CN101556442B - Method and device for manufacturing toner, and toner manufactured by method - Google Patents

Abstract

The invention relates to a method and a device for manufacturing a toner by particle spraying, and the toner manufactured by the particle spraying method. Aiming at the problems that because the priorart only can use a piezoelectric body to spray liquid drops from a nozzle, the liquid drop spraying dose per hour is little, and the production efficiency is low, the invention proposes the solutionas follows: a film (12) with a plurality of nozzles (11) and a vibration device (13) enabling the film (12) to vibrate are adopted to form a liquid drop nozzle unit (2), wherein the vibration device (13) comprises a vibration generating device (21) for generating vibration and an amplitude amplifying device (22) for amplifying amplitude; and after the toner component liquid which at least contains resin and colorant is dripped, the dripped liquid drops are sprayed from the nozzles (11) through the vibration of the film (12).

Description

The manufacturing approach of toner and manufacturing installation and the toner made from this method

Technical field

The present invention relates to the manufacturing approach of toner, the manufacturing installation and the toner of toner, relate in particular to the method for preparing toner of making toner with the particulate gunite and apparatus for producing toner and with the toner of particulate gunite manufacturing.

Background technology

In the developing process of electronic photo, electrostatic recording, xeroprinting etc.; The developer that is used for developing electrostatic charge image is fixed on paper through following operation; Such as; Carry and put the body iseikonia and carry the developer of putting on the body in case be attached to the electrostatic latent image that forms electrostatic charge image, in transfer printing process from electrostatic latent image carry put body and be transferred on the transfer medium such as transfer paper after, in the photographic fixing operation, be fixed on the paper.At this moment; As carrying the sub-image of putting body and carry the developer that the electrostatic charge image on the face of putting develops to being formed on electrostatic latent image; Known two compositions of being made up of carrier and toner are developer; And the single composition developer that does not need carrier, this list composition developer comprises magnetic color tuner and nonmagnetic toner.

In the past; The dry toner that is widely used in electronic photo, electrostatic recording and xeroprinting etc. has so-called crush type toner; Such as being phenylethylene resin series, polyester based resin etc., this crush type toner is that toner adhesive is soluble and fused with colorant etc. and integrates stirring micro mist is broken and form again in addition.

Recently, there are the employing of discussion suspension polymerization and emulsion polymerization coagulation to make toner, promptly so-called aggretion type toner.In addition, also have, be called the macromolecule dissolution suspension method such as open the disclosed manufacturing approach that volumetric contraction takes place of following in the flat 7-152202 communique patent documentation 1 spy.After this method is disperseed toner materials and is dissolved in the volatile solvent such as lower boiling organic solvent,, remove volatile solvent subsequently, obtain toner this solution emulsification and droplet treatment in having the water solvent of spreading agent.This method is different with suspension polymerization and emulsion polymerization coagulation; The resin that can be applied to this method has versatility widely; Especially can use vibrin, be effective on the transparency in the panchromatic processing, the characteristic requirements such as image smoothing property after the photographic fixing very superior.

But; Above-mentioned aggretion type toner is the polymerization prerequisite to use spreading agent in the water solvent, like this, the disadvantageous spreading agent of toner charged characteristic is able to remain in toner surface; The accident that is unfavorable for environment stability etc.; And need remove this spreading agent with a large amount of water, therefore, the difficult difficulty of the manufacturing approach of aggretion type toner has become gratifying manufacturing approach.

On the other hand, according to patent documentation 2 special public clear 57-201248 communiques, spray drying process is arranged about not using the method for preparing toner of water solvent, knowing in the past.This method is used various sprayers, sprays after melting liquid or the toner components solution of dissolving toner components is formed particulate, and carries out drying, obtains particulate thus, and the discomfort because of using the WS to cause so just can not take place.

Yet, use the particulate of spray particles method for making gained in the past thicker, and size distribution is wide, this becomes the reason of toner characteristic variation.

To this, No. 3786034 communique of the special permission of patent documentation 3 proposes to utilize piezoelectricity pulse shaping fine droplet, and then is dried the method and apparatus that solidify to form toner, is used to replace above-mentioned method for preparing toner.In No. 3786035 communiques of special permission of patent documentation 4, also further proposed to utilize the thermal expansion in the nozzle to form fine drop, and then be dried the manufacturing approach that solidify to form toner.

Yet there are following problem in above-mentioned patent documentation 3 and 4 described method for preparing toner and manufacturing installation, promptly can only use piezoelectrics liquid droplets from a nozzle, and the amount of droplets of per hour spraying is few, and production efficiency is low.

To this, the inventor proposes following toner particle fabrication scheme in the TOHKEMY 2006-293320 of patent documentation 5 communique.That is, cause vibration, make nozzle spray the drop of toner constituent liquid, and solidify this liquid formation toner particle with certain frequency by the piezoelectrics of vibration generating arrangement are flexible.In the TOHKEMY 2006-297325 of patent documentation 6 communique, also advise following fabrication scheme in addition.That is, have the injecting-unit of spray-hole and this spray-hole is applied the vibrating device of assigned frequency vibration,, make drop spray, with after dry solidification forms toner particle from spray-hole through as vibrating mass it being vibrated injecting-unit.

But; Structure described in patent documentation 5 is about to nozzle periphery portion in the face of piezoelectrics, through the flexible structure that makes nozzle that vibration take place of piezoelectrics; Owing to have only the mentioned nozzle area corresponding to vibrate, thereby nozzle is difficult to obtain bigger displacement with the piezoelectrics peristome.That is to say that such structure is being sprayed high viscosity, for example viscosity is 10mPas, and when having disperseed the toner composition liquid of a large amount of solid compositions, injection orifice takes place easily stop up, and can not stablize and carry out high efficiency toner production.And, just narrated with piezoelectrics in the patent documentation 6 injecting-unit is vibrated, and its structure is not made any detailed description, thereby this description does not surmount the narration scope of patent documentation 5.

Summary of the invention

To this, the inventor has carried out detailed discussion to the structure that can make jet element produce big displacement quantity, has accomplished the present invention.

The present invention is the innovation and creation of accomplishing in view of above-mentioned problem; Purpose is in order to improve the production efficiency of toner; And then the many toner characteristic values that reduce to take place in the existing manufacturing approach follow particulate to change and the change of generation the toner that the acquired character amplitude of fluctuation is little such as flowability, charging property etc.

In order to address the above problem, the present invention proposes following scheme.

(1) a kind of method for preparing toner is characterized by, and carries out following operation: droplet treatment operation periodically, use the droplet treatment device, and toner composition liquid is carried out the periodicity droplet treatment, and with the drop of this toner composition liquid of nozzle ejection; And, the micronize operation, the drop of the toner composition liquid that curing is ejected forms toner particle, and wherein, the droplet treatment device comprises: film has a plurality of nozzles; Vibration unit, by constituting with lower device: vibration generating arrangement is used for vibrating; The amplitude multiplying arrangement has in the face of film and the vibration plane parallel with film, is used to amplify the amplitude of the vibration that vibration generating arrangement takes place, and toner composition liquid is to be supplied between film and the vibration plane, and to contain resin and colorant at least.

(2) at this, the droplet treatment device is formed the faying face of the vibration plane of amplitude multiplying arrangement greater than said amplitude multiplying arrangement and vibration generating arrangement be combined into.At this moment, vibration plane in the amplitude multiplying arrangement and faying face are rectangle, and the ratio of long limit and minor face is more than 2.0.

(3) the amplitude multiplying arrangement in the droplet treatment device can adopt the horn shape structure.Vibration unit can be with the fixing ten thousand bright type Vib.s of anchor pole.

(4) in the droplet treatment device, vibration generating arrangement can be that occurrence frequency is that 20kHz is above but less than the structure of the vibration of 2.0MHz.Can be at the pressure that the vibration of the vibration plane of droplet treatment device is paid more than the 10kPa to 500kPa following scope with interior film zone in, said a plurality of nozzle is set.Can also be provided with in the film zone of a plurality of nozzles at the droplet treatment device, the ratio R that a plurality of nozzles are arranged on vibration of thin membrane direction displacement is 2.0 with in the interior zone, and wherein, R is the maximal value Δ Lmax of displacement and the ratio of minimum value Δ Lmin.

(5) in addition, in the droplet treatment device, film is the metallic film formation of 5 to 500 μ m with thickness, and the opening diameter of a plurality of nozzles is in 3 to 35 mu m ranges.The nozzle number can be in 2 to 3000.

(6) the micronize operation can comprise drying and solidify the drop of toner composition liquid, and at this moment, the dry gas that preferably flows along the drop injection direction of toner composition liquid comes dry drop, preferred air of dry gas or nitrogen.

(7) in the micronize operation, can comprise the operation of the electric charge of gained toner particle being removed electricity.At this moment, removing electricity can shine with soft X line or plasma.

(8) in addition, can also form the structure of collecting toner particle through air-flow.At this moment, toner is collected by the toner collection portion that preferably has the conical surface that the opening diameter that exports from entering the mouth to diminishes gradually, and also preferred air-flow is an eddy current, and then the toner particle of collecting is sent to the portion of stockpiling by air-flow.

(9) apparatus for producing toner of the present invention comprises: the droplet treatment device, toner composition liquid is carried out the periodicity droplet treatment, and with the drop of this toner composition liquid of nozzle ejection; And micro-granulating device solidifies the drop by the toner composition liquid of droplet treatment device ejection, forms toner particle, and wherein, the droplet treatment device possesses: film is formed with a plurality of nozzles; Vibration unit, by constituting with lower device: vibration generating arrangement is used for vibrating; The amplitude multiplying arrangement has in the face of film and the vibration plane parallel with film, is used to amplify the amplitude of the vibration that vibration generating arrangement takes place, and toner composition liquid does, is supplied between film and the vibration plane and resin and colorant at least.

(10) at this, preferred droplet treatment device is formed, and the vibration plane of amplitude multiplying arrangement is greater than the faying face of said amplitude multiplying arrangement and vibration generating arrangement be combined into.In this case, vibration plane in the amplitude multiplying arrangement and faying face are rectangle, and the ratio of long limit and minor face is more than 2.0.

(11) the said amplitude multiplying arrangement in the droplet treatment device can adopt horn shape.Vibration unit can be the fixing ten thousand bright type Vib.s of anchor pole.

(12) in the droplet treatment device, preferably with more than the 20kHz but make film vibrate less than the vibration frequency of 2.0MHz.In the film of droplet treatment device, the pressure of preferably toner composition liquid being paid is more than the 10kPa in the zone to the following scope of 500kPa, and said a plurality of nozzle is set.Also preferred in the film zone that a plurality of nozzles are set of said droplet treatment device, the ratio R that a plurality of nozzles are set at vibration of thin membrane direction displacement is 2.0 with in the interior zone, and R is the maximal value Δ Lmax of said displacement and the ratio of minimum value Δ Lmin.

(13) and then, the film of preferred droplet treatment device is the metallic film of thickness 5 to 500 μ m, the opening diameter of a plurality of nozzles is in 3 to 35 mu m ranges.Also have 2 to 3000 nozzles in the film of preferred droplet treatment device.

(14) micro-granulating device can comprise solvent evaporates portion, is used for dry solidification toner composition liquid drop, and at this moment, the dry gas that preferably flows along the injection direction of the drop of toner composition liquid comes dry drop, preferred air of dry gas or nitrogen.

(15) can also comprise the operation of the electric charge of resulting toner particle in the micronize operation being removed electricity.At this moment, removing electricity can shine with soft X line or plasma.

(16) can also comprise toner collecting device, collect toner particle through air-flow.At this moment, preferably have the toner collection portion of the conical surface that diminishes gradually from the exit opening diameter that enters the mouth, in addition, preferred air-flow is an eddy current.

(17) can also comprise the portion of stockpiling, be used to stockpile the toner particle of sending here by air-flow of collecting.At this moment; Can possess toner collecting device, toner and stockpile portion and connect toner collecting device and toner stockpiles the conduit component of portion, this toner collecting device, toner stockpile portion and conduit component and are processed by conductive material and have a ground structure.

(18) toner of the present invention is to use the toner that method for preparing toner of the present invention is made, and this toner is 1.00 to 1.15 scopes with the size-grade distribution of (weight average mean particle dia/number average particle diameter) expression preferably.And the weight average granularity of this toner is 1 to 20 mu m range.

Effect of the present invention does; According to method for preparing toner of the present invention and manufacturing installation; When making that vibration takes place the film with a plurality of nozzles; Toner composition liquid is formed drop and sprays this drop, improve the production efficiency of toner, and then obtain the toner of in the past unprecedented single dispersed size-grade distribution.

Toner of the present invention is owing to be the toner of making according to method for preparing toner of the present invention; Therefore can reduce to occur in the existing manufacturing approach; Toner requires characteristic, and the amplitude of fluctuation as characteristic values such as flowability, charging property follow particulate to change obtains the little toner of amplitude of fluctuation.

Description of drawings

Fig. 1 is the summary construction diagram that an example has been used the apparatus for producing toner of the present invention of method for preparing toner of the present invention.

Fig. 2 is the enlarged diagram that is used for explaining apparatus for producing toner drop injection unit shown in Figure 1.

Fig. 3 be from beneath to the synoptic diagram of Fig. 2 bottom surface.

Fig. 4 is the pattern diagram that constitutes the notch cuttype trumpet type Vib. example of vibration generating arrangement in the drop injection unit shown in Figure 2.

Fig. 5 is the pattern diagram that constitutes the exponential curve type trumpet type Vib. example of vibration generating arrangement in the drop injection unit shown in Figure 2.

Fig. 6 is the pattern diagram that constitutes the pyramid type trumpet type Vib. example of vibration generating arrangement in the drop injection unit shown in Figure 2.

Fig. 7 is the routine enlarged diagram of other drop injection units that is used to explain apparatus for producing toner shown in Figure 2.

Fig. 8 is the other routine enlarged diagram of other drop injection units that is used to explain apparatus for producing toner shown in Figure 2.

Fig. 9 is used to explain that above-mentioned drop injection unit carries out the film pattern diagram of droplet treatment operating principle.

Figure 10 is the mode chart that is used to explain above-mentioned film fundamental vibration.

Figure 11 is the mode chart that is used to explain above-mentioned film secondary index vibration.

Figure 12 is the mode chart that is used to explain three index vibrations of above-mentioned film.

Figure 13 is at the vibration mode figure of above-mentioned film when core is formed with projection.

Figure 14 is the summary construction diagram of other examples that is used to explain the apparatus for producing toner of relevant above-mentioned embodiment.

Figure 15 is the enlarged diagram of other example shows about the drop injection unit of above-mentioned apparatus for producing toner of further giving an example.

Figure 16 is the synoptic diagram that is provided with a plurality of drop injection unit examples shown in Figure 15.

Figure 17 is the front elevation of the pattern of the routine drop injection unit in other embodiments of the present invention.

Figure 18 is the test pattern in Figure 17 left side.

Figure 19 is the oblique view of the vibration unit in the above-mentioned drop injection unit.

Figure 20 is the pattern diagram of the film in the above-mentioned drop injection unit.

Figure 21 is the mode chart that is used to explain above-mentioned film fundamental vibration.

Figure 22 is the mode chart that is used to explain above-mentioned film secondary index vibration.

Figure 23 is the pattern diagram that shows the drop injection unit example of other embodiments of the present invention.

Figure 24 is the side view in Figure 23 left side.

Embodiment

Below with reference to description of drawings embodiment of the present invention.

