CN101004564A

CN101004564A - Carrier and developer for electrostatic image development, and image formation method and apparatus

Info

Publication number: CN101004564A
Application number: CN 200610005406
Authority: CN
Inventors: 松本晃; 饭塚章洋; 福田裕之; 清野英子; 矢野敏行
Original assignee: Fuji Xerox Co Ltd
Current assignee: Fujifilm Business Innovation Corp
Priority date: 2005-07-25
Filing date: 2006-01-18
Publication date: 2007-07-25
Anticipated expiration: 2026-01-18
Also published as: JP2007033720A; CN100533286C; JP4525507B2

Abstract

The present invention provides a carrier for electrostatic image development, and a developer, an image formation method and an image formation apparatus using the carrier. The carrier is carrier particles. When the carrier particles each have a coating layer on a magnetic particle, the carrier has a total energy amount of 1500 to 3000 mJ. When the carrier particles each have a coating layer on a magnetic powder-dispersed particle, the carrier has a total energy amount of 1000 to 1500 mJ. The total energy amount is measured with a powder rheometer at a tip end speed of a rotor of 100 mm/s and a helix angle of the rotor of -5 DEG . The total energy amount is a value of a portion of the carrier in a measurement container which portion is contained in the region between the packed surface of the carrier and a surface disposed under the packed surface by 70 mm.

Description

The carrier and developer and formation method and the device that are used for electrostatic image development

Technical field

The present invention relates to a kind of electrostatic image developing carrier, electrostatic image developing, developer for static charge image development, formation method and imaging device that for example in xerography or electrostatic recording, is used to make latent electrostatic image developing.

Background technology

Use xerography to make the method for information visualization be used for every field at present by electrostatic latent image.In the xerography, obtain image: in charging and step of exposure, go up the formation electrostatic image at photoreceptor (sub-image maintenance body) by following steps; Make electrostatic image development with the developer that comprises toner, to obtain toner image, wherein said toner comprises colorant and adhesive resin; The transfer printing toner image is to the recording materials surface; And make toner image on recording materials with for example hot roll.The cleaning sub-image keeps body to remove remaining toner after the transfer printing, so that can form next electrostatic image; But when almost not having residual toner to stay after the transfer printing, for example under the situation of using spherical toner, cleaning can omit.

The developer that uses in the development (dried developer) comprises the two-component developing agent that contains toner and carrier, and only comprises for example monocomponent toner of magnetic color tuner of toner.Monocomponent toner can be divided into magnetic single component developer, and it comprises Magnaglo and utilizes magnetic force to be sent to the district of developing by means of the developer carrying part; And the non-magnetic mono-component developer, it does not comprise Magnaglo, and utilizes by the charging unit electric field that applies of charging roller for example, is sent to the district of developing by means of the developer carrying part.On the other hand, with regard to two-component developing agent, carrier is shared stirring, transmission and charge function, so carrier and toner are shared the corresponding function of developer separately.Therefore, the performance of described developer is controlled easily, so extensively adopt two-component developing agent at present.The controlled excellence especially of electric charge that comprises the developer of the carrier that is coated with resin-coated layer is opened and it is easier to be improved to the dependence of environment and stability in time.

As developing method, once adopted series process (cascade method) before; Yet using magnetic roll is present main stream approach as the magnetic brush method of developer transfer body/maintenance body.

Since the latter half of the 1980s, on electrofax market, multifunction device and the material that can be used for such device have been starved of.With regard to the full-color image quality, wish the image that obtains having the quality suitable with the quality of senior printing and silver halide picture.With regard to monochrome image, wish to obtain to be similar to the high image quality of the quality of full-color image.In addition, for device, need high productivity, miniaturization and low cost.High-quality in order to obtain, the digitizing of device is absolutely necessary, and digitizing makes can carry out complex image processing at a high speed, and independent control literal and photographic image.Correspondingly, the reappearance of full color and monochrome image is compared obvious improvement with using analogue technique.Specifically, for photographic image, color range is proofreaied and correct and color correction feasible, and it is highly beneficial to make it compare with situation of using analog imaging, and color range characteristic, fineness, acutance, color reproducibility and granularity all are better than resulting these characteristics under the situation of use analog imaging.For image output, must carry out visually accurately to the electrostatic latent image that produces by optical system, therefore, further advanced the granulation of toner, and speeded up efforts so that reappear more accurate.

On the other hand, in order to realize miniaturization, must reduce number of components.In addition, for cutting down cost, must prolong the life-span of expendable parts.In addition, require developer to have higher function and high reliability more.Particularly, need have the more two-component developing agent of long life, with the replacing frequency that reduces developer or make and do not need to change.In addition, in order to obtain high productivity, need to improve the speed that sub-image keeps body.Therefore, in order to keep high-quality, improve each step of development, transfer printing, photographic fixing and cleaning and become extremely important.

Along with the miniaturization of duplicating machine and printer and the propelling of high speed processing trend, developing apparatus itself must also can run up in miniaturization.Therefore, also need to improve the physical strength of carrier.

In order to satisfy these requirements, disclose by using Magnaglo decentralized carrier and increase flowability of carrier to prevent that carrier from breaking and prevent that carrier is transferred to the technology (referring to for example TOHKEMY 2002-328493) on the photoreceptor.Yet flowability is still not enough, and can not prevent fully that carrier from breaking.

Under the situation of using small particle size toner, flowability is tended to relatively poor, thereby guarantees the flowability of toner by the external additive that adds small particle diameter in toner.Yet the external additive with small particle diameter does not desirably separate with toner, and migrates on the carrier.

In order to address the above problem, to have proposed to control toner particle diameter/carrier particle diameter/carrier proportion and suppressed method (referring to for example TOHKEMY 2001-330985) by the collision energy due to stirring.Yet triboelectric charge reduces in this method.Therefore, when continuous output video high density, the concentration reappearance worsens and photographic fog also occurs.In addition, when lower to the ratio of the new support (tricle) of developer feeding or when not carrying out the supply of new support, can not prevent the pollution that brings by external additive between the long-term operating period fully.

In addition, proposed wax is joined the method (referring to for example TOHKEMY 2004-170714) of the resin of the carrier core that is used for being covered.

Yet if the soft material of existence as wax on the carrier surface, the flowability of carrier reduces, and it is inhomogeneous that this causes particularly toner concentration occurring in the developing cell under high temperature and high humility.

Under the situation of this external use two-component developing agent, the charged ability of carrier is polluted by toner components along with carrier surface and is reduced, and this may cause photographic fog and toner to gather.In addition, coated with resin can be peeled off from carrier surface, and this makes that having low-resistance core material particles partly exposes, and reduces the resistance of developer, and, increased the amount of the carrier that desirably is not attached to sub-image maintenance body owing in developing regional, inject electric field to this developer.If dwindle the particle diameter of toner, then the toner surface of per unit weight is long-pending can increase.In this case, if the carrier particle diameter does not change, then toner lining rate is very high on the carrier surface, to such an extent as to can not make toner fully charged, and tend to often occur that toner gathers or play photographic fog.For fear of this problem, when dwindling the particle diameter of toner, tend to dwindle the particle diameter of carrier.In such a way, the particle diameter that makes carrier is long-pending and dwindle corresponding to toner surface, makes that enlarged surface is long-pending and make toner fully charged, suppresses toner and gathers and rise photographic fog.

Yet,, also can reduce the magnetic force of each carrier granular although dwindle the surface area that the particle diameter of carrier can increase per unit weight.Therefore, the magnetically confined power of developer carrier weakens, and therefore is attached to sub-image and keeps the amount of the carrier of body to increase.

In order to address this problem, proposed the small particle diameter carrier is kept to sub-image the method that suppresses of adhering to of body.For example, for the developing regional that applies oscillating electric field, the resistance that discloses by carrier in the electric field that increases this developing regional suppresses the method (referring to for example Japanese kokai publication sho 60-131549) that carrier adheres to.

Although increase carrier resistance for preventing that the carrier by due to the electric field injection from adhering to beyond doubt effectively, its also increases the resistance of developer simultaneously.Therefore, sub-image keeps on the body that the influence degree of effective electric field becomes too big in the developing regional.In addition, after development, the opposite polarity electric charge of the residual toner on polarity and the carrier can not promptly be escaped to developer carrier, and worsens at the image quality at high density part and low-density segment boundary place.Therefore, the developer that comprises this carrier and toner can not satisfy in recent years the needs to high image quality.

In addition, proposed to limit the relation (referring to for example Japanese kokai publication hei 5-66614) between carrier bulk resistance, carrier particle diameter and the carrier magnetic force, and suppressed carrier by control by the lining rate of resin-coated slug particle and adhere to (referring to for example Japanese kokai publication hei 7-234548).

Certainly, these methods can effectively suppress carrier at first sub-image is kept adhering to of body.Yet, do not mention image stability in time.In order in bi-component is developed, to obtain stabilized image, need often to stir the inclusions in the developing cell, so that developer is stablized charged and promptly make the toner that appends charged.Yet it is not little to stir stress.Therefore, the long-term stirring stress resin that carrier particle surface was covered that can cause comprising in this developer is peeled off gradually.Therefore, carrier can not keep initial resistance, and its resistance will approach the level that electric charge does not desirably inject carrier, and the carrier that finally causes the initial stage not occur adheres to.This is obvious especially in double-sided copying or full color imaging.Under the situation of double-sided copying, after development on a surface, transfer printing and the photographic fixing, once more recording materials are sent to exposure region, and on the back side of these recording materials, form image.During this step, need often to stir the inclusions in the developing cell, to such an extent as to the time ratio that the stirring stress that developer is applied is continued will be grown usually.Under the situation of full color imaging, particularly adopt under the situation of tandem development, for example in the formation method that uses four look developers, even obtain seldom to use or use not at all the image of certain color, also need to stir the inclusions in each developing cell that comprises the pairing developing cell of this color.Therefore the amount of the stress that developer is applied is higher than the situation of forming monochrome image.As a result, peeling off often appears in the coated with resin of carrier, causes carrier resistance obviously to reduce.

Therefore, proposed with the surface nature of control carrier, thereby to take into account the charged ability of carrier and the wearing quality of coated with resin (referring to for example Japanese kokai publication hei 11-133672) with the crosslinked silicone carrier surface that is covered.

Yet the wearing and tearing described in the document suppress only to reach the degree that the charged ability that makes carrier does not reduce, and do not mention relevant carrier and be attached to any description that sub-image keeps body.Peeling off really of the coated with resin of carrier can reduce carrier resistance.Yet the carrier with residual coated with resin has charged ability to a certain degree.Therefore, in the starting stage, the reduction degree of carrier resistance is not too high.Correspondingly, can photographic fog not appear or toner disperses in this stage.Yet resistance can continue to reduce during continuing to use carrier, and finally reaches the level that causes that electric charge injects.Therefore, electric charge does not desirably inject carrier, and carrier can be attached to sub-image and keep body.Consider this fact, the carrier of the document is in wearing quality and to suppress carrier still not enough aspect adhering to.

Therefore, need have the electrostatic image developing carrier, electrostatic image developing of flowability of increase and formation method and the imaging device that uses this carrier, because this carrier has high fluidity, therefore can prevent owing to the break powder that produces and of carrier by the blank (lost part) in the caused image of this powder.

In addition, need following electrostatic developer, formation method and imaging device: this developer can suppress external additive to the adhering to of carrier, and makes the electric charge/resistance long-term stability of carrier, and high quality image can be provided.

In addition, need following electrophotographic developer, formation method and imaging device: the surface-coated resin of this developer by suppressing carrier peeling off in time, high quality image can be provided for a long time, and can not produce the image quality defective due to adhering to by carrier.

Summary of the invention

First aspect present invention provides a kind of electrostatic image developing carrier, electrostatic image developing (carrier granular), described carrier all comprises the coating as the surface of the magnetic-particle of core and this magnetic-particle of lining, wherein, when measuring with-5 ° rotation oar entering angle with the rotation oar terminal velocity of 100 mm/second with powder rheometer, the gross energy of a part of carrier is 1500mJ to 3000mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

Second aspect present invention provides a kind of developer for static charge image development, it comprises electrostatic image developing toner and electrostatic image developing carrier, electrostatic image developing (carrier granular), wherein said electrostatic image developing toner comprises the female particle of toner, the female particle of described toner all comprises adhesive resin and colorant, and have 140 or less than 140 average shape factor SF1, and described electrostatic image developing carrier, electrostatic image developing all comprises the coating as the surface of the magnetic-particle of core and the described magnetic-particle of lining, and when measuring with the rotation oar entering angle of the rotation oar terminal velocity of 100 mm/second and-5 ° with powder rheometer, the gross energy of a part of carrier is 1500mJ to 3000mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

Third aspect present invention provides a kind of developer for static charge image development, it comprises toner and carrier (carrier granular), wherein, described toner comprises adhesive resin, colorant, with volume average particle size be the external additive of 10nm to 40nm, described carrier comprises the coating as the magnetic-particle of core and this magnetic-particle surface of lining, and, with the air-flow of powder rheometer with 10 ml/min, when the rotation oar terminal velocity of 100 mm/second and-10 ° rotation oar entering angle are measured, the gross energy of a part of carrier is 1420mJ to 2920mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

A fourth aspect of the present invention provides a kind of formation method, described method comprises: keep body to charge to sub-image, charged described sub-image is kept the body exposure, so that keep forming electrostatic latent image on the body at described sub-image, make described latent electrostatic image developing with the developer that comprises toner and carrier, forming toner image, and keep body to be transferred to recording materials from described sub-image described toner image; Wherein, described carrier comprises the electrostatic image developing carrier, electrostatic image developing of first aspect, and in described development, developer carrier is provided, this supporting body keeps body towards described sub-image, maintain described developer on this supporting body surface, and this supporting body thereby being sent to described sub-image, described developer keeps body with the peripheral speed rotation of 200 mm/second to 600 mm/second.

A fifth aspect of the present invention provides a kind of imaging device, and described imaging device has sub-image and keeps body; Charhing unit, this charhing unit are used for keeping body to charge to described sub-image; Exposing unit, this exposing unit are used for keeping forming electrostatic latent image on the body at described sub-image; Developing cell, this developing cell are used to use developer to make described latent electrostatic image developing to form toner image; Transfer printing unit, this transfer printing unit are used for keeping body to be transferred to recording materials from described sub-image described toner image; Wherein, described developer comprises the described electrostatic image developing carrier, electrostatic image developing of first aspect.

Sixth aspect present invention provides a kind of electrostatic image developing carrier, electrostatic image developing (carrier granular), described carrier all comprises the coating as the Magnaglo discrete particles of core and the described Magnaglo discrete particles of lining surface, wherein, when measuring with-5 ° rotation oar entering angle with the rotation oar terminal velocity of 100 mm/second with powder rheometer, the gross energy of a part of carrier is 1000mJ to 1500mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

A seventh aspect of the present invention provides a kind of developer for static charge image development, described developer comprises electrostatic image developing toner and electrostatic image developing carrier, electrostatic image developing, wherein said electrostatic image developing toner comprises the female particle of toner, the female particle of described toner all comprises adhesive resin and colorant, and have 140 or less than 140 average shape factor SF1, described electrostatic image developing carrier, electrostatic image developing comprises the coating as the surface of the Magnaglo discrete particles of core and the described magnetic-particle of lining, and, when measuring with-5 ° rotation oar entering angle with the rotation oar terminal velocity of 100 mm/second with powder rheometer, the gross energy of a part of carrier is 1000mJ to 1500mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

Eighth aspect present invention provides a kind of developer for static charge image development, described developer comprises toner and carrier (carrier granular), wherein, described toner comprises adhesive resin, colorant, with volume average particle size be the external additive of 5nm to 40nm, described carrier comprises the coating as the Magnaglo discrete particles of core and this Magnaglo discrete particles surface of lining, and, with the air-flow of powder rheometer with 10 ml/min, when the rotation oar terminal velocity of 100 mm/second and-10 ° rotation oar entering angle are measured, the gross energy of a part of carrier is 890mJ to 1390mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

Ninth aspect present invention provides a kind of formation method, and described method comprises: keep body to charge to sub-image; Charged described sub-image is kept the body exposure, to keep forming electrostatic latent image on the body at described sub-image; Make described latent electrostatic image developing with the developer that comprises toner and carrier, to form toner image; And keep body to be transferred to recording materials from described sub-image the described toner image; Wherein, described carrier comprises the described electrostatic image developing carrier, electrostatic image developing in the 6th aspect; And in described development, developer carrier is provided, this supporting body keeps body towards described sub-image, and maintain described developer on this supporting body surface, and this supporting body keeps body with the peripheral speed rotation of 200 mm/second to 600 mm/second thereby described developer is sent to described sub-image.

The the of the present invention the first, the 4th to the 6th and the 9th aspect can provide electrostatic image developing carrier, electrostatic image developing, formation method and the imaging device with mobile carrier that increases, described carrier can prevent that carrier from breaking becomes powder, and described powder can cause forming the image with lost part.

The of the present invention the 3rd and eight aspect the electrostatic development developer can be provided, described developer can suppress external additive to the adhering to of carrier, and makes electric charge and/or resistance long-term stability, and makes it possible to export high quality image.

The of the present invention second and the 7th aspect can provide developer for static charge image development; described developer can suppress the coated with resin of carrier and peel off; and As time goes on described peeling off take place through regular meeting in conventional carrier; described developer also can suppress carrier sub-image is kept adhering to of body, therefore can form the high quality image that does not have defective.

Description of drawings

Describe the preferred embodiments of the invention in detail based on following accompanying drawing, wherein:

Figure 1A is the method for gross energy is measured in explanation by powder rheometer a accompanying drawing, Figure 1B shows the normal load of the carrier layer that comprises in the measuring vessel and the chart of the relation between the degree of depth, and Fig. 1 C shows the rotary torque of the carrier layer that comprises in the measuring vessel and the chart of the relation between the degree of depth;

Fig. 2 is the chart that shows the relation between the carrier layer degree of depth that comprises in the energy gradient that obtains and the measuring vessel of measuring by powder rheometer; With

Fig. 3 is the front view of rotation oar used in the powder rheometer.

Embodiment

Usually, the core of electrostatic image developing carrier, electrostatic image developing (hereinafter, being sometimes referred to as carrier) can roughly be divided into two classes: the core and the core that is the Magnaglo discrete particles that are magnetic-particle.The former example comprises iron powder carrier, ferrite carrier and ferrite-iron powder.The latter is that the example of Magnaglo discrete particles comprises the carrier that Magnaglo is dispersed in the resin and form.

As the former is the saturation magnetization that the core of magnetic-particle has high specific gravity and high level, and its mobile and whipping property worsens easily thus.In addition, it has greater impact to toner and photoreceptor during the stirring, thereby does not desirably occur toner exhaustion (toner-spent) phenomenon (toner contamination carrier) easily, and easy scratch photoreceptor.

Consider this problem, on each magnetic-particle surface, form coating, with flowability and the electric charge controllability of improving toner.Usually use the solution that comprises resin to form coating by solwution method.Yet, because iron powder or ferrite have low-surface-energy, and with the wetting state deficiency of resin, so that coating tends to is inhomogeneous, and owing to stir in developing cell, coating is not desirably peeled off easily.

On the other hand, the latter is that the Magnaglo dispersible carrier is compared the former magnetic-particle carrier, can form more soft magnetic brush (being also referred to as fringe (ears)).This makes it possible to form has height and uniform image concentration and high-precision image.

Yet in a kind of carrier in back, the wetting state between Magnaglo and the resin is relatively poor, and Magnaglo not desirably aggegation under the influence of remanent magnetization easily.Therefore, in the aforementioned production method, be difficult in resin, disperse Magnaglo equably and aggegation does not take place.When using wherein Magnaglo not desirably during the Magnaglo dispersible carrier of aggegation, because the cause that in developing cell, stirs, carrier granular little by little ftractures or is cracked, this will desirably not change the charged ability and the flowability of carrier, hard magnetic particles is exposed on ground, carrier surface top, or the scratch photoreceptor.

Therefore, in a kind of carrier of preceding a kind of carrier and back, the equal and carrier of the problem of relevant carrier mobile closely related.

Therefore, the of the present invention the first, the 4th to the 6th and each electrostatic image developing carrier, electrostatic image developing of the 9th aspect coating of all having core and lining core surface, cause the flowability and the controlled improvement of electric charge of carrier.

The entering angle that the terminal velocity that the inventor uses air-flow to be set at 10 ml/min, rotation oar is set at 100 mm/second and rotation oar is set at-10 ° powder rheometer and measures described gross energy, has been found that the mobile closely related of carrier in gross energy that records with this powder rheometer and the developing cell that frequently appends toner.

In addition, the inventor also finds the following fact.When the gross energy that records with powder rheometer and the character that is added into the external additive on toner-particle surface all are within the above-mentioned limited range, can guarantee the flowability of toner, simultaneously, can reduce owing to stirring the stress that is applied to carrier, suppress undesirable external additive adhering to carrier.

Be in the reduction of the chargeding performance that carrier under this state and toner can suppress carrier in the developing cell and reduce by " playing photographic fog " frequency due to the low charging.In addition, be suppressed, can obtain for example not have the image of " color spot " or defectives such as " white points " because the resistance of carrier reduces.In addition, because the good fluidity of carrier so the contact frequency between toner and the carrier increases, can make toner fully charged.Therefore, even export video high density continuously, also can obtain to have the reproducible image of good concentration.

The present inventor considered following item when design is of the present invention.For peeling off of the coated with resin on the carrier surface that thoroughly prevents to cause, in the process that importantly in developing apparatus, stirs, under the situation that does not almost stir stress, use developer by stirring stress in the developing cell.Mixing power by the rotary body such as for example spiral drill or magnetic roll etc. in the developing apparatus flows (moving) developer, and makes developer on the magnetic roll flow (in the flow control part) before at development nip (development nip).At that time, developer is applied very strong power, caused the coated with resin of carrier that undesirable peeling off taken place.Simultaneously, the developer operational throughput is controlled in described flow control part, and developer was detained before this part and extruding (pack) thus.This has increased the stress that puts on developer and has caused the carrier lining desirably not peeled off.

In addition, the present inventor has been found that the following fact.In order to obtain to reduce described in the developing cell developer that stirs stress, it is highly important that the female particle of toner that toner comprises has 140 or less than 140 shape factor S F1.Simultaneously, it is highly important that, under use comprises situation as the electrostatic image developing carrier, electrostatic image developing of the coating on the magnetic-particle of core and each magnetic-particle surface of lining, described carrier has the gross energy of about 1500mJ to about 3000mJ, or under use comprised situation as the electrostatic image developing carrier, electrostatic image developing of the coating on the Magnaglo discrete particles of core and each Magnaglo discrete particles surface of lining, described carrier had the extremely gross energy of about 1500mJ of about 1000mJ.Described gross energy adopts powder rheometer to record, and the terminal velocity of wherein rotating oar is set at 100 mm/second, and the entering angle of rotation oar is set at-5 °.Described gross energy is the measured value of a part of carrier in the measuring vessel, filling surface (upper surface) that this part carrier is a carrier and the carrier that comprises in the zone between the surface at 70 millimeters places under this filling surface.In the case, even when stirring carrier with tommy bar or magnetic roll in developing apparatus, the carrier lining also is difficult to peel off.

In other words, gross energy is meant that more greatly stirring stress is higher to the load that carrier applies.That is to say that the energy that is applied to developer is bigger, and also bigger for the amount of stress of developer.Therefore, for the coated with resin that suppresses carrier is simply peeled off, desirable is to make gross energy reach minimum value.Yet when gross energy was minimum value, the flowability of the developer in the developer flow control part before the development nip became fabulous, to such an extent as to excessive developer has passed through the flow control part.Therefore, no longer stable at the developer level of development nip part, thus make the image color significant change.Under extreme case, excessive developer can cause occurring photographic fog and obstruction.In addition, under the too little situation of the gross energy of carrier, by stir producing and the friction force of toner contact electrification can be reduced, so charging rate reduces.

Here, when making the average shape factor SF1 of the female particle of toner greater than 140, when improving the friction force between carrier and the toner, even under the too little situation of gross energy, really can guarantee that the friction force between toner and the carrier acquires a certain degree, and charging rate can not reduce so many yet.Yet the less meeting of the gross energy of carrier causes in the developing apparatus not reaching desired value at the reduction degree of the amount of stress of developer, and therefore the coated with resin of carrier can be peeled off.

It is the reasons are as follows.When the average shape factor of the female particle of toner surpasses 140, will be difficult to make that the toner on the carrier surface flows.Therefore, when being subjected to stress in the developer flow control part of developer before the development nip, be difficult for making toner to flow, developer is rolled, can not discharge stress fully.On the contrary, when the female coating of particles factor of toner is 140 or less than 140 the time, and when developer is subjected to stress in the flow control part, toner carries out little moving on carrier surface, therefore developer can be smoothly by the flow control part, and can be transported to development nip part, and can not be subjected to stress.

Specifically, when external additive being added into the female particle of toner surperficial, be present in external additive particle on the female particle surface of toner and reduced contact point quantity between toner and the carrier, thereby can control the adhesion between toner and the carrier.The effect that can provide as roller is provided this rotation on toner surface of this point and external additive, and it causes developer to flow easily, and prevents that developer is subjected to stress.Therefore, among the present invention, described toner preferably comprises external additive.

Above-mentioned condition is effective especially under the situation of using speeder, and above-mentioned condition is effective especially especially for following developing system: wherein the peripheral speed of sub-image maintenance body is that about 100 mm/second are to about 600 mm/second, wherein, even in order in speeder, also fully to guarantee development property, the peripheral speed of developer carrier is very high, and in this system the peripheral speed of developer carrier and sub-image to keep the peripheral speed ratio of body be about 1.5 to about 2.0.

Therefore, the present inventor finds, when controlling the gross energy of female coating of particles factor S F1 of toner and carrier respectively, can not obtain the effect of the present invention second and the 7th aspect, but, when making two factors be in separately the scope based on optimal charge speed, can obtain described effect.

Therefore, can be by the peeling off of coated with resin on the long term inhibition carrier surface, electron gain is taken a picture with developer and is used the image forming method of this developer, by described image forming method, can obtain to have high quality images, can not occur owing to carrier adheres to the image deflects that cause.

Next, will flowability that measure carrier with powder rheometer be described.

The factor that influences the mobility of particle measurement is more than influencing liquid, solid or gas flow measurement factor.Therefore, be difficult to use parameter commonly used such as for example particle grain size or surfaceness etc. to determine the accurate flowability of particle.In addition, even when finding that a kind of factor (for example particle diameter) influence is mobile, this factor also may only produce less influence to flowability.Perhaps, having only when with other specific factor combination of this factor and one or more, just can be significant to the measurement of this factor.Therefore, be difficult to the definite factor that will measure.

In addition, the flowability of powder greatly depends on external environmental factor.In contrast, even measurement environment has change, for example the mobile fluctuation range of liquid is also not too big.Simultaneously, the flowability of particle greatly depends on external environmental factor, for example is used to make the humidity and the state of the gas of particle flow.Do not know still that up to now which measurement factor is subjected to the influence of these external environmental factors.Therefore, measure even carry out flowability under the measuring condition of strictness, the reappearance of measured value is still very poor in practice.

For being filled into the toner-particle in the developing tank or the flowability of carrier, used repose angle and bulk density as index.Therefore yet these physics values only are indirect correlation to flowability, are difficult to flowability is quantized and controls.

On the contrary, powder rheometer can record the gross energy that carrier puts on the rotation oar of measurement mechanism, the feasible numerical value that can obtain to reflect owing to the various factors of flowability.Therefore, powder rheometer can directly be measured the flowability of carrier, and do not need as in the past: determine to have the measurement project of the carrier of surface physical properties through regulating and size-grade distribution, and find out the best physics value of projects and it is measured through regulating.As a result,, can assess carrier and whether be suitable for electrostatic image development whether in scope separately by the numerical value confirming to measure with powder rheometer.The relevant carrier that makes keeps constant flowability, compares with the conventional method of the indirect numerical value of control, and the described production control of carrier is extremely practical method.Further, make measuring condition keep constant easily, the reappearance of the measured value in this production control is also higher thus.

In other words, the method for determining flowability by the numerical value that is obtained by powder rheometer is simpler, more accurate and reliability is higher than conventional method.

Here, for first, second, the the 4th to the 7th and the 9th aspect, the present inventor finds, in order to suppress owing to breaking of carrier granular forms powder, and inhibition is by the appearance of the image with lost part of powder generation, or peeling off for the surface-coated resin that suppresses carrier, very effectively be, when using powder rheometer under above-mentioned condition, to measure, electrostatic image developing carrier, electrostatic image developing comprises at described carrier and has about 1500mJ under the situation of magnetic-particle as its core to the numerical value of about 3000mJ, or comprises under the situation of Magnaglo discrete particles as its core described numerical value at described carrier and be about 1000mJ about 1500mJ extremely.When the carrier of numerical value is used for electrostatic image development in having above-mentioned scope, can guarantees its flowability, and can reduce the amount of stress that produces by the collision between carrier granular.As a result, because can not take place owing to carrier cracking forms powder, so, for example can prevent to lose on transfer materials such as the paper image deflects such as image section, wherein said losing owing to powder migrates to photoreceptor produces.

For core is the carrier of magnetic-particle, is lower than under the situation of about 1500mJ at the above-mentioned numerical value of measuring with powder rheometer, and the friction effect deficiency of carrier makes to be difficult to make toner fully charged.On the other hand, under this numerical value surpassed the situation of about 3000mJ, the stress quantitative change that acts on carrier was big, made that being difficult to inhibition forms powder owing to carrier breaks, and was difficult to suppress the peeling off of surface-coated resin of carrier.The preferably about 1800mJ of this measured value is more preferably about 2000mJ to about 2500mJ to about 2700mJ.

For core is the carrier of Magnaglo discrete particles, is lower than under the situation of about 1000mJ at the above-mentioned numerical value of measuring with powder rheometer, and the friction effect deficiency of carrier makes to be difficult to make toner fully charged.On the other hand, under numerical value surpassed the situation of about 1500mJ, the stress quantitative change that acts on carrier was big, made that being difficult to inhibition forms powder owing to carrier breaks, and was difficult to suppress the peeling off of surface-coated resin of carrier.The preferably about 1100mJ of this measured value is more preferably about 1200mJ to about 1300mJ to about 1400mJ.

In addition, for the 3rd and eight aspect, the present inventor finds, in order to suppress to form powder owing to carrier granular breaks, and inhibition is by the appearance of the picture white of powder generation, very effectively be, when measuring under these conditions with powder rheometer, electrostatic image developing carrier, electrostatic image developing comprises at described carrier and has about 1420mJ under the situation of magnetic-particle as its core to the numerical value of about 2920mJ, or described carrier comprise the Magnaglo discrete particles as the situation of its core under this numerical value be about 890mJ about 1390mJ extremely.When the carrier of numerical value is used for electrostatic image development in having above-mentioned scope, its flowability can be guaranteed, and the amount of stress that produces by the collision between carrier granular can be reduced.As a result because can not occur owing to carrier cracking forms powder, so, can prevent on transfer materials for example such as the paper image section image deflects such as lose, wherein said losing owing to powder migrates to photoreceptor produces.

For core is the carrier of magnetic-particle, is lower than under the situation of about 1420mJ at the above-mentioned numerical value of measuring with powder rheometer, and the friction effect deficiency of this carrier makes to make toner fully charged.On the other hand, surpass under the situation of about 2920mJ at this numerical value, the stress quantitative change that acts on carrier is big, makes and can not suppress to form powder owing to carrier breaks.The preferably about 1720mJ of this measured value is more preferably about 1920mJ to about 2420mJ to about 2620mJ.

For core is the carrier of Magnaglo discrete particles, is lower than under the situation of about 890mJ at the above-mentioned numerical value of measuring with powder rheometer, and the friction effect deficiency of carrier makes to make toner fully charged.On the other hand, surpass under the situation of about 1390mJ at this numerical value, the stress quantitative change that acts on carrier is big, makes and can not suppress to form powder owing to carrier breaks.The preferably about 990mJ of this measured value is more preferably about 1090mJ to about 1190mJ to about 1290mJ.

The composition of various carriers hereinafter will be described.

Next, will measuring method that use powder rheometer be described.

Powder rheometer is a kind of mobile device of measuring, wherein, and simultaneously to measuring, with the flowability of direct acquisition particle by the normal load and the rotary torque that in filler particles, obtain with the form rotation rotation oar of spiral.Measuring simultaneously that rotary torque and normal load make can be with the high-sensitivity detection flowability, mobile reflection be the influence of powder self character and external environment.Equally, because this measurement is to carry out under particles filled state keeps constant state, so can obtain to have the data of good reproduction.

Among the present invention, will be used as described powder rheometer by the FT4 that Freeman Technology makes.

At first, in container, fill the carrier that to measure flowability.This container has 50 millimeters internal diameter, the capacity of 88 millimeters height and 160 milliliters.The carrier layer of filling in the container has 88 millimeters height.Secondly, the 3rd and eight aspect in, it is the container of 200mL that the carrier of filling is sent to 50 millimeters of internal diameters, 140 millimeters of height and capacity.

Before the measurement, under 22 ℃ and 50% relative humidity, placed eight hours or the longer time, to prevent because the error that the external environmental factor during measurement produces.

After placing carrier, because the measured value that the change of the condition of filling causes fluctuation, before measuring flowability, fill the adjustment processing (conditioning) of carrier in order to get rid of.When adjusting processing, the rotation oar is slowly rotated with certain sense of rotation (opposite with sense of rotation in the measurement) in filling carrier, this rotation oar is not subjected to the resistance of carrier on this sense of rotation, so that not to the carrier stress application.Thereby, remove excess air and local stress, and the homogenize sample carrier.

First, second, in the the 4th to the 7th and the 9th aspect, finish adjust handle after, this rotation oar of rotation makes the rotation oar move down simultaneously in filling carrier.

The 3rd and eight aspect in, finish adjust to handle after, carry out following operation.When air being introduced container, will rotate oar and put into the filling carrier, and in carrier, rotate with the air-flow of 10 ml/min.In this case, the reason of measuring when air is introduced container is to make the flow state of toner and carrier during the state of the carrier of filling in the container is near stirring apparatus.The flow state of developer has correlativity in the air-flow of 10 ml/min and the developing cell that frequently appends toner.In the FT4 that Freeman Technology makes, the inflow state of air-flow is appointment.

Shown in Figure 1A, when rotation oar when the filling surface H1 of filler particles moves to plane H2 from container with the entering angle of-5 ° (first, second, the the 4th to the 7th and the 9th aspects) or-10 ° (the 3rd and eight aspect), measure rotary torque and normal load, simultaneously, the rotation oar is with the terminal velocity rotation of 100 mm/second.The reason that entering angle is controlled to-5 ° is that when measuring the carrier flow state, the sensitivity of powder rheometer reaches mxm. in this entering angle.The reason that entering angle is controlled to-10 ° is the mobile closely related of developer in this entering angle and the developing apparatus.

Angle between the axle that described entering angle is meant measuring vessel and the turning axle that rotates oar.

Figure 1B and Fig. 1 C have shown rotary torque and normal load respectively and from the relation of the depth H of filling surperficial H1.Fig. 2 has shown the energy gradient corresponding to depth H (mJ/mm) that is drawn by rotary torque and normal load.The area (area of the oblique line of drawing among Fig. 2) that energy gradient integration among Fig. 2 is obtained is equivalent to gross energy (mJ).Among the present invention, plane H2 is positioned at the position that reaches 70 millimeters deep from the surperficial H1 of filling.

Among the present invention,, described measuring operation is repeated five times in order to suppress the influence of error, and with the digital average that obtains, the gross energy that the mean value that obtains is defined as narrating among the present invention (mJ).

As the rotation oar, can use the twayblade propeller-type blade shown in Fig. 3, this blade has 48 mm dias, and is produced by Freeman Technology.

Below description is had the composition of the carrier of gross energy in the above-mentioned scope.

As long as carrier of the present invention satisfies above-mentioned condition, in addition be not particularly limited.The example that satisfies the carrier granular of above-mentioned numerical value comprises the carrier with fully narrow size-grade distribution; The carrier that has the coating of the material that can reduce frictional resistance on the carrier wicking surface; Carrier spherical in shape; Carrier with fully narrow distribution of shapes; The carrier that comprises agglutination body hardly; Has more low-gravity carrier; Has low-density carrier; Has the carrier in space with inside.The a kind of of these carriers can use separately, and perhaps two or more uses together.

In the carrier of the present invention, core material is not particularly limited.Hereinafter, has magnetic-particle as the carrier (first embodiment of carrier) of core with have the carrier (second embodiment of carrier) of Magnaglo discrete particles with describing respectively as core.

The carrier of first embodiment (having the carrier granular of magnetic-particle) as core

In the carrier of first embodiment, the example of core material comprises: magnetic metals such as iron, steel, nickel and cobalt for example; At least a metal in these metals and the alloy of manganese, chromium and/or rare earth element (for example iron-nickel alloy, ferro-cobalt and alfer); And magnetic oxide, for example ferrite and magnetic iron ore.Consider and adopt the magnetic brush method as visualization way, core is magnetic-particle preferably.

In the carrier of first embodiment, the preferably about 10 μ m of the volume average particle size of core are to about 500 μ m.In the first and the 3rd to the 5th aspect, volume average particle size is more preferably about 30 μ m to about 150 μ m, is more preferably about 30 μ m to about 100 μ m.In the second aspect, volume average particle size is more preferably about 20 μ m to about 150 μ m, is more preferably about 25 μ m to about 100 μ m.When the core volume mean grain size was used for electrostatic image development less than the carrier granular of about 10 μ m, the adhesion between toner and the carrier was stronger, and this can reduce the amount of the toner that uses in the development.On the other hand, when the volume average particle size of carrier core surpassed about 500 μ m, this particle that constitutes magnetic brush was coarse, and this makes the image that is difficult to form meticulous densification.Consider gross energy, if the volume average particle size of core less than about 10 μ m, the magnetic force of single carrier granular is less, and carrier takes place easily sub-image is kept adhering to of body.Simultaneously, if it surpasses about 500 μ m, the surface area of carrier granular is too little with respect to the surface area of toner-particle, and this makes and can not make toner fully charged.

In the carrier of first embodiment, the value that the volume average particle size of core is to use laser diffraction/scatter-type particle size distribution measurement device (LS PARTICLE SIZE ANALYZER LS13 320 is produced by BECKMAN COULTER) to record.When the whole particle size range of the size-grade distribution that obtains is divided into a plurality of particle size ranges (passage), and during from minimum zone rendered volume cumulative distribution curve, volume average particle size D _50vIt is the particle diameter that cumulative statistics reached 50% o'clock.

For the size-grade distribution of the core in the carrier of first embodiment, volume average particle size D _84vWith volume average particle size D _50vRatio (D _84v/ D _50v) preferably 1.20 or less than 1.20, more preferably 1.15 or less than 1.15.Number average bead diameter D _50PWith number average bead diameter D _16p(D _50P/ D _16P) ratio preferably 1.25 or less than 1.25, be more preferably 1.20 or less than 1.20.

In order to obtain to have the core of above-mentioned size-grade distribution, can distribute according to desired particle size, use vibrating screen device, gravity-type clasfficiator, centrifugal type clasfficiator, inertial classification device or screen cloth to come magnetic-particle is carried out classification.

In order to obtain to have the carrier core of above-mentioned size-grade distribution, especially preferably use vibrating screen device and air classifier.Especially preferably carry out the multistep screening, or remove fine powder and corase meal simultaneously.

Under the situation of size-grade distribution than above-mentioned wide ranges of carrier core, the gross energy of measuring with powder rheometer can exceed described scope.On the other hand, make size-grade distribution, therefore significantly worsen work efficiency than for example too much operation such as classification of the narrow needs of above-mentioned scope.

Use laser diffraction/scatter-type particle size distribution measurement device (LS PARTICLE SIZEANALYZER LS13 320 is produced by BECKMAN COULTER) to measure the size-grade distribution of core.When the whole particle size range of the size-grade distribution that obtains is divided into a plurality of particle size ranges (passage), and during from minimum zone rendered volume cumulative distribution curve, it is particle diameter D that cumulative statistics reaches 84% o'clock particle diameter _84vWhen drawing the quantity cumulative distribution curve from minimum zone, it is particle diameter D that cumulative statistics reaches 50% o'clock particle diameter _50p, and cumulative statistics to reach 16% o'clock particle diameter be particle diameter D _16pVolume average particle size D _84vWith volume average particle size D _50vRatio be defined as the particle size distribution index of coarse particle side.Number average bead diameter D _50pWith number average bead diameter D _16pRatio be defined as the particle size distribution index of particle side.

In the carrier of first embodiment, the preferably about 3.0g/cm of the density of core ³To about 8.0g/cm ³, 3.5g/cm more preferably from about ³To about 7.0g/cm ³, be more preferably about 4.0g/cm ³To about 6.0g/cm ³If density is lower than about 3.0g/cm ³, the flowability of carrier is near the flowability of toner, and this causes the electric charge deliverability of carrier to worsen.If density is higher than about 8.0g/cm ³, the mobile relatively poor and gross energy of carrier tends to surpass higher limit.

The method of describing among the Density Section (density portion) with Physicochemical Experimental Methods (" Physical Chemistry Experiment method ") (third edition, the Tokyo chemistry is published with people society) is measured the density of core.In the measurement, use the pure water of resistance, and carry out described measurement at 25 ℃ more than or equal to 17 megohms.

Carrier of the present invention has core and the coating on core surface.This coating preferably comprises the coated with resin layer of matrix resin.

Matrix resin can be common resin.The example comprises: polyolefin resin, for example tygon and polypropylene; Polyvinyl resin and polyvinylene resin, for example polystyrene, acryl resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol (PVA), polyvinyl butyral, Polyvinylchloride, polyvinylcarbazole, polyvinylether and tygon ketone; Vinyl chloride vinyl acetate copolymer; The styrene-propene acid copolymer; Pure silicon ketone resin and its modified product of including the organic siloxane key; Fluoride resin, for example teflon, polyvinyl fluoride, polyvinylidene fluoride and polychlorotrifluoroethylene; Polyester; Polyurethane; Polycarbonate; Phenol resin; Amino resins, for example urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin and polyamide; Silicone resin; And epoxy resin.

A kind of can the use separately in these resins, perhaps two or more uses together.

For the pollution that prevents to produce by toner components, preferred use have than the resin of low-surface-energy for example fluoride resin or silicone resin as described coated with resin.Be more preferably and use fluoride resin to be used for lining.

The example of fluoride resin comprises: fluorinated polyolefin; (methyl) acrylic acid fluoroalkyl ester homopolymer and multipolymer; Foraflon and multipolymer; With its potpourri.Raw material as described fluoride resin, can be one or more monomers that comprise at least one fluorine atom, the described representative instance that comprises the monomer of at least one fluorine atom includes, but are not limited to: methacrylic acid fluoroalkyl ester monomer, for example tetrafluoropropyl propyl diester, methacrylic acid five fluorine butyl esters, methacrylic acid octafluoro amyl group ester, methacrylic acid perfluoro capryl ethyl ester and methacrylic acid trifluoroethyl ester.

With respect to whole monomers of described coated with resin, the preferably about 0.1 quality % of the content of described one or more fluorochemical monomers is to about 50.0 quality %, and more preferably from about 0.5 quality % is more preferably about 1.0 quality % to about 30.0 quality % to about 40.0 quality %.If this content is lower than about 0.1 quality %, will be difficult to guarantee anti fouling performance.If this content surpasses about 50.0 quality %, the stickability of coated with resin and core a little less than, this may cause the charging property reduction.

With respect to the overall weight of carrier, the preferably about 0.5 quality % of the content of the matrix resin that comprises in the coated with resin layer is to about 10 quality %, and more preferably from about 1.0 quality % are more preferably about 1.0 quality % to about 4.0 quality % to about 5.0 quality %.If this content is lower than about 0.5 quality %, the magnetic core particles is exposed on carrier surface easily, and carrier resistance reduces easily.On the other hand, if this content surpasses about 10 quality %, the mobile non-constant of carrier, and will be difficult to make the toner uniform charged.

Described coating can comprise the resin particle that is scattered in wherein.

Described resin particle can be for example thermoplastic resin particle or thermosetting resin particles.Wherein, thermosetting resin particles preferably is because it can relatively easily increase the hardness of coating.In addition, the resin particle of preferred nitrogen atom is to provide the toner with electronegative performance.Can use the particle of a kind of resin in these resins, perhaps two or more uses together.

Preferred described resin particle all is evenly dispersed in the matrix resin on the direction of the direction of the thickness that is parallel to the coated with resin layer and the tangent line that is parallel to carrier surface as far as possible.If the resin of resin particle and matrix resin have higher compatibility, then can improve the dispersing uniformity of resin particle in the coated with resin layer.

The examples of resins of thermoplastic resin particle comprises: polyolefin resin, for example tygon and polypropylene; Polyvinyl resin and polyvinylene resin, for example polystyrene, acryl resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol (PVA), polyvinyl butyral, Polyvinylchloride, polyvinylcarbazole, polyvinylether and tygon ketone; Vinyl chloride vinyl acetate copolymer; The styrene-propene acid copolymer; Pure silicon ketone resin and its modified product of including the organic siloxane key; Fluoride resin, for example teflon, polyvinyl fluoride, polyvinylidene fluoride and polychlorotrifluoroethylene; Polyester; Polyurethane; And polycarbonate.

The example of the resin of thermosetting resin particles comprises: phenol resin; Amino resins, for example urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin and polyamide; Silicone resin; And epoxy resin.

The resin of resin particle can be identical or different with matrix resin.The resin of preferred resin particle is different with matrix resin.

If use thermosetting resin particles as described resin particle, can improve the physical strength of carrier.Specifically, described resin preferably has cross-linked structure.In addition, in order to improve the function of resin particle, thus resin particle is used as charged site, the resin of preferred resin particle can promptly make toner charged.The particle of this resin is the particle of resinamines such as nylon resin, amino resins or melamine resin for example preferably.

Can produce resin particle in order to following method: by polymerization emulsion polymerization or the suspension polymerization method of producing the granular resin particle for example; By making at least a monomer and/or at least a oligomer that are dispersed in the solvent crosslinked so that thereby the product granulation is produced the method for resin particle; Or by fusion and knead,, by air blast or mechanical force product is carried out classification to reach the resin particle production method of predetermined particle diameter again so that at least a low molecular weight compositions and crosslinking chemical mix and make it reaction.

The preferably about 0.1 μ m of the volume average particle size of resin particle is to about 2.0 μ m, and more preferably from about 0.2 μ m is to about 1.0 μ m.If it is less than about 0.1 μ m, the dispersibility of particle is relatively poor in the coated with resin layer.On the other hand, if it is greater than about 2 μ m, particle breaks away from the coated with resin layer easily, therefore can not obtain stable chargeding performance sometimes.The method of the volume average particle size of measurement resin particle is identical with the method for the volume average particle size of measuring core.

The preferably about 1 volume % of the content of resin particle is to about 50 volume % in the coating, and more preferably from about 1 volume % is more preferably about 1 volume % to about 20 volume % to about 30 volume %.If the content of resin particle is less than about 1 volume % in the coating, possibly can't demonstrate the effect of resin particle.If it surpasses about 50 volume %, resin particle disengaging easily covers resin-coated layer, and can not obtain the stabilized zone electrical property sometimes.

Described coating can also comprise the electroconductive powder that is dispersed in wherein.

The examples of materials of electroconductive powder comprises: metal, for example gold, silver and copper; Carbon black; Metal oxide, for example titanium dioxide, magnesium oxide, zinc paste and aluminium oxide; Lime carbonate; Aluminium borate; Potassium titanate and calcium titanate; And the powder such as titanium dioxide, zinc paste, barium sulphate, aluminium borate and potassium titanate powder that are coated with tin oxide, carbon black or metal.A kind of can the use separately in these powder, perhaps two or more uses together.When metal oxide powder is used as electroconductive powder, can reduce the degree of dependence of chargeding performance to environment.Titanium dioxide especially preferably.

Preferably use the powder of these materials of coupling agent treatment.Specifically, the preferably metal oxide of crossing with coupling agent treatment, the more preferably titanium dioxide of crossing with coupling agent treatment.Can obtain the electroconductive powder crossed with coupling agent treatment by the following method: for example disperseing untreated electroconductive powder in the toluene equal solvent, mixing and handle the powder of described dispersion with coupling agent, then with described powder drying under reduced pressure.

In addition, can pulverize the electroconductive powder of crossing with coupling agent treatment with comminutor in case of necessity, to remove agglutination body.The example of comminutor comprises known comminutor, for example needle mill (pin mill), disc mill, hammer-mill, centrifugal type attrition mill, roller mill and aeropulverizer usually.Preferred especially aeropulverizer.Described coupling agent can be usually known coupling agent, for example silane coupling agent, titanium coupling agent, aluminum coupling agent or zirconium coupling agent.

Wherein, the electroconductive powder of handling with silane coupling agent, particularly methyltrimethoxy silane is effective for the environmental stability of chargeding performance.

The preferably about 0.5 μ m of the volume average particle size of electroconductive powder or less than 0.5 μ m, more preferably from about 0.05 μ m is more preferably about 0.05 μ m to about 0.35 μ m to about 0.45 μ m.The method of measuring the volume average particle size of electroconductive powder can be according to the method for the volume average particle size of above-mentioned measurement core.

If the volume average particle size of electroconductive powder surpasses about 0.5 μ m, powder breaks away from the coated with resin layer easily, and can not obtain stable chargeding performance sometimes.

The volume resistance of electroconductive powder preferably about 10 ¹Ohmcm is to about 10 ¹¹Ohmcm, more preferably from about 10 ³Ohmcm is to about 10 ⁹Ohmcm.In this instructions, the volume resistance of electroconductive powder is the value of measuring with following method.

Under normal temperature and common humidity, be 2 * 10 at cross-sectional area ^-4m ²Container in the filled conductive powder, to form the about 1 millimeter powder bed of thickness, apply 1 * 10 with hardware to this layer then ⁴Kg/m ²Load.Between the electrode on hardware and the container bottoms, apply and produce 10 ⁶The voltage that the electric field of V/m is required, current value with thus time the and magnitude of voltage calculate numerical value be called volume resistance.

The normally about 1 volume % of the content of the electroconductive powder that comprises in the coated with resin layer is to about 80 volume %, and preferably about 5 volume % are more preferably about 2 volume % to about 20 volume % to about 50 volume %, and being more preferably is that about 3 volume % are to about 10 volume %.

The method that forms coating on the surface of the core of each carrier granular can be: infusion process, and in this method, the carrier core is immersed in coating forms with in the solution, described solution comprises above-mentioned resin and solvent, and conductive material in case of necessity; Spray-on process in this method, forms coating with the surface of solution spray to each carrier core, and described solution comprises resin, solvent and conductive material in case of necessity; Bed process in this method, forms each the carrier core surface that extremely flows with moving air with solution spray with coating, and wherein said solution comprises resin, solvent and conductive material in case of necessity; Or the coating machine method of kneading, in this method, coating formation being mixed with the carrier core with solution, and in the coating machine of kneading, remove and desolvate, described solution comprises resin, solvent and conductive material in case of necessity.

The solvent that coating forms with solution only need get final product resin dissolves therein, in addition is not particularly limited.The example comprises: aromatic hydrocarbon, for example toluene and dimethylbenzene; Ketone, for example acetone and methyl ethyl ketone; And ether, for example tetrahydrofuran is with diox.

The preferably about 0.1 μ m of the average thickness of coating is to about 10 μ m, and more preferably from about 0.1 μ m is more preferably about 0.1 μ m to about 1.0 μ m to about 3.0 μ m.If the average thickness of coating is thinner than about 0.1 μ m, because the long-term use of carrier, coating can desirably not peeled off, and the resistance of carrier is reduced.If average thickness surpasses about 10 μ m, need just to make for a long time the carried charge of the toner carried charge that reaches capacity.

Its core is coated with the preferably about 3.0g/cm of density (true specific gravity) of carrier of first embodiment of resin ³To about 8.0g/cm ³, 3.5g/cm more preferably from about ³To about 7.0g/cm ³, be more preferably about 4.0g/cm ³To about 6.0g/cm ³If density is lower than about 3.0g/cm ³, the flowability of carrier approaches the flowability of toner, and carrier has the electric charge supply performance of deterioration.If density is higher than about 8.0g/cm ³, carrier mobile relatively poor, and gross energy tends to surpass higher limit.The method of measuring support density is identical with the method for the density of measuring the carrier core.

The shape factor S F1 of the carrier of first embodiment preferably about 130 or less than 130, more preferably from about 120 or less than 120, described shape factor S F1 is defined by following formula (1).

Shape factor S F1 is more near 100, the approaching more complete sphere of carrier granular.Along with the form factor increase of carrier, because due to its shape strain, the quantity that bumps between the carrier granular uprises, and the flowability of carrier worsens.Therefore, if shape factor S F1 surpasses 130, the too high upper limit that surpasses to such an extent as to gross energy tends to become.

Formula (1): shape factor S F1=(ML ²/ A) * (π/4) * 100

In the formula (1), ML is meant the absolute maximum length of carrier granular, and A is meant the projected area of carrier granular.

Can obtain the mean value of shape factor S F1 by the following method: by respectively with 50 or amplify 250 times more than 50 carrier granular and obtain optical microscopic image, catch described optical microscopic image, and with its input picture analyzer (LUZEX III, produce by NIRECO Corp.), obtain the described maximum length and the projected area of each image, calculate the SF1 of each particle according to maximum length that records and projected area, and will calculate the SF1 value average.

The preferably about 40emu/g of the saturation magnetization of the carrier of first embodiment (electromagnetic unit/gram) or greater than 40emu/g, more preferably from about 50emu/g or greater than 50emu/g.

In order to measure magnetic characteristic, use sample oscillation mode Magnetic Measurement device VSMP 10-15 (industrial society produces by eastern English).Fill measuring samples in the measuring cell of 7 millimeters of internal diameters, 5 millimeters of height, described measuring cell is located in this device.Measure by applying magnetic field to sample, and carry out scanning until 1000 Oe (oersted).Then, weaken the magnetic field that is applied, and on recording chart, draw B-H loop.Data according to the curve of being drawn obtain saturation magnetization, remanent magnetization and coercive force.Among the present invention, saturation magnetization is the magnetization of measuring under the magnetic field of 1000 oersteds.

The volume resistance of carrier preferably is controlled at about 1 * 10 ⁸To about 1 * 10 ¹⁴Ohmcm, more preferably from about 1 * 10 ⁸To about 1 * 10 ¹³Ohmcm is more preferably about 1 * 10 ⁸To about 1 * 10 ¹²Ohmcm.

If the volume resistance of carrier surpasses about 1 * 10 ¹⁴Ohmcm, resistance is higher, and carrier will be difficult to play the effect of development electrode in the time of development.Therefore, edge effect does not desirably appear in the image, image section on the spot particularly, and the reappearance of part worsens on the spot.On the other hand, if volume resistance is lower than about 1 * 10 ⁸Ohmcm, resistance is lower.Therefore, when toner concentration in the developer reduced, developer roll can inject carrier with electric charge, and carrier itself does not desirably migrate to sub-image.

Measure the volume resistance (ohmcm) of carrier as follows.The control survey environment makes that temperature is 20 ℃, and humidity is 50%RH (relative humidity).

To flatly be placed on as the carrier of measuring object on the surface of circular clamp, with form thickness about 1 millimeter to about 3 millimeters carrier layer, wherein said circular clamp has area 20cm ²Battery lead plate.With another area is 20cm ²Battery lead plate be placed on the carrier layer, make two battery lead plates clamp carrier layer.4kg load is applied to the battery lead plate that is positioned on the carrier layer, to get rid of the space between the carrier granular, measure then carrier layer thickness (centimetre).Battery lead plate on the carrier layer and the battery lead plate under the carrier layer are electrically connected to electrometer and high-voltage power device respectively.Apply high pressure to two battery lead plate, to produce 10 ^3.8The electric field of V/cm, and read at that time current value (A).Based on these data, calculate the volume resistance (ohmcm) of carrier according to following formula (2).

Formula (2): R=E * 20/ (I-I ₀)/L

In this formula, R represents the volume resistance (ohmcm) of carrier; E is the voltage (V) that is applied; I is current value (A); I ₀Be that the magnitude of voltage (V) that applied is 0 o'clock a current value (A); L be carrier layer thickness (centimetre).Coefficient 20 is area (cm of each battery lead plate ²).

The carrier of second embodiment (having the carrier of Magnaglo discrete particles) as core

In the carrier of second embodiment, core is the Magnaglo discrete particles, and wherein Magnaglo is dispersed in the resin.

The material of Magnaglo can be identical with the material of above-mentioned magnetic-particle.Wherein, described material iron oxide preferably.Croci (particle) is being favourable aspect stability of characteristics and the hypotoxicity.

Can be used alone Magnaglo, perhaps the Magnaglo with two or more uses together.

The preferably about 0.01 μ m of the particle diameter of Magnaglo is to about 1 μ m, and more preferably from about 0.03 μ m is more preferably about 0.05 μ m to about 0.35 μ m to about 0.5 μ m.If the particle diameter of Magnaglo is less than about 0.01 μ m, saturation magnetization may reduce or the viscosity of composition (monomer mixture) may increase, and possibly can't obtain to have the carrier granular of uniform grading.On the other hand, if the particle diameter of Magnaglo surpasses about 1 μ m, can not obtain the Magnaglo discrete particles of homogeneous sometimes.

The preferably about 30 quality % of the content of the Magnaglo in the Magnaglo discrete particles are to about 95 quality %, and more preferably from about 45 quality % are more preferably about 60 quality % to about 90 quality % to about 90 quality %.If content is lower than about 30 quality %, dispersing of magnetic material dispersible carrier may appear.If content surpasses about 95 quality %, the fringe that the magnetic material dispersible carrier forms is harder, and breaks easily.

The example of the resin that comprises in the Magnaglo discrete particles (matrix) comprises cross-linked styrene resin, acryl resin, styrene-propene acid copolymer resin, phenol resin, urea resin, polyamide and polyimide resin.

The Magnaglo discrete particles that uses among the present invention can also comprise other composition according to purposes except comprising matrix and Magnaglo.The example of described other composition comprises charge control agent and fluorine-containing particle.

For the size-grade distribution of Magnaglo discrete particles, volume average particle size D _84vWith volume average particle size D _50vRatio preferably 1.20 or less than 1.20, more preferably 1.15 or less than 1.15.Number average bead diameter D _50PWith number average bead diameter D _16pRatio preferably 1.25 or less than 1.25, more preferably 1.20 or less than 1.20.

The method of producing the Magnaglo discrete particles can be the fusion method of kneading, in this method, with banbury mixers or kneading machine with insulating resin fusions such as Magnaglo and for example styrene-propene acid resins and knead, with cooling of gained potpourri and pulverizing, then resulting granules is carried out classification (Japanese Patent Publication 59-24416 communique and special fair 8-3679 communique); Suspension polymerization, in this method, at least a monomer and the Magnaglo of dispersing binder resin in solvent, and in the suspending liquid that obtains this monomer of polymerization (Japanese kokai publication hei 5-100493 communique etc.); Or spray drying process, in this method, obtain dispersion liquid, again with this dispersion liquid spraying and dry by in resin solution, disperseing Magnaglo.

Knead method, suspension polymerization and spray drying process of fusion includes in resin solution the step of disperseing previously prepared Magnaglo.

When the method for kneading with fusion is produced the Magnaglo discrete particles, can use centrifugal type clasfficiator, inertial classification device or screen cloth, to obtain the having particle that desired particle size distributes.

When having the Magnaglo discrete particles of desired particle size distribution with suspension polymerization production, it is highly important that the particle diameter of regulating discrete particles.For this reason, must regulate the temperature when disperseing, the type of surfactant and the speed and the duration of amount and stirring.Can be in conjunction with these controlling factors to regulate particle.

When having the Magnaglo discrete particles of desired particle size distribution with spray drying process production, importantly regulate spraying and drying condition.For example, because can control the size of Magnaglo discrete particles by regulating drop size, so requisite is to control the size of drop by the pressure of adjusting nozzle and/or the rotating speed of turntable, or controls the state of carrier surface by the adjusting drying condition.

In the carrier of second embodiment, the preferably about 10 μ m of the volume average particle size of core are to about 500 μ m, and more preferably from about 30 μ m are more preferably about 30 μ m to about 100 μ m to about 150 μ m.If volume average particle size is less than about 10 μ m, carrier does not desirably migrate to photoreceptor easily, and the production performance of this core particles worsens.If volume average particle size surpasses about 500 μ m, can occur the carrier striped in the image is so-called brush mark (brush mark), and image has coarse surface marking.

The method of measuring the core volume mean grain size and core are that the situation of magnetic-particle is identical.

In the carrier of second embodiment, the preferably about 2.0g/cm of the density of core (true specific gravity) ³To about 5.0g/cm ³, 2.5g/cm more preferably from about ³To about 4.5g/cm ³, be more preferably about 3.0g/cm ³To about 4.0g/cm ³If density is lower than about 2.0g/cm ³, the flowability of carrier approaches the flowability of toner, and carrier has the electric charge supply performance of deterioration.If density is greater than about 5.0g/cm ³, carrier mobile relatively poor, and gross energy tends to surpass higher limit.The method of the density of measurement core is identical with the situation of the carrier of first embodiment.

The material of the coating that forms on the surface of each Magnaglo discrete particles can be identical with the material of the coating that forms on the surface of each magnetic-particle.In second embodiment, the representative instance of the material of coating can be identical with first embodiment.In second embodiment, the method that forms coating is also identical with the situation that forms coating on each magnetic-particle.

The coating that the carrier of described second embodiment comprises the Magnaglo discrete particles and forms on each Magnaglo discrete particles surface, the preferably about 2.0g/cm of the density of the carrier of second embodiment (true specific gravity) ³To about 5.0g/cm ³, 2.5g/cm more preferably from about ³To about 4.5g/cm ³, be more preferably about 3.0g/cm ³To about 4.0g/cm ³If density is lower than about 2.0g/cm ³, the flowability of carrier approaches the flowability of toner, and carrier has the electric charge supply performance of deterioration.If density is greater than about 5.0g/cm ³, carrier mobile relatively poor, and gross energy tends to surpass higher limit.

The preferably about 0.1 μ m of the average thickness of the lip-deep coating of each Magnaglo discrete particles is to about 10 μ m, and more preferably from about 0.1 μ m is more preferably about 0.1 μ m to about 1.0 μ m to about 3.0 μ m.If the average thickness of resin coating is thinner than about 0.1 μ m, because long-time the use due to the carrier, coating can desirably not peeled off, and the resistance of carrier is reduced.If average thickness surpasses about l0 μ m, needs just can make the carried charge of the toner carried charge that reaches capacity for a long time.

The shape factor S F1 of the carrier of second embodiment preferably about 150 or less than 150 is more preferably about 130 or less than 130, described shape factor S F1 is defined by above-mentioned formula (1).Use the method identical to calculate described shape factor S F1 with first embodiment.

The preferably about 30emu/g of the saturation magnetization of the carrier of second embodiment or greater than 30emu/g, 40emu/g or greater than 40emu/g more preferably from about is more preferably about 50emu/g or greater than 50emu/g.

The method of measurement magnetic characteristic is identical with the method in first embodiment.

The volume resistance of carrier preferably is controlled to be about 1 * 10 ⁷To about 1 * 10 ¹⁴Ohmcm, more preferably from about 1 * 10 ⁸To about 1 * 10 ¹³Ohmcm is more preferably about 1 * 10 ⁸To about 1 * 10 ¹²Ohmcm.

If the volume resistance of carrier surpasses about 1 * 10 ¹⁴Ohmcm, the resistance of carrier is higher, and carrier will be difficult to play the effect of development electrode when developing.Therefore, in the image edge effect can appear, image section on the spot particularly, and the reappearance of part worsens on the spot.On the other hand, if volume resistance is lower than about 1 * 10 ⁷Ohmcm, the resistance of carrier is lower.Therefore, when the concentration of toner in the developer reduced, developer roll can inject carrier with electric charge, and carrier itself can desirably not migrate to sub-image.

In second embodiment, the method for the volume resistance of measurement carrier is identical with the method in first embodiment.

Next, toner will be described.

Developing toner for electrostatic latent images of the present invention (hereinafter, abbreviating toner sometimes as) comprises adhesive resin and colorant, and has 140 or less than 140 average shape factor SF1 in aspect the second and the 7th.Preferred toner has the female particle of toner and is added into the external additive on the surface of the female particle of toner.

Here, the shape factor S F1 among the present invention is defined by following formula (1).

Formula (1): SF1=100 * π * ML ²/ 4A

In the formula (1), SF1 represents form factor; ML represents the absolute maximum length of particle; A represents the projected area of particle.When particle is complete when spherical, shape factor S F1 is 100.Particle answer variation remarkable more, form factor is big more, it is greater than 100.

The female particle of preferred each toner is subglobular as far as possible, to obtain to reduce the developer of the stirring stress in the developing cell.In the second and the 7th aspect, the average shape factor SF1 of the female particle of toner is necessary for 140 or less than 140.Average shape factor SF1 preferably about 110 is more preferably about 120 to about 135 to about 138.If it is about 140 that average shape factor SF1 surpasses, this distortion toner-particle can desirably not quicken on the carrier resin-coated layer peeling off.

Can obtain average shape factor SF1 by the following method: by respectively with 50 or more a plurality of carrier granular amplify 250 times of optical microscopic images that obtain particle, catch described optical microscopic image and with its input picture analyzer (LUZEX III, produce by NIRECO Corp.), obtain the maximum length and the projected area of each image, the SF1 that calculates each particle according to the maximum length of measuring and projected area, and will calculate the SF1 value average.

For the toner particle size distribution index, volume average particle sizes profile exponent GSDv preferably about 1.30 or less than 1.30, number average particle size profile exponent GSDp preferably about 1.38 or less than 1.38, and the ratio GSDv/GSDp preferably about 0.95 of volume average particle sizes profile exponent GSDv and number average particle size profile exponent GSDp or greater than 0.95.

If it is about 1.30 that volume average particle sizes profile exponent GSDv surpasses, or number average particle size profile exponent GSDp surpasses approximately 1.38, and the image that obtains has the resolution of reduction.Be lower than at ratio GSDv/GSDp under about 0.95 the situation, the charging property of toner reduces, and occurs dispersing and playing image deflects such as photographic fog of toner for example sometimes.

Volume average particle size and particle size distribution index can be defined as follows.The whole particle size range of the size-grade distribution that the COULTER COUNTER TAII that is produced by BECKMANCOULTER when use records is divided into a plurality of particle size ranges (passage), and during from minimum zone rendered volume cumulative distribution curve, with cumulative statistics reach 16%, 50% and 84% o'clock particle diameter be defined as D respectively _16v, D _50vAnd D _84VWith volume average particle size D _50vBe defined as volume average particle size.Similarly, when drawing the quantity cumulative distribution curve from minimum zone, with cumulative statistics reach 16%, 50% and 84% o'clock particle diameter be defined as D respectively _16P, D _50PAnd D _84PTo be worth (D _84v/ D _16v) ^1/2Be defined as volume particle size distribution index GSDv, will be worth (D _84P/ D _16P) ^1/2Be defined as number average particle size profile exponent GSDp.

With ultrasound wave toner was disperseed 30 seconds in aqueous electrolyte (water-based Isoton solution) or the longer time after, carry out described measurement.

The actual measurement process is as follows.Measuring samples with 0.5 to 50mg adds two milliliters aqueous solution, and this aqueous solution comprises surfactant or the spreading agent of 5 quality %, and preferred described surfactant or spreading agent are sodium alkyl benzene sulfonate.The material that obtains added 100 to 150ml above-mentioned electrolytic solution.With resulting suspending liquid stir about 1 minute, sample was suspended in the electrolytic solution in the described suspending liquid with the ultrasonic dispersing device.With COULTER COUNTER TA-II and aperture is the size-grade distribution of the aperture measuring samples of 100 μ m, and volume calculated mean grain size in the above described manner.The quantity of the particle that is used to measure is 50000.

(1) method for producing toner and toner

Hereinafter, use description to the composition of toner of the present invention.

1) adhesive resin

The example of adhesive resin comprises the homopolymer and the multipolymer of following monomer (one or more): for example mono-olefins such as ethene, propylene, butylene, and isoprene; Vinyl esters, for example vinyl acetate, propionate, vinyl benzoate and vinyl butyrate; Alpha-methylene aliphatic monocarboxylic acid ester, for example methyl acrylate, phenyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate and lauryl methacrylate; Vinyl ether, for example vinyl methyl ether, EVE and vinyl butyl ether; And vinyl ketone, for example ethenyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone.Wherein, normally polystyrene, styrene-propene acid copolymer of described adhesive resin; Styrene-Butadiene, styrene-maleic anhydride copolymer or polypropylene.Adhesive resin can also be polyester, polyurethane, epoxy resin, silicone resin, polyamide or modified rosin.

In the second and the 7th aspect, the adhesive resin of toner can be crystalline resin or amorphous resin (non-crystalline resin).Both can use together.

In the time can using crystalline resin and amorphous resin together, can be according to the usage of toner and the ratio between suitable selective freezing resin of purposes and the amorphous resin (non-crystalline resin), to obtain for example good balance between the multiple performances such as low-temperature fixing performance, a photographic fog or image keeping quality.Equally, when crystalline resin and amorphous resin can use together, the preferably about 20 weight % of ratio of crystalline resin and whole adhesive resins were to about 60 weight %.Further, can produce the toner with nucleocapsid structure, it comprises the shell of stratum nucleare and lining sandwich layer, and described stratum nucleare comprises crystalline resin, and described shell comprises amorphous resin.

" crystallinity " of the crystalline resin that can comprise in the used toner of the present invention is meant in differential scanning calorimetry (DSC) to have endothermic peak clearly, rather than has change of heat absorption progressively.Specifically, when it was meant and measures with 10 ℃/minute heating rate, the half width of endothermic peak was in 10 ℃.Having the resin of the half width that surpasses 10 ℃ or not having the resin of clear endothermic peak is non-crystalline resin (amorphous resin).

Non-crystalline resin

The type of non-crystalline resin is not particularly limited.Usually known resin material can be used as non-crystalline resin.The example comprises the homopolymer of following compounds: phenylethylene, for example styrene, to chlorostyrene and α-Jia Jibenyixi; The ester that contains vinyl, for example methyl acrylate, ethyl acrylate, butyl acrylate, propyl acrylate, dodecylacrylate, acrylic acid ethylhexyl, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, propyl methacrylate, lauryl methacrylate, methacrylic acid ethylhexyl, vinyl acetate and vinyl benzoate; Carboxylate with two keys, for example maleic acid methyl esters, ethyl maleate and maleic acid butyl ester; Alkene, for example ethene, propylene, butylene and butadiene; Carboxylic acid with two keys, for example acrylic acid, methacrylic acid and maleic acid.Equally, the multipolymer of the compound of two or more in these compounds and two or more homopolymer and the potpourri of multipolymer can be used as non-crystalline resin.

Alternatively, non-crystalline resin can be at least a resin in epoxy resin, vibrin, urethane resin, polyamide, celluosic resin, polyether resin, non-vinyl condensation resin, these resins and the potpourri or the graft polymer by in the presence of at least a resin in these resins at least a polymerization of vinyl monomer being obtained of above-mentioned vinylite (one or more).

During polymerization, at least a dissociable vinyl monomer can use with the monomer (one or more) of non-crystalline resin of the present invention, with the degree of polymerization of control resin.The example of dissociable vinyl monomer comprises the raw material of macromolecule bronsted lowry acids and bases bronsted lowry, for example acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, azacyclopropane, vinylpyridine and vinylamine.With regard to the easiness that polymkeric substance forms reaction, dissociable vinyl monomer is the acid of high molecular preferably.Especially, have the dissociable vinyl monomer of carboxyl, for example acrylic acid, methacrylic acid, maleic acid, cinnamic acid or fumaric acid are being preferred aspect the degree of polymerization that is easy to control resin and the glass transition temperature.During the non-crystalline resin polymerization, usually dissociable vinyl monomer and other monomer (one or more) are carried out copolymerization.

In the presence of ionic surfactant, can make vinyl monomer carry out emulsion polymerization or seeding polymerization, with the preparation particulate resin dispersion.Under the situation of using oil-soluble and other resin that dissolves in the solvent that in water, has relative low solubility, can with this resin dissolves in solvent, the solution of resulting solution with dissolved ions type surfactant and/or polyelectrolyte in water be mixed.Can with diverting device for example homogenizer resulting potpourri is stirred, with dispersion resin particle in water.Then, can heat or reduced pressure treatment, to evaporate described solvent resulting particulate resin dispersion.Thus, can obtain particulate resin dispersion.

The weight-average molecular weight Mw of non-crystalline resin preferably about 10000 is to about 100000, and more preferably from about 20000 to about 50000, is more preferably about 20000 to about 35000.If Mw occurs the plasticising of resin easily, and can not prevent offset sometimes less than about 10000.If it is about 100000 that Mw surpasses, can not carry out normal photographic fixing sometimes.

Under following condition, carry out the measurement of Mw with gel permeation chromatography (GPC).To be used as GPC equipment by device HLC-8120 GPC, the SC-8020 that ToshoCorp. produces, [TSK gel, SUPER HM-H (have 6.0 millimeters internal diameter and 15 centimetres length to use two chromatographic columns, produce by Tosho Corp.)], and use tetrahydrofuran (THF) as eluant, eluent.Measuring condition is as follows: sample concentration is 0.5%, and flowing velocity is 0.6 ml/min, and the sample injection rate IR is 10 μ 1, and measuring temperature is 40 ℃.Use infrared detector in the measurement.Draw calibration curve: A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128 and F-700 based on polystyrene standard sample that comprises following 10 samples or TSK reference material (producing) by Tosho Corp..

Can use chain-transferring agent during the non-crystalline resin polymerization that comprises in the toner of the present invention.The type of chain-transferring agent is not particularly limited.Compound with thiol moiety can be used as described chain-transferring agent.Chain-transferring agent is alkyl sulfhydryl preferably, for example hexyl mercaptans, heptyl mercaptan, octyl mercaptan, nonyl mercaptan, decyl mercaptan or lauryl mercaptan.Reason is that these compounds have narrow molecular weight distribution, therefore can improve the keeping quality of toner at high temperature.

Can come non-crystalline resin among production the present invention by making at least a polymerisable monomer carry out free radical polymerization.

Can use polymerization initiator in the described free radical polymerization.The type of polymerization initiator is not particularly limited.The example comprises superoxide, for example hydrogen peroxide, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, the peroxidating propionyl, benzoyl peroxide, chlorine peroxide is for benzoyl, dichlorobenzoyl peroxide, peroxidating bromomethyl benzoyl, lauroyl peroxide, ammonium persulfate, sodium peroxydisulfate, potassium persulfate, peroxidating carbonic acid diisopropyl ester, the hydroperoxidation tetralin, 1-phenyl-2-methyl-propyl-1-hydroperoxides, triphenyl t-butyl peroxy-acetate hydroperoxides, the performic acid tertiary butyl ester, the peracetic acid tertiary butyl ester, t-butyl perbenzoate, phenyl peracetic acid tertiary butyl ester, methoxyl peracetic acid tertiary butyl ester and tert-butyl group N-(3-tolyl) cross carbamate; Azo-compound, for example 2,2 '-the azo bis propane, 2,2 '-two chloro-2,2 '-the azo bis propane, 1,1 '-azo (methyl ether) diacetate esters, 2,2 '-two (2-amidine propane) hydrochlorides of azo, 2,2 '-two (2-amidine propane) nitrate of azo, 2,2 '-the two isobutanes of azo, 2,2 '-the two isobutyramides of azo, 2,2 '-azobis isobutyronitrile, 2,2 '-azo two (2 Methylpropionic acid methyl esters), 2,2 '-two chloro-2,2 '-the two butane of azo, 2,2 '-azo is two-the 2-methylbutyronitrile, 2,2 '-azo two (isobutyric acid dimethyl ester), 1,1 '-azo two (1-methylbutyronitrile-3-sodium sulfonate), 2-(4-aminomethyl phenyl azo)-2-methyl-prop dintrile, 4,4 '-azo two (4-cyanopentanoic acid), 3,5-dihydroxymethyl phenyl azo-2-methyl-prop dintrile, 2-(4-bromophenyl azo)-2-allyl malononitrile, 2,2 '-azo is two-2-methyl valeronitrile, 4,4 '-azo two (4-cyanopentanoic acid dimethyl esters), 2,2 '-azo two-2, the 4-methyl pentane nitrile, 1,1 '-the two cyclohexanenitriles of azo, 2,2 '-azo two (2-propyl group butyronitrile), 1,1 '-azo two (1-chlorphenyl ethane), 1,1 '-azo two (1-cyclohexane nitrile), 1,1 '-azo two (1-cycloheptane nitrile), 1,1 '-azo two (1-diphenylphosphino ethane), 1,1 '-the two cumenes of azo, 4-nitrobenzophenone azobenzyl cyanoacetic acid ethyl ester, the phenylazo diphenyl-methane, the phenylazo triphenylmethane, 4-nitrobenzophenone azo triphenylmethane, 1,1 '-azo two (1, the 2-diphenylethane), poly-(bisphenol-A-4,4 '-azo is two-4-cyanopentanoic acid ester), with poly-(tetraethylene glycol-2,2 '-the two isobutyrates of azo); 1, two (five the ethylidene)-2-tetrazenes and 1 of 4-, 4-dimethoxy carbonyl-1, the 4-diphenyl-2-tetrazene.

The molecular weight of resin mainly is subjected to the influence of the amount of polymerization initiator in the polymerization.Usually, the amount along with polymerization initiator reduces the molecular weight increase.

The glass transition temperature of non-crystalline resin is preferably about 45 ℃ to about 60 ℃ among the present invention, more preferably about 50 ℃ to about 60 ℃.If glass transition temperature is lower than about 45 ℃, toner tend to lump (phenomenon that toner-particle coagulates integrated package) between the storage life or in developing apparatus.On the other hand, if glass transition temperature surpasses about 60 ℃, the fixing temperature of toner is desirably not high.

-crystalline resin-

Crystalline resin only need have crystallinity and get final product, in addition without limits.

Specifically, crystalline resin can be crystalline polyester resin or crystallinity vinylite.With regard to toner on paper fixing performance, charging property and regulate within the required range with regard to the easiness of melting point resin, described crystalline resin is preferably crystalline polyester resin.Crystalline polyester resin preferably has the straight chain group aliphatic resin of suitable fusing point.

Can be from acid (dicarboxylic acid) composition and alcohol (glycol) composition synthetic crystallization vibrin.Among the present invention, be also included within the scope of crystalline polyester resin by making crystalline polyester main chain and the multipolymer that other composition copolymerization that is equal to or less than 50 quality % obtains.

The type of the method for production crystalline polyester resin is not particularly limited.Described crystalline polyester resin can make with the conventional polyester polymerization, in this method, makes the reaction of sour composition and pure composition.The example of this method comprises direct polycondensation method and ester-interchange method.Can suitably select production method according to the type of monomer.

Can be in about 180 ℃ of productions of carrying out crystalline polyester resin to about 230 ℃ polymerization temperature scope.If necessary, can reduce the pressure of reaction system, the water or the alcohol that produce when removing polycondensation.When not fusion of described monomer under temperature of reaction or when incompatible each other, high boiling solvent can be added to reaction system as dissolution aids, with dissolved monomer.Distillation and remove described dissolution aids when carrying out polycondensation reaction.If raw material comprises the bad monomer of other monomer (one or more) compatibility in the poly-together reaction, can make the bad monomer of compatibility and acid or the pure condensation of wanting polycondensation in advance, make product and principal ingredient polycondensation then.

Can use catalyzer when making crystalline polyester resin.The example comprises: comprise for example compound of sodium and lithium of alkaline metal; Comprise for example compound of magnesium and calcium of earth alkali metal; Comprise for example compound of zinc, manganese, antimony, titanium, tin, zirconium and germanium of metal; Bi-ester of phosphite, phosphate compound and amines.

Its instantiation comprises sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, four titanium propanolates, titanium tetraisopropylate, four butanols titaniums, antimony trioxide, antimony triphenyl, tributyl antimony, formic acid tin, ethane diacid tin, tetraphenyltin, the dichloride dibutyl tin, dibutyltin oxide, diphenyl tin oxide, four butanols zirconiums, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octoate, germanium oxide, the triphenyl phosphite ester, three (2, the 4-tert-butyl-phenyl) phosphite ester, bromination Yi base triphenyl phosphonium, triethylamine and triphenylamine.

The instantiation that makes thus and can be used for crystalline polyester resin of the present invention comprises: poly-(isophthalic acid-1,2-cyclopropylene dimethylene ester), poly-(hexane diacid decamethylene ester), poly-(azelaic acid decamethylene ester), poly-(ethane diacid decamethylene ester), poly-(decanedioic acid decamethylene ester), poly-(succinic acid decamethylene ester), poly-(malonic acid two decamethylene esters), tygon-to (carbonyl phenoxy group) butyric ester, tygon-to (carbonyl phenoxy group) undecane acid esters, tygon-TOPOT 2,2 acetic acid esters, poly-decanedioic acid second diester, poly-succinic second diester, the poly-own diester of carbonic acid, polyhexamethylene is to (carbonyl phenoxy group) undecane acid esters, the poly-own diester of ethane diacid, the poly-own diester of decanedioic acid, the poly-own diester of suberic acid, the own diester of poly-succinic, poly-(hexane diacid-4,4-isopropylidene diphenylene ester), poly-(malonic acid-4,4-isopropylidene diphenylene ester), trans-poly-(1-methyl cyclopropane dicarboxylic acid-4,4-isopropylidene diphenylene ester), poly-(azelaic acid azelaoyl), poly-(terephthalic acid (TPA) azelaoyl), poly-(the hot diester of dodecanedioic acid), poly-(terephthalic acid (TPA) penta diester), trans-poly-(cyclopropane dicarboxylic acid's metaphenylene ester), cis-poly-(cyclopropane dicarboxylic acid's metaphenylene ester), poly-(carbonic acid fourth diester), poly-(the oxalic acid tetramethylene is to the benzene diester), poly-(butylene sebacate), poly-(decane diacid propylene diester), poly-(octadecane diacid propylene diester), poly-(ethane diacid propylene diester), poly-(heneicosanedioic acid propylene diester), poly-(hexane diacid P-xylene diester), poly-(azelaic acid P-xylene diester), poly-(decanedioic acid P-xylene diester), poly-(diethylene glycol terephthalate), cis-poly-[decanedioic acid 1,4-(2-butylene) diester] and polycaprolactone.

Also the multipolymer of at least two kinds of monomers in the ester monomer of above-mentioned polymkeric substance and the multipolymer of at least a described ester monomer and at least a other copolymerisable monomer can be used as crystalline polyester resin.

The fusing point of crystalline resin is preferably about 40 ℃ or be higher than 40 ℃ among the present invention, more preferably from about 60 ℃ or be higher than 60 ℃.The upper limit of fusing point is preferably about 100 ℃ or be lower than 100 ℃, more preferably from about 90 ℃ or be lower than 90 ℃.Specifically, for low-temperature fixing, the fusing point of crystalline resin is preferably about 60 ℃ to about 95 ℃.

If the fusing point of crystalline resin is lower than about 40 ℃, toner is storing or may lump between the operating period.If the fusing point of crystalline resin is higher than about 100 ℃, toner can not be in low temperature photographic fixing preferably.

Can measure the fusing point of the crystalline resin among the present invention with above-mentioned differential scanning calorimeter.Specifically, described fusing point is, according to ASTM D3418-8, and resulting melting peak temperature when room temperature to 150 ℃ is carried out differential thermal analysis and measured with 10 ℃/minute heating rate.When in measuring, a plurality of melting peak occurring, maximum peak temperature is considered as fusing point.

The molecular weight of crystalline resin is not particularly limited, yet weight-average molecular weight Mw is preferably about 8000 to about 80000, and more preferably from about 10000 to about 50000, is more preferably about 15000 to about 30000.If the weight-average molecular weight of crystalline resin is less than about 8000, the intensity of photographic fixing image may be not enough, and in developing apparatus during churning toner may break.On the other hand, about 80000 if the crystalline resin weight-average molecular weight is higher than, fixing temperature tends to higher.

Can use the method identical to measure the molecular weight of crystalline resin with non-crystalline resin.

In the toner of the present invention, preferred non-crystalline resin is suitably compatible with crystalline resin.If non-crystalline resin and crystalline resin are compatible fully, then toner viscosity is too low, to such an extent as to the property possible deviation is stain in the solar heat protection of toner during fusion.If non-crystalline resin and crystalline resin are incompatible fully, then crystalline resin can not infiltrate toner inside, and in toner surface localization, and it may have a negative impact to the charging property of toner, comminuted and fixation performance.

2) colorant

Colorant among the present invention can be usually known organic or inorganic pigment or dyestuff, or oil-soluble dyes.

The example comprises C.I. (Colour Index) pigment red 48: 1, CI. paratonere 57: 1, C.I. pigment red 122, C.I. pigment yellow 17, C.I. pigment yellow 97, C.I. pigment Yellow 12, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3, dim (C.I. number 77266), rose-red (C.I. number 45432), carbon black, aniline black byestuffs (C.I. 50415B), aniline blue, the calco oil blue, chrome yellow, ultramarine, Du Pont's oil red, quinoline yellow, protochloride methyl indigo plant, phthalocyanine blue, the peacock green oxalates, premetallized dye, the derivant of premetallized dye, with its potpourri.

Other example comprises various metal oxides, for example silicon dioxide, aluminium oxide, magnetic iron ore and various ferrite, cupric oxide, nickel oxide, zinc paste, zirconia, titanium dioxide and magnesium oxide and their potpourri.Select colorant can consider hue angle, colourity, brightness, weatherability, OHP (elevated projecting) transparency and the dispersiveness in toner.

Although the content of colorant depends on the development amount of toner particle diameter and toner, with respect to 100 mass parts adhesive resins, this content preferably about 1 is more preferably about 2 to about 25 mass parts to about 50 mass parts.

Can only use a kind of in these colorants, maybe in these colorants two or more can be used together or use with the solid solution form.Can colorant be dispersed in the adhesive resin with conventional method.In this method, can preferably use: utilize the diverting device or the high pressure collision type diverting device of medium, for example rotational shear type homogenizer, bowl mill, sand mill or masher.

Be used at colorant with homogenizer colorant being dispersed in the water-based system that comprises the polar surfactant under the situation of emulsion agglutination.

3) external additive

Among the present invention, preferably external additive is added into the surface of the female particle of toner, controlled with the transfer printing, flowability, clean-up performance and the electric charge that improve toner, particularly mobile.External additive is the inorganic particle that is attached to the surface of the female particle of each toner.

The example of inorganic particulate material comprises SiO ₂, TiO ₂, Ti (OH) ₂, Al ₂O ₃, CuO, ZnO, SnO ₂, CeO ₂, Fe ₂O ₃, MgO, BaO, CaO, K ₂O, Na ₂O, ZrO ₂, CaO-SiO ₂, K ₂O-(TiO ₂) n (n is 1 to 4 integer), Al ₂O ₃-2SiO ₂, CaCO ₃, MgCO ₃, BaSO ₄And MgSO ₄Particularly, inorganic particle is silica dioxide granule or titan oxide particles preferably, because they can improve the flowability of toner.

The volume average particle size of external additive preferably about 5 is to about 40nm among the present invention, and more preferably from about 10 to about 40nm, is more preferably about 12 to about 35nm, and most preferably from about 15 to about 30nm.If the volume average particle size of external additive is less than about 5nm, adjuvant is imbedded the toner surface part, and does not contribute for the flowability of toner.On the other hand, if volume average particle size surpasses about 40nm, adjuvant separates with toner easily, and the flowability of toner is not contributed, and free adjuvant desirably is not attached to the surface of carrier.

Can obtain the volume average particle size of external additive as described below.Measure the size-grade distribution of external additive with laser diffraction type particle size distribution analysis instrument LA-700 (being produced) by the making of hole field.The whole particle size range of measured size-grade distribution is divided into a plurality of particle size ranges (passage), and from minimum zone rendered volume cumulative distribution curve.The particle diameter that cumulative statistics is reached at 50% o'clock is defined as volume average particle size D _50v

External additive with volume average particle size of above-mentioned scope can be imbedded the toner surface part hardly, and can separate from toner-particle hardly, therefore when the toner that comprises this external additive mixed with the carrier described in the present invention, this toner can show and keep good flowability.

For the addition of external additive, the surface-coated rate of calculating according to following formula (3) is preferably about 10% to 100%, and more preferably from about 12% to about 80%, is more preferably about 15% to about 60%.

In the formula (3), D _NRepresent the female particle grain size (μ m) of toner; ρ _NRepresent the density of the female particle of toner; D _aRepresent the particle diameter (nm) of external additive; ρ _aRepresent the density of external additive; X represents the addition (weight %) of external additive.

When various types of external additives are added into the female particle of toner, the summation of each surface coverage preferably 100% or less than 100%.

Preferably handle carrying out hydrophobization as the surface of the inorganic particle of external additive.Make the external additive surface have the powder flowbility that hydrophobic processing can improve toner, also can reduce the toner charging property effectively to the environment degree of dependence, and prevent carrier contamination.Can provide hydrophobic reagent to carry out this processing by inorganic particle is immersed.The type of this reagent is not particularly limited, and this reagent can be silane coupling agent, silicone oil, titanate coupling agent or aluminum coupling agent.Can only use a kind of in these reagent, or they two or more can use together.Particularly, this reagent is preferably silane coupling agent.

Silane coupling agent can be any chlorosilane, alkoxy silane, silazane and specific sillylation reagent.Its instantiation comprises methyl trichlorosilane, dimethyldichlorosilane, trimethyl chlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane, tetramethoxy-silicane, methyltrimethoxy silane, dimethyldimethoxysil,ne, phenyltrimethoxysila,e, dimethoxydiphenylsilane, tetraethoxysilane, methyl triethoxysilane, dimethyldiethoxysilane, phenyl triethoxysilane, the diphenyl diethoxy silane, the isobutyl triethoxysilane, the decyl trimethoxy silane, hexamethyldisilazane, N, two (trimethyl silyl) acetamides of O-, N, N-(trimethyl silyl) urea, tert-butyl group dimethyl chlorosilane, vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-methacryloxypropyl trimethoxy silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, γ-glycidoxypropyl methyldiethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, and γ-Lv Daibingjisanjiayangjiguiwan.The consumption of this reagent depends on the type of inorganic particle, cannot treat different things as the same.Yet with respect to 100 weight portion inorganic particles, this consumption is generally about 5 to about 50 weight portions.

The hydrophobization degree preferably about 40% that increases its hydrophobic external additive by above-mentioned processing is to about 100%, and more preferably from about 50% to about 90%, is more preferably about 60% to about 90%.

Among the present invention, can obtain hydrophobization degree (M) as described below.0.2 gram particle is added 50 ml waters, and stir resulting potpourri with stirrer.After this, use methyl alcohol to carry out titration.The amount that setting is used at the methyl alcohol of the whole particles of solvent suspension is T (milliliter), calculates the hydrophobization degree according to following equation.

Hydrophobization degree (M)=[T/ (50+T)] * 100 (volume %)

4) other composition

If necessary, toner of the present invention can comprise other composition for example antistain agent or detackifier.

The instantiation that can be used for detackifier of the present invention comprises following compounds.

Detackifier can be a wax.The example comprises: vegetable wax, for example carnauba wax, cotton wax, Japan tallow and rice bran wax; Animal wax, for example beeswax and sheep oil; Mineral wax, for example montan wax and its derivant, ceresine and ceresin (sercine); Pertroleum wax, for example paraffin and its derivant, microcrystalline wax and its derivant and oil lactam (petrolactam).Alternatively, detackifier can be synthetic chloroflo, for example Fischer-Tropsch synthetic wax or derivatives thereof; The polyolefin-wax that comprises Tissuemat E; The synthetic wax of fatty acid amide, ester, ketone, ether, alcohol or fatty acid, for example 12-hydroxyl stearmide, stearmide, phthalate anhydride acid imide or chlorohydrocarbon; Or low-molecular-weight polypropylene or low molecular weight polyethylene.The example of derivant comprise oxide, with polymer of vinyl monomer and graft modification product.

Alternatively, detackifier can also be the crystalline polymer that has long alkyl in one or more side chains.The example of crystalline polymer comprises the homopolymer and the multipolymer of acrylate, for example poly-(the positive stearyl of methacrylic acid), poly-(methacrylic acid dodecyl ester) and the positive stearyl/ethyl methacrylate copolymers of acrylic acid.Wherein, detackifier is pertroleum wax or synthetic wax preferably, for example paraffin or microcrystalline wax.

All in the toner-particle, the preferably about 10 quality % of the content of detackifier are to about 40 quality %, and more preferably from about 10 quality % are more preferably about 15 quality % to about 30 quality % to about 30 quality %, and most preferably from about 15 quality % are to about 25 quality %.If the content of detackifier is about 10 quality % or greater than 10 quality %, can guarantees enough antistick characteristics, and can prevent heat and stain.On the other hand, if content is about 40 quality % or less than 40 quality %, can prevents that detackifier is exposed on the toner surface, and can obtain good toner flowability and charging property.

If necessary, toner can also comprise lubricant and/or charge control agent among the present invention.

The example of lubricant comprises: fatty acid amide, for example ethylenebis (stearmide) and oleamide; With the slaine of fatty acid, for example zinc stearate and calcium stearate.

To comprise charge control agent in the toner and be in order to improve and the charging property of stable toner.This reagent can use for example quarternary ammonium salt compound, nigrosine compound, the dyestuff that comprises aluminium, iron or chromium complex or triphenylmethane pigment usually.In the aggegation step and fusion-fusion steps when producing toner described later, consider the ionic strength that influence agglutinating particle stability controlled and contaminated wastewater when suppressing aggegation that preferably charge control agent is difficult to water-soluble by the emulsion agglutination.

Specifically, charge control agent preferably is selected from the material in the group of being made up of the material that is included in the powder toner, the slaine of for example benzoic slaine, salicylic slaine, alkyl salicylate, the slaine of catechol, metallic bisazo dye, tetraphenyl boric ester derivative, quaternary ammonium salt and Fixanol, or preferably two or more combination in these compounds.

In the time will adding toner with wet type as the inorganic particle of charge control agent, the example of described inorganic particle comprises the inorganic particle that is used as the external additive on the surface that is added into toner-particle usually, for example particle of silicon dioxide, aluminium oxide, titanium dioxide, lime carbonate, magnesium carbonate and tricalcium phosphate.In this case, can in the presence of the alkali of the acid of ionic surface active agent, high molecular or high molecular, inorganic particle be dispersed in the solvent.

The charge control agent that is comprised in the color toner is preferably colourless or light, has a negative impact to prevent the tone of exchanging toner.Charge control agent can be normally used material, preferably the metal complex of azo metal complex or salicylic acid or alkyl salicylate or slaine.

Further, toner can comprise inorganic particle as internal additives, so that easily carry out oilless fixing.In order to obtain the transparency on the OHP sheet material, the refractive index of inorganic particle preferably is lower than the refractive index of toner binder resin.If refractive index is too high, the color of toner even also may be muddy in normal image.The instantiation of inorganic particulate material comprises SiO ₂, TiO ₂, Al ₂O ₃, CuO, ZnO, SnO ₂, CeO ₂, Fe ₂O ₃, MgO, BaO, CaO, K ₂O, Na ₂O, ZrO ₂, CaO-SiO ₂, K ₂O-(TiO ₂) n, Al ₂O ₃-2SiO ₂, CaCO ₃, MgCO ₃, BaSO ₄And MgSO ₄

Wherein, preferably silicon dioxide or titan oxide particles of inorganic particle.Silica dioxide granule can comprise anhydride silica, alumina silicate, sodium silicate and/or potassium silicate.The preferred composition of regulating inorganic particle makes it have 1.5 or less than 1.5 refractive index.

Can carry out hydrophobization to the surface of inorganic particle handles.Make the inorganic particle surface have hydrophobic processing and can improve the dispersiveness of inorganic particle in toner.In addition, when the part in the inorganic particle that is present in toner inside occurred from the teeth outwards, described particle can reduce the degree of dependence of toner charging property to environment effectively, and prevents carrier contamination.Can provide hydrophobic reagent to carry out this processing by inorganic particle is immersed.The type of this reagent is not particularly limited, and this reagent can be silane coupling agent, silicone oil, titanate coupling agent or aluminum coupling agent.Can only use a kind of in these reagent, perhaps two or more in them can use together.Particularly, described reagent is preferably silane coupling agent.

The consumption of this reagent depends on the type of inorganic particle, cannot treat different things as the same.Yet with respect to the inorganic particle of 100 weight portions, this consumption is generally about 5 to about 50 weight portions.

Female particle of toner can have core/shell structure among the present invention.The type of the adhesive resin of nuclear part is not particularly limited, and this adhesive resin can be to be selected from a kind of in above-mentioned crystalline resin and the non-crystalline resin, or its combination.The type of the adhesive resin of shell part is not particularly limited, but described adhesive resin non-crystalline resin preferably.When the adhesive resin of nuclear part and shell part was non-crystalline resin, they can be identical or different.

(2) method of production toner

In aspect the the the first, the 3rd to the 6th, the 8th and the 9th, the type of producing the method for toner is not particularly limited.In the second and the 7th aspect, the method for producing toner only need prepare the toner of shape factor S F1 in above-mentioned scope and get final product, and in addition is not particularly limited.This method can be knead comminuting method, suspension polymerization, solution suspension method or emulsion polymerization agglutination.In order to produce toner, preferably carry out wet granulation with suitable form factor and suitable particle diameter.Wet granulation can be usually known fusion suspension method, emulsification agglutination or solution suspension method.Wherein, preferably carry out the emulsification agglutination.

In the comminuting method of kneading, adhesive resin, colorant, detackifier and other adjuvant are kneaded together, and resulting potpourri is pulverized, the particle that obtains is carried out classification.Have the size-grade distribution and the irregular shape of relative broad with the particle of the comminuting method production of kneading, wherein most of shape factor S F1 surpass 140.If use the toner-particle through kneading and pulverizing, the sharp part of this toner-particle can cause the resin-coated layer of carrier to be peeled off.For fear of this situation, among the present invention, preferably the particle to the comminuting method production of kneading carries out classification, obtaining particle with narrow size-grade distribution, and resulting granules is heated so that its shape becomes sphere.

Among the present invention, can use known usually method as the described comminuting method of kneading.Can utilize gravity classifier, centrifugal type clasfficiator, inertial classification device or screen cloth to come resulting granules is carried out classification.Can carry out described thermal treatment with fluidized-bed layer or spray dryer.

In suspension polymerization, make to comprise at least a solution that is used for polymerizable monomer, colorant and other adjuvant of adhesive resin and suspend, and in resulting suspending liquid, make described monomer polymerization at aqueous solvent.

In the solution suspension method, the solution that comprises adhesive resin, colorant, detackifier and other adjuvant is suspended in aqueous solvent, then resulting suspending liquid is carried out granulation.

In the emulsion polymerization agglutination, to mix with the colorant dispersion that makes by the toner that in solvent, is scattered here and there by the particulate resin dispersion that emulsion polymerization makes, to form the agglutination body of size corresponding to the toner particle diameter, described agglutination body is heated, combines together, thereby form toner.Therefore, comminuting method is compared with kneading, the emulsion polymerization agglutination can easily provide the toner with small particle diameter and narrow size-grade distribution, and can provide surface and the controlled toner of sphericity with smoothing by the condition that is controlled at the fusion unificationization step in the liquid.

＜formation method 〉

Formation method of the present invention preferably includes: keep body to charge to sub-image; Charged described sub-image is kept the body exposure, so that keep forming electrostatic latent image on the body at described sub-image; Make described latent electrostatic image developing with the developer that comprises toner and carrier, to form toner image; And keep body to be transferred to recording materials from described sub-image the described toner image.The carrier that is used for imaging comprises above-mentioned electrostatic image developing carrier, electrostatic image developing.Described toner is above-mentioned toner.

In charging, exposure, development and the transfer step of formation method of the present invention, can suitably use known technology usually.Formation method of the present invention may further include to sub-image keep body to clean and after the transfer step with recording materials on the toner image of institute's transfer printing.

In the development step, the preferred developer carrier (so-called magnetic roll) that keeps body towards described sub-image that is provided with maintains described developer on the surface of this supporting body, and rotates this supporting body so that described developer is sent to described sub-image maintenance body.

Preferably about 200 mm/second of the peripheral speed of developer carrier are to about 600 mm/second, and more preferably from about 300 mm/second are to about 500 mm/second.If the peripheral speed of magnetic roll is lower than about 200 mm/second, can not satisfies recent high speed requirement, and cause the high concentration reappearance relatively poor.On the other hand, if peripheral speed surpasses about 600 mm/second, if and the developing cell that comprises this parts has compact size, the physical strength deficiency of this developing cell then, this causes joist (trimmer) that strain takes place, thereby thickness that causes the whole developer layers on the developer carrier etc. becomes inhomogeneous, and concentration reappearance variation.

In the second and the 7th aspect, it is about 100 to about 600 mm/second that preferred sub-image keeps the peripheral speed of body, and the peripheral speed of developer carrier to keep the ratio of the peripheral speed of body with respect to sub-image be about 1.2 to about 2.0.

If sub-image keeps the peripheral speed of body to be lower than about 100 mm/second, can not satisfy recent high speed requirement.On the other hand, if peripheral speed surpasses about 600 mm/second, then by making charged sub-image keep the body exposure to cause optical attenuation so that when sub-image keeps forming sub-image on the body, before described optical attenuation fully took place, the sub-image on the described sub-image maintenance body was developed.Therefore, can not obtain enough contrasts, cause forming the image of low resolution.

If the peripheral speed of developer carrier and sub-image keep the ratio of peripheral speed of body less than about 1.2, then use developer to make sub-image keep the time of the image development on the body to shorten.Therefore, under the situation of video high density, the quantitative change of the toner that is used to develop gets not enough, can only obtain the image of low concentration.If it is about 2.0 that this ratio is higher than, then can make developer and sub-image keep body to contact time enough, and the toning dosage that is used to develop is enough.Yet with respect to the speed of sub-image maintenance body, it is too fast that the relative velocity of developer carrier but becomes, so developer meeting scratch sub-image maintenance body, and obtain mixed and disorderly image.

＜imaging device 〉

Imaging device of the present invention preferably has: sub-image keeps body (Electrophtography photosensor); Charhing unit, this charhing unit are used for keeping body to charge to described sub-image; Exposing unit, this exposing unit are used for keeping forming electrostatic latent image on the body at described charged sub-image; Developing cell, this developing cell are used to use developer to make described latent electrostatic image developing to form toner image; Transfer printing unit, this transfer printing unit are used for keeping body to be transferred to recording materials from described sub-image described toner image.

Imaging device of the present invention can also have after transfer printing unit and is used to clean the cleaning unit that sub-image keeps body, and has the electric unit that removes that is used to remove the residual charge on the described image holding body after the described transfer printing.In the present invention, these unit, promptly Electrophtography photosensor, charhing unit, exposing unit, developing cell, transfer printing unit, cleaning unit and the structure that removes electric unit are not particularly limited.These unit can have any known structure usually, and unrestricted.

Described developing cell preferably has the developer carrier (so-called magnetic roll) that is used to stir the stirrer of developer and developer is sent to described sub-image maintenance body.

Embodiment

Hereinafter, the present invention is described reference example.Yet the present invention is not limited to these embodiment.

The measuring method of＜various performances 〉

At first, will the method for the physical property etc. of the measurement carrier that uses in embodiment and the Comparative Examples be described.

-form factor-

Capture is dispersed in the optical microscope image of the toner-particle on the microslide, with image input picture analyser (the LUZEX III that traps, produce by NIRECO Corp.), and measure 50 particles separately be equal to circular diameter (having and projected area diameter of a circle of the same area), maximum length and projected area, the SF1 value of calculating each particle according to above-mentioned equation (1) and the maximum length of measuring and projected area, and to calculate the SF1 value average.

-volume average particle size and size-grade distribution-

The device that is used for measurement volumes mean grain size and size-grade distribution is that (LS PARTICLE SIZE ANALYZER LS13 320 produces 1 by BECKMANCOULTER to laser diffraction/scatter-type particle size distribution measurement device.

Implement measuring method as described below.Measuring samples is added 2 ml water solution, and described aqueous solution comprises surfactant or the spreading agent of 5 quality %, and described surfactant or spreading agent are preferably sodium alkyl benzene sulfonate.The amount of sample is 10 to 200mg.The material that obtains is added to pure water.The consumption of pure water is 100 to 150ml.With the ultrasonic dispersing device with the suspending liquid stir about that wherein is suspended with sample of gained 1 minute.With the size-grade distribution of LS PARTICLE SIZE ANALYZER LS 13 320 with 80% pump speed measuring samples.Then, obtain the volume average particle size of sample, in the size-grade distribution of coarse particle side with in the size-grade distribution of particle side.

In embodiment 16 to 23 and Comparative Examples 16 to 21, TA-II type COULTERCOUNTER (being produced by BECKMAN COULTER) as the volume average particle size measurement mechanism, is used as electrolytic solution with ISOTON II (being produced by BECKMAN COULTER).Implement measuring method as described below.Measuring samples is added 2 ml water solution, and described aqueous solution comprises surfactant or the spreading agent of 5 quality %, and described surfactant or spreading agent are preferably sodium alkyl benzene sulfonate.The amount of sample is 0.5 to 50mg.The material that obtains is added described electrolytic solution.The amount of electrolytic solution is 100 to 150ml.With resulting suspending liquid stir about 1 minute, wherein said suspending liquid was that described sample is suspended in the electrolytic solution and the suspending liquid that obtains with the ultrasonic dispersing device.With TA-II type COULTER COUNTER and aperture is the size-grade distribution of the aperture measuring samples of 100 μ m, and the volume average particle size of calculation sample in the above described manner.The granule number that is used to measure is 50000.

The measurement of-molecular weight distribution-

In embodiment 1 to 15 and the Comparative Examples 1 to 15, the molecular weight distribution of the coated with resin of the resin of every kind of toner of measurement and carrier under following condition.

Will be by the device HLC-8120 GPC of Tosoh Corp. production, SC-8020 is as GPC equipment, and use two chromatographic columns: TSK gel, SUPER HM-H (have 6.0 millimeters internal diameter and 15 centimetres length, produced by Tosoh Corp.), use tetrahydrofuran (THF) is as eluant, eluent.Its measuring condition is as follows: sample concentration is 0.5%, and flowing velocity is 0.6 ml/min, and the sample injection rate IR is 10 μ l, and measuring temperature is 40 ℃.Draw calibration curve: A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128 and F-700 based on following 10 samples.During sample analysis, data collection intervals is set at 300 milliseconds.

The measurement of-density-

In embodiment 9 to 15 and the Comparative Examples 7 to 15, measure the density of the core of carrier with said method.

-glass transition temperature-

In embodiment 16 to 23 and the Comparative Examples 16 to 21, measure glass transition temperature (Tg) with 3 ℃/minute heating rates with differential scanning calorimeter (DSC-50 is produced by Shimadzu Seisakusho Ltd.).The temperature at the baseline of heat absorbing part and place, the point of crossing of riser is defined as glass transition temperature.

-weight-average molecular weight and number-average molecular weight-

In embodiment 16 to 23 and the Comparative Examples 16 to 21, measure weight-average molecular weight Mw and number-average molecular weight Mn with gel permeation chromatography (GPC).To be used as GPC equipment by device HLC-8120 GPC, the SC-8020 that Tosoh Corp. produces, and use two chromatographic columns: TSK gel, SUPER HM-H (have 6.0 millimeters internal diameter and 15 centimetres length, produce by Tosoh Corp.), use tetrahydrofuran (THF) as eluant, eluent.Measuring condition is as follows: sample concentration is 0.5%, and flowing velocity is 0.6 ml/min, and the sample injection rate IR is 10 μ l, and measuring temperature is 40 ℃.Use pyroscan in the measurement.Draw calibration curve: A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128 and F-700 based on polystyrene standard sample that comprises following 10 samples or TSK reference material (producing) by Tosoh Corp..

The acid number of-resin-

In embodiment 16 to 23 and the Comparative Examples 16 to 21, measure the acid number (AV) of resin as described below.Basic operation is according to JIS K-0070-1992.By removing the composition that is insoluble to THF from adhesive resin in advance, can obtain each sample.Alternatively, sample can be the solvable composition of the usefulness apparatus,Soxhlet's of acquisition in above-mentioned tetrahydrofuran insoluble is measured with the THF solvent extraction.Accurately take by weighing the 1.5 gram products that obtain by pulverizing each sample, and put the beaker that volume is 300ml into.The toluene of 100 milliliter 4/1 ratio and the potpourri of ethanol are added beaker, and dissolve described product therein.(DiaInstruments Co. Ltd.) carries out the potentiometric titration of gained solution to use 0.1mol/L KOH ethanolic solution and autotitrator GT-100.The use amount of KOH solution is expressed as A (milliliter).Carry out the potentiometric titration of blank sample simultaneously, and the use amount of KOH solution is expressed as B (milliliter) at this moment.According to these numerical value, calculate described acid number according to following formula.In the formula, w is the example weight that accurately takes by weighing, and f is the coefficient of KOH.

Acid number (mgKOH/g)=(A-B) * f * 5.61}/w

[embodiment 1]

Spraying (elbow-jet) equipment (production number: EJ-LABO, iron ore mining industry society produces by day) with elbow at the classification point of 25 μ m and 45 μ m, (comprises Cu-Zn, and has 4.5g/cm the ferrite particle ³Density, the volume average particle size of 35 μ m and 125 shape factor S F1) carry out classification, removing powder and corase meal, thereby obtain the core particles that remains to be covered.

For the size-grade distribution of the core particles that remains to be covered of gained, at the particle size distribution index (D of coarse particle side _84v/ D _50v) be 1.18, at the particle size distribution index (D of particle side _50P/ D _16P) be 1.20, volume average particle size is 37 μ m, shape factor S F1 is 124.

The core particles that remains to be covered that the toluene solution (solids content is 15 mass parts) of 20 mass parts styrene-methylmethacrylate copolymers (weight-average molecular weight 80000) is added 100 mass parts.With batch (-type) kneading machine resulting potpourri was stirred 10 minutes with 50 liters of capacity and chuck.When stirring, with mixture heated to 120 ℃ or be higher than 120 ℃, and this temperature was kept 20 minutes.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.After this, take out resulting lining particle.Under these conditions the lining particle is carried out three classifications with the elbow spraying equipment, to remove powder and corase meal.Thereby obtain lining carrier (1).

For the size-grade distribution of carrier (1), be 1.15 at the particle size distribution index of coarse particle side, be 1.16 at the particle size distribution index of particle side, volume average particle size is 37 μ m, shape factor S F1 is 123.

Measure the gross energy of carrier (1) in the above described manner with POWDER RHEOMETER FT4 (producing) by Freeman Technology.Concrete measuring method is as described below.

At first, aid is connected to the upper end that capacity is the container of 160ml.Put carrier (1) into container to overflow container.Then, the container that carrier (1) will be housed is arranged in the measurement mechanism, and will be arranged on the container top by the rotation oar (propeller-type blade as shown in Figure 3 has 48 mm dias and 10 millimeters width) that Freeman Technology produces.Rotation oar terminal velocity with-5.0 ° entering angles and 60 mm/second is adjusted processing, repeats altogether four times.

Subsequently, carrier (1) by adjust handling the fully degassing is flushed with container head, and will rotate oar and be moved downward to position (entering (moving) length is 70 millimeters) apart from the height of 10 millimeters of container bottoms with the rotation oar terminal velocity of-5.0 ° entering angle and 100 mm/second.The integrated value that obtains moment of torsion is as described gross energy.The gross energy of carrier (1) is 2400mJ.

[embodiment 2 to 4]

With with embodiment 1 in identical method produce carrier (2) to (4), difference is, handles the repetitive operation number of times that is coated with the carrier of resin with acquisition for the removal of carrying out powder/corase meal with the elbow spraying equipment, changes into 2 to 5 times from three times.Carrier (2) to (4) gross energy is separately listed in table 1.

[embodiment 5]

With the classification point of elbow spraying equipment the ferrite particle (is comprised Cu-Zn, and has 4.5g/cm at 22 μ m and 45 μ m ³Density, the volume average particle size of 35 μ m and 120 shape coefficient SF1) carry out classification, removing powder and corase meal, and obtain the core particles that will be covered.

For the size distribution of the core particles that will be covered that obtains, be 1.18 at the particle size distribution index of coarse particle side, be 1.20 at the particle size distribution index of particle side, volume average particle size is 37 μ m, shape factor S F1 is 118.

(preceding a kind of monomer is 80/20 with the copolymerization ratio of a kind of monomer in back with the methyl methacrylate-acrylic acid perfluoro hexyl ester copolymer of 60 mass parts, weight-average molecular weight is 50000, changing into society by Sanyo produces) toluene solution (solids content is 5 quality %) and the toluene solution (solids content is 15 quality %) of 10 mass parts styrene-methylmethacrylate copolymers (weight-average molecular weight 80000) add the core particles that 100 mass parts will be covered.With the batch (-type) kneading machine resulting potpourri was stirred 10 minutes, this kneading machine has 50 liters capacity and chuck.When stirring, with mixture heated to 120 ℃ or be higher than 120 ℃ temperature, and kept 20 minutes in this temperature.Then, cooling just is reduced to 60 ℃ in stirred mixture until temperature., take out resulting lining particle, and be that the screen cloth of 75 μ m sieves, to remove coarse particle with the aperture thereafter.Thus, obtain carrier (5).The gross energy of carrier (5) is listed in table 1.

[embodiment 6]

Styrene-propene butyl acrylate copolymer (80/20) (Mw=1.9 * 10 ⁵) 30 mass parts

Methyl methacrylate-acrylic acid perfluoro hexyl ester 10 mass parts

Magnetic iron ore (EPT-1000, society produces by the industry of field, family) 100 mass parts

With pressurization kneading machine fusion and mix mentioned component, and with turbo-mill and annealing device with its pulverizing and make sphere.Further, with the elbow spraying equipment in the classification of 22 μ m and the 45 μ m resulting granules classification four times of naming a person for a particular job, to obtain carrier (6).

For the size distribution of carrier (6), be 1.17 at the particle size distribution index of coarse particle side, be 1.19 at the particle size distribution index of particle side, volume average particle size is 33 μ m, and shape factor S F1 is 110, and density is 3.5g/cm ³The gross energy of carrier (6) is listed in table 1.

[embodiment 7]

With with embodiment 6 in identical method produce carrier (7), difference is the multiplicity that classification is handled is changed into three times.The gross energy of carrier (7) is listed in table 1.

[embodiment 8]

With with embodiment 6 in identical method produce carrier (8), difference is, changes the amount of styrene-propene butyl acrylate copolymer (80/20) into 30 mass parts, and changes the amount of methyl methacrylate-acrylic acid perfluoro hexyl ester copolymer into 20 mass parts.The gross energy of carrier (8) is listed in table 1.

[Comparative Examples 1]

The ferrite particle (is not comprised Cu-Zn, and has 4.5g/cm ³Density, the volume average particle size of 35 μ m and 125 shape factor S F1) carry out classification.The toluene solution (solids content is 15 quality %) of 20 mass parts styrene-methylmethacrylate copolymers (weight-average molecular weight is 80000) is added 100 mass parts ferrite particles.With batch (-type) kneading machine resulting potpourri was stirred 10 minutes with 50 liters of capacity and chuck.When stirring, with mixture heated to 120 ℃ or be higher than 120 ℃ temperature, and this temperature was kept 20 minutes.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.After this, take out resulting lining particle, and be that the screen cloth of 75 μ m sieves, to remove coarse particle with the aperture.Obtain carrier (9) thus.

The gross energy of carrier (9) is 3800mJ.

[Comparative Examples 2 and 3]

Adopt with Comparative Examples 1 in identical method production carrier (10) and (11), difference is, not using the aperture is that the screen cloth of 75 μ m sieves removing coarse particle, and is to use the classification of elbow spraying equipment to remove corase meal and powder once or twice.The gross energy of carrier (10) and (11) is listed in table 2.

[Comparative Examples 4]

With the elbow spraying equipment ferrite particle (is comprised Cu-Zn, and has 4.5g/cm ³Density, the volume average particle size of 35 μ m and 120 shape factor S F1) carry out classification, removing powder and corase meal, thereby obtain the core particles that will be covered.For the size-grade distribution of the core particles that remains to be covered that is obtained, be 1.18 at the particle size distribution index of coarse particle side, be 1.20 at the particle size distribution index of particle side, volume average particle size is 37 μ m, shape factor S F1 is 109.

The toluene solution (solids content is 5 quality %) of 60 mass parts methacrylic acid perfluoro hexyl ester-methylmethacrylate copolymers (weight-average molecular weight is 50000, changes into society by Sanyo and produces) and the toluene solution (solids content is 15 quality %) of 10 mass parts styrene-methylmethacrylate copolymers (weight-average molecular weight 75000) are added the core particles that 100 mass parts will be covered.With batch (-type) kneading machine resulting potpourri was stirred 10 minutes with 50 liters of capacity and chuck.When stirring, with mixture heated to 120 ℃ or be higher than 120 ℃ temperature, and this temperature was kept 20 minutes.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.Obtain carrier (12) thus.The gross energy of carrier (12) is listed in table 2.

[Comparative Examples 5]

The carrier of the embodiment 1 of-TOHKEMY 2002-328493 communique-

The employing method production identical with the carrier of the embodiment 1 of TOHKEMY 2002-328493 communique has the carrier (13) of Magnaglo discrete particles as core.

Specifically, produce carrier by following mode.

The manufacturing of hydrophobicity iron oxide

The magnesium sulphate and the sodium carbonate that 2646 grams are comprised the magnesium elements of 9.9 quality % are added to 57 liters of Fe that comprise 2.4mol/l ²⁺The ferrous sulfate aqueous solution of ion is adjusted to 9 mixed aqueous solution to obtain the pH value.The 65 premium on currency solution that will comprise 4.4mol/l NaOH mix with above-mentioned mixed aqueous solution.Remain in 80 ℃ in temperature, air is blown into products therefrom, so that made crystal growth 30 minutes with 40 liters/minute speed.With 6.5 liters of Fe that comprise 2.4mol/l ²⁺The ferrous sulfate aqueous solution of ion adds the ferric hydroxide slurries that comprise seed crystal grain.Sodium hydrate aqueous solution is added products therefrom and the pH value is adjusted to 8 to 9, simultaneously, air is blown into the gained system, thereby make oxidation reaction carry out finishing in 6 hours reaction 85 ℃ of speed with 40 liters/minute.After reaction is finished, resulting magnetic iron ore slurries are also pulverized with conventional method washing, filtration, drying.The magnetite ore particles of Huo Deing has the content of magnesium that adds up to 2.1 quality % in this way, and the total amount that is present in the magnesium on surface is 0.26 quality %.

With 0.5 mass parts γ-glycidyl trimethoxysilane the described magnetic iron ore of 100 mass parts is carried out surface treatment, to obtain hydrophobicity iron oxide 1.

The production of carrier

Phenol (hydroxy benzenes) 50 mass parts

37 quality % formalins, 80 mass parts

Water 50 mass parts

Hydrophobicity iron oxide 1 600 mass parts

25 quality % ammoniacal liquor, 15 mass parts

Above-mentioned material is put into four neck flasks, and through 60 minutes with the gained mixture heated to 85 that stirs ℃, this temperature was kept 120 minutes, to solidify phenol and formalin.Then, reaction product is cooled to 30 ℃, 500 mass parts water is added reaction product, and remove supernatant liquor, wash resulting sediment and it is air-dry with water.Further in 150 to 180 ℃ temperature range under the reduced pressure of 5 mm Hg with described drying precipitate 24 hours, thereby obtain to have the carrier core of phenol resin as its adhesive resin.

With the toluene solution that comprises 5 quality % gamma-amino propyl trimethoxy silicanes as the be covered surface of described carrier core of silane coupling agent.

The amount that is used for surface-treated gamma-amino propyl trimethoxy silicane is 0.2 quality %.During being covered, be continuously applied shearing force to the carrier core, and evaporation toluene.Confirmed that following groups is present in the surface of treated carrier core.

The gamma-amino propyl trimethoxy silicane is added into silicone resin KR-221 (being produced by SHIN-ETSU HANTOTAI's chemical industry (strain)), and its content is 3 quality % of this silicone resin solids.With the resulting potpourri of dilution with toluene, make the concentration of silicone resin solids become 20 quality %.When 70 ℃ are stirred, the gained potpourri under reduced pressure is added in carried out the magnetic carrier core handled with described silane coupling agent in the above-mentioned treating apparatus, so that with this potpourri described core that is covered.With respect to the carrier core of 100 mass parts, the amount of coating of silicone resin solids is 0.8 mass parts.

Stir after two hours, in 140 ℃, nitrogen atmosphere with coated core heating 2 hours, after agglutination body disintegrates, with 82 μ m (200 order) or greater than the coarse particle of 82 μ m from by removing the resin-coated core particles, to obtain carrier (13).

The gross energy of carrier (13) is listed in table 2.

[Comparative Examples 6]

Adopt the method acquisition carrier (14) identical with embodiment 8, difference is to change the amount of styrene-propene acid butyl ester (80/20) multipolymer and perfluorinated acrylate multipolymer into 15 mass parts and 25 mass parts respectively.The gross energy of carrier (14) is listed in table 2.

The production of＜developer 〉

By kneading and pulverizing and produce toner

The production of-toner a-

Vibrin: 100 weight portions

(linear polyester of terephthalic acid (TPA)/bisphenol-A-ethylene oxide adduct/cyclohexane has 10000 weight-average molecular weight);

Carbon black (by the REGAL 330 of Cabot Corp. production): 6 weight portions;

With the knead potpourri of mentioned component of extruder, and it is pulverized, resulting granules is carried out classification with jet mill.Subsequently, (toner a) to obtain black toner on the surface that external additive is added into classified particle.

The production of-toner b-

Adopt the method identical with toner a to obtain cyan toner (toner b), difference is, with the phthalocyanine covellite pigment C.I. pigment blue 15 of 5 weight portions: 3 replace the carbon blacks all measured.

The production of-toner c-

Adopt the method identical with toner a to obtain magenta toner (toner c), difference is to replace all carbon blacks of amount at 57: 1 with the C.I. paratonere of 5 weight portions.

The production of-toner d-

Adopt the method identical with toner a to obtain Yellow toner (toner d), difference is to replace all carbon blacks of amount with the C.I pigment yellow 180 of 6 weight portions.

Various toners with 6 weight portions mix with the embodiment 1 to 8 of 100 weight portions and the various carriers of Comparative Examples 1 to 6 respectively, with the developer group (1) of the toner that obtains to have four kinds of colors (yellow, magenta, cyan and black) respectively to (14).

＜assessment 〉

Use the transformation apparatus of the DOCU PRINT C1616 that is produced by Fuji Xerox Co., Ltd to carry out following copy test, wherein place developer group (1) respectively to (14), the peripheral speed of magnetic roll sleeve pipe is 350 mm/second.

By copy image on 10000 paper, carry out described copy test at normal temperature and the area coverage of common humidity (22 ℃ and 50%RH) with 0.5%.Assess the 10th (initially) and image color, photographic fog level and the level of fish eyes separately of the copy image on the 10000th paper according to following method.

The concentration appraisal procedure

The repeat print image of the versicolor 2cm of being of a size of * 5cm is measured the concentration of the 10th printed images and the 10000th printed images with reflection of the concentration X-RITE 938 (being produced by X-rite Corp.).The results are shown in table 1, each embodiment that lists in the table 1 and the concentration value of Comparative Examples are represented the concentration value of black, cyan, magenta and yellow image successively.That is, first concentration is the concentration value of black image.

The standard of comprehensive assessment is as follows.

A: for all colours, the ratio of the image color on the image color on the 10000th and the 10th is 97% or greater than 97%.

B: for all colours, the ratio of the image color on the image color on the 10000th and the 10th is 95% or greater than 95%.

C: for all colours, the ratio of the image color on the image color on the 10000th and the 10th is 90% or greater than 90%.

D: at least a for four kinds of colors, the ratio of the image color on the image color on the 10000th and the 10th is less than 90%.

The photographic fog appraisal procedure

Add up every 100cm in the white background part of each image ²The number of toner-particle.

The standard of comprehensive assessment is as follows.

A: do not have toner-particle

B: less than three

C: be no less than three, but less than five

D:6 or the particle more than 6

The appraisal procedure of white point/color spot

The printing area coverage rate is 100% full size image on the paper of A4 size, and statistics white point number.In addition, export another not paper of the A4 size of printed images, and statistics color spot number.

The standard of comprehensive assessment is as follows.

A: do not have white point and color spot

B: total is less than five:

C: total is no less than 5, but is less than 10

D: add up more than 10 or 10.

Comprehensive assessment

The mark of supposing mark A, B, C and D representative in concentration, photographic fog level and each evaluation item of color spot level is respectively 0,1,2 and 3, with whole marks of following criterion evaluation all items add and.Mark A and B are in fact acceptable levels.

A: add and be 3 or less than 3.

B: add and be 4 to 6.

C: add and be 7 to 9.

D: add and be 10 or greater than 10.

The assessment result that is obtained is listed in table 1 and 2.

Table 1

	Gross energy	Peripheral speed (meter per second)	The initial pictures quality			Image quality after the 10000th printing			Comprehensive assessment
			The initial pictures quality			Image quality after the 10000th printing				Density	The photographic fog level	The white point number	Density	The photographic fog level	The white point number
			Embodiment 1	2400	350	1.30 1.41 1.35 1.38	0	0		Density	The photographic fog level	The white point number	Density	The photographic fog level	The white point number	1.28 1.40 1.32 1.38	1	0	A
Embodiment 2	3000	350	Embodiment 1	2400	350	1.30 1.41 1.35 1.38	0	0	1.32 1.39 1.34 1.40	1	1	1.28 1.38 1.32 1.38	1	4	B	1.28 1.40 1.32 1.38	1	0	A
Embodiment 2	3000	350	Embodiment 3	1900	350	1.29 1.35 1.35 1.38	1	1	1.32 1.39 1.34 1.40	1	1	1.28 1.38 1.32 1.38	1	4	B	1.25 1.34 1.35 1.32	1	1	B
Embodiment 4	1500	350	Embodiment 3	1900	350	1.29 1.35 1.35 1.38	1	1	1.33 1.42 1.39 1.42	1	1	1.33 1.37 1.35 1.38	2	1	B	1.25 1.34 1.35 1.32	1	1	B
Embodiment 4	1500	350	Embodiment 5	2300	350	1.31 1.33 1.34 1.34	0	1	1.33 1.42 1.39 1.42	1	1	1.33 1.37 1.35 1.38	2	1	B	1.30 1.33 1.33 1.33	0	1	A
Embodiment 6	1300	350	Embodiment 5	2300	350	1.31 1.33 1.34 1.34	0	1	1.30 1.38 1.38 1.33	0	1	1.29 1.35 1.33 1.32	0	2	A	1.30 1.33 1.33 1.33	0	1	A
Embodiment 6	1300	350	Embodiment 7	1500	350	1.32 1.35 1.38 1.40	1	1	1.30 1.38 1.38 1.33	0	1	1.29 1.35 1.33 1.32	0	2	A	1.31 1.33 1.35 1.35	1	4	B
Embodiment 8	1000	350	Embodiment 7	1500	350	1.32 1.35 1.38 1.40	1	1	1.30 1.30 1.35 1.34	1	1	1.25 1.24 1.30 1.30	2	1	B	1.31 1.33 1.35 1.35	1	4	B

Table 2

	Gross energy	Peripheral speed (meter per second)	The initial pictures quality			Image quality after the 10000th printing			Comprehensive assessment
			The initial pictures quality			Image quality after the 10000th printing			Comprehensive assessment	Density	The photographic fog level	The white point number	Density	The photographic fog level	The white point number
			Comparative Examples 1	3800	350	1.32 1.38 1.36 1.38	1	1	1.18 1.25 1.26 1.24	Density	The photographic fog level	The white point number	Density	The photographic fog level	The white point number		3	10	D
Comparative Examples 2	3500	350	Comparative Examples 1	3800	350	1.32 1.38 1.36 1.38	1	1	1.18 1.25 1.26 1.24	1.30 1.36 1.35 1.38	1	1	1.20 1.27 1.27 1.31	3	7	C	3	10	D
Comparative Examples 2	3500	350	Comparative Examples 3	3100	350	1.29 1.38 1.37 1.36	1	1	1.20 1.29 1.29 1.30	1.30 1.36 1.35 1.38	1	1	1.20 1.27 1.27 1.31	3	7	C	3	5	C
Comparative Examples 4	1400	350	Comparative Examples 3	3100	350	1.29 1.38 1.37 1.36	1	1	1.20 1.29 1.29 1.30	1.33 1.40 1.38 1.36	2	1	1.20 1.30 1.30 1.31	6	1	C	3	5	C
Comparative Examples 4	1400	350	Comparative Examples 5	1600	350	1.31 1.33 1.35 1.35	1	1	1.25 1.21 1.28 1.30	1.33 1.40 1.38 1.36	2	1	1.20 1.30 1.30 1.31	6	1	C	3	6	C
Comparative Examples 6	900	350	Comparative Examples 5	1600	350	1.31 1.33 1.35 1.35	1	1	1.25 1.21 1.28 1.30	1.30 1.39 1.29 1.30	1	1	1.19 1.27 1.20 1.20	7	1	C	3	6	C

Shown in table 1 and 2, when the gross energy (recording under these conditions with powder rheometer) with magnetic-particle and the electrostatic image developing carrier, electrostatic image developing that is positioned at the lip-deep coating of each magnetic-particle is 1500mJ to 3000mJ, maybe when the gross energy (recording under these conditions) that has the Magnaglo discrete particles and be positioned at the carrier of the coating on each particle surface during for 1000mJ to 1500mJ with powder rheometer, flowability is good, therefore, can prevent because photographic fog appears in breaking of carrier, and can prevent the image that powder caused that produces by breaking with lost part because of carrier.In addition, because better mobile, so the transfer printing performance is also better, and image color is enough.

[embodiment 9 to 15 and Comparative Examples 7 to 15]

The production of＜female toner 〉

The production of female toner (21)

Vibrin: 100 mass parts (linear polyester of terephthalic acid (TPA)-bisphenol-A ethylene oxide adduct-cyclohexanedimethanol has 62 ℃ Tg, 12000 Mn and 32000 Mw);

Cyan colorant (C.I. pigment blue 15: 3): 4 mass parts

With the knead potpourri of mentioned component and it is pulverized of extruder, with wind-force formula clasfficiator resulting granules is carried out classification, to obtain the female toner-particle (21) of cyan that mean grain size is 6.2 μ m with jet mill.

The production of＜external additive 〉

Production with toner (21) of external additive

Use the Henschel mixer, the Titanium Dioxide Rutile Top grade of 0.8 weight portion (is handled through positive decyl trimethoxy silane, and have the particle diameter of 20nm and 4.1 proportion) and the silicon dioxide of 1.0 weight portions (make with the vapour-phase oxidation method, handle through silicone oil, and have the particle diameter of 40nm and 2.2 proportion) mixes with the female toner-particles of 100 weight portions (21), have the toner (21) of external additive with acquisition.

Production with toner (22) to (26) of external additive

Adopt toner (22) that the method production identical with the toner with external additive (21) has external additive to (26), difference is, changes the particle diameter of titanium dioxide and silicon dioxide in the table 3 listed numerical value.

Production with toner (27) of external additive

The employing method production identical with the toner a of the embodiment of TOHKEMY 2004-170714 communique has the toner (27) of external additive.

Specifically, produce by following mode.

The production of toner-particle a

The production of particulate resin dispersion (1)

Styrene 370 weight portions

N-butyl acrylate 30 weight portions

Acrylic acid 8 weight portions

Dodecyl mercaptans 24 weight portions

Carbon tetrabromide 4 weight portions

Mix mentioned component to obtain material solution.(NONIPOL 400 for dissolving 6 weight portion non-ionics in 550 parts by weight of deionized water, changing into (strain) by Sanyo produces) and 10 weight portion anionic surfactant (NEOGEN SC, produce by the first industrial pharmacy (strain)) and obtain surfactant solution, material solution is added in the surfactant solution, and in flask, disperse and emulsification.Resulting potpourri was slowly stirred 10 minutes, will in 50 parts by weight of deionized water, dissolve the solution that 4 weight portion ammonium persulfates obtain again and add described potpourri.Behind the air in the nitrogen replacement flask, in oil bath, be heated to 70 ℃ when the content in the flask is stirred, and kept 5 hours, to carry out emulsion polymerization at 70 ℃.Thus, obtain particulate resin dispersion (1).Resin particle in the dispersion liquid has the mean grain size of 155nm, 59 ℃ Tg and 12000 weight-average molecular weight Mw.

The production of particulate resin dispersion (2)

Styrene 280 weight portions

N-butyl acrylate 120 weight portions

Acrylic acid 8 weight portions

Mix mentioned component to obtain material solution.(NONIPOL 400 for dissolving 6 weight portion non-ionics in 550 parts by weight of deionized water, changing into (strain) by Sanyo produces) and 12 weight portion anionic surfactant (NEOGEN SC, produce by the first industrial pharmacy (strain)) and obtain surfactant solution, material solution is added in the surfactant solution, and in flask, disperse and emulsification.Resulting potpourri was slowly stirred 10 minutes, will in 50 parts by weight of deionized water, dissolve 3 weight portion ammonium persulfates again and the solution that obtains adds described potpourri.Behind the air in the nitrogen replacement flask, in oil bath, be heated to 70 ℃ when content stirs in to flask, and kept 5 hours, to carry out emulsion polymerization at 70 ℃.Thus, obtain particulate resin dispersion (2).Resin particle in the dispersion liquid has the mean grain size of 105nm, 53 ℃ Tg and 550000 weight-average molecular weight Mw.

The production of colorant dispersion (1)

Carbon black (MOGUL L is produced by Cabot Corp.) 50 weight portions

Non-ionics (NONIPOL 400, change into (strain) by Sanyo and produce) 5 weight portions

Deionized water 200 weight portions

Use homogenizer (ULTRA TURRAX T50 is produced by IKA Co.) mixes mentioned component and stirred 10 minutes, to obtain colorant dispersion (1), wherein is dispersed with the colorant that mean grain size is 250 μ m (carbon black) particle.

The production of detackifier dispersion liquid (1)

Paraffin (HNP 0190, produced by the smart wax of Japan (strain), and has 85 ℃ fusing point)

50 weight portions

Cationic surfactant (SANISOL B 50 is produced by flower king (strain)) 5 weight portions

Deionized water 200 weight portions

Mentioned component is heated to 95 ℃, stir with homogenizer (ULTRA TURRAX T50 is produced by IKA Co.), and further it is stirred with pressure discharge type homogenizer, to obtain detackifier dispersion liquid (1), wherein be dispersed with the anti-sticking agent particle that mean grain size is 550nm.

The production of agglutination body dispersion liquid

Particulate resin dispersion (1) 120 weight portion

Particulate resin dispersion (2) 80 weight portions

Colorant dispersion (1) 30 weight portion

Detackifier dispersion liquid (1) 40 weight portion

Cationic surfactant (SANISOL B 50 is produced by flower king (strain)) 1.5 weight portions

Usefulness homogenizer in the round flask of being made by stainless steel (ULTRA TURRAX T50 is produced by IKA Co.) mixes mentioned component and stirs.When being stirred, the inclusions in the flask in heater oil is bathed, is heated to 50 ℃.After this, cool off resulting potpourri to 45 ℃, and kept 25 minutes, to obtain the agglutination body dispersion liquid in this temperature.With the agglutination body of observation by light microscope agglutination body dispersion liquid, obtaining its mean grain size is about 5.0 μ m.

The production of attaching particles dispersion liquid

60 parts by weight resin particle dispersions (1) slowly are added to the agglutination body dispersion liquid.Rise to 50 ℃ heater oil in temperature and resulting potpourri is heated in bathing, and this temperature was kept 40 minutes, to obtain the attaching particles dispersion liquid.With the attaching particles of observation by light microscope attaching particles dispersion liquid, obtaining its mean grain size is about 5.8 μ m.

The production of the female particle of toner

3 weight portion anionic surfactants (NEOGEN SC is produced by the first industrial pharmacy (strain)) are added the attaching particles dispersion liquid, and resulting potpourri is put into the flask of being made by stainless steel, seal this flask.With the described potpourri of magnetic seal continuous stirring, meanwhile be heated to 105 ℃, and kept 4 hours in this temperature.After this, cool off this potpourri, and leach reaction product, fully wash, be dried, to obtain the female particle of toner with deionized water.The female particle of this toner has the volume average particle size D of 6.1 μ m ₅₀With 128 shape factor S F1.

The female particle of toner that following external additive (1) and (2) of 1 weight portion are added 100 weight portions respectively.Resulting potpourri was stirred 10 minutes with 30 meter per seconds with the Henschel mixer, and sieve, to remove coarse particle with the screen cloth of 45 μ m sieve meshes.Thus, obtain to have the toner of external additive.

External additive (1)

Needle-like Titanium Dioxide Rutile Top grade particle (volume average particle size and 10 through the processing of decyl silane compound with 15nm ¹³The powder resistance of ohmcm)

External additive (2)

Spherical monodispersive silica particle (volume average particle size and 10 with shape factor S F1,135nm of 105 ¹⁵The powder resistance of ohmcm), described particle is to handle by the silicon dioxide gel that obtains with sol-gel process is carried out HMDS (hexamethyldisilazane), and dry and crushed products and obtaining.

The production of＜carrier 〉

The production of carrier (21)

(production number: EJ-LABO, iron ore mining industry society produces by day) at the classification point of 25 μ m and 45 μ m, (comprises Cu-Zn, and has 4.5g/cm the ferrite particle with the elbow spraying equipment ³Density, the volume average particle size of 35 μ m and 125 shape factor S F1) carry out classification, removing powder and corase meal, thereby obtain the core particles that will be covered.

For the size-grade distribution of the resulting core particles that remains to be covered, at the particle size distribution index (D of coarse particle side _84v/ D _50v) be 1.18, at the particle size distribution index (D of particle side _50P/ D _16P) be 1.20, volume average particle size is 37 μ m, shape factor S F1 is 124.

The toluene solution (solids content is 15 quality %) of 20 mass parts styrene-methyl methacrylates (weight-average molecular weight 80000) is added to the core particles that will be covered of 100 mass parts.With batch (-type) kneading machine resulting potpourri was stirred 10 minutes with 50 liters of capacity and chuck.Gained is mixed stir in, with this mixture heated to 120 ℃ or be higher than 120 ℃ temperature, and kept 20 minutes in this temperature.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.After this, take out resulting lining particle.Under these conditions the lining particle is carried out 3 classifications with the elbow spraying equipment, to remove powder and corase meal.Thus, obtain carrier (21).

For the size-grade distribution of carrier (21), be 1.15 at the particle size distribution index of coarse particle side, be 1.16 at the particle size distribution index of particle side, volume average particle size is 37 μ m, shape factor S F1 is 123.

Measure the gross energy of carrier (21) in the above described manner with POWDER RHEOMETER FT4 (producing) by Freeman Technology.Concrete measuring method is as described below.

At first, aid is connected to the upper end that capacity is the 160ml container.Put carrier (21) into this container until overflow container.Then, the container that carrier (21) will be housed is arranged in the measurement mechanism, and will be arranged on the container top by the rotation oar (propeller-type blade as shown in Figure 3 has 48 mm dias and 210 millimeters width) that Freeman Technology produces.Rotation oar terminal velocity with-5.0 ° of entering angles and 60 mm/second is adjusted processing, repeats four times.

Subsequently, make by adjusting the carrier (21) of handling and fully outgasing to flush, and the capacity of being transferred to is the container of 200ml with container head.To rotate oar with the rotation oar terminal velocity of the air-flow of 10 ml/min ,-10.0 ° entering angle and 100 mm/second from upper surface and be moved downward to position (entering 70 millimeters of (moving) length) apart from the height of 10 millimeters of container bottoms.With the moment of torsion integrated value that obtained as gross energy.The gross energy of carrier (21) is 2170mJ.

The production of carrier (22) and (23)

Adopt the method identical with carrier (21) to produce carrier (22) to (23), difference is, handles the multiplicity of operation that is coated with the carrier of resin with acquisition for the removal of carrying out powder/corase meal with the elbow spraying equipment, changes into 2 to 5 times from 3 times.The gross energy separately of carrier (22) and (23) is listed in table 3.

The production of carrier (24)

With the classification point of elbow spraying equipment the ferrite particle (is comprised Cu-Zn, and has 4.5g/cm at 22 μ m and 45 μ m ³Density, the volume average particle size of 35 μ m and 120 shape factor S F1) carry out classification, removing powder and corase meal, thereby obtain the core particles that will be covered.

For the size-grade distribution of the core particles that remains to be covered that obtains, be 1.18 at the particle size distribution index of coarse particle side, be 1.20 at the particle size distribution index of particle side, volume average particle size is 37 μ n, shape factor S F1 is 118.

(preceding a kind of monomer is 80/20 with the copolymerization ratio of a kind of monomer in back with the methyl methacrylate-acrylic acid perfluoro hexyl ester copolymer of 60 mass parts, weight-average molecular weight is 50000, changes into society by Sanyo and produces) toluene solution (solids content is 5 quality %) and the core particles that will be covered of toluene solution (solids content is 15 quality %) adding 100 mass parts of the styrene-methylmethacrylate copolymer (weight-average molecular weight 80000) of 10 mass parts.With batch (-type) kneading machine resulting potpourri was stirred 10 minutes with 50 liters of capacity and chuck.When being stirred, described potpourri, and kept 20 minutes in this temperature with this mixture heated to 120 ℃ or greater than 120 ℃ temperature.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.After this, take out resulting lining particle, and be that the screen cloth of 75 μ m sieves, to remove coarse particle with the aperture.Thus, obtain carrier (24).The gross energy of carrier (24) is listed in table 3.

The production of carrier (25)

Methyl methacrylate-acrylic acid perfluoro hexyl ester copolymer 10 mass parts

With pressurization kneading machine fusion and mix mentioned component, and with turbo-mill and annealing device with its pulverizing and make sphere.Further, at the classification point of 22 μ m and 45 μ m resulting granules is carried out 4 classifications, to obtain carrier (25) with the elbow spraying equipment.

For the size-grade distribution of carrier (25), be 1.17 at the particle size distribution index of coarse particle side, be 1.19 at the particle size distribution index of particle side, volume average particle size is 33 μ m, and shape factor S F1 is 110, and density is 3.5g/cm ³The gross energy of carrier (25) is listed in table 3.

The production of carrier (26)

Adopt the method identical with carrier (25) to produce carrier (26), difference is the multiplicity that classification is handled is changed into 3 times.The gross energy of carrier (26) is listed in table 3.

The production of carrier (27)

Adopt the method identical to produce carrier (27) with carrier (25), difference is to change the amount of styrene-propene butyl acrylate copolymer (80/20) into 30 mass parts, and changes the amount of methyl methacrylate-acrylic acid perfluoro hexyl ester copolymer into 20 mass parts.The gross energy of carrier (27) is listed in table 3.

The production of carrier (28)

Adopt the method identical with carrier (21) to produce carrier (28), difference is, will be injected in the multiplicity that the same hierarchical point carries out the removal operation of powder/corase meal with elbow and change into once.The gross energy of carrier (28) is listed in table 3.

The production of carrier (29)

With the elbow spraying equipment ferrite particle (is comprised Cu-Zn, and has 4.5g/cm ³Density, the volume average particle size of 35 μ m and 110 shape factor S F1) carry out classification, removing powder and corase meal, thereby obtain the core particles that will be covered.For the size-grade distribution of the core particles that remains to be covered that obtains, be 1.18 at the particle size distribution index of coarse particle side, be 1.20 at the particle size distribution index of particle side, volume average particle size is 37 μ m, shape factor S F1 is 109.

The core particles that will be covered with toluene solution (solids content is 15 quality %) adding 100 mass parts of the toluene solution (solids content is 5 quality %) of the methacrylic acid perfluoro hexyl ester-methylmethacrylate copolymer of 60 mass parts (weight-average molecular weight is 50000, changes into society by Sanyo and produces) and 10 mass parts styrene-methylmethacrylate copolymers (weight-average molecular weight is 75000).Stirred the potpourri obtain 10 minutes with batch (-type) kneading machine with 50 liters of capacity and chuck.When described potpourri is stirred,, and kept 20 minutes in this temperature with described mixture heated to 120 ℃ or greater than 120 ℃ temperature.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.Thus, obtain carrier (29).The gross energy of carrier (29) is listed in table 3.

The production of carrier (30)

The carrier of the embodiment 1 of-TOHKEMY 2002-328493 communique-

The employing method production identical with the carrier of the embodiment 1 of TOHKEMY 2002-328493 communique has the carrier (30) of Magnaglo discrete particles as core.Its production method is identical with the Comparative Examples 5 of this instructions.The gross energy of carrier (30) is listed in table 3.

The production of carrier (31)

Adopt the method identical with carrier (27) to produce carrier (31), difference is, changes the amount of styrene-propene acid butyl ester (80/20) multipolymer and perfluorinated acrylate multipolymer into 15 mass parts and 25 mass parts respectively.The gross energy of carrier (31) is listed in table 3.

The production of carrier (32)

Adopt the identical method production carrier of describing among the embodiment with TOHKEMY 2004-170714 communique (32) of carrier (I).Specifically, produce by following mode.

The production of coated with resin A

In toluene, pass through solution polymerization process as solvent, making 38 parts by weight of methylmethacrylate, 50 weight portion isobutyl methacrylates, 2 weight portion methacrylic acids and 10 weight portion methacrylic acid perfluoro capryl ethyl ester random copolymerizations, is 52000 coated with resin A with acquisition weight-average molecular weight Mw.

The production of carrier

(Mn-Mg ferrite particle has 4.7g/cm to the ferrite particle ³True specific gravity, the volume average particle size of 40 μ m, the saturation magnetization of 66emu/g and 114 shape factor S F1)

100 weight portion coated with resin A, 1.4 weight portion carbon black (VXC-72, produce by Cabot Corp.) the crosslinked melamine resin particle of 0.12 weight portion (is insoluble to toluene, EPOSTAR S is produced by Japanese catalyst society) 0.3 weight portion

POLYWAX 725 powder (fusing point with 103 ℃, by Toyo-Petrolite Co., Ltd. produces) 0.3 weight portion

Toluene 14 weight portions

Coated with resin A, carbon black and crosslinked melamine resin particle are added toluene, and resulting potpourri is stirred, to make resin-coated layer formation solution with sand mill.This solution and ferrite particle are put into vacuum outgas type kneading machine, and stirred 10 minutes at 60 ℃.Then, reduce internal pressure, with distillation and remove toluene, thereby on the surface of ferrite particle, form resin-coated layer.After this, POLYWAX 725 powder are added to the lining particle, and resulting potpourri were stirred 10 minutes at 110 ℃.Then, be that the net of 75 μ m sieves the described particle that is coated with resin-coated layer with size of mesh, to obtain carrier (32).The lining rate of resin-coated layer is 95%.The gross energy of carrier (34) is listed in table 3.

The production of＜developer 〉

The production of developer (21)

The toner (21) that 100 mass parts carriers (21) and 7 mass parts have external additive (1) was mixed 20 minutes with 40rpm with the V-mixer, to produce developer (21).

The production of developer (22) to (36)

Adopt the method identical with developer (21) to produce developer (22) to (36), difference is by changing used carrier shown in the table 3 and having the type of the toner of external additive.

＜assessment 〉

Use with the magnetic roll sleeve pipe peripheral speed of 200 mm/second, is carried out copy test to developer (21) to (36) by the transformation apparatus of the Docu Print Color of Fuji Xerox Co., Ltd's production.

Use is carried out following copy test by the transformation apparatus of the DOCUPRINT COLOR that Fuji Xerox Co., Ltd produces, developer (21) is set to (36) in described transformation apparatus respectively, and the peripheral speed of magnetic roll sleeve pipe is 200 mm/second.

At low temperature with than the area coverage of low humidity (10 ℃ and 15%RH) with 80% copy image on 20000 paper, thereby carry out described copy test.Assess image color separately, photographic fog level and the white point/color spot level of the copy image on the 10th (initially) and the 20000th according to following method.

Development amount (concentration) appraisal procedure

When duplicating has two on the spot during the image of color lump (size that all has 2cm * 5cm), before toner image is transferred to paper, force to stop printing machine, and measure development amount (not being transferred to the toning dosage of paper as yet).Specifically, prepare two adhesive tapes of accurately weighing, and push down two parts that sub-image keeps the developed image (toner image) on the surface respectively, the toner in these two parts is transferred to adhesive tape.Then, accurately take by weighing the weight that transfer printing has the adhesive tape of toner once more.There is the adhesive tape weight of toner to deduct the weight of the adhesive tape that does not comprise toner from transfer printing respectively, and the difference of gained is averaged to obtain the development amount.

Evaluation criteria is as follows.Mark A and B are in fact acceptable levels.

A: the development amount is 4.5 ± 0.5g/m ²

B: the development amount is 4.5 ± 0.6g/m ²

C: the development amount is 4.5 ± 0.75g/m ²

D: the development amount is 4.5 ± 0.75g/m ²Or has a higher deviation

The photographic fog appraisal procedure

In development amount appraisal procedure, when keeping the surface of body (photoreceptor) that toner is transferred to adhesive tape from sub-image, another adhesive tape is pressed in the background parts of developed image, and a described background parts distance color lump in the color lump on the spot is 10 millimeters, and statistics is transferred to every 1cm of adhesive tape ²The toner-particle number.

Evaluation criteria is as follows.Mark A and B are in fact acceptable levels.

A: be less than 50 particles

B: be no less than 50 particles, but be less than 100 particles

C: be no less than 100 particles, but be less than 200 particles

D:200 particle or more than 200 particles

White point/color spot appraisal procedure

The printing area coverage rate is 30% full-scale half tone image on the paper of A3 size, and the number of statistics color spot and white point (lost part of image).

Evaluation criteria is as follows.Mark A and B are in fact acceptable levels.

A: do not have color spot and white point

B: add up to be less than 5 points

C: add up to and be no less than 5 points, but be less than 10 points

D: add up to 10 or more than 10 points.

Comprehensive assessment

The mark of supposing mark A, B, C and D in concentration, photographic fog level and each evaluation item of color spot level is respectively 0,1,2 and 3, with whole marks of following criterion evaluation all items add and.Mark A and B are in fact acceptable levels.

A: describedly add and be 5 or less than 5.

B: describedly add and be 6 or 7.

C: describedly add and be 8 or 9.

D: describedly add and be 10 or greater than 10.

Table 3

	Carrier	The gross energy of carrier	Toner	External additive Ti		External additive Si		Peripheral speed (meter per second)	The initial pictures quality			Image quality after 20000 printings			Comprehensive assessment
				External additive Ti		External additive Si			The initial pictures quality			Image quality after 20000 printings				D50	Weight %	D50	Weight %	Concentration	The photographic fog level	White point	Concentration	The photographic fog level	White point
				Embodiment 9	(21)	2170	(21)		20	0.8	40	1	200	B		D50	Weight %	D50	Weight %	Concentration	The photographic fog level	White point	Concentration	The photographic fog level	White point	A	A	B	B	A	A
Embodiment 10	(23)	1420	(21)	Embodiment 9	(21)	2170	(21)	20	20	0.8	40	1	200	B	0.8	40	1	200	B	B	A	B	C	B	B	A	A	B	B	A	A
Embodiment 10	(23)	1420	(21)	Embodiment 11	(24)	2190	(22)	20	-	-	30	1.5	200	B	0.8	40	1	200	B	B	A	B	C	B	B	A	A	C	B	A	A
Embodiment 12	(22)	2910	(21)	Embodiment 11	(24)	2190	(22)	20	-	-	30	1.5	200	B	0.8	40	1	200	B	A	A	C	B	C	B	A	A	C	B	A	A
Embodiment 12	(22)	2910	(21)	Embodiment 13	(25)	910	(21)	20	20	0.8	40	1	200	B	0.8	40	1	200	B	A	A	C	B	C	B	A	A	B	B	B	A
Embodiment 14	(26)	1190	(23)	Embodiment 13	(25)	910	(21)	15	20	0.8	40	1	200	B	1.2	-	-	200	B	A	A	B	B	C	B	A	A	B	B	B	A
Embodiment 14	(26)	1190	(23)	Embodiment 15	(27)	1340	(21)	15	20	0.8	40	1	200	B	1.2	-	-	200	B	A	A	B	B	C	B	B	A	C	C	B	B
Comparative Examples 7	(28)	3400	(21)	Embodiment 15	(27)	1340	(21)	20	20	0.8	40	1	200	B	0.8	40	1	200	B	A	A	D	D	C	C	B	A	C	C	B	B
Comparative Examples 7	(28)	3400	(21)	Comparative Examples 8	(29)	1330	(21)	20	20	0.8	40	1	200	B	0.8	40	1	200	B	A	A	D	D	C	C	C	A	C	D	D	D
Comparative Examples 9	(21)	2170	(24)	Comparative Examples 8	(29)	1330	(21)	-	20	0.8	40	1	200	B	-	50	2.2	200	B	A	A	C	D	C	C	C	A	C	D	D	D
Comparative Examples 9	(21)	2170	(24)	Comparative Examples 10	(21)	2170	(25)	-	8	1.2	-	-	200	B	-	50	2.2	200	B	A	A	C	D	C	C	B	A	C	C	C	C
Comparative Examples 11	(30)	1450	(22)	Comparative Examples 10	(21)	2170	(25)	-	8	1.2	-	-	200	B	-	30	1.5	200	B	A	A	D	C	D	C	B	A	C	C	C	C
Comparative Examples 11	(30)	1450	(22)	Comparative Examples 12	(31)	840	(23)	-	15	1.2	-	-	200	B	-	30	1.5	200	B	A	A	D	C	D	C	C	A	C	D	C	D
Comparative Examples 13	(25)	910	(26)	Comparative Examples 12	(31)	840	(23)	-	15	1.2	-	-	200	B	-	43	2	200	C	A	A	C	D	D	C	C	A	C	D	C	D
Comparative Examples 13	(25)	910	(26)	Comparative Examples 14	(25)	910	(25)	-	8	1.2	-	-	200	B	-	43	2	200	C	A	A	C	D	D	C	B	A	C	D	D	D
Comparative Examples 15	(32)	4060	(27)	Comparative Examples 14	(25)	910	(25)	15	8	1.2	-	-	200	B	As described in No. 714 communiques of TOHKEMY 2004-170	135	As described in No. 714 communiques of TOHKEMY 2004-170	200	B	C	B	C	D	D	D	B	A	C	D	D	D

As shown in table 3, for the developer that comprises carrier and toner, if the gross energy of contained carrier (recording under these conditions with powder rheometer) is in scope of the present invention, contained toner comprises the external additive with about volume average particle size of 5 to about 40nm, then this developer has good flowability, it can suppress external additive to the adhering to of carrier, and can make electric charge/resistance long term stabilization, and can export high quality images.

Embodiment 16 to 23 and Comparative Examples 16 to 21

The production of＜toner-particle 〉

The production of toner-particle (41)

Vibrin (linear polyester of terephthalic acid (TPA)/bisphenol-A ethylene oxide adduct/cyclohexanedimethanol has 60 ℃ Tg, 3600 Mn, 28000 Mw and 15 acid number)

85 mass parts

Vegetable wax (Brazil wax) 6 mass parts

Si0 ₂Particle (R 972, and by Nippon Aerosil Co., Ltd. produces) 3 mass parts

C.I. pigment blue 15: 36 mass parts

With Henschel mixer abundant mixing said ingredients in advance,, be rolled with its cooling and to it again with its fusion and knead with Banbury mixer, after its precomminution, it is broken with jet mill it to be carried out micro mist.To resulting granules fluidized bed type annealing device SFP-LABO (PowrexCo., Ltd. production) the blade rotating speed with 1 liter/minute dry air amount (the setting drying air temperature is 70 ℃) and 500rpm carries out 60 minutes spheroidization processing, carry out classification with the grader elbow thrower (producing) that utilizes Coanda effect then, thereby obtain being used for the female particle (41) of toner of cyan toner by Matuzaka trade society.

In the female particle of toner (41), its volume average particle size is 6.0 μ m, and particle diameter is 4 μ m or is 5 quantity % less than the female number of particles of the toner of 4 μ m with respect to the ratio of the female number of particles of whole toners, particle diameter is 16 μ m or is 1 volume % greater than the cumulative volume of the female particle of the toner of 16 μ m with respect to the ratio of the cumulative volume of the female particles of whole toners that its shape factor S F1 is 132.

Is the hydrophobic titanium oxide particle (STT30A of 30nm with the female particle of the toner of 100 mass parts with particle diameter as 1.0 mass parts of external additive with Henschel mixer, produce by Titan KogyoK.K.) and the particle diameter of 1.0 mass parts be the hydrophobic silica particles (RX50 of 40nm, by Nippon Aerosil Co., Ltd. produce) mix, to produce toner-particle (41).

The production of toner-particle (42)

The employing method identical with the female particle of toner (41) produced the female particle (42) of toner, and difference is the spheroidization that particle carried out 90 minutes is handled (other condition of the spheroidization processing of particle is identical with the condition in producing the female particle of toner (41)).

In the female particle of toner (42), its volume average particle size is 5.9 μ m, particle diameter is 4 μ m or is 4.9 quantity % less than the female number of particles of the toner of 4 μ m with respect to the ratio of the female number of particles of whole toners, particle diameter is 16 μ m or is 1.1 volume % greater than the cumulative volume of the female particle of the toner of 16 μ m with respect to the ratio of the cumulative volume of the female particles of whole toners that its shape factor S F1 is 128.

Adopt the method identical with toner-particle (41) to produce toner-particle (42), difference is the female particle of toner (42) as the particle that mixes with external additive, to replace the female particle (41) of toner.

The production of toner-particle (43)

The employing method identical with the female particle of toner (41) produced the female particle (43) of toner, and difference is the spheroidization that particle carried out 30 minutes is handled (other condition of the spheroidization processing of particle is identical with the condition in producing the female particle of toner (41)).

In the female particle of toner (43), its volume average particle size is 6.1 μ m, particle diameter is 4 μ m or is 5.1 quantity % less than the female number of particles of the toner of 4 μ m with respect to the ratio of the female number of particles of whole toners, particle diameter is 16 μ m or is 1 volume % greater than the cumulative volume of the female particle of the toner of 16 μ m with respect to the ratio of the cumulative volume of the female particles of whole toners that its shape factor S F1 is 139.

Adopt the method identical with toner-particle (41) to produce toner-particle (43), difference is the female particle of toner (43) as the particle that mixes with external additive, to replace the female particle (41) of toner.

The production of toner-particle (44)

The employing method identical with the female particle of toner (41) produced the female particle (44) of toner, and difference is the spheroidization that particle carried out 5 minutes is handled (other condition of the spheroidization processing of particle is identical with the condition in producing the female particle of toner (41)).

In the female particle of toner (44), its volume average particle size is 5.1 μ m, particle diameter is 4 μ m or is 5.1 quantity % less than the female number of particles of the toner of 4 μ m with respect to the ratio of the female number of particles of whole toners, particle diameter is 16 μ m or is 4.9 volume % greater than the cumulative volume of the female particle of the toner of 16 μ m with respect to the ratio of the cumulative volume of the female particles of whole toners that its shape factor S F1 is 146.

Adopt the method identical with toner-particle (41) to produce toner-particle (44), difference is the female particle of toner (44) as the particle that mixes with external additive, to replace the female particle (41) of toner.

The production of＜carrier 〉

The production of carrier (41)

(manganese magnesium ferrite particle has 4.5g/cm to the ferrite particle with elbow thrower (EJ-LABO, iron ore mining industry society produces by day) ³True specific gravity, the volume average particle size of 35 μ m and 125 shape factor S F1) carry out classification, removing powder and corase meal, thereby obtain the core particles that will be covered.

(the copolymerization ratio of preceding a kind of monomer and latter's monomer is 20/80 with 20 mass parts styrene-methylmethacrylate copolymers, weight-average molecular weight is 80000, by Mitsubishi Rayon Co., Ltd. produces) toluene solution (solids content is 15 quality %) add the core particles that will be covered of 100 mass parts.With batch (-type) kneading machine resulting potpourri was stirred 10 minutes with 50 liters of capacity and chuck.When described potpourri is stirred, with this mixture heated to 120 ℃ or be higher than 120 ℃ temperature, and kept 20 minutes in this temperature.Then, cooling is reduced to 60 ℃ just in stirred mixture up to its temperature.After this, take out resulting lining particle.With the elbow spraying equipment particle that is covered is carried out 3 classifications, to remove powder and corase meal.Thus, obtain carrier (41).

For the size-grade distribution of carrier (41), be 1.15 at the particle size distribution index of coarse particle side, be 1.16 at the particle size distribution index of particle side, volume average particle size is 37 μ m, shape factor S F1 is 123.

Measure the gross energy of carrier (41) in the above described manner with POWDER RHEOMETER FT4 (producing) by Freeman Technology.Concrete measuring method is as described below.

At first, aid is connected to the upper end that capacity is the 160ml container.Put carrier (41) into container until overflow container.Then, the container that carrier (41) will be housed is arranged in the measurement mechanism, and will be arranged on the container top by the rotation oar (propeller-type blade as shown in Figure 3 has 48 mm dias and 10 millimeters width) that Freeman Technology produces.Rotation oar terminal velocity with-5.0 ° entering angles and 60 mm/second is adjusted processing, repeats four times.

Subsequently, making by adjusting processing fully, the carrier (41) of the degassing flushes with container head.To rotate oar with the rotation oar terminal velocity of-5.0 ° entering angles and 100 mm/second from upper surface and be moved downward to position (entering (moving) length is 70 millimeters) apart from the height of 10 millimeters of container bottoms.With the moment of torsion integrated value that obtains as gross energy.The gross energy of carrier (41) is 2400mJ (mean value).

The production of carrier (42) and (43)

Adopt the method identical with carrier (1) to produce carrier (42) and (43), difference is that the multiplicity that powder/corase meal removal is handled that will be used for the coated with resin carrier changes twice (carrier 42) or four times (carrier 43) into from three times.Carrier (42) and (43) gross energy are separately listed in table 4.

The production of carrier (44)

Styrene-propene butyl acrylate copolymer (80/20) (have 190000 weight-average molecular weight, by Mitsubishi Rayon Co., Ltd. produces) 30 mass parts

Perfluorinated acrylate copolymer 10 mass parts

With pressurization kneading machine fusion and mixing said ingredients, and with turbo-mill and annealing device with its pulverizing and make sphere.Spray clasfficiator with elbow resulting granules is advanced four classifications, to obtain carrier (44).

For the size-grade distribution of carrier (44), be 1.17 at the particle size distribution index of coarse particle side, be 1.19 at the particle size distribution index of particle side, volume average particle size is 33 μ m, and shape factor S F1 is 110, and true specific gravity is 3.5g/cm ³The gross energy of carrier (44) is listed in table 4.

The production of carrier (45)

Adopt the method identical with carrier (44) to produce carrier (45), difference is the multiplicity that classification is handled is changed into three times.The gross energy of carrier (45) is listed in table 4.

The production of carrier (46)

Adopt the method identical with carrier (44) to produce carrier (46), difference is to change the amount of styrene-propene butyl acrylate copolymer (80/20) into 30 mass parts, and changes the amount of perfluorinated acrylate multipolymer into 20 mass parts.The gross energy of carrier (46) is listed in table 4.

The production of comparison vehicle (47)

Ferrite particle (manganese magnesium ferrite particle has the true specific gravity of 4.5g/cm3, the volume average particle size of 35 μ m and 125 shape factor S F1) is not carried out classification.The ferrite particle that the toluene solution (solids content is 15 quality %) of 20 mass parts styrene-methacrylate copolymers is added 100 mass parts.With capacity is that 50 liters and batch (-type) kneading machine with chuck stir resulting potpourri 10 minutes.When described potpourri is stirred, with this mixture heated to 120 ℃ or be higher than 120 ℃ temperature, and kept 20 minutes in this temperature.Then, cooling is reduced to 60 ℃ just in stirred mixture until its temperature., take out resulting lining particle, and be that the screen cloth of 75 μ m sieves, to remove coarse particle with the aperture thereafter.Thus, obtain comparison vehicle (47).

The gross energy of carrier (47) is 3800mJ.

The production of comparison vehicle (48)

Adopt the method production comparison vehicle (48) identical with carrier (41), difference is, will spray powder/corase meal that clasfficiator carries out with elbow and remove the multiplicity of handling and change into six times from three times.The gross energy of comparison vehicle (48) is listed in table 4.

The production of comparison vehicle (49)

Adopt the method identical with carrier (46) to produce carrier (49), difference is to change the amount of styrene-propene butyl acrylate copolymer (80/20) into 15 mass parts, and changes the amount of perfluorinated acrylate multipolymer into 25 mass parts.The gross energy of carrier (49) is listed in table 4.

The production of comparison vehicle (50)

Adopt the method production comparison vehicle (50) identical with carrier (44), difference is, changes the amount of magnetic iron ore (EPT-1000, society produces by the industry of field, family) into 120 mass parts, and classification handled repeat 3 times.The gross energy of comparison vehicle (50) is listed in table 4.

The production of comparison vehicle (51)

Adopt the identical method production comparison vehicle (51) of carrier of description among the embodiment 1 with Japanese kokai publication hei 11-133672 communique.

Specifically, production method is as described below.

With wet ball mill with 23 moles of %Li ₂O ₃With 77 moles of %Fe ₂O ₃Pulverizing also mixed 3 hours, was dried again., this potpourri at 900 ℃ kept 2 hour,, product was pulverized 3 hours, to obtain slurry with bowl mill so that this potpourri is carried out roasting in advance thereafter.Spreading agent and bonding agent are added to slurry, and with spray dryer with resulting potpourri granulation and drying.1200 ℃ with resulting granules roasting 3 hours, to obtain the ferrite core particles, this particle has the volume average particle size of 60 μ m.

Then, the silicone resin (solids content is 50%) and the 0.2 weight portion gamma-amino propyl trimethoxy silicane of 100 weight portions are added toluene (solvent), and the segment of being represented by following general formula (I) in the described silicone resin is 2/98 with respect to the ratio of the segment of being represented by following general formula (II).The solution and the ferrite core particles that obtain are put into fluidized bed, so that with this solution of 0.5 weight % described ferrite core particles that is covered.170 ℃ of lining particle roastings that will obtain 2 hours.With the speed of V-Mixer the particle of 600 grams through roasting stirred 60 minutes, to obtain carrier (51) with 30rpm.

The gross energy of carrier (51) is 3900.

General formula (I) general formula (II)

In this comparison vehicle, general formula (I) and (II) in R ⁵To R ⁸It is methyl.

[embodiment 16]

The production of developer (41)

The V-Mixer that with useful capacity is 2 liters mixes the carrier (41) of 100 mass parts and the toner-particle (41) of 7 mass parts 20 minutes with the speed of 40rpm, thereby obtains developer (41).

[embodiment 17 and 18]

The production of developer (42) and (43)

Adopt the method identical with developer (41) to produce developer (42) and (43), difference is, uses toner-particle (42) and (43) to replace toner-particle (41) respectively.

[embodiment 19 to 23]

The production of developer (44) to (48)

Adopt the method identical with developer (41) to produce developer (44) to (48), difference is, uses carrier (42) to (46) to replace carrier (41) respectively.

[Comparative Examples 16]

Contrast developer's (49) production

Adopt the method identical with developer (41) to produce developer (49), difference is, uses contrast toner-particle (49) to replace toner-particle (41).

[embodiment 17 to 21]

Contrast developer's (50) to (54) production

Adopt the method identical with developer (41) to produce contrast developer (50) to (54), difference is to use respectively comparison vehicle (47) to (51) to replace carrier (41).

＜assessment 〉

Use is carried out copy test by the transformation apparatus of the DOCUPRINT COLOR that Fuji Xerox Co., Ltd produces, various developers (41) to (54) are arranged in this transformation apparatus, it is 420 mm/second that sub-image keeps the peripheral speed of body, and the peripheral speed of developer carrier to keep the ratio of the peripheral speed of body with respect to sub-image be 1.75.

By copy image on 20000 paper carries out described copy test at low temperature and the area coverage of low humidity (10 ℃ and 15%RH) with 80%.Adopt with embodiment 9 in identical mode assess image color separately, photographic fog level and the white point/color spot level of the copy image on the 10th (initially) and the 20000th.

Table 4

	Toner		Carrier			The initial pictures quality			Image quality after 20000 printings
	Toner		Carrier			The initial pictures quality			Image quality after 20000 printings			Numbering	Shape factor S F1	Numbering	Core	The gross energy of carrier	Concentration	The photographic fog level	White point	Concentration	The photographic fog level	White point
	Embodiment 16	(41)	132	(41)	The ferrite particle	2400	A	A	A	A	A	Numbering	Shape factor S F1	Numbering	Core	The gross energy of carrier	Concentration	The photographic fog level	White point	Concentration	The photographic fog level	White point	A
Embodiment 17	Embodiment 16	(41)	132	(41)	The ferrite particle	2400	A	A	A	A	A	(42)	128	(41)	The ferrite particle	2400	A	A	A	B	B	A	A
Embodiment 17	Embodiment 18	(43)	139	(41)	The ferrite particle	2400	A	A	A	A	A	(42)	128	(41)	The ferrite particle	2400	A	A	A	B	B	A	B
Embodiment 19	Embodiment 18	(43)	139	(41)	The ferrite particle	2400	A	A	A	A	A	(41)	132	(42)	The ferrite particle	3000	A	A	A	A	B	B	B
Embodiment 19	Embodiment 20	(41)	132	(43)	The ferrite particle	1500	A	A	A	B	A	(41)	132	(42)	The ferrite particle	3000	A	A	A	A	B	B	A
Embodiment 21	Embodiment 20	(41)	132	(43)	The ferrite particle	1500	A	A	A	B	A	(41)	132	(44)	The Magnaglo discrete particles	1300	A	A	A	A	B	A	A
Embodiment 21	Embodiment 22	(41)	132	(45)	The Magnaglo discrete particles	1500	A	A	A	B	B	(41)	132	(44)	The Magnaglo discrete particles	1300	A	A	A	A	B	A	B
Embodiment 23	Embodiment 22	(41)	132	(45)	The Magnaglo discrete particles	1500	A	A	A	B	B	(41)	132	(46)	The Magnaglo discrete particles	1000	A	A	A	B	B	A	B
Embodiment 23	Comparative Examples 16	(44)	146	(41)	The ferrite particle	2400	A	A	A	B	B	(41)	132	(46)	The Magnaglo discrete particles	1000	A	A	A	B	B	A	C
Comparative Examples 17	Comparative Examples 16	(44)	146	(41)	The ferrite particle	2400	A	A	A	B	B	(41)	132	(47)	The ferrite particle	1300	A	A	A	C	B	B	C
Comparative Examples 17	Comparative Examples 18	(41)	132	(48)	The ferrite particle	3800	A	A	A	B	B	(41)	132	(47)	The ferrite particle	1300	A	A	A	C	B	B	C
Comparative Examples 19	Comparative Examples 18	(41)	132	(48)	The ferrite particle	3800	A	A	A	B	B	(41)	132	(49)	The Magnaglo discrete particles	900	B	B	B	C	C	B	C
Comparative Examples 19	Comparative Examples 20	(41)	132	(50)	The Magnaglo discrete particles	1700	A	A	A	B	C	(41)	132	(49)	The Magnaglo discrete particles	900	B	B	B	C	C	B	C
Comparative Examples 21	Comparative Examples 20	(41)	132	(50)	The Magnaglo discrete particles	1700	A	A	A	B	C	(41)	132	(51)	Carrier described in the embodiment 1 of Japanese kokai publication hei 11-133672 communique	3900	B	B	A	C	D	C	C

As shown in table 4, for the developer that all comprises carrier and toner, when its contained carrier is 1500mJ to 3000mJ with the gross energy that powder rheometer records under these conditions for comprising the carrier of magnetic-particle as core, for comprising the carrier of Magnaglo discrete particles as core is 1000mJ to 1500mJ, and its contained toner has 140 or during less than 140 average shape factor SF1, the peeling off of resin coating layer that can suppress carrier, electric charge/resistance long term stabilization can be made, and high quality image can be exported.

Claims

1. electrostatic image developing carrier, electrostatic image developing, described carrier comprises the coating as the surface of the magnetic-particle of core and this magnetic-particle of lining, wherein, when measuring with-5 ° rotation oar entering angle with the rotation oar terminal velocity of 100 mm/second with powder rheometer, the gross energy of a part of carrier is 1500mJ to 3000mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

2. electrostatic image developing carrier, electrostatic image developing as claimed in claim 1, wherein, volume average particle size D _84vWith volume average particle size D _50vBetween ratio be 1.20 or less than 1.20, number average bead diameter D _50PWith number average bead diameter D _16PBetween ratio be 1.25 or less than 1.25.

3. electrostatic image developing carrier, electrostatic image developing as claimed in claim 1, wherein, the density of described core is 3.0g/cm ³To 8.0g/cm ³

4. electrostatic image developing carrier, electrostatic image developing as claimed in claim 1 wherein, comprises matrix resin in the described coating, and the content of described matrix resin is 0.5 quality % to 10 quality % with respect to the general assembly (TW) of described carrier.

5. electrostatic image developing carrier, electrostatic image developing as claimed in claim 1, wherein, the shape factor S F1 of described carrier is that 100 (containing 100) are to 130 (containing 130).

6. electrostatic image developing carrier, electrostatic image developing as claimed in claim 1, wherein, the saturation magnetization of described carrier is 40emu/g or greater than 40emu/g.

7. electrostatic image developing carrier, electrostatic image developing as claimed in claim 1, wherein, the volume resistance of described carrier is 1 * 10 ⁸Ohmcm to 1 * 10 ¹⁴Ohmcm.

8. developer for static charge image development, described developer comprises electrostatic image developing toner and electrostatic image developing carrier, electrostatic image developing, wherein, described electrostatic image developing toner comprises the female particle of toner, the female particle of described toner all comprises adhesive resin and colorant, and have 140 or less than 140 average shape factor SF1, and described electrostatic image developing carrier, electrostatic image developing comprises the coating as the surface of the magnetic-particle of core and the described magnetic-particle of lining, and when measuring with the rotation oar entering angle of the rotation oar terminal velocity of 100 mm/second and-5 ° with powder rheometer, the gross energy of a part of carrier is 1500mJ to 3000mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

9. developer for static charge image development that comprises toner and carrier at least, wherein, described toner comprises adhesive resin, colorant, with volume average particle size be the external additive of 10nm to 40nm, described carrier comprises the coating as the magnetic-particle of core and this magnetic-particle surface of lining at least, and, with the air-flow of powder rheometer with 10 ml/min, when the rotation oar terminal velocity of 100 mm/second and-10 ° rotation oar entering angle are measured, the gross energy of a part of carrier is 1420mJ to 2920mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

10. formation method, this method comprises: keep body to charge to sub-image, charged described sub-image is kept the body exposure, so that keep forming electrostatic latent image on the body at described sub-image, make described latent electrostatic image developing with the developer that comprises toner and carrier, forming toner image, and keep body to be transferred to recording materials from described sub-image described toner image; Wherein, described carrier comprises the described electrostatic image developing carrier, electrostatic image developing of claim 1, and in described development, developer carrier is provided, this supporting body keeps body towards described sub-image, maintain described developer on this supporting body surface, and this supporting body thereby being sent to described sub-image, described developer keeps body with the peripheral speed rotation of 200 mm/second to 600 mm/second.

11. an imaging device, this device comprises: sub-image keeps body; Charhing unit, this charhing unit are used for keeping body to charge to described sub-image; Exposing unit, this exposing unit are used for charged described sub-image is kept the body exposure, so that keep forming electrostatic latent image on the body at described sub-image; Developing cell, this developing cell are used to use developer to make described latent electrostatic image developing to form toner image; Transfer printing unit, this transfer printing unit are used for keeping body to be transferred to recording materials from described sub-image described toner image; Wherein, described developer comprises the described electrostatic image developing carrier, electrostatic image developing of claim 1.

12. electrostatic image developing carrier, electrostatic image developing, this carrier comprises the coating as core Magnaglo discrete particles and the described Magnaglo discrete particles of lining surface, wherein, when measuring with-5 ° rotation oar entering angle with the rotation oar terminal velocity of 100 mm/second with powder rheometer, the gross energy of a part of carrier is 1000mJ to 1500mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

13. electrostatic image developing carrier, electrostatic image developing as claimed in claim 12, wherein, volume average particle size D _84vWith volume average particle size D _50vBetween ratio be 1.20 or less than 1.20, number average bead diameter D _50PWith number average bead diameter D _16PBetween ratio be 1.25 or less than 1.25.

14. electrostatic image developing carrier, electrostatic image developing as claimed in claim 12, wherein, the density of described core is 2.0g/cm ³To 5.0g/cm ³

15. electrostatic image developing carrier, electrostatic image developing as claimed in claim 12, wherein, the saturation magnetization of described carrier is 40emu/g or is higher than 40emu/g.

16. electrostatic image developing carrier, electrostatic image developing as claimed in claim 12, wherein, the volume resistance of described carrier is 1 * 10 ⁸Ohmcm to 1 * 10 ¹⁴Ohmcm.

17. electrostatic image developing carrier, electrostatic image developing as claimed in claim 12, wherein, the content of Magnaglo is 30 quality % to 95 quality % in the described Magnaglo discrete particles.

18. developer for static charge image development that comprises electrostatic image developing toner and electrostatic image developing carrier, electrostatic image developing, wherein, described electrostatic image developing toner comprises the female particle of toner, the female particle of described toner all comprises adhesive resin and colorant, and have 140 or less than 140 average shape factor SF1, described electrostatic image developing carrier, electrostatic image developing comprises the coating as the surface of the Magnaglo discrete particles of core and the described magnetic-particle of lining, and, when measuring with-5 ° rotation oar entering angle with the rotation oar terminal velocity of 100 mm/second with powder rheometer, the gross energy of a part of carrier is 1000mJ to 1500mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

19. developer for static charge image development that comprises toner and carrier at least, wherein, described toner comprises adhesive resin, colorant, with volume average particle size be the external additive of 5nm to 40nm, described carrier comprises the coating as the Magnaglo discrete particles of core and this Magnaglo discrete particles surface of lining at least, and, with the air-flow of powder rheometer with 10 ml/min, when the rotation oar terminal velocity of 100 mm/second and-10 ° rotation oar entering angle are measured, the gross energy of a part of carrier is 890mJ to 1390mJ in the measuring vessel, and this part carrier is the carrier that comprises in the zone of filling between the planes surperficial and 70 millimeters places under this filling surface.

20. a formation method, this method comprises: keep body to charge to sub-image; Charged described sub-image is kept the body exposure, so that keep forming electrostatic latent image on the body at described sub-image; Make described latent electrostatic image developing with the developer that comprises toner and carrier, to form toner image; And keep body to be transferred to recording materials from described sub-image the described toner image; Wherein, described carrier comprises the described electrostatic image developing carrier, electrostatic image developing of claim 12; And in described development, developer carrier is provided, this supporting body keeps body towards described sub-image, and maintain described developer on this supporting body surface, and this supporting body keeps body with the peripheral speed rotation of 200 mm/second to 600 mm/second thereby described developer is sent to described sub-image.