1 preparations and the carrier of preparation thus then obtain having the two-component developer that toner concentration is 3.5wt%.

(embodiment 5.2)

Except that under 200 ℃ of temperature, heat-treating, prepare developer by the method identical with embodiment 5.1.

(embodiment 5.3)

Except that under 170 ℃ of temperature, heat-treating, prepare developer by the method identical with embodiment 5.1.

The coating agent of table 5 embodiment 5.1-5.3

Component (weight portion) embodiment 5.1 embodiment 5.2 embodiment 5.3 resins 1 acryloyl group changes acryloyl group and changes acryloyl group and change

Property siloxane (2.5) property siloxane (2.5) property siloxane (2.5) resin 2* 2.5 2.5 2.5 solvents: toluene 200 200 200 solidification temperatures (℃) 180 200 170 curing degrees (%) 87 95 80

* methylated melamines

(evaluation of developer)

By following every clauses and subclauses to estimating at the developer of the foregoing description and comparative example's gained.Xerox is improved to be easier to estimate sample, use this improved duplicating machine in evaluation procedure, this duplicating machine is by Mita IndustrialCo., and Ltd. produces, and trade mark is called DC-4685.

(a) transfer efficiency:

At first measure in the duplicating machine amount of toner in the toner magazine, and carry out the duplicating of predetermined number.Then, measure remaining toning dosage in the toner magazine.By poor before the copying operation, calculate the consumption of toner with toner quantity afterwards.Simultaneously, also measure the toning dosage collected in the cleaning during the copying operation as collecting amount.Based on these quantity, calculate the transfer efficiency of toner by following formula (i).To have the black region ratio be 8 ‰ to used original paper in the copying operation.Do this evaluation, to carry out following (b)-(i) every various evaluation tests.

For embodiment 4.1-4.4 and 5.1-5.3, carry out 50,000 times and duplicate, the results are shown in table 9 and 10 by these developer gained.

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

With having the black region ratio is that 8% original paper carries out copying operation, for the developer of embodiment 4.1-4.4 and 5.1-5.3 up to duplicating 50,000 parts, for other developer till its transfer efficiency is less than 70%.With reflection-densitometer (by Tokyo Denshoku Co., Ltd. preparation TC-6D) is measured the concentration of the copy image black part of per 5000 parts of copies, with mean concentration as image color (I.D.).It was 15% (comprising the solid black part) that the original paper that is used to prepare per 5000 parts of copy samples has the black region ratio.The results are shown in Table 6 by embodiment 1.1-1.3 and comparative example's 1 developer gained, embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8, embodiment 4.1-4.4 the results are shown in table 9, embodiment 5.1-5.3 the results are shown in table 10.

(c) photographic fog concentration (F.D.):

With having the black region ratio is that 8% original paper carries out copying operation, for the developer of embodiment 4.1-4.4 and 5.1-5.3 up to duplicating 50,000 parts, for other developer till its transfer efficiency is less than 70%.(prepare by Tokyo Denhuku Co.Ltd., TC-6D) concentration of white portion in the copy image of the per 5000 parts of copies of measurement with reflection-densitometer.Calculate the difference between the concentration of the concentration record thus and the paper (basic paper) that is used as copying operation that records by reflection-densitometer, with maximum difference as photographic fog concentration (F.D.).It was 15% (comprising the solid black part) that the original paper that is used to prepare per 5000 parts of copy samples has the black region ratio.The results are shown in Table 6 by embodiment 1.1-1.3 and comparative example's 1 developer gained, embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8, embodiment 4.1-4.4 the results are shown in table 9, embodiment 5.1-5.3 the results are shown in table 10.

(d) resolution:

With having the black region ratio is that 8% original paper carries out copying operation.When duplicating 50, during 000 part of copy (if duplicating 50, transfer efficiency becomes less than 70% before 000 part of copy, it then is this moment), duplicate a conventional picture original paper (original paper that has a series of patterns, all be decorated with the parallel lines of predetermined quantity in every middle 1mm), observation post gets copy image with eyes.Developer gained by embodiment 1.1-1.3 and comparative example 1 the results are shown in table 6, and embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8, embodiment 4.1-4.4 the results are shown in table 9, embodiment 5.1-5.3 the results are shown in table 10.

(e) amount of charge:

With having the black region ratio is that 8% original paper carries out copying operation, for the developer of embodiment 4.1-4.4 and 5.1-5.3 up to duplicating 50,000 parts, for other developer till its transfer efficiency is less than 70%.Have during the copying operation, duplicate 5000 parts after, measure the quantity of electric charge of 200mg developer with the amount of charge measurement mechanism that dusts (producing) by Toshiba chemical company, based on this measured value, calculate the mean charge amount of per 1 gram toner.Developer gained by embodiment 1.1-1.3 and comparative example 1 the results are shown in table 6, and embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8, embodiment 4.1-4.4 the results are shown in table 9, embodiment 5.1-5.3 the results are shown in table 10.

(f) toner diffusion:

With having the black region ratio is that 8% original paper carries out copying operation, for the developer of embodiment 4.1-4.4 and 5.1-5.3 up to duplicating 50,000 parts, for other developer till its transfer efficiency is less than 70%.Then, with toner diffusion-condition in the eyes O﹠A duplicating machine.Developer gained by embodiment 1.1-1.3 and comparative example 1 the results are shown in table 6, embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8, embodiment 4.1-4.4 the results are shown in table 9, embodiment 5.1-5.3 the results are shown in table 10, in these tables, zero not diffusion of expression toner, the diffusion of * expression toner.(g) permanance:

After all duplicating 10,000 parts of copies, based on the consumption and the collecting amount calculating transfer efficiency of toner, with the copy quantity of finding before transfer efficiency becomes less than 70%, to be duplicated.With the labelled amount of this quantity as the developer permanance.Developer gained by embodiment 1.1-1.3 and comparative example 1 the results are shown in table 6, and embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8.(h) because the attachment quantity of the carrier particle surface that waste material causes:

With having the black region ratio is that 8% original paper duplicates.Duplicating 50, after 000 part of copy (if duplicating 50, transfer efficiency becomes less than 70% before 000 part of copy, then at this moment), developer is done following test: developer is placed on the 400 purpose sieves, with fan blower developer is drunk up from below, because of toner and carrier are separated.Residual carrier on the 5 gram sieves is packed in the beaker, add toluene.Therefore, because waste material and dissolved attached to the toner component on the carrier particle surface.By with magnet carrier being adsorbed on beaker bottom and toluene solvant being poured out.Repeat this step several times, become transparent up to this gained toluene solution.Afterwards, with baking oven for heating gained carrier will adhere to the toluene evaporates on it.And the weight of measurement gained residue.With the difference between the residue weight after the weight of carrier in the beaker of packing into originally (i.e. 5 grams) and the toluene evaporates as the amount that is attached to the toning component on the carrier particle surface (being the waste material amount) that causes owing to waste material.The waste material amount is to represent attached to the toner component weight (mg) on the 1 gram carrier.By the table 6 that the results are shown in of embodiment 1.1-1.3 and comparative example's 1 developer gained, embodiment 2.1 the results are shown in table 7, embodiment 3.1 and 3.2 the results are shown in table 8.(i) film forming:

With having the black region ratio is that 8% original paper carries out copying operation.After duplicating 50,000 parts of copies, observe the situation of photosensitive drums in the duplicating machine with eyes, the results are shown in table 10, wherein film forming is not observed in zero expression, and * expression observed film forming.

Table 6 embodiment 1.1-1.3 and comparative example's 1 evaluation

Embodiment 1.1 embodiment 1.2 embodiment 1.3 comparative example 1I.D. 1.340 1.275 1.342 1.306F.D. 0.004 0.003 0.004 0.006 resolution 5555 quantities of electric charge-22.3-24.2-23.8-19.4 (μ c/g) toner spreads 0000 permanance 100,000 100,000 90,000 60,000 (number) waste material amount (mg) 0.45 0.43 0.51 0.67 (in 50,000 copies)

Table 7 embodiment 2.1 and comparative example's 2 evaluation

Embodiment 2.1 comparative example 2I.D. 1.352 1.306F.D., 0.003 0.006 resolution, 55 quantities of electric charge (μ c/g)-22.3-19.4 toners spread 00 permanance (number) 110,000 60,0.42 0.67 waste material amount (mg) of 00050,000 copy

Table 8 embodiment 3.1 and 3.2 and comparative example 3 evaluation

Embodiment 3.1 embodiment 3.2 comparative example 3I.D. 1.334 1.228 1.306F.D., 0.004 0.003 0.006 resolution, 555 quantities of electric charge (μ c/g)-23.4-25.8-19.4 toners spread 000 permanance (number) 110,000 110,000 60,000 waste material amount (mg) 0.41 0.42 0.67 (50,000 copy)

The evaluation of table 9 embodiment 4.1-4.4

Embodiment 4.1 embodiment 4.2 embodiment 4.3 embodiment 4.4I.D. 1.362 1.354 1.315 1.372F.D., 0.003 0.004 0.005 0.009 resolution ratio, 5555 quantities of electric charge (μ c/g)-23.0 22.1-26.4-14.5 toners spread 0000 transfer efficiencies (%), 78.4 77.6 73.1 71.0 waste material amounts (mg) 0.40 0.44 0.45 0.57 (50,000 copy)

The evaluation of table 10 embodiment 5.1-5.3

Embodiment 5.1 embodiment 5.2 embodiment 5.3I.D. 1.351 1.358 1.328F.D., 0.004 0.003 0.005 resolution ratio, 555 quantities of electric charge (μ c/g)-22.5-23.4-20.8 toners spread 000 transfer efficiencies (%), 77.4 79.2 72.1 waste material amount (mg) 0.41 0.38 0.64 (50,000 copy) film forming 00 *

[summary of evaluation]

The developer of embodiment 1.1-1.2 preparation all is being very stable aspect image color, photographic fog concentration, resolution and the quantity of electric charge.In addition, when using these developers, do not observe the toner diffusion.Compare with the comparative example's 1 of containing the carrier that does not contain coating developer, the developer of embodiment 1.1-1.3 have still less the waste material amount and the permanance of improvement.

The developer of embodiment 2.1 preparations all is being very stable aspect image color, photographic fog concentration, resolution and the quantity of electric charge.Also have, when using this developer, do not find the toner diffusion.Especially, compare with the comparative example's 1 of containing the carrier that does not contain coating developer, this developer have still less the waste material amount and the permanance of improvement.

The developer of embodiment 3.1 and 3.2 preparations all is being very stable aspect image color, photographic fog concentration, resolution and the quantity of electric charge.Also have, when using these developers, do not observe the diffusion of toner.Compare with the comparative example's 1 of containing the carrier that does not contain coating developer, embodiment 3.1 and 3.2 developer have still less the waste material amount and the permanance of improvement.

The developer of embodiment 4.1-4.4 preparation is being very stable aspect image color and the resolution, and has waste material seldom.Also have, with contain coating in do not contain quaternary ammonium group carrier embodiment 4.3 with contain coating in contain the quaternary ammonium group of excessive concentrations the embodiment 4.4 of carrier compare, contain the embodiment 4.1 of carrier of the quaternary ammonium group that contains predetermined concentration in the coating and 4.2 developer have less amount attached to attachment on the carrier particle surface.

The developer of embodiment 5.1-5.3 preparation all is being very stable aspect image color, photographic fog concentration, resolution and the quantity of electric charge.When using these developers, do not observe the diffusion of toner.Also having, is that the developer of the embodiment 5.3 of 80% carrier is compared with containing the coating degree of cure, contain the coating degree of cure and be 85% or the embodiment 5.1 of higher carrier and 5.2 developer have the transfer efficiency of further improvement and waste material amount still less.Have again, in the developer of embodiment 5.1 and 5.2, suppressed the film forming of photoreceptor effectively.

Under scope and spirit of the present invention, various other variation for present technique field those of ordinary skill be easily see and be easy to accomplish.Therefore, the claims scope is not limited to the intention of the above-mentioned explanation of this paper, and this what is claimed is widely formation.

Claims (14)

1. two-component developer, this developer contains toner and carrier, wherein said toner comprises toner-particle, described toner-particle comprises adhesive resin and the magnetic that is dispersed in this adhesive resin, described adhesive resin is to be made by the composition that contains the resin with anionic group, the scope of described magnetic in this toner-particle is the described adhesive resin 0.1-5 of per 100 weight weight portion, each carrier granular in described carrier has slug particle and covers the coating of described slug particle, and described slug particle is to be made by the magnetic material of following formula (A) expression:

Formula (A): MOFe ₂O ₃M represents to be selected from least a metal among Cu, Zn, Fe, Ba, Ni, Mg, Mn, Al and the Co in the formula.

2. the two-component developer of claim 1 does not wherein have absorption peak basically with the described toner gained of methanol extraction extract in the 280-350nm scope, is substantially zero absorption in the 400-700nm scope.

3. the two-component developer of claim 1, the content of wherein said magnetic is the described adhesive resin 0.5-3 of per 100 weight portions weight portion scope.

4. the two-component developer of claim 1, wherein said toner-particle has volume base mean grain size 5-15 μ m, and to have volume base mean grain size be that the separant particle of 0.05-1.0 μ m is attached on the described toner-particle surface.

5. the two-component developer of claim 1, wherein said coating is to be made by the resin combination that contains the resin with cation group.

6. the two-component developer of claim 1, wherein said coating is to be made by the resin combination that contains alkylation melmac and acryloyl group modified siloxane resin, described alkylation melmac has the weight average molecular weight M by following formula (B) expression:

C represents the contained carbon number of groups in the described alkylation melmac in formula (B): M 〉=1100C-400 formula.

7. the two-component developer of claim 1, wherein said coating are by containing the methylsiloxane resin and the resin combination of the melmac that methylates is made, and this melmac that methylates has 700 or bigger weight average molecular weight.

8. the two-component developer of claim 1, wherein said coating be by contain T unit ratio be 70% or the resin combination of bigger methylsiloxane resin make.

9. the two-component developer of claim 1, wherein said coating is to be made by the resin combination that contains thermoset resin and thermoplastic resin, this thermoplastic resin contains the quaternary ammonium group that concentration is the described resin combination 0.1-20mmol of per 100 grams.

10. the two-component developer of claim 1, wherein said coating contains thermoset resin, and has 85% or higher degree of cure.

11. the two-component developer of claim 1, the content of wherein said coating are the described slug particle 0.001-2.5 of per 100 weight portions weight portion.

12. any two-component developer of claim 9 and 10, wherein said thermoset resin are be selected from following thing group at least a: modification or unmodified silicone resin, thermosetting acrylic resin, thermosetting styrene-acryl resin, phenol resin, polyurethane resin, thermosetting polyester resin, epoxy resin and amino resins.

13. the two-component developer of claim 5, wherein said cation resin is to have the resin that contains the basic nitrogen group.

14. the two-component developer of claim 1, the particle diameter of wherein said slug particle are 50-150 μ m.

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