At first, with reference to model structure chart shown in Figure 1, illustrate the manufacturing installation of the present invention of carrying out manufacturing approach of the present invention.Apparatus for producing toner 1 of the present invention comprises at least: drop injection unit 2, carry out the toner composition liquid that contains resin and colorant at least droplet treatment and spray the droplet treatment device of this droplet treatment drop; Particulate formation portion 3 is arranged at the top of drop injection unit 2, be used to solidify by drop injection unit 2 spray and droplet treatment the drop of toner composition liquid, form toner particle T; The toner particle T that particulate formation portion 3 forms collects in toner collection portion 4; Toner stockpiles portion 6, as the device that stockpiles of toner, stockpiles by 4 collections of toner collection portion and through pipeline 5 and carries the toner particle T that shifts; Raw material storage part 7 is deposited toner composition liquid 10; Woven hose 8 is transported to liquid ejection unit 2 with toner composition liquid 10 from raw material storage part 7; And, infusion pump 9, pressurization and supplying toner composition liquid 10 such as when operation.

About to drop injection unit 2 toner composition liquid 10 being provided from raw material storage part 7, can provide voluntarily through the droplet treatment phenomenon of drop injection unit 2, also can in the device operation process, use above-mentioned infusion pump 9 to pressurize provides complementaryly.Also have, the toner composition liquid 10 among the present invention uses solution or the dispersion liquid that in solvent, dissolves or disperseed to contain at least the toner constituent of resin and colorant.

Secondly, referring to figs. 2 and 3 the above-mentioned drop injection unit 2 of explanation.

Fig. 2 for summary represent the schematic cross-section of drop injection unit 2, Fig. 3 be from the beneath of Fig. 2 to the bottom surface want portion's synoptic diagram.This drop injection unit 2 comprises: film 12, and wherein being formed with a plurality of nozzles 11 is injection orifice; Vibration unit 13 vibrates film 12; And channel member 15, the solution stream that is used for formation toner composition liquid 10 between film 12 and vibration unit 13 promptly stockpiles portion 14, contains the toner constituent of resin and colorant in this toner composition liquid 10 at least.

Carry out secure bond with welding of channel member 15 usefulness or the insoluble resin bonding material of separating toner composition liquid around the film 12.For the material of this film 12 and the shape of nozzle 11; Can not do suitable selection though there is particular restriction; But can from nozzle 11 when spraying the drop of toner composition liquid 10, can take place particle diameter extremely uniformly the viewpoint of fine droplets carry out preferably; Such as, film 12 is the sheet metal formation in 5 to 500 mu m ranges with thickness, and the opening bore scope of nozzle 11 is 3 to 35 μ m.At this, the opening bore of said nozzle 11 is when nozzle 11 is circle, to refer to then mean the minor axis that this is oval when oval by this diameter of a circle.In addition, the number of nozzle 11 is preferably between 2 to 3000.

Vibration unit 13 is made up of the amplitude multiplying arrangement 22 of the vibration generating arrangement that vibration takes place 21 with the Oscillation Amplitude that strengthens these vibration generating arrangement 21 generations.Through drive signal the driving loop 23 in source applies required frequency between the electrode 21a of vibration generating arrangement 22,21b driving voltage taking place is drive signal; 12 vibrations of excited vibration generating means; This vibration amplitude is amplified by amplitude multiplying arrangement 22; And make and vibration plane 13a generating period property vibration that film 12 laterally arranges, make film 12 vibrate by the caused periodic pressure of vibration of this vibration plane 13a with required frequency.

This vibration unit 13 so long as the device that can extensional vibration be provided reliably to film 12 with certain frequency just can, do not have other particular restriction, can do suitably to select to use.Consider that excitation film 12 produces vibration, the piezoelectrics 21A that can preferably encourage two piezo-electric type flexural vibrations is as vibration generating arrangement 21.Piezoelectrics 21A has the function that electric energy is changed into mechanical energy.Be specially through applying voltage and encouraged flexural vibrations, make film 12 produce vibration.

To forming the piezoelectrics 21A of vibration generating arrangement 21, can enumerate lead zirconate titanate piezoelectric ceramics such as (PZT) etc., because of displacement is little, use after the lamination usually.Other can also enumerate Kynoar piezoelectricity macromolecules such as (PVDF) or crystal, LiNbO ₃, LiTaO ₃, KNbO ₃Deng single crystals, or the like.

Vibration unit 13 is as long as provide vertical vibration to the film 12 with nozzle, anyway dispose can, but vibration plane 13a and film 12 are configured in parallel.

Can use such as the trumpet type Vib. for the above-described vibration unit 13 that constitutes by vibration generating arrangement 21 and amplitude multiplying arrangement 22.Because the amplitude of vibration generating arrangements 21 such as piezoelectric element can be amplified by the loudspeaker 22A of amplitude multiplying arrangement 22, thereby the vibration of mechanical vibrator itself is little, has alleviated mechanical load like this, helps prolonging the life-span of production equipment.

The trumpet type Vib. can be representational known Vib., at this, can give an example out such as Vib.s such as notch cuttype shown in Figure 4, exponential curve type shown in Figure 5, pyramid types.These trumpet type Vib.s are provided with piezoelectrics 21A on the big one side of the area of loudspeaker 22A; Utilize the extensional vibration of piezoelectrics 21A to bring out effective vibration of loudspeaker 22A; And the one side that the area of loudspeaker 22A is little is as vibration plane 13a, and 13a is designed to the maximum vibration face with this vibration plane.

Vibration unit 13 can also use has fixing Lang Zhiwan (Lagevin) the type Vib. of High strength bolt.Piezoelectric ceramics in the fixing bright ten thousand type Vib.s of this anchor pole adopts mechanicalness to engage, and also breakage can not take place receiving having encouraged significantly when vibrating.

At least more than a place, connecting respectively in the channel member 15 to stockpiling portion 14 provides the solution supply pipe 18 of toner composition liquid 10 and is used to get rid of the bubble vent pipe of bubble or the pipeline 19 of liquid circulation usefulness.Through being arranged at the not shown holding components on this channel member 15, drop injection unit 2 is set up and remains on the over top of particulate formation portion 3.In this explanation, given an example and drop injection unit 2 has been arranged at the over top of particulate formation portion 2, also can adopt drop injection unit 2 is arranged on the drying section sidewall of particulate formation portion 3 or the structure of bottom.

The size that produces the vibration unit 13 of mechanical vibration is generally followed the minimizing of vibration frequency and is become big.Can suitably on vibration unit, directly implement perforate processing the portion that stockpiles is set according to required frequency.The whole portion of stockpiling is effectively vibrated, and the vibration plane of this moment is defined as the above-mentioned face with film of a plurality of nozzles of having puted up.

According to Fig. 7 and Fig. 8, explain that two examples are different from the drop injection unit 2 of said structure below.

Example shown in Figure 7 does, adopts trumpet type Vib. 80 that the loudspeaker 82 of piezoelectrics 81 and the amplitude expansion section of vibration generation portion constitute as vibration unit 13, and the part in the loudspeaker 82 is used to form the portion of stockpiling 14.Be flange portion 83 preferably, this drop injection unit 2 be fixed on the sidewall of particulate formation portion 3 through loudspeaker 82 integrally formed fixed parts with trumpet type Vib. 80.Consider to prevent vibration loss, can also use not shown elastic body to fix.

Example shown in Figure 8 does, with anchor pole piezoelectrics 91A, 91B and loudspeaker 92A, the 92B of mechanical fixation vibration generating arrangement securely, constitutes the fixing ten thousand bright type Vib.s 90 of anchor pole as vibration unit 13, and in loudspeaker 92A, forms the portion 14 that stockpiles.

Illustrate the example that a drop injection unit 2 only is set in the above-mentioned explanation in particulate formation portion 3; But from the angle of enhancing productivity; Preferably be set up in parallel a plurality of drop injection units 2 on the top of particulate formation portion 3; From the angle of control difficulty or ease, the number preferable range that is provided with of drop injection unit 2 is 100 to 1000 in addition.In this case, it is common hydraulic accumulator through pipeline 8 towards raw material storage part 7 that each of drop injection unit 2 stockpiles portion 14, forms the Supply Structure of toner composition liquid 10.About supplying toner composition liquid 10, both followed droplet treatment to carry out self-supporting structure, also can be the structure that liquid is provided with infusion pump 9 when the device operation complementaryly.

Secondly, the drop that is drop injection unit 2 with reference to the above-mentioned droplet-shaped apparatus for converting of figure 9 explanations forms principle.

As stated; In drop injection unit 2; Vibration unit 13 through mechanical vibrator with the vibration propagation that takes place to facing the film 12 that stockpiles a plurality of nozzles 11 of having of portion 14; Make film 12 produce periodic vibrations, and more than the diameter phi 1mm than large area region on a plurality of nozzles 11 of being provided with, through these nozzles 11 stable formation and liquid droplets.

Under and the situation that marginal portion 12A this circular membrane 12 is fixed rounded at film 12; The operating principle of this drop injection unit 2 is shown in Fig. 9 (a) and Fig. 9 (b); After circular membrane 12 was paid vibration, this circular membrane 12 carried out the periodicity up-down vibration of transversal section shown in Fig. 9 (b) on direction of vibration, and fundamental vibration is shown in figure 10; Surrounding edge 12A with film 12 is a vibration node, and the displacement L at center 0 is maximal value Δ Lmax.Preferably with shown in figure 10, film 12 is a vibration node with the surrounding edge, and does not exist the vibration mode of vibration node to vibrate in diametric(al).Also know in addition and exist as the index of Figure 11 and higher power shown in Figure 12 vibrates.These vibration modes are at the circular membrane 12 inner vibration nodes that form one or more concentric circles, and the distortion on diametric(al) is symmetric shape.Shown in figure 13 in addition, the central part formation protrusion shape 12C with circular membrane 12 in order to the direction of motion of control drop, can adjust the amount of Oscillation Amplitude simultaneously.

At this, because the vibration of circular membrane 12, near the liquid in circular membrane 12 a plurality of nozzles 11 the proportional pressure Pa of vibration velocity Vm that has taken place in the toner composition liquid with film 12.Known this pressure results from the retroaction that medium is the radiation impedance Z r of toner composition liquid, in following formula (1) with the product representation of radiation impedance Z r and mould vibration velocity Vm.

Pa(r，t)＝Zr·Vm(r，t) (1)

The vibration velocity Vm of film 12 is the function of time, and intercropping cyclical variation at any time such as sine wave, square wave etc., can form various cyclical movements.Because the displacement of each position of film 12 on direction of vibration is different, so vibration velocity Vm also is the coordinate function of the position of film 12.And in fact, from above-mentioned radial symmetry deformed shape, the preferred vibration shape of film is the function of radius coordinate.

As stated,, can produce pressure proportional, be injected in the gas phase according to the cyclical variation toner composition liquid 10 of this pressure with it for 12 vibration velocities of the film with period profile.The toner composition liquid 10 that periodically is discharged in the gas phase forms spheroid because of the surface tension difference between the liquid and gas, generating period property fluidization, and toner composition liquid 10 is by ejection from a plurality of nozzles 11 behind the fluidization.

At this, film 12 vibration frequency range that fluidization preferably can take place are 20kHz to 2.0MHz, especially preferred 50kHz to 500kHz.If vibration frequency more than 20kHz, through the excitation liquid vibration, can promote the dispersion of particulate such as pigment or wax in the toner composition liquid, prevent nozzle 11 cause clogging.

In addition, when pressure be the facilitation that 10kPa can bring into play above-mentioned microparticulate when above more effectively.

Under these circumstances, the vibration displacement that forms a plurality of nozzles 11 zones in the film 12 is big more, and it is big more that formed liquid-drop diameter also is tending towards becoming, and when vibration displacement hour, form droplet or do not form drop.Like this, the size deviation between the drop that reduces to form in a plurality of nozzles 11 zones need be defined in a plurality of nozzles 11 are set on the position that is suitable for film 12 vibration displacements.

For formation the toner particle of hi-vision image quality is provided, its nozzle setting area obtains following result according to experiment, promptly; Like Figure 10 and shown in Figure 11, vibration unit 13 brings out film 12 and vibrates, and the ratio R of the maximal value Δ Lmax of direction of vibration displacement Δ L and minimum value Δ Lmin in the film 12 (=Δ lmax/ Δ lmin) is in 2.0; Promptly; At R is 2.0 a plurality of nozzles 11 to be set in interior zone, can guarantee that the size deviation between the drop is within the claimed range, that is to say; The diameter Distribution scope of the drop that forms like this is narrow, and toner size-grade distribution shape becomes precipitous.

At this moment; The condition that changes toner composition liquid makes an experiment; Its result does, in viscosity be below the 20mPa/s, surface tension is that the beginning generation area of subsidiary body is identical in 20 to 75mN/m the zone, thereby; Preferred above-mentioned pressure is below the above 500kPa of 101Pa, below the wherein especially preferred 100kPa.Like this, among above-mentioned scope, just a plurality of nozzles 11 being arranged on becomes in the film 12 in the zone of this scope with interior pressure with pressure control, just can restrain the generation of subsidiary body.

Secondly, return Fig. 1, drop 31 that solidifies toner composition liquid 10 and the particulate formation portion 3 that forms toner particle T are described.

As stated, be solution or the dispersion liquid that dissolving or disperseed contains the toner constituent of resin and colorant at least in solvent at the toner composition liquid 10 of this use, therefore, just form toner particle T through dry solidification drop 31.That is, in this embodiment, particulate formation portion 3 is dry and removes the solvent of drop 31, forms the solvent evaporates portion of toner particle T, at following solvent evaporates portion or the drying section of being also referred to as.

Be specially; The dry gas 35 that this particulate formation portion 3 usefulness are dry transports the drop 31 that goes out from the nozzle ejection of drop injection unit 2; The flow direction of this dry gas 35 is identical with the direction of circling in the air of drop 31; The solvent of drop 31 is removed because of dry gas 35 is able to volatilization, forms toner particle 33.Above-mentioned dry gas 35 is meant that under atmospheric pressure dewpoint temperature is the gas of state below-10 ℃, as long as just drop 31 dry gases can be adopted as dry gas 35, such as, air, nitrogen etc.

To be used to collect the toner collecting device of the toner particle T that above-mentioned particulate formation portion 3 forms be toner collection portion 4 in explanation below.

This toner collection portion 4 is arranged on the below of particulate formation portion 3 and is connected with particulate formation portion 3 along the particulate direction of circling in the air, and has conical surface 41, and opening diameter begins to dwindle gradually towards Way out from the inlet near liquid ejection unit 2.And, such as attracting from toner collection portion 4 inside, make that the eddy current that in toner collection portion 4, takes place towards downside is an air-flow 42 with not shown suction pump etc., collect toner particle T by this air-flow 42.Like this, be that centrifugal force takes place air-flow 42 with eddy current, collect toner particle T, the toner that makes toner particle T can be collected and be transplanted on downside reliably stockpiles in the portion 6.

Porch in toner collection portion 4; Also possesses neutralizer 43; Be used for electric charge temporary transient and the toner particle T that particulate formation portion 3 forms; This neutralizer 43 adopts soft roentgen radiation x device 43A that toner particle T is carried out soft roentgen radiation x, can also shown in figure 14ly carry out the plasma irradiation with plasma irradiation unit 43B.

The toner particle T that this toner collection portion 4 collects is transported to toner by eddy current through piping 5 and stockpiles portion's 6 storages.At this, if stockpiling portion 6, toner collection portion 4, pipeline 5 and toner adopt conductive material to form, then preferred these device ground connection.And then preferably this manufacturing installation integral body adopts explosion-proof specification.In addition, when toner particle T being sent to toner from toner collection portion 4 stockpiling portion 6, the structure that both can adopt gaseous tension to transport also can be with stockpile the structure that container attracts toner particle T from toner.

Secondly, brief description is made the manufacture process of toner involved in the present invention with the apparatus for producing toner of said structure.

As stated; When the portion that stockpiles in the drop injection unit 2 14 obtains to provide when having dispersed or dissolved the toner composition liquid 10 that contains resin and colorant at least; Through the vibration generating arrangement 21 of the vibration unit in the drop injection unit 2 13 being applied the drive signal of required driving frequency; Make vibration generating arrangement 21 vibration that bends, obtain amplification through 22 these vibrations of amplitude multiplying arrangement, vibration plane 13a begins vibration.

The vibration of vibration plane 13a propagates into film 12 through the toner composition liquid 10 that stockpiles in the portion 14 in vibration unit 13; Make film 12 produce periodic vibration; Vibration through this film 12; Toner composition liquid generating period property droplet treatment is among the drop 31 that forms thus is ejected into the particulate formation portion 3 of solvent evaporates portion from a plurality of nozzles 11.

Subsequently, be ejected into drop 31 in the particulate formation portion 3 in particulate formation portion 3, through flow direction and drop 31 the transporting of the identical dry gas 35 of direction of circling in the air, solvent is removed in volatilization, forms toner particle T.The toner particle T that forms in the particulate formation portion 3 is collected by air-flow 42 in the toner collection portion 4 that is arranged in downside, is sent to toner through pipeline 5 and stockpiles portion 6 and stockpile.

Like this,, can spray the drops 31 of the toner composition liquid that forms through droplet treatment the while continuously in a large number, make the production efficiency of toner obtain the leap rising owing to be provided with a plurality of nozzles 11 in the drop injection unit 2.In addition; The vibration unit 13 that vibration takes place film 12 is made up of vibrative vibration generating arrangement 21 and the amplitude multiplying arrangement 22 that strengthens the vibration amplitude that is taken place; Can obtain enough amplitudes in order to big displacement to be provided to film 12; And then through in the zone in obtaining the film 12 of this big displacement quantity a plurality of nozzles 11 being set, can stably once spraying a large amount of drops 31 and nozzle blockage does not take place, make and stablize and high efficiency toner creates possibility.Confirmed to obtain the unprecedented monistic toner of granularity that has.

In addition; The solution or the dispersion liquid that use dissolving in this embodiment or disperseed to breathe out at least the toner constituent that resin and colorant are arranged are as toner composition liquid 10; And; For the mode of solidifying drop, be employed in and make the organic solvent evaporation that contains in the drop in the solvent evaporates portion in dry gas, shrink through drying and solidify to form toner particle.Yet the present invention is not limited to these modes.

For example, can stockpile in the portion, the melt and dissolved formation liquid condition of toner constituent as toner composition liquid, after ejecting drop, is formed toner particle with this drop cooling curing what heat.In addition, can also use the toner that contains the thermosetting material to form liquid, spray the back heating at drop and make it that sclerous reaction take place, solidify to form toner particle.

Below, describe with reference to Figure 15 other drop injection units of giving an example.

Figure 15 is the schematic cross-section of this drop injection unit pattern.This drop injection unit 2 is identical with precedent; Use the trumpet type Vib. as vibration unit 13; Around this vibration unit 13, be provided with the channel member 15 that toner composition liquid 10 is provided, the inside in the face of film 12 parts in the loudspeaker 22A of vibration unit 13 forms the portion 14 that stockpiles.And then, around channel member 15, separate predetermined distance gas channel formation parts 36 are set, be used to form air-flow 35 airflow flowing passages 37.In addition, because of simply in film 12, only having shown a nozzle 11, but be provided with a plurality of nozzles in fact as stated among the figure.

Preferred shown in figure 16 on the 3A of the portion that stockpiles that constitutes drying tower, the arrangement is provided with a plurality of drop injection units 2, and such as the viewpoint from being easy to control, the number of drop injection unit 2 is 100 to 1000.Can promptly further enhance productivity like this.

Describe in the face of relevant toner of the present invention down.

Toner of the present invention is the toner that adopts above-mentioned apparatus for producing toner to make, and the mean particle dia of this toner is the unicity dispersed and distributed.

Be specially, with (weight average mean particle dia/quantity average particle diameter) expression size distribution, preferably this size distribution is in 1.00 to 1.05 scopes.In addition, the average weight mean particle dia is preferably in 1 to 20 mu m range.

From the static bucking effect, being not difficult, it disperses promptly to be suspended in the air-flow once more with the toner of the invention described above manufacturing approach manufacturing.For this reason, even do not use, also can easily toner be transported to developing regional as the conveyer in the existing electronic fax mode.That is to say,, just develop after can adopting simple pneumatic pump that toner is transported to developing regional even if from faint air-flow, also can obtain enough transporting powers.So-called strong cloud (power cloud) phenomenon taking place in the development, can not occur upsetting picture because of air-flow and form, can carry out extremely good latent electrostatic image developing.In addition, toner of the present invention is used for existing visualization way and also any problem can take place.At this moment, parts such as carrier or development sleeve become the device that only is used to transport toner, needn't consider the frictional electrification body function of in existing mode, being born fully.Like this, the increase significantly of material degree of freedom, permanance is improved, and can use cheap materials, and expense reduces cost.

Below, the toner materials (toner composition liquid) that the present invention is used describes.As toner materials, can use existing electrophoto-graphic toner.That is, the toner adhesive of styrene-acrylonitrile copolymer acid resin, polyester resin, polyalcohols resin, epikote etc. is dissolved in various organic solvents, colorant is disperseed, and release agent is dispersed or dissolved.Then, this potpourri is processed fine droplet according to above-mentioned method for preparing toner, dry solidification just can be processed desired toner particle.In addition, above-mentioned material is carried out thermosol melt mixingly, the liquid with the mixing thing that obtains dissolves or disperses in various solvents makes fine droplet and dry solidification with above-mentioned method for preparing toner, just can obtain desired toner.

(toner is used material)

Above-mentioned toner comprises resin and colorant at least with material, as required, can also comprise other composition such as carrier, wax.

(resin)

For above-mentioned resin, the binding resin of can giving an example at least.

To above-mentioned binding resin, there is not special system limit.Can suit to select from normally used resin, for example, the polyvinyl of the styrene monomer of can giving an example, acrylic monomer, methacrylic monomer etc.These monomer or co-polymer, polyester polymer, polyalcohols resin, phenolic resin, the silicone resin formed more than 2 kinds, gather urethane resin, polyamide, furane resin, epoxy resin, xylene resin, terpene resin, coumarone indeneresin, polycarbonate resin, petroleum resinoid etc.

As styrene monomer; For example styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-styryl phenyl, p-ethyl styrene, 2; 4-dimethyl styrene, p-n-amylbenzene ethene, p-tert-butyl styrene, the own styrene of p-n-, the hot styrene of p-n-, p-n-nonylbenzene ethene, p-n-certain herbaceous plants with big flowers base styrene, p-n-hendecane base styrene, p-methoxy styrene, p-chlorostyrene, 3, the styrene or derivatives thereof of 4-dichlorostyrene, m-nitre styrene, o-nitre styrene, p-nitre styrene etc. etc.

As acrylic monomer, for example acrylic acid or its ester class of acrylic acid, methyl acrylate, acrylic acid ethyl ester, acrylic acid propyl diester, acrylic acid n-butyl ester, acrylic acid isobutyl, acrylic acid n-monooctyl ester, acrylic acid n-hendecane base ester, 2-EHA, stearyl acrylate base, acryllic acid 2-chloroethyl, acrylic acid phenyl etc.

As the methacrylic monomer, the for example methacrylic acid of methacrylic acid, methyl methacrylate, methacrylic acid ethyl ester, methacrylic acid propyl diester, methacrylic acid n-butyl ester, methacrylic acid isobutyl, methacrylic acid n-monooctyl ester, methacrylic acid n-hendecane base ester, methacrylic acid 2-Octyl Nitrite, methacrylic acid stearyl, methacrylic acid phenylester, dimethylaminoethyl acrylate methyl base aminoethyl ester, methacrylic acid diethyl aminoethyl ester etc. or its ester class etc.

Forming above-mentioned polyvinyl or co-polymer obtains other and obtains monomer, following (1)～(18) of can giving an example.(1) the monoene hydro carbons of ethene, propylene, butylene, isobutylene etc.; (2) the polyenoid class of butadiene, isoprene etc.; (3) chloro ethene, partially ethylene dichloride, smelly generation ethene, fluorinated ethylene base etc. vinyl halides; (4) vinyl ester of vinyl-acetic ester, vinyl propionate base ester, benzoic acid vinyl esters etc.; (5) vinyl ethers of vinyl methyl ether, EVE, vinyl isobutyl ether etc.; (6) vinyl ketones of ethenyl methyl ketone, vinyl hexanone, methyl isopropenyl ketone etc.; (7) the N-vinyl compound of N-vinyl pyrrole, N-VCz, N-vinyl indoles, N-vinyl pyrrolidone etc.; (8), vinyl naphthalene class; (9) acryllic acid of vinyl cyanide, methacrylonitrile, acrylic acid amides etc. or methacrylic acid derivative etc.; (10) unsaturated dibasic acid of maleic acid, citraconic acid, itaconic acid, alkenyl succinic, fumaric acid, mesaconic acid etc.; (11) maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydrides like the I unsaturated dicarboxylic acid anhydride; (12) monoesters of the unsaturated dibasic acid of maleic acid monomethyl ester, maleic acid list ethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid list ethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester etc.; (13) the unsaturated dibasic acid ester of dimethyl maleic acid, dimethyl fumarate etc.; (14) α of crotonic acid, cinnamic acid etc., beta-unsaturated acid; (15) α of crotonic anhydride, cinnamic anhydride etc., the beta-unsaturated acid acid anhydride; (16) this α, the monomer that carboxyl is arranged of the acid anhydride of beta-unsaturated acid and lower fatty acid, alkenyl malonic acid, alkenyl glutamic acid, alkenyl suiphonic acid, these sour acid anhydrides and their monoesters etc.; (17) acryllic acid or the methacrylic acid hydroxyl alkyl esters of 2-hydroxyethylmethacry,ate, 2-hydroxyethyl methacrylate, 2-hydroxy propyl methacrylate etc.; (18) monomer that hydroxyl is arranged of 4-(1-hydroxyl 1-methyl butyl) styrene, 4-(1-hydroxyl 1-methyl is own) styrene etc.

Among the toner of the present invention, the polyvinyl of binding resin or co-polymer also can have with there being the crosslinking chemical of the vinyl more than 2 to carry out crosslinked cross-linked structure.Share crosslinking agent as this, as divinyl aromatic compound, for example divinylbenzene, divinyl naphthalene etc.As the diacrylate compounds that connects with alkyl chain; Glycol diacrylate, 1 for example; 3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentane diol diacrylate, 1; 6-hexane diol diacrylate, neopentylglycol diacrylate, the material that these the acrylic ester of compound is replaced with methacrylate etc.With the diacrylate compounds that the alkyl chain of ether-containing key couples together, the diethylene glycol diacrylate of can giving an example, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyglycol #400 diacrylate, polyglycol #600 diacrylate, propylene glycol diacrylate and material that these the acrylic ester of compound is replaced with methacrylate etc.

In addition, the diacrylate ester compounds, the dimethylacrylate compound that are coupled together by the chain that contains aromatic series base and ehter bond also can.As polyester-type diacrylate class, for example, trade name MANDA (Japanese chemical drug corporate system).

As polyfunctional crosslinking chemical; The material that can give an example pentaerythritol triacrylate, front three hydroxyl ethane triacrylate, front three hydroxy propane triacrylate, tetramethyl hydroxyl methane tetraacrylate and the acrylic ester of above compound is replaced with methacrylate, cyanuric acid triaryl ester, tri trimellitate aromatic ester.

The content of these crosslinking chemical, with respect to other monomer components of 100 weight portions, 0.01～10 weight portion is preferred, 0.03～5 weight portion is for more preferably.In these the cross-linkable monomer; In the resin for toner; The viewpoint of fixation performance, anti-skew property, is contained diacrylate compounds that the chain of an aromatic series base and ehter bond couples together for preferred at divinyl aromatic compound (particularly divinylbenzene).Among these, being combined as of the monomer of phenylethylene co-polymer, styrene-acrylonitrile copolymer acids co-polymer is preferred.

In the manufacturing of polyvinyl of the present invention or co-polymer; The polymerization initiator that uses; Can give an example 2; 2 '-azobis isobutyronitrile, 2; Two (the 4-methoxyls 2 of 2 '-azo; The 4-methyl pentane nitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2; 2 '-azo two (2-methylbutyronitrile), dimethyl 2; The two isobutyrates, 1 of 2 '-azo, 1 '-azo two (1-cyclohexane nitrile), 2-(carbamyl azo)-isobutyronotrile, 2,2 '-azo two (2; 4; The 4-trimethylpentane), 2-phenylazo 2 ', 4 '-dimethyl 4 '-methoxyl valeronitrile, 2, the ketone peroxide class, 2 of 2 '-azo two (2-methylpropane), methyl-ethyl-ketone peroxide, acetyl acetone peroxide, cyclohexanone superoxide etc.; Two (tert-butyl peroxide) butane of 2-, tert-butyl hydroperoxides, cumene hydroperoxide, 1; 1,3,3-tetramethyl butyl hydroperoxides, two tert-butyl superoxide, tert-butyl cumyl peroxide, dicumyl peroxide, α-(tert-butyl peroxide) cumene, isobutyl peroxide, decoyl superoxide, certain herbaceous plants with big flowers acyl superoxide, lauroyl peroxide, 3; 5,5-trimethyl acetyl superoxide, benzoyl peroxide, m-tolyl superoxide, diisopropyl peroxydicarbonate, own peroxide two carbonic esters of two 2-ethyls, two n-propyl group peroxides, two carbonic esters, two 2-ethoxyethyl group peroxy carbonates, diethoxy isopropyl peroxide two carbonic esters, two (3-methyl 3-methoxyl butyl) peroxy carbonates, acetyl group hexamethylene sulphonyl superoxide, tert-butyl Peracetic acid ester, tert-butyl peroxide isobutyrate, tert-butyl peroxide 2 ethyl hexanoic acid ester, tert-butyl peroxide laurate, tert-butyl oxybenzoic acid ester, tert-butyl peroxy isopropyl base carbonic ester, two tert-butyl peroxide isophthalic acid esters, tert-butyl peroxy carbonates, isopentyl peroxide 2-Ethylhexyl Alcohol thing, two tert-butyl peroxides, six hydrogen terephthalate, tert-butyl peroxide azelate etc.

Binder resin is a styrene acrylic resin, from the fixing resistance, offset resistance, storage stability viewpoint, according to the resin component soluble in tetrahydrofuran (THF) the molecular weight distribution by GPC, the molecular weight of 3,000 to 50,000 (Number average molecular weight equivalent) in areas of at least one peak exists, the molecular weight area of 100,000 or more in at least one peak of the resin is preferable.Further, the THF soluble fraction, the molecular weight distribution is preferably 100,000 or less content of 50 to 90% of the binder resin, the molecular weight of 5,000 -30,000 peak appeared in the field of the binder resin is more preferably 5,000 to 2 has a main peak area of a million of the binder resin is most preferred.

The acid number of the polyvinyl of binding resin styrene-acrylonitrile copolymer acid resin etc., preferred 0.1mgKOH/g～100mgKOH/g, more preferably 0.1mgKOH/g～70mgKOH/g, most preferably 0.1mgKOH/g～50mgKOH/g.

As the structure monomer of polyester polymer, can give an example as follows: as the pure composition of 2 value, for example 7 glycol, propylene glycol, 1; 3-butanediol, 1; 4-butanediol, 2,3-butanediol, diglycol, triethylene glycol, 1,5-pentane diol, 1; 6-hexane diol, neopentyl glycol, 2-ethyl 1, the ethylene oxide of 3-hexane diol, hydrogenation bisphenol-A or bisphenol-A, third alkylene oxide etc. with the glycol that obtains of cyclic ether polymerization etc.In order to be that vibrin is crosslinked, preferably also use with the alcohol more than 3 yuan.

As the polyvalent alcohol more than 3 yuan, the D-sorbite, 1,2 of can giving an example, 3; 6-hexane tetrol, 1,4-sorbitan, pentaerythrite, for example, dipentaerythritol, tripentaerythritol, 1,2,4-butane triol, 1; 2,5-penta triol, glycerine, 2-methylpropane triol, 2-methyl 1,2; 4-butane triol, front three hydroxyl ethane, front three hydroxy propane, 1,3,5-trihydroxy benzene etc.

As forming polyester polymer acid composition, the unsaturated dicarboxylic acid anhydride of the unsaturated dibasic acid of alkyl dicarboxylic aid's class of the benzene dicarboxylic acid class of can give an example phthalic acid, iso-phthalic acid, terephthalic acid (TPA) etc. or its acid anhydride, succinic acid, suiphonic acid, certain herbaceous plants with big flowers diacid, azelaic acid etc. or its acid anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic, fumaric acid, mesaconic acid etc., maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydrides etc. etc.In addition, as the many value carboxylic acid composition more than 3 yuan, trimellitic acid, 1,2,4,5-benzenetetracarboxylic acid, 1; 2,4-benzene tricarbonic acid, 1,2,5-benzene tricarbonic acid, 2,5,7-naphthalene tricarboxylic acids, 1; 2,4-naphthalene tricarboxylic acids, 1,2,4-butane tricarboxylic acids, 1,2; 5-hexane tricarboxylic acids, 1,3-dicarboxyl 2-methyl 2-methylene carboxylic propane, four (methylene carboxylic) methane, 1,2,7,8-octane tetrabasic carboxylic acid or these acid anhydride, part lower alkyl esters etc.

When binding resin was polyester resin, from the fixation performance of toner, anti-skew, the material that in the field of molecular weight 3,000～50,000, has at least 1 mountain peak to exist in the molecular weight distribution of the solvable composition of THF of resinous principle was preferred.In addition, preferably as the solvable composition of THF, the composition of molecular weight below 100,000 is 60～100% such binding resins, and the binding resin that in the field of molecular weight 5,000～20,000, has at least 1 mountain peak to exist is more preferred.

Binding resin is the occasion of mylar, its acid number and preferred 0.1mgKOH/g～100mgKOH/gg, more preferably 0.1mgKOH/g～70mgKOH/g, 0.1mgKOH/g～50mgKOH/g.

Among the present invention, the molecular weight distribution of binding resin is to utilize THF to measure as the gel permeation chromatography (GPC) of solvent.

Binding resin as toner of the present invention uses can contain the monomer component material that Gai both resinous principles of Yu react but use at least one side of above-mentioned polyvinyl composition and polyester resin composition.Among the monomer of structure polyester resin composition, can with the compound of polyvinyl reaction, the unsaturated dicarboxylic of can give an example phthalic acid, maleic acid, citraconic acid, itaconic acid etc. or its acid anhydride, etc.As the monomer of structure polyvinyl composition, can give an example has carboxyl or hydroxylated material, acryllic acid or methyl acrylic ester.

In addition, also with polyester polymer, polyvinyl and other binding resin the time, the whole acid number of preferred binding resin is that the resin of 0.1～50mgKOH/g is more than the 60 weight %.

Among the present invention, the acid number of the binding resin composition of method for producing toner and toner calculates with following method: basic operation is as the criterion with JIS K-0070.

(1) use of sample will be removed binding resin (component of polymer) additive in addition in advance, perhaps tries to achieve the acid number and the amount of the composition beyond binding resin and the crosslinked binding resin in advance.The accurate pulverizing article 0.5～2.0g of weighing sample, with the weight of component of polymer as W g.For example, when toner is always measured the acid number of binding resin, measure the acid number and the amount of colorant or magnetic etc. in addition, obtain the acid number of binding resin through calculating.

(2) beaker to 300 (ml) adds sample, and the mixed liquor 150 (ml) that adds toluene/ethanol (volume ratio 4/1) dissolves.

(3) ethanolic solution of the KOH of use 0.1mol/l carries out titration with the potential difference (PD) titration apparatus.

(4) the use amount of KOH solution that will this moment is carried out blank determination simultaneously as S (ml), and the use amount of the KOH solution of this moment as B (ml), and is calculated with following formula.But f is the factor of K O H.

Acid number (mgKOH/g)=[(S-B) * f * 5.61]/W (2)

For the binding resin of toner and the composition that contains binding resin, consider the toner keeping quality, preferred 35～80 ℃ of glass temperature (Tg), more preferably 40～75 ℃.Tg is as being lower than 35 ℃, and toner is easy to wear out under high-temperature atmosphere, is prone to have during photographic fixing skew to take place in addition.In addition, Tg is as surpassing 80 ℃, and fixation performance can variation.

Using the present invention, a magnetic body can be, for example, (1) magnetite, hematite, ferrite, etc. The magnetic iron oxide, and other metal oxide containing iron oxide, (2) iron, palladium, nickel or the like metals, or these metals with aluminum, palladium, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, palladium and other metals and alloys.(3) and the potpourri of these materials etc.

The object lesson of magnetic has Fe ₃O ₄, γ-Fe ₂O ₃, ZnFe ₂O ₄, Y ₃Fe ₅O ₁₂, CdFe ₂O ₄, Gd ₃Fe ₅O ₁₂, CuFe ₂O ₄, PbFe ₁₂O, NiFe ₂O ₄, NdFe ₂O, BaFe ₁₂O ₁₉, MgFe ₂O ₄, MnFe ₂O ₄, LaFeO ₃, iron powder, palladium powder, nickel powder etc.These materials can a kind use separately, and use also can combine more than 2 kinds.Wherein, particularly the micropowder of four oxidations, three iron, γ-three oxidation two iron is used by preferred.

In addition, can use magnetic oxygenated iron or its potpourri of the MAG that contains different in nature element, maghemite, ferrite etc.Examples of opposite elements include lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, palladium, chromium, manganese, palladium, nickel, copper, zinc, potassium, .Can be selected from magnesium, aluminium, silicon, phosphorus or zirconium as preferred different in nature element.Opposite sex element may reside in the oxidation iron lattice, also can be used as oxide and is present in the oxidation iron, perhaps has oxide or hydroxylate from the teeth outwards.Preferably exist as oxide.

Above-mentioned different in nature element can be sneaked into the salt of different in nature element respectively when magnetic generates, and through adjustment pH value, gets in the particle.In addition, also can after the magnetic particle generate,, perhaps add the salt of various elements and carry out the pH adjustment, just can separate out surface thus in particle through the adjustment of pH.As the use amount of above-mentioned magnetic, for binding resin 100 weight portions, preferred 10～200 weight portions of the amount of magnetic, more preferably 20～150 weight portions.Preferred 0.1～2 μ m of the number average particle diameter of these magnetic, more preferably 0.1～0.5 μ m.Above-mentioned number average particle diameter can be measured and try to achieve the photo of transmission electron microscope bust shot with numeric device etc.

In addition, as the magnetic characteristic of magnetic, preferably the magnetic characteristic when applying 10KOe is coercive force 20～1500e, saturation magnetization 50～200emu/g, the residual magnetization 2～20emu/g.

Above-mentioned magnetic can be used as colorant and uses.

(colorant)

As the use of above-mentioned colorant, there is not special system limit.Can suit to select normally used resin.Such as carbon black, aniline dyes, iron black, Naphthol Yellow S, Hansa Yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, loess, yellow lead, titanium yellow, poly azo yellow, oil yellow, Han Caesar yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Wu Erkang Fast Yellow (5G, R), quinoline yellow lake, isoindole indole least one yellow, red iron oxide, red lead, lead Zhu, cadmium red, cadmium red mercury, antimony Zhu, Permanent Red 4R, Para Red, red, red aniline nitrate Parra epichlorohydrin, Lithol Fast Scarlet G , light fastness scarlet, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD,, bright scarlet G, Li Saul Yuhong GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Claret 5B, toluidine brown, permanent Claret F2K, He Liao Claret BL, Bordeaux 10B, state Maroons, Alizarine Lake, eosin lake, Rhodamine Lake B, Rhodamine Lake Y, alizarin lake , thioindigo red B, thioindigo brown, oil red, quinoline mouth + Ah one red, pyrazolone red, poly-azo red, chrome vermilion, benzidine orange, oil orange, palladium blue, sky blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, purple blue, anthraquinone blue, fast violet B, methyl violet lake, palladium purple, manganese violet, dioxane violet, anthraquinone violet, chromium chloride, zinc chloride, chromium oxide, viridian, gem chlorine, chlorine pigment B, naphthol chloride B, chlorine gold, acid chloride lake, peacock chlorine lake, phthalocyanine chloride, anthraquinone chlorine, titanium oxide, zinc China, lithopone and their mixtures thereof.

The amount of above-mentioned colorant does, to preferred 1～15 weight % of toner, more preferably 3～10 weight %.

The colouring agent that toner of the present invention uses can use the masterbatch with resin compounded.The manufacturing of masterbatch or with the mixing resin glue of masterbatch; Except the top modification that exemplifies, unmodified polyester resin, can be for example polystyrene, gather p-chlorostyrene, polyvinyl toluene etc. styrene with and the polymer of replacement; Styrene p-chlorostyrene co-polymer; The styrene-acrylonitrile copolymer co-polymer; Styrene ethylene base toluene co-polymer; Styrene ethylene base naphthalene co-polymer; Styrene acrylic acid methyl co-polymer; Styrene acrylic acid ethyl co-polymer; Styrene acrylic acid butyl co-polymer; The misery co-polymer of styrene acrylic; Styrene methacrylic acid methyl co-polymer; Styrene methacrylic acid ethyl co-polymer; Styrene metering system acid butyl co-polymer; Styrene α-chloromethyl propylene acid methyl co-polymer; The styrene-acrylonitrile co-polymer; Styrene ethylene ylmethyl ketone co-polymer; The styrene butadiene co-polymer; The styrene isoprene co-polymer; Styrene-acrylonitrile indenes co-polymer; The styrene maleic acid co-polymer; The phenylethylene co-polymer of styrene maleic acid ester co-polymer etc.; Poly methyl methacrylate, gather butyl methyl acrylate, polychlorostyrene vinyl, polyvinyl acetate base, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyalcohols resin, gather urethane, polyamide, polyvinyl butyral, polyacrylic acid acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, fragrant same clan Petropols, chlorinated paraffin wax, paraffin etc.They can a kind of independent use, also can two or more mixing get up to use.

Resin that above-mentioned masterbatch can be used masterbatch and colorant and in addition high shear force mix, mixing and obtain.At this moment, in order to improve the interaction of colorant and resin, can be with an organic solvent.In addition, because the wet cake of colorant can not added any processing use, just can not use so-called flushing (flushing) method so need not carry out drying; Promptly; With the moisture water base paste of colorant, resin and organic solvent are mixed together mixing, make colorant move to the resin part; Remove moisture and organic solvent composition thus.Mixed milling can use the high shear diverting device of 3 roller mills etc.

The use amount of above-mentioned masterbatch is preferably used 0.1～20 weight portion to binding resin 100 amount portions.

In addition; The resin that above-mentioned masterbatch uses preferably use acid number as below the 30mgKOH/g, the amine value is 1～100 and wherein disperseed the resin of colorant, more preferably use acid number as below the 20mgKOH/g, the amine value is 10～50, wherein disperseed the resin of colorant.Surpass 30mgKOH/g like acid number, the charging property meeting variation under high humility, face material dispersiveness is also insufficient.In addition, if the amine value less than 1, and the amine value surpasses at 100 o'clock, face material dispersiveness just becomes insufficient.In addition, acid number can be measured by the method for JIS K0070 record, and the amine value is measured by the method for JIS K7237 record.

In addition; Spreading agent is on the dispersed point of face material; Preferably the intermiscibility with binding resin is high, is specially commercially available dispersible pigment dispersion JISPER PB821 and AJISPER PB822 (corporate system of aginomoto Finetech), Disperbyk-2001 (BYK JAPAN KK corporate system), EFKA-4010 (EFKA corporate system) etc.

Above-mentioned spreading agent is in toner, and the preferred ratio of toner vis-a-vis is that 0.1～10 weight % uses.As cooperate ratio less than 0.1 weight %, and then face material dispersiveness is insufficient, as greater than 10 weight %, and the charging property variation under high humility then.

The weight average molecular weight of above-mentioned dispersant is with the styrene converted weight in gel permeation chromatography, and the molecular weight of the maximum of its main peak is preferred 500～100000, from the dispersed viewpoint of face material more preferably 3000～100000.Preferred especially 5000～50000, most preferably 5000～30000.Molecular weight is as less than 500, and then polarity uprises, and the dispersed variation of colorant surpasses 100000 like molecular weight, and then the compatibility with solvent uprises, and the dispersiveness of colorant can step-down.

The addition of above-mentioned spreading agent toner 100 weight portions vis-a-vis is preferably 1～200 weight portion, more preferably 5～80 weight portions.Like less than 1 weight portion, dispersed step-down is as surpassing 200 weight portions, charging property step-down.

(other composition)

< carrier >

Toner of the present invention can mix being used as the tow-component developer use with carrier.Above-mentioned carrier can use the carrier and the resin-coated carrier of common ferrite, MAG etc.

Above-mentioned resin-coated carrier is that lining material forms by the carrier core particle with the resin that is coated on carrier core particle surface.

This is used for the resin of lining material; Can give an example styrene-acrylate co-polymer, styrene methacrylates co-polymer etc. styrene-acrylonitrile copolymer acid resin, acrylic acid acid esters co-polymer, methacrylate co-polymer etc. acrylic resin, teflon, monochloro trifluoro-ethylene polymkeric substance, gather 1, the fluorine of 1-two fluoro ethene etc. contains resin, silicone resin, vibrin, polyamide, polyvinyl butyral, ammonia acrylate resin.In addition, ionic polymer resin, polyphenylene sulfides resin etc. also can be as lining (coating) materials of carrier.These resin can a kind of independent use, and use also can two or morely combine.In addition, also can use the carrier core of the binder-type that is dispersed with the magnetic powder in the resin.

In the resin-coated carrier, the method for resin-coated dose of coating is used on the surface of carrier core at least, be meant resin dissolves or outstandingly turbidly make after in solvent it, perhaps only carry out method of mixing at the powder state attached on the carrier core that has been coated with.

With respect to above-mentioned resin-coated carrier, the ratio of resin-coated material can determine aptly, but preferred 0.01～5 weight %, more preferably 0.1～1 weight %.

Be used for to give an example (1) for titanium oxide fine powder body 100 weight portions to two or more mixing lining (coating) agent that magnetic applies; With the material that potpourri 12 weight portions of dimethyldichlorosilane and dimethicone oils (weight ratio 1: 5) are handled, the material that handle with potpourri 20 weight portions of dimethyldichlorosilane and dimethicone oils (weight ratio 1: 5) fine silica powder body 100 weight portions (2).

In the above-mentioned resin, styrene methacrylic acid methyl co-polymer, fluorine resin and phenylethylene co-polymer and potpourri, silicone resin can use particularly preferred silicone resin well.As fluorine resin and phenylethylene co-polymer and potpourri; For example have and gather 1; The potpourri, 1 of the potpourri of 1-two fluoro ethene and styrene methyl methacrylate co-polymer, teflon and styrene methyl methacrylate co-polymer, 1-two fluoro ETFE copolymerizations are (with styrene acrylic 2-Octyl Nitrite co-polymer (co-polymer weight ratio 10: 90～90: 10) and styrene acrylic 2-Octyl Nitrite methyl methacrylate co-polymer (co-polymer weight ratio 20～60: 5～30: potpourri 10～50).

As silicone resin, can give an example nitrogenous silicone resin and nitrogenous silane coupling agent and silicone resin react and the modified siloxane resin of generation.As the magnetic material of carrier core, for example can use ferrite, iron excess type ferrite, MAG, gamma oxidation iron etc. oxide and, the metal of that kind of iron, palladium, nickel or the alloy of these elements.

In addition, elements contained in these magnetic materials include, for example iron, palladium, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, palladium.Among these, especially copper, zinc, and iron as the main components of the Cu - Zn - type ferrite iron, manganese, magnesium and iron as the main components in the Mn-Mg ferrite iron suitable class and use.

The resistance value of above-mentioned carrier, the preferred amount of the resin of concavo-convex degree, the coating on the surface through the adjustment carrier, making resistance value is 10 ⁶-10 ¹⁰Ω cm.

The particle diameter of above-mentioned carrier can be 4～200 μ m, but preferred 10～150 μ m, more preferably 20～100 μ m.The particle diameter of resin-coated carrier especially preferred 50% is 20～70 μ m.

At two compositions is in the developer, relative carrier 100 weight portions, and preferred toner 1～200 weight portion of the present invention, more preferably relative carrier 100 weight portions, toner is 2～50 weight portions.

< wax >

In addition, among the present invention, can outside binding resin and colorant, contain wax.As wax, not special system limit can be selected normally used material, for example the aliphatic hydrocarbon wax of the aliphatic hydrocarbon wax of low molecular weight polyethylene, low-molecular-weight polypropylene, polyolefin-wax, microcrystalline wax, paraffin wax etc., OPE etc.

The plant class wax of oxide or its block copolymer, candelila wax, palm wax, haze tallow, Jojoba wax etc.; The mineral substance wax of the animal class wax of beeswax, adeps lanae hydrosus, spermaceti etc., ceresine, ceresin etc., be the wax class of major component with the fatty acid ester of montanic acid ester type waxes etc.The material of a part of or whole deoxygenated of the fatty acid ester of depickling palm wax etc.

For above-mentioned wax; Can further exemplify with palmitic acid, stearate acid, montanic acid, or exemplify further that unrighted acid, stearyl alcohol, the eicosyl of saturated straight chain aliphatic acid, tung oil stearate acid, parinaric acid etc. of straight-chain alkyl carboxylic acid's class etc. of the alkyl with straight chain is pure, the two oleamides of saturated fatty acid bisamide, ethene, hexa-methylene pair oleamides, the N of the fatty acid amide of many value alcohol of the saturated alcohols of tadenan, palmityl alcohol, cerul alcohol or long-chain alkyl alcohol etc., D-sorbite etc., inferior oleamide, olefin acid acid amides, lauric amide etc., di-2-ethylhexylphosphine oxide certain herbaceous plants with big flowers acid acid amides, ethene dilaurate acid amides, the two stearate acid acid amides of hexa-methylene etc.; N '-two oleyl suiphonic acid acid amides, N; The unrighted acid amide-type of N '-two oleyl certain herbaceous plants with big flowers diacid acid acid amides etc., the two stearate acid acid amides of m-dimethylbenzene, N, partial esterification compound, the hydrogenation vegetative grease of the aliphatic acid of the wax of the vinyl monomer grafting of the fatty acid metal salts of the fragrant same clan bisamide of N-distearyl iso-phthalic acid acid amides etc., stearate acid calcium, calcium laurate, stearate acid zinc, stearate acid magnesium etc., aliphatic hydrocarbon wax To styrene and acryllic acid etc., docosanoic acid monoglyceride etc. and many value alcohol obtains has the hydroxymethyl ester compounds.

Preferred for example have alkene is under high pressure carried out the polyolefin that free radical polymerization obtains; The secondary product of the low-molecular-weight that obtains during with the high molecular polyolefine polymerization is made with extra care and is obtained polyolefin; Low pressure is following carries out polymerization and the polyolefin that obtains with the such catalyst of Ziegler catalyst; With for example radioactive ray; Electromagnetic wave or light utilization are carried out polymerization and are obtained polyolefin; High molecular polyolefine is carried out thermal decomposition and the low-molecular-weight polyolefin that obtains; Paraffin wax; Microcrystalline wax; Fischer-Tropsch (Fisher-Tropsch) wax; The synthetic chloroflo that A Gefa etc. are synthetic; Several 1 compound of carbon element is as the synthetic wax of monomer; Functional group's hydrocarbon wax with hydroxyl or carboxyl; Hydrocarbon wax and the potpourri that functional group's hydrocarbon wax is arranged; Wax with these is the styrene of parent; Maleate; Acrylic ester; Methacrylate; Maleates etc. come the wax of graft modification with vinyl monomer.

In addition; With these wax with pressurization diaphoresis, solvent method, again crystallisation, vacuum steam study in France, supercritical gas extraction method or solution crystallization handle, material and low-molecular-weight solid fatty acid, low-molecular-weight solid alcohol, low-molecular-weight solid chemical compound and other the material that impurity is removed that the molecular weight distribution that obtains is sharp shape are used by preferred.

In order between fixation performance and anti-skew property, to average out, the melting point of preferred above-mentioned wax is 70～140 ℃, more preferably 70～120 ℃.As less than 70 ℃, the step-down of anti-the caking capacity is as surpassing 140 ℃, anti-offset effect variation.

In addition, and, can obtain plasticization effect and demoulding effect simultaneously as wax with two or more different types of wax.

Kind with wax of plasticization effect, for for example, the material etc. that on the low wax of melting point, the structure of molecule the material of side chain is arranged and the structure of polar group is arranged.

The wax that demoulding effect is arranged is the high wax of melting point, and the molecular structure of can giving an example is the wax of linear chain structure, and the nonpolarity wax that does not have the functional group.As usage, can use two or more melting point differences is combination and the combination of polyolefin and graft-modified polyolefin etc. of 10 ℃～100 ℃ wax.

When selecting this wax of two kinds, in the identical occasion of the structure of wax, the low wax of melting point can be brought into play the plasticization effect relatively, the wax performance demoulding effect that melting point is high.At this moment, the melting point difference is 10-100 ℃ a occasion, can bring into play the effect that function is separated.During less than 10 ℃, be difficult to obtain the function separating effect, surpass 100 ℃ occasion, be difficult to bring into play the function that produces because of interaction and strengthen.The melting point of preferred at least one side's wax is 70～120 ℃, and more preferably 70～100 ℃, at this moment, the function separating effect has the tendency that is easy to bring into play.

Above-mentioned wax; Relatively say; Have apparatus derivatorius or bring into play plastic effect, have more linear chain structure or then bring into play demoulding effect just as functional group's nonpolarity base or unmodified straight chain thing just as functional group's etc. polar group or with the wax that the composition that is different from major component carries out modification.As preferred combination, can give an example with ethene is that Polyethylene homo compound or the co-polymer of major component and the alkene beyond the ethene are the polyolefin homopolymer of major component or the combination of co-polymer; Polyolefin and the polyolefinic combination of grafting sex change; The combination of alcohol wax, fatty acid wax or ester type waxes and hydrocarbon wax; The combination of fischer-tropsch wax or polyolefin-wax and paraffin wax or microcrystalline wax; The combination of fischer-tropsch wax and polyolefin-wax; The combination of paraffin wax and microcrystalline wax; The combination of palm wax, candelila wax, rice wax or montan wax and hydrocarbon wax.

Whether in any case, to allow for easy storage stability of toner and the fixing of the balance between the toner is preferably observed in the DSC measurement among the endothermic peak, 70 ~ 110 ℃ area of the maximum peak appearing in the peak temperature, more preferably 70 ~ 110 ℃ in the areas of maximum peak.

As total amount of above-mentioned wax, to binding resin 100 weight portions, preferred 0.2～20 weight portion, more preferably 0.5～10 weight portion.

Among the present invention, the temperature of the summit of the maximum endothermic peak of wax is the melting point of wax in measuring with DSC.

The DSC determining instrument of above-mentioned wax or toner, the differential scanning calorimetry of the internal heat type input offset type of preferred high accuracy.Assay method is undertaken by ASTM D3418-82.The DSC curve that uses among the present invention does, after carrying out heating up for 1 time, lower the temperature and obtaining the transition data, and the data of measuring when heating up with 10 ℃/minute temperature speed again.

< fluidity enhancers >

Also can add fluidity enhancers in the toner of the present invention.Through this fluidity enhancers being added on the surface of toner, improve the flowability (become and be easy to flow) of toner.

As above-mentioned fluidity enhancers; The carbon black, 1 of can giving an example, 1-two fluoro ethene micropowders, fluorine-type resin powder, wet type method for making silicon dioxide, as the micropowder silicon dioxide of dry type method for making silicon dioxide, micro mist titanium dioxide, micro mist aluminium oxide not just as the ptfe micropowder end; Carry out surface-treated with silane coupling agent, titanium couplant or silicone oil and handle silicon dioxide, handle titanium dioxide, the processing aluminium oxide, etc.Wherein, preferred micropowder silicon dioxide, micro mist be titanium dioxide, micro mist aluminium oxide not, has more preferably carried out surface-treated silicon dioxide with silane coupling agent and with silicone oil.

For the particle diameter of above-mentioned fluidity enhancers, average initial particle is preferably 0.001～2 μ m, more preferably 0.002～0.2 μ m.

Above-mentioned micropowder silicon dioxide can be that the silicon halogenation contains the gaseous oxidation of thing and the powder body that generates, the powder body of promptly so-called dry process silicon dioxide or calcined silica.

The commercially available fine silica powder body that generates with the gaseous oxidation of silicon halogen compounds; For example AEROSIL (Japanese AEROJIL company trade name, below identical)-130 ,-300 ,-380 ,-TT600 ,-MOX170 ,-MOX80 ,-COK84:Ca-O-SiL (CABOT company trade name)-M-5 ,-MS-7 ,-MS-75 ,-HS-5 ,-EH-5, Wacker HDK (WACKER-CHEMIE company trade name)-N20 V15 ,-N20E ,-T30 ,-T40:D-CFineSilica (DOW CORNING company trade name): Fransol (Fransil company trade name) etc.

Further, and more preferably by vapor phase oxidation of a silicon halide fine silica powder generated by a processing for Shu hydrated fine silica powder.Fine silica powder being treated, particularly preferably determined by a methanol titration Shu after hydration degree of 30 to 80% of silica fine powder silica body.Shu hydration with the fine silica powder can be used for the reaction or physical adsorption of the organic silicon compound such as chemical or physical treatment is obtained.Preferable methods does, the method that the fine silica powder body and function organo-silicon compound that the gaseous oxidation of silicon halogen compounds is generated are handled.

As organo-silicon compound; Can give an example hydroxypropyl trimethoxy silane, phenyltrimethoxysila,e, n-hexadecane base trimethoxy silane, n-octadecyl trimethoxy silane, vinyl methoxy silane, VTES, dimethyl vinyl chlorosilane, divinyl chlorosilane, γ-methacrylic acid oxygen propyl trimethoxy silicane, hexamethyldisilane, trimethyl silane, trimethyl chlorosilane, dimethyldichlorosilane, methyl trichlorosilane, fragrant dimethylchlorosilane, fragrant diphenyl dichlorosilane, benzyl dimethyl chlorosilane, bromomethyl dimethylchlorosilane, α-chloroethyl trichlorosilane, β-chloroethyl trichlorosilane, CMDMCS chloromethyl dimethyl chlorosilane, three Organosilyl mercaptan, trimethyl silyl mercaptan, three Organosilyl acrylic ester, dimethylethoxysilane, trimethylethoxysilane, trimethyl methoxy silane, MTES, isobutyl trimethoxy silane, dimethyldimethoxysil,ne, diphenyl diethoxy silane, HMDO, 1; 3-divinyl tetramethyl disiloxane, 1; Have the siloxane unit of 2～12 of 2 powder bodies in 3-diphenyl tetramethyl disiloxane and 1 molecule, on the end unit dimethyl polysiloxane of 0～1 hydroxyl that combines with Si etc. is not being arranged respectively.Further, can the give an example silicone oil of dimethicone oils etc.These materials can a kind of independent use, also can two or more mixing use.

The number average particle diameter of fluidity enhancers, preferred 5～100nm, more preferably 5～50nm.

With the nitrogen adsorption specific surface area that B E T method is measured, preferred 30m ²More than/the g, more preferably 60～400m ²/ g.The occasion of surface-treated powder body, preferred 20m ²More than/the g, more preferably 40～300m ²/ g.

The dosage of these powder body, toner particle 100 weight portions are 0.03～8 weight portion relatively.

The toner of the present invention, other additives may be added, such as the electrostatic latent image bearing body protection cleanability enhanced thermal characteristics, electrical characteristics, physical characteristics adjustment resistance adjustment, softening point adjustment, the fixing rate enhancement as the purpose can add various metal soaps, fluorine surfactant, dioctyl phenyl;, and imparting agent as the conductive oxide, tin oxide, zinc oxide, carbon black, antimony oxide, etc., and if necessary to add titanium oxide , alumina, alumina and other inorganic fine powder.The inorganic fine powder, may be performed according to Shu hydration.In addition; Can add teflon, stearate acid zinc, gather 1; Lapping compound, the anticaking agent of the lubrication prescription of 1-two fluoro ethene etc., cesium oxide, silit, metatitanic acid tungsten etc., and can white particles of toner particle and antipolarity be added as development property reinforcing agent to reach look particulate on a small quantity.

Preferred these adjuvant; With control carried charge control etc. is purpose; With the treating agent of siloxane finish, various modified siloxane varnish, silicone oil, various modified siloxane oil, silane coupling agent, the silane coupling agent with functional group and other organo-silicon compound etc., or the treating agent of other kinds 々 is handled.

The preparation of the developer, the developer in order to improve fluidity and storage stability, developability, transferability may be added as exemplified above hydrophobized inorganic fine silica powder particles.The mixing of additive can be selected the mixer of general powder aptly, but heating jacket etc. preferably is housed, the device that can regulate temperature inside.In order to change the process that gives the additive load; Also can be on the way or increase gradually and separate additive, the winding number of mixer, velocity of rotation, time, temperature etc. are changed, also can add stronger load earlier; Apply the weak load of comparison then, otherwise also can.

For example having of operable mixer, V-Mixer, Locking mixer, Loedge mixer, Nauter mixer, Henschel mixer etc.

Make the further method of adjusting for the toner shape that obtains, do not have special system limit, can suitably select according to purpose.These methods for example have; To dissolve by the toner materials that binding resin and colorant are formed mixing after; Fine material is used mixing (Hybridizer), machinery fused (mechanofusion) etc.; Carry out method that mechanical form regulates, or so-called spray drying process; This method is after being distributed to toner dissolving in the solvent of solvable toner adhesive, to carry out the precipitation thinner with spray-drying installation, obtains spherical toner and in water base medium, toner is heated method that coating reaches spheroidization etc.

As above-mentioned additive, preferably use inorganic fine particles.

As above-mentioned inorganic fine particles, can exemplified by silica, aluminium oxide, titanium oxide, barium titanate, magnesium titanate, calcium titanate, metatitanic acid tungsten, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomite, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesia, zirconia, barium sulfate, brium carbonate, calcium carbonate, carborundum, silicon nitride etc.

The preferred 5 μ m of the initial particle of above-mentioned inorganic fine particles～2 μ m, more preferably 5 μ m～500 μ m.

The specific surface area that above-mentioned BET method obtains is preferably 20～500m ²/ g.

The usage ratio of above-mentioned inorganic fine particles is preferably 0.01～5 weight % of toner, more preferably 0.01～2 weight %.

In addition, macromolecule based fine particles can with for example do not have that soap emulsion polymerization and outstanding turbid polymerization, dispersin polymerization obtain the bunching class, the polymer particle that obtains by thermosetting resin etc. of polystyrene, methacrylate and acrylic ester copolymerization thing and siloxane, benzoguanamine, nylon etc.

Such an external additive agent, a surface treatment agent to increase the hydrophobicity, so that even under high humidity can be prevented aging of the external additive itself.

As above-mentioned surface conditioning agent, can give an example silane coupling agent, silane-based agent, the silane coupling agent that fluoro-alkyl is arranged, organic titanate class couplant, the couplant of aluminium class, silicone oil, modified siloxane wet goods.

The initial particle of above-mentioned inorganic fine particles, preferred 5 μ m～2 μ m, more preferably 5 μ m～500 μ m.In addition, with the specific surface area that B E T method obtains, preferred 20～500m ²/ g.The usage ratio of this inorganic fine particles is preferably 0.01～5 weight % of toner, more preferably 0.02～2.0 weight %.

Be used to remove the spatter property reinforcing agent of the developer after the transfer printing remaining on electrostatic latent image carrier and the primary transfer medium, the polymeric microsphere of making by no soap emulsion polymerization of the fatty acid metal salts of the stearate acid zinc of can giving an example, stearate acid calcium, stearate acid etc., poly methyl methacrylate particulate, ps particle etc. etc.Polymeric microsphere has narrow size distribution, and volume average particle size is 0.01～1 μ m.

Use the developing method of toner of the present invention can be used for all existing xerographies and used the electrostatic latent image supporting body.But for example be particularly useful for organic electrostatic latent image carrier, amorphous silica electrostatic latent image carrier, selenium electrostatic latent image carrier, zinc oxide electrostatic latent image carrier etc.

Below, the toner composition liquid that uses when carrying out cooling curing with particlized method (particlized engineering) is described.

As the toner constituent that heating and melting and cooling curing obtain, the material that the melting below preferred the use obtains low viscous fused solution is as major component.

Specifically, for one or more from the following compound of selecting: monoamides, bisamide, four acid amides, polyamide, esteramides, polyester, gather jealous woman acid vinyl, acrylic compounds and methacrylic acid family macromolecule, phenylethylene macromolecule, ethene jealous woman acid vinyl copolymer, polyketone, siloxanes, coumarone, fatty acid ester, triglycerides, natural resin, natural and synthetic wax etc.

As a polyamide resin, can be exemplified Ba Sami Island (versamide) 711, Ba Sami Island (versamide) 725, Ba Sami Island (versamide) 930, Ba Sami Island (versamide) 940, Busayyah Long (versalon) 1117, Busayyah Long (versalon) 1138, Busayyah Long (versalon) 1300 (above Henkel system), Tao Ma B Island (Tohmide) 391, Tao Ma B Island (Tohmide) 393, Tao Ma B Island (Tohmide) 394, Tao Ma B Island (Tohmide) 395, peach Ma B Island (Tohmide) 397, Tao Ma B Island (Tohmide) 509, Tao Ma B Island (Tohmide) 535, Tao Ma B Island (Tohmide) 558, Tao Ma B Island ( Tohmide) 560, Tao Ma B Island (Tohmide) 1310, Tao Ma B Island (Tohmide) 1396, Tao Ma B Island (Tohmide) 90, Tao Ma B Island (Tohmide) 92 (above Fuji Kasei Co., Ltd.), as polyesters, KTR 2150 (Kao above); as polylactic acid, vinyl esters of Health may, for example AC 401, AC 540, AC 580 (above the Allied Chemical International Co., Ltd. system); as silicone alkyl, a siloxane SH 6018 (Toray Silicone Co., Ltd.), a silicone KR 215, silicone KR 216, silicone KR 220 (above-Etsu Silicone Co., Ltd.); as incense beans ketone, Escron G-90 (Nippon Steel Chemical Co., Ltd.).

As fatty acid, be one or more compounds of selecting from following acid or their ester kind: for example stearic acid, arachidic acid, docosanoic acid, carnaubic acid, cerinic acid, montanic acid, three decane acid etc.

As fatty acid amide, can be for from following a kind of or mixture more than two kinds: lauramide, stearmide, oleamide, erucyl amide, stearate acid amides, palmitamide, docosanoic acid acid amides, brassidic acid acid amides etc.; As N-displacement fatty acid amide; Can exemplify N, N '-2-hydroxystearic acid acid amides, N, the two oleamides of N '-ethene, N; The two stearic amides of N '-dimethylbenzene, stearic acid list first hydroxy amide, N-oil base stearic amide, N-stearylstearic amide, N-oleyl palmitamide, N-stearyl erucyl amide, N; N '-two oil base adipic acid acid amides, N, N '-two oil base certain herbaceous plants with big flowers diacid amide, N, the different terephthalic acid (TPA) acid amides of N '-distearyl, 2-stearmide ethyl stearate.

As N-displacement fatty acid amide; Can be for from following one or more compounds of selecting: N; N '-2-hydroxystearic acid acid amides, N; The two oleamides of N '-ethene, N, the two stearic amides of N '-dimethylbenzene, stearic acid list first hydroxy amide, N-oil base stearic amide, N-stearylstearic amide, N-oleyl palmitamide, N-stearyl erucyl amide, N, N '-two oil base adipic acid acid amides, N; N '-two oil base certain herbaceous plants with big flowers diacid amide, N, the different terephthalic acid (TPA) acid amides of N '-distearyl etc.

As fatty acid ester; Preferred monobasic or polyol fatty acid ester; For example, sorbierite monopalmitate, sorbitol monostearate, sorbierite list docosane acid esters, macrogol monostearate, macrogol distearate, propylene glycol monostearate, ethylene glycol distearate etc.

Specifically, can use Leodol SP-S 10, Leodol SP-S 30, LeodolSA 10, Emasol P-10, Emasol S-10, Emasol S-20, Emasol B, Leodol Super SP-S 10, Emanorn 3199, Emanorn 3299, ExepearlPE-MS (above) etc. for spending king's system.

More preferably use the fatty acid ester of glycerine, for example glyceryl monostearate, palm monoglyceride, monoolein, docosanoic acid monoglyceride etc.Specifically, can use LeodolM S-50, Leodol MS-60, Leodol MS-165, Leodol MO-60, Exepearl G-MB (above colored king's system), deodorizing and refining palm wax No.1, refining candelila wax No.1 (with field, u'eno wax corporate system), Synchro wax ERL-C, Synchro wax H R-C (above Croda International Corp. system), KF2 (length of schooling that becomes more meticulous is ground in the river).In addition, as special ester wax, can use Exepearl DS-C2 (flower king system), Kawaslip--L, KawaslipR (length of schooling that becomes more meticulous is ground in above river) etc.Also can be selected from the high alcohol ester class etc. of the higher fatty acid of myricyl cerotate, cerinic acid cerul ester, montanic acid cerul ester, myricyl palmitate, stearic acid melissa ester, palmitic acid cetyl ester, stearic acid cetyl ester etc.

At this, alkyl is present in two sides of fatty acid and alcohol.Can use at least a or mixing use more than two kinds.These fatty acid ester melt viscosity is low, the flowability during the printing ink fusion is stable, compares with carbon-carbon bond, and pliability is high, and surface protection power is strong, so printed images can tolerate bending.The pen. of preferred fatty acid ester can make pressurized treatments easy greater than 1.Further, the viscosity during injection is to be advisable less than 20mPas.

As polyamide-based, generally be divided into aromatic polyamide and dimer acid polyamide.During this development of Zai is bright, the polyamide of preferred dimer acid.Further, the acid basis of this dimer acid is preferably oleic acid, linoleic acid, leukotrienes acid or paulownia eleostearic acid.Specifically, Macromelt 6030, Macromelt 6065, Macromelt6071, Macromelt6212, Macromelt 6217, Macromelt 6224, Macromelt 6228, Macromelt 238, Macromelt 6239, Macromelt 6240, Macromelt 6301, Macromelt 6900, DPX 335-10, DPX H-415, DPX 335-11, DPX 830, DPX850, DPX 925, DPX 927, DPX 1160, DPX 1163, DPX 1175, DPX 1196, DPX1358 (above Henkel plain boiled water corporate system), SYLVAMIDE-5 (Arizona Chemical Co. system), UNIREZ 2224, UNIREZ 2970 (above Union Camp Corp. system) etc.

As glyceride, can be selected from following one or more: the extreme fixed oil of the extreme fixed oil of rosin fat, agnolin, sclerosis castor oil, partial hydrogenation castor oil, soybean oil, colza oil, vegetalitas is fixed oil etc. extremely.

As the wax class, the petroleum-type wax of concrete can give an example paraffin, microcrystalline wax etc.; The plant class wax of candelila wax, palm wax etc.; The higher fatty acid and the higher alcohol of Tissuemat E and sclerosis castor oil, stearic acid, docosanoic acid etc.; The ketone of stearone, laurone etc.; Particularly preferred fatty acid esteramides, saturated or unsaturated fatty acid acid amides, fatty acid ester.

Further, as long as other ink composition such as above-mentioned fatty acid, fatty acid amide, glyceride, wax suitable, can use their various combinations.

In addition, painted drug etc. is with aforementioned identical.

The mixing of above-mentioned composition, the device of dispersion can use various known pulverizing or diverting device, have no particular limits.In these devices, there are high-speed rotary mill, roller mill, container Rated current media mill, stirred media mill, jet mill or the like as well as the distinction between the rotary cylinder mill, vibrating ball mills, centrifugal ball mills, stirred media mill and colloid mill distinction, for example, shear mill, cage mill, hammer mill, centrifugal classification grinding, pounding mill, grinding friction, centrifugal mill, ball mill bearing ring, the ring roller mill, desktop grinding, turning milling, tube mill, cone mill, triangular cone grinding, cylindrical grinding, step mill, centrifugal fluidized grinding, circular grinding, high speed disperser, doors mixer, bead mill, sand mill, pearl mill, coconut-like mill, pin mill, mixing mill, universal mill century mill, grinding pressure, grinding mixer, two roll extruder, a two roll mill, three-roll mill, an extruder, mixer, stone, KD mill, a planetary mill, a ring mill, stirred tank type mixing mill, vertical-type flow pipe stirred mill, ball mill, paddle mixers, tower mill, vertical ball mill, centrifugal mill, sand mill, attritor mill, planetary mill, vibration mill, mobile jet mixer, nail grinding, Microfluidiser, homomixer, with pin bead mill, horizontal type bead mill, pin mill and so on.

Above-mentioned pulverizing or dispersal device mix, pulverize, disperse the back with toner materials and the toner composition liquid that forms melts under the state keeping, and import the portion 14 that stockpiles; Make its nozzle 11 ejections,, or will but solidify with the toner composition liquid cooling that above-mentioned pulverizing or dispersal device obtain earlier from the formation drop from drop injection unit 2; Carry out coarse crushing, this meal is minced to import stockpiles portion 14, behind the heating and melting; From nozzle 11 ejections of drop injection unit 2, thereby form drop.

Then, explanation will contain the toner composition liquid particlesization of radioactive ray hardening material, and through rayed the anti-ying of sclerosis, the toner composition liquid when forming particulate take place.

Here, the radiation-curable material may, for example generally used as radiation-sensitive or radiation-curing resin, a known resin cyclized polyisoprene, cyclized polybutadiene, polyether poly (meth) acrylate , polyvinyl alcohol, cinnamic esters, phenol novolak resins, glycidyl methacrylate, polyethylene, chlorinated poly-methyl styrene and the like.

These radioactive ray hardening materials can dilute with solvent or polymerizable monomer, add radioactive ray glue and join or the radioactive ray polymerization initiator.As polymerizable monomer, the propylene class monomer of the vinyl aromatic monomers of can give an example styrene, AMS, vinyltoluene, chlorostyrene, divinylbenzene etc., (first) acrylic acid, (first) methyl acrylate, (first) acrylic acid n-butyl ester, (first) acrylic acid hydroxyethyl ester, ethylene glycol two (first) acrylic ester, (first) vinyl cyanide etc.; The vinyl ester monomer of formic acid vinyl esters, jealous woman acid vinyl esters etc.; The vinyl halides base class monomer of chloro vinyl, the inclined to one side vinyl of chloro etc. and terephthalic acid (TPA) two aromatic radical esters, cyanuric acid three aromatic radical esters etc.

These polymerizable monomers can be separately, also can be that two or more combinations is used.As comprise and styrene, (first) acrylic ester, the divinylbenzene of 0.05～3 weight portion when can keep good deciding property, and can prevent shift phenomenon.

Above-mentioned radioactive ray glue joins or the radioactive ray polymerization initiator, can exemplify the triazo-compound of aromatic series triazo-compound, trichloromethyl triazide etc.; Silver halide, double imidazole derivative, quinoline blue pigment etc.In addition, the azo class base polymerization initiator of azobis isobutyronitrile, azo valeronitrile etc.

In addition, the radiation-curable material containing a toner constituent liquid 31 in the float process droplets hardened light wavelength of ultraviolet ~ 480nm, preferably 250 ~ 410nm.As light source, can exemplify high pressure or Cooper-Hewitt lamp.The preferred several mJ/cm of energy that sclerosis needs ²～several J/cm ²

Below, concrete embodiment is described.

Embodiment only is in order to explain, the present invention not to be done any restriction.

(embodiment 1)

The preparation of-colorant dispersion-

At first, as colorant, the dispersion liquid of preparation carbon black.

Carbon black (Rega1400, Cabot corporate system) 17 weight portions, face material spreading agent 3 weight portions are dissolved in acetate ethyl ester 80 weight portions, and the mixer with having the paddle plumage once disperses.This face material spreading agent can use above-mentioned AJISPERPB821 (corporate system of aginomoto Finetech).With a dispersion liquid obtaining with the in addition powerful shearing force of horizontal type wet type dispersion machine (Dyno-mill), thereby can carry out fine dispersion, make the secondary dispersion liquid that the above agglutination body of 5 μ m is removed fully.

The adjustment of-wax dispersion-

Then, wax dispersion is adjusted.

Palm wax 18 weight portions, dispersing agent for wax 2 weight portions are added in acetate ethyl 80 weight portions, once disperse with mixer with paddle.This dispersion liquid is stirred on one side, Yi Bian be warmed up to 80 ℃, make palm wax dissolving after, fluid temperature is reduced to room temperature, the wax particle is separated out, so that maximum particle diameter becomes below the 3 μ m.As dispersing agent for wax, make styrene acrylic acid butyl co-polymer be grafted on the material on the Tissuemat E.With the dispersion liquid that obtains further with above-mentioned liquid with horizontal type wet type dispersion machine, apply and carry out finely dividedly with powerful shearing force, maximum diameter is adjusted at below the 2 μ m.

The preparation of-toner composition dispersion liquid-

Then, the toner component dispersion liquid that the resin as binding resin, above-mentioned colorant dispersion and above-mentioned wax dispersion have following composition has been added in preparation.To add in acetate ethyl 840 weight portions as vibrin 100 weight portions of binding resin, above-mentioned colorant dispersion 30 weight portions, wax dispersion 30 weight portions, and carry out stirring in 10 minutes, its homogeneous is disperseed with mixer with stirring blade.The aggegation that can not produce face material and wax particle owing to the impact of solvent dilution.In addition, the electric Den degree of leading of this dispersion liquid is 1.8 * 10 ^-7S/m.

The work system of-toner-

The nozzle 11 of the drop injection unit 2 of the manufacturing installation of the toner that the dispersion liquid supply that obtains is above-mentioned.The film 12 that uses is at external diameter 8.0mm, and thickness is on the nickel plate of 20 μ m, and the diameter that uses electrocasting to process garden shape is that the squit hole (nozzle) 11 of 10 μ m obtains.Squit hole is staggered layout, and the distance between each squit hole is 100 μ m, and nozzle only is provided with in the scope of the about 5mm φ in the center of nozzle plate.Effective ejection hole count on calculating this moment is about 1000.

After the dispersion liquid preparation, make the system condition, after the drop ejection,, make the toner parent particle through this drop of dry solidification with following toner.

(toner is made the system condition)

Dispersion liquid proportion: ρ=1.154g/cm ³

Dry air flow: device inner drying nitrogen 30.0L/ branch

Dry temperature in: 60 ℃

Dry outlet temperature: 45 ℃

Dewpoint temperature :-20 ℃

Drive vibration number: 180kHz

The toner particle of dry solidification uses the filtrator of the pore with 1 μ m to attract to capture, and obtains the toner parent particle thus.Particulate to trapping is measured size distribution with flow-type particle image resolver (FPIA-2000), and the mensuration result under following condition determination is weight average particle diameter D ₄Be 5.1 μ m, number average particle diameter D _nBe 4.9 μ m, D ₄/ D _nBe 1.04.

The evaluation of-toner-

To the toner that obtains, carry out following evaluation, its result lists in table 1.

< size distribution >

Carry out following explanation to using flow-type particle image analytical equipment (Flow Particle Image Analyzer) to carry out method for measuring.

Use the mensuration of flow-type particle image analytical equipment, for example can use the flow-type particle image analytical equipment FPIA-2000 of East Asia medical electric company (strain) system toner, toner particle and additive.

Mensuration is performed such, and promptly uses filtrator that fine impurity is removed, and its result does, 10 ^-3Cm ³Water in measurement range (for example justifying mutually electric diameter is more than the 0.60 μ m; Less than 159.21 μ m) be in the 10ml water of population below 20, add the several nonionic class surfactants ContaminonN of the pure medicine corporate system of light (preferably with), further; Add and measure sample 5mg; With STM corporate system UH-50 type ultrasonic disperser, at 20kHz, 50W/10cm ³Condition under, carry out 1 minute dispersion treatment, and then add up to 5 minutes dispersion treatment, obtaining particle concentration is 4000～8000/10 ^-3Cm ³The sample dispersion liquid of (particle to measure the mutually electric diameter range of circle is an object).To this sample dispersion liquid measure have 159.21 μ m more than the 0.60 μ m less than the size distribution of particle of the mutually electric diameter of circle.

Make the stream of sample dispersion liquid, this stream streamwise expansion through the mobile part of flat transparent of the about 200 μ m of thickness.In order to form the light path of reporting to the leadship after accomplishing a task with the thickness of mobile part, flashlamp and CCD camera be installed in for mobile part becomes opposite location.Between sample dispersion liquid flow periods, in order to obtain the image of particle, flashlamp whenever at a distance from flash of light in 1/30 second once consequently obtains the two dimensional image of each particle in the certain limit that is parallel to the part that flows.From having the diameter in the garden identical, calculate the garden equivalent diameter with the area of the two dimensional image of each particle.

With about 1 minute, just can measure the garden equivalent diameter of the particle more than 1200, and measure number that distributes based on the garden equivalent diameter and particle ratio (number %) with regulation garden equivalent diameter.Result (frequency % and accumulation %) is as shown in table 1, and the scope of 0.06～400 μ m is divided into 226 sections.In the mensuration of reality, to the garden equivalent diameter be more than the 0.06 μ m 159.21 μ m less than the particle of scope measure.

< carried charge >

Measure with aspiration-type carried charge determinator.Specifically, be that the toner of 200～250mg is attracted to the faraday's instrument with the filtrator that can capture toner with weight, connect electronic device, the total charge dosage of the toner that attracts is measured.Will gaining in weight on the filtrator weight of measuring in advance as the toner weight on the filtrator; Chemical Libra with 5 precision measures; Total charge dosage is removed with the toner weight that traps, and the value that obtains like this is as the carried charge (q/m) of unit weight.The commercially available carried charge determinator with same measuring principle has " the 210HS-2A type " of TREK Japan corporate system.But in this mensuration, used homemade determinator with same structure.As the toner catcher/filter, used the glass microfiber (Whatman corporate system) of diameter 21mm.The length of pull up time can cause mensuration poor hardly, and still, in this mensuration, pull up time was defined in 30 seconds.

(NH) carried charge under the normal temperature high humidity

In temperature is that 30 ℃, humidity are to measure with above-mentioned carried charge determination method in 90% the laboratory environment.Sample was placed 12 hours in this environment, measured then.

< carried charge distribution >

The carried charge of toner distributes and measures with carried charge measure of spread device (Hosokawamicron corporate system E-Spart analyser EST-2 type).Specifically, be the toner suction mouthpart that a certain amount of toner is directly imported the mensuration machine with feeder, measure carried charge and distribute.As the distribution index of carried charge, with the dispersion of distribution of 1/2nd high positions of maximum frequency (peak) value [q/d] and maximum frequency, promptly so-called half breadth is represented.As the characteristic of toner, it is more sharply good more that carried charge distributes, but generally have the big more tendency of the high more half breadth of carried charge.

< line reproducibility >

Developer is imported commercially available manifolder (Imagio Neo 271; Ricoh's corporate system) transformation apparatus that developer part has been transformed carries out actual duplicating with Ricoh's corporate system 6000 paper of image occupation rate 7% and tests.The thin thread part and the original copy document of the 10th the image at initial stage and the 30,000 's image are compared, amplify 100 times with optical microscope and observe, with line the state and the comparison of grade sample of incompleteness, carry out 4 grade evaluations simultaneously.◎＞zero＞△＞* height of presentation video quality order.Particularly the evaluation of " * " can not be adopted as product.When using the toner of negative charging polarity, use organic electrostatic latent image carrier; Use the uncrystalline silicon electrostatic latent image carrier during toner of just charged polarity.

In developing method 1, with toner with the direct conveyance of air-flow to the development position, develop with powder cloud.In developing method 2, as carrying device, with the resin-coated carrier that uses in the existing electrofax.Material below carrier adopts.

(carrier)

Core material: the spherical ferrite particle of mean grain size 50 μ m

Coating material composition material: silicone resin

Silicone resin is distributed in the toluene, behind the adjustment dispersion liquid, under warm-up mode to the coating of spraying of above-mentioned core material, calcining, cool off after, process the carrier particle of average coating resin film thickness 0.2 μ m.

(embodiment 2)

Except the drop ejection unit 2 of the vibration generating arrangement of forming by trumpet type ticker head 13 that uses Fig. 7, complete identical with embodiment 1, make desired toner.The weight average particle diameter D of toner ₄Be 5.0 μ m, number average particle diameter D _nBe 4.8 μ m.To the toner that obtains, carried out above-mentioned evaluation.The result lists in table 1.

(embodiment 3)

Except ten thousand types by bright that use Fig. 8 vibrate the drop ejection unit 2 of molecular vibration generating arrangement 13, operate equally in embodiment 1 fully, obtain the toner of purpose.The weight average particle diameter D of toner ₄Be 5.2 μ m, number average particle diameter D _nBe 5.0 μ m.To the toner that obtains, carry out above-mentioned evaluation.The result lists in table 1.

(embodiment 4)

The piezoelectrics that will in embodiment 1, be used in drop injection unit 2 promptly vibrate generation portion 21 and become the piezoelectrics that resonant frequency is 540kHz, and will drive vibration number and become 540kHz.In addition, the complete and embodiment of portion operates equally, obtains desired toner.The weight average particle diameter D of toner ₄Be 5.2 μ m, number average particle diameter D _nBe 4.8 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(embodiment 5)

To become the piezoelectrics that resonant frequency is 1.2MHz at the piezoelectrics (vibration generation portion 21) that embodiment 1 is used in drop injection unit 2, and will drive vibration number and change 1.2MHz into.In addition, operate equally with embodiment 1, the toner of purpose.The weight average particle diameter of toner (D4) is 5.5 μ m, and number average particle diameter (Dn) is 4.8 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(embodiment 6)

Except the nozzle 11 of the film 12 that will in embodiment 1, use is that squit hole becomes the distance 75 μ m between each squit hole, other are all operated with embodiment 1 equally, obtain the toner of purpose.Theoretic effective ejection hole count is about 1600.The weight average particle diameter D of the toner that obtains ₄Be 5.3 μ m, number average particle diameter D _nBe 4.9 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(embodiment 7)

Except the nozzle 11 of the film 12 that will in embodiment 1, use is that squit hole becomes the distance 50 μ m between each squit hole, other are all operated with embodiment 1 equally, obtain the toner of purpose.Theoretic effective ejection hole count is about 2200.The weight average particle diameter D of the toner that obtains ₄Be 5.8 μ m, number average particle diameter D _nBe 5.2 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(embodiment 8)

Except the thickness of the film 12 that will in embodiment 1, use becomes 10 μ m, other are all operated with embodiment 1 equally, obtain desired toner.The weight average particle diameter D of the toner that obtains ₄Be 5.2 μ m, number average particle diameter D _nBe 5.0 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(embodiment 9)

Except the thickness of the film 12 that will in embodiment 1, use becomes 50 μ m, other are all operated with embodiment 1 equally, obtain desired toner.The weight average particle diameter D of the toner that obtains ₄Be 5.2 μ m, number average particle diameter D _nBe 5.1 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(embodiment 10)

Except the thickness of the film 12 that will in embodiment 1, use becomes 200 μ m, other are all operated with embodiment 1 equally, obtain desired toner.The weight average particle diameter D of the toner that obtains ₄Be 5.3 μ m, number average particle diameter D _nBe 5.0 μ m.Toner to obtaining carries out above-mentioned evaluation.The result lists in table 1.

(Comparative Examples 1)

The preparation of-toner composition dispersion liquid-

The dispersion liquid of colorant and wax and the dispersion liquid that added resin are by with the condition preparation same with embodiment 1.

The work system of-toner-

With the device of using among the embodiment 1, become such device, promptly this device has the storage part of storage dispersion liquid and this storage part is applied the piezoelectricity pulse and can make the head of drop from the nozzle ejection through the flexible of piezoelectrics.Make the system condition with following toner, after the drop ejection, this droplet drying is solidified, make toner thus.In addition, the device of embodiment 1 is that nozzle self is applied vibration, and the device of Comparative Examples 1 is to apply the piezoelectricity pulse to the dispersion liquid storage part, therefore has very big difference.

(toner is made the system condition)

Dispersion liquid proportion: ρ=1.154g/cm ³

Dry air flow: device inner drying nitrogen 30.0L/ branch

Dry temperature in: 60 ℃

Dry outlet temperature: 45 ℃

Dew point temperature :-20 ℃

Piezoelectricity pulsed frequency: 20kHz

The toner particle of dry solidification, the filtrator with pore of 1 μ m attracts to capture.The size distribution of the particle that traps is measured with flow-type particle image resolver (FPIA-2000), its as a result the time weight average particle diameter be 7.8 μ m, number average particle diameter is 5.2 μ m, what obtain is the broad toner parent particle of size distribution.In addition, to the toner that obtains, carry out above-mentioned evaluation, the result lists in table 1.

(comparative example 2)

The preparation of-dispersion liquid-

The dispersion liquid of colorant and the dispersion liquid that adds resin and wax are used with embodiment 1 same condition to prepare.

The work system of-toner-

With the device of using among the embodiment 1; Become such device; Promptly this device has the storage part of storage dispersion liquid and this storage part is applied the flexible electric pulse that takes place through piezoelectrics, further uses with the sound equipment lens and restrains and head that the pressure pulse that obtains makes drop spray from nozzle.In addition, the device of embodiment 1 is that nozzle self is applied vibration, and the device of comparative example 2 is to apply the piezoelectricity pulse to the dispersion liquid storage part, therefore has very big difference.

The toner particle of dry solidification, the filtrator with pore of 1 μ m attracts to capture.The size distribution of the particle that traps is measured with flow-type particle image resolver (FPIA-2000), its as a result the time weight average particle diameter be 7.2 μ m, number average particle diameter is 5.6 μ m, what obtain is the broad toner parent particle of size distribution.In addition, to the toner that obtains, carry out above-mentioned evaluation, the result lists in table 1.

Table 1

	Carried charge (μ C/g)	NH carried charge (μ C/g)	Carried charge distribution peak value (fc/ μ m)	Carried charge distribution half breadth (fc/ μ m)	Line reproducibility (development method 1)	Line reproducibility (development method 2)
							Embodiment 1	-33.5	-31.8	-0.42	0.13	◎	◎
Embodiment 2	-31.3	-30.2	-0.43	0.16	◎	◎
							Embodiment 3	-32.5	-29.8	-0.41	0.17	○	○
Embodiment 4	-33.5	-31.6	-0.41	0.15	◎	◎
							Embodiment 5	-31.9	-30.0	-0.39	0.15	◎	◎
Embodiment 6	-30.1	-26.9	-0.37	0.16	◎	◎
							Embodiment 7	-30.9	-28.0	-0.38	0.17	◎	○
Embodiment 8	-33.0	-28.5	-0.35	0.16	◎	◎
							Embodiment 9	-32.5	-30.2	-0.40	0.17	◎	◎
Embodiment 10	-33.7	-32.3	-0.43	0.16	○	○
							Comparative Examples 1	-25.4	-24.3	-0.18	0.25	△	×
Comparative Examples 2	-27.4	-26.4	-0.24	0.32	○	△

As shown in table 1, the present invention can make toner expeditiously, and the characteristic of toner is also very good.In addition, the image with the toner for preparing in the present invention develops and obtains can verily reproduce electrostatic latent image, and image quality is good.

Below, with reference to the figure below Figure 17 other embodiment of the present invention is described.

At first, the drop injection unit in this embodiment of example is described with reference to Figure 17 to Figure 19.Figure 17 sprays the front view (FV) of unit mode for this drop, and Figure 18 is the left side side view from Figure 17, and Figure 19 is the oblique view of vibration unit in this drop injection unit.

Drop injection unit 102 is identical with above-mentioned embodiment, and the film 112 that comprises is formed with a plurality of nozzles 111 on it; Vibration unit 113 vibrates above-mentioned film 112; And; Channel member 115 between film 112 and vibrating mass 113, forms the portion that stockpiles 114 that toner composition liquid 10 is provided; This toner composition liquid 10 contains resin and colorant at least; The toner composition liquid 10 that stockpiles in the portion 114 is supplied through woven hose 118, in addition, the pipeline 119 of liquid circulation usefulness can be set as required.

Shown in figure 19, in vibration unit 113, the face on the opposite of the faying face 113b that vibration generating arrangement 121 combines with amplitude multiplying arrangement 122, i.e. vibration plane 113a, the area of this face is greater than the area of this faying face 113b.Vibration plane 113a is a rectangle.At this moment, the long limit b of vibration plane 113a is that (a) big more vibration area is also big more for long limit b/ minor face with the ratio of minor face a.Therefore, the viewpoint from production effect is preferably formed (long limit b/ minor face relation a)＞2.0.And corresponding with the rectangle vibration plane 113a of this vibration unit 113, film 112 also forms the rectangle that becomes shown in figure 20.In addition, other structures such as material, shape and so on are identical with aforementioned embodiments, omit explanation at this.

In the drop injection unit 102 of said structure; When shown in Figure 20 (a) and (b) with film 112 around fixedly the time; Film 112 forms cross section shown in Figure 20 (b), on direction of vibration, makes periodic vibration, and fundamental vibration becomes shown in figure 21; Be film 112 around become vibration node, the displacement Δ L at center 0 be a maximum.In addition, the index vibration mode that also has higher power shown in figure 22.In example shown in Figure 22, in 2.0, that is, it is in 2.0 that 3 place's region R are arranged in the film 112 to film 112, and nozzle 111 can be set in these zones at the ratio R of the maximal value Δ Lmax of the displacement Δ L of direction of vibration and minimum value Δ Lmin.

In above-mentioned droplet treatment device; Form the vibration plane of amplitude multiplying arrangement in the vibration unit bigger than the faying face of this amplitude multiplying arrangement and vibration generating arrangement be combined into; So just can make film that bigger vibration takes place with less vibration generating arrangement; Produce big displacement quantity, and improve the production efficiency that unicity is disperseed toner.At this moment, if vibration plane and faying face are rectangle, and the ratio of long limit and minor face is more than 2.0, can guarantee to obtain big vibration area.

Secondly, give an example with reference to Figure 23 and Figure 24 other drop injection units of this embodiment are described.

Figure 23 is the front view (FV) of this drop injection unit pattern, and Figure 24 is the side view on Figure 24 right side.Like the explanation of being done among Fig. 7 of front and Fig. 8; In the ordinary course of things; Generating means for mechanical vibration is the combination of vibration generating arrangement and amplitude multiplying arrangement, and its size is followed reducing of vibration frequency and increased, therefore can be according to required frequency; Suitably on vibration unit, directly implement perforate processing, the portion that stockpiles is set.The whole portion of stockpiling is effectively vibrated.In this case, so-called vibration plane promptly is defined as the face of having been puted up the film with a plurality of nozzles.

At this, this structure applications in the above-mentioned vibration unit 113 that vibration plane is formed greater than the drop injection unit 102 of faying face, is become shown in the part of Figure 24 middle section in this example, the structure that stockpiles portion 114 is set on amplitude multiplying arrangement 122.Amplitude multiplying arrangement 122 preferably is fixed on the side wall surface of particulate formation portion 3 through fixture.Consider to prevent vibration loss, also can use elastic body to fix.In addition, can also be set up in parallel a plurality of portions 114 that stockpile in order to form optimal vibration.

Below, describe with concrete embodiment to above-mentioned embodiment, but the present invention is not limited to following embodiment.

(embodiment 11)

-preparation colorant dispersion-

At first, preparation is as the carbon black dispersion liquid of colorant.

Carbon black (Regal400, Cabot corporate system) 17 weight portions, face material spreading agent 3 weight portions are dissolved in acetate ethyl ester 80 weight portions, and the mixer with having the paddle plumage once disperses.This face material spreading agent uses dispersible pigment dispersion AJISPER PB821 (corporate system of aginomoto Finetech).A dispersion liquid obtaining with the in addition powerful shearing force of horizontal type wet type dispersion machine, is carried out trickleer dispersion, make the secondary dispersion liquid that the above agglutination body of 5 μ m is removed fully thus.

The adjustment of-wax dispersion-

Then, wax dispersion is adjusted.

Palm wax 18 weight portions, dispersing agent for wax 2 weight portions are added in acetate ethyl 80 weight portions, once disperse with mixer with paddle.This dispersion liquid is stirred on one side, Yi Bian be warmed up to 80 ℃, make palm wax dissolving after, fluid temperature is reduced to room temperature, the wax particulate is separated out, maximum particle diameter becomes below the 3 μ m.Dispersing agent for wax makes styrene acrylic acid butyl co-polymer be grafted on the material on the Tissuemat E.The dispersion liquid that obtains further applied with horizontal type wet type dispersion machine carry out finely dividedly with powerful shearing force, maximum diameter is adjusted at below the 2 μ m.

The preparation of-toner composition dispersion liquid-

Then, prepare the toner composition dispersion liquid that has added the resin as binding resin, above-mentioned colorant dispersion and above-mentioned wax dispersion and had following composition.

To add in acetate ethyl 840 weight portions as vibrin 100 weight portions of binding resin, above-mentioned colorant dispersion 30 weight portions, wax dispersion 30 weight portions, stir 10 minutes, make its even dispersion with mixer with stirring blade.The aggegation that the impact of not diluting because of solvent produces face material and wax particulate.

The work system of-toner-

The dispersion liquid that obtains is offered the stockpile portion 114 of Figure 17 to drop injection unit 102 illustrated in fig. 19.The film 112 that uses is on the nickel plate of electrocasting processing, form diameter and be 10 μ m garden shape nozzle 11 and with 100 μ m at interval interleaved arrange.Nozzle 11 is provided with the vibration plane 113a of face in the face of vibration rotating unit 113.

In addition, vibration unit 113 uses the device of combining vibration generating means 121 and amplitude multiplying arrangement 122.Vibration generating arrangement 121 the has been lamination piezoelectrics of two layers of thickness 7.0mm diameter 20mm, amplitude multiplying arrangement 122 has the rectangle vibration plane of long limit 50mm/ minor face 10mm.In addition, the peak swing of film 112 is 4.0 μ m in each embodiment.

Behind the preparation dispersion liquid, make the system condition,, make toner parent particulate after the drop ejection this droplet drying being solidified in order to following toner.

(toner is made the system condition)

Dispersion liquid solid constituent: 7.0%

Dispersion liquid proportion: ρ=1.154g/cm ³

The dry air flow: disperse the nitrogen 2.0L/ branch of usefulness,

Device inner drying nitrogen 30.0L/ branch

Dry temperature in: 60 ℃

Dry outlet temperature: 45 ℃

Dewpoint temperature :-20 ℃

Drive vibration number: 40kHz

Toner particle behind the dry solidification captures with cyclone separator, obtains toner parent particulate thus.Particulate to trapping is measured size distribution with flow-type particle image resolver (FPIA-2000), and the mensuration result under following condition determination is weight average particle diameter D ₄Be 5.4 μ m, number average particle diameter D _nBe 5.0 μ m, D ₄/ D _nBe 1.04.In addition, the toning dosage of per hour producing is 230g.

The evaluation of-toner-

Toner to obtaining is estimated as follows, and its result lists in table 2.

< size distribution >

Assay method according to the use flow-type particle image analytical equipment (Flow Particle ImageAnalyzer) of front narration is tested.

< line reproducibility >

Developer is imported developer part commercially available manifolder (the Imagio Neo 271 through having transformed; Ricoh's corporate system) transformation apparatus is that Ricoh's corporate system 6000 paper of 7% are carried out and duplicated operation with the image occupation rate.The 10th image at initial stage and the thin thread part and the original copy document of the 30,000 image are compared, amplify 100 times with optical microscope and observe,, make 4 grade evaluations simultaneously with the incomplete state of grade sample alternative line.◎＞zero＞△＞* height of presentation video quality order.Particularly the evaluation of " * " can not be adopted as product.When using the toner of negative charging polarity, use organic electrostatic latent image carrier; Use the uncrystalline silicon electrostatic latent image carrier during toner of just charged polarity.

Transport the carrier of toner with the resin-coated carrier conduct of using in the existing electrofax.Material below carrier adopts.

(carrier)

Core material: the spherical ferrite particle of mean grain size 50 μ m

Coated material composition material: silicones

Silicones is distributed in the toluene, behind the adjustment dispersion liquid, under warm-up mode to the coating of spraying of above-mentioned core material, sintering, cool off after, processing coated with resin film average thickness is the carrier particles of 0.2 μ m.

(embodiment 12)

Among the embodiment 12, the vibration unit 113 of drop injection unit 102 except the rectangle vibration plane 113a that uses long limit 50mm/ minor face 5mm and vibration frequency as the 100kHz, other and embodiment 11 are identical, obtain desired toner with this.The weight average particle diameter D of toner ₄Be 5.2 μ m, number average particle diameter D _nBe 4.9 μ m.In addition, the toning dosage of per hour producing is 200g.Toner to obtaining carries out above-mentioned evaluation, has shown evaluation result in the table 2.

(embodiment 13)

Among the embodiment 13, except 10 drop injection units 2 being set up in parallel in particulate formation portion 3 tops, other and embodiment 11 are identical, obtain desired toner with this.The weight average particle diameter D of toner ₄Be 5.3 μ m, number average particle diameter D _nBe 4.9 μ m.In addition, the toning dosage of per hour producing is 2100g.Toner to obtaining carries out above-mentioned evaluation, has shown evaluation result in the table 2.

(embodiment 14)

Among the embodiment 14, except the vibration generating arrangement 121 of vibration vibration unit 113 adopts the fixing ten thousand bright type Vib.s of anchor poles, other and embodiment 11 are identical, obtain desired toner with this.The weight average particle diameter D of toner ₄Be 5.4 μ m, number average particle diameter D _nBe 5.1 μ m.In addition, the toning dosage of per hour producing is 235g.Toner to obtaining carries out above-mentioned evaluation, has shown evaluation result in the table 2.

(embodiment 15)

Among the embodiment 15, the drop injection unit of in adopting Figure 23 and Figure 24, explaining 2 that in amplitude multiplying arrangement 122, has formed the portion that stockpiles 114, other and embodiment 11 are identical, obtain desired toner with this.Stockpiling the vibration plane 113a that portion 114 forms 10 amplitude multiplying arrangements 122.The weight average particle diameter D of toner ₄Be 5.3 μ m, number average particle diameter D _nBe 5.0 μ m.In addition, the toning dosage of per hour producing is 200g.Toner to obtaining carries out above-mentioned evaluation, has shown evaluation result in the table 2.

(Comparative Examples 3)

Example adopts and embodiment 11 same structures as a comparison, but uses the drop injection unit 2 that does not possess amplitude multiplying arrangement 122 to come liquid droplets, obtains desired toner.At this moment, the amplitude of film 112 is 0.8 μ m.

In this Comparative Examples 3, liquid drop speed is slow, and the phenomenon of the synthetic drop of several drops took place before drying.And then, because the obturation of disperse particles becomes and can not spray through about about the 10 minutes nozzles with nearly half after drop sprays, almost stop after 30 minutes spraying.The output of toner also reduces thereupon, and the toning dosage of 30 minutes work production is 2g.The weight average particle diameter D of toner ₄Be 10.4 μ m, number average particle diameter D _nBe 5.3 μ m.

Table 2

	Weight average particle diameter (μ m)	Number average particle diameter (μ m)	Production per hour (g)	Line reproducibility
					Embodiment
11	5.4	5.0	230	◎
					Embodiment 12	5.2	4.9	200	◎
Embodiment 13	5.3	4.9	2,100	○
					Embodiment 14	5.4	5.1	235	○

[0382]

Embodiment 15	5.3	5.0	200	◎
					Comparative Examples 3	10.4	5.3	2.0 (30min)	*

Can know that according to table 2 the present invention has improved toner and made efficient, and the characteristic of this toner is very good.In addition, adopt the image of the toner development gained of manufacturing of the present invention verily to reproduce electrostatic latent image, picture quality is very superior.

Method for preparing toner of the present invention can improve the production efficiency of toner; Toner according to this method manufacturing has the single dispersiveness of the granularity of having no precedent; Do not have fully or the amplitude that many characteristic requirements values such as flowability common in the existing manufacturing approach, charged characteristic change with particulate almost seldom occurs, can be used as the developer use that is used for developing electrostatic charge image among electronic photo, electrostatic recording and the xeroprinting etc.

Claims (20)

1. a method for preparing toner is characterized by, and carries out following operation:

Periodically the droplet treatment operation is used the droplet treatment device, and toner composition liquid is carried out the periodicity droplet treatment, and with the drop of this toner composition liquid of nozzle ejection; And,

The micronize operation, the drop of the said toner composition liquid that curing is ejected forms toner particle,

Wherein, said droplet treatment device comprises:

Film has a plurality of said nozzles; With,

Vibration unit, by constituting with lower device:

Vibration generating arrangement is used for vibrating;

The amplitude multiplying arrangement has in the face of said film and the vibration plane parallel with said film, is used to amplify the amplitude of the vibration that said vibration generating arrangement takes place,

Said toner composition liquid is to be supplied between said film and the said vibration plane, and to contain resin and colorant at least.

2. method for preparing toner according to claim 1 is characterized by, and said droplet treatment device is formed, and the said vibration plane of said amplitude multiplying arrangement is greater than the faying face of said amplitude multiplying arrangement and said vibration generating arrangement be combined into.

3. method for preparing toner according to claim 2 is characterized by, and said vibration plane in the said amplitude multiplying arrangement and faying face are rectangle, and the ratio of long limit and minor face is more than 2.0.

4. method for preparing toner according to claim 1 is characterized by, and the said amplitude multiplying arrangement in the said droplet treatment device adopts horn shape.

5. method for preparing toner according to claim 1 is characterized by, and said vibration unit is the fixing ten thousand bright type Vib.s of anchor pole.

6. method for preparing toner according to claim 1 is characterized by, and the vibration frequency that the said vibration generating arrangement in the said droplet treatment device produces is that 20kHz is above but less than 2.0MHz.

7. method for preparing toner according to claim 1 is characterized by, in said droplet treatment device, the pressure of paying by the vibration of vibration plane be more than the 10kPa to the following scope of 500kPa with in the interior film zone, said a plurality of nozzle is set.

8. method for preparing toner according to claim 1; It is characterized by; Be provided with in the film zone of said a plurality of nozzles at said droplet treatment device; The ratio R that a plurality of said nozzles are set at vibration of thin membrane direction displacement is 2.0 with in the interior zone, and wherein, R is the maximal value Δ Lmax of said displacement and the ratio of minimum value Δ Lmin.

9. method for preparing toner according to claim 1 is characterized by, and in said droplet treatment device, said film is the metallic film formation of 5 to 500 μ m with thickness, and the opening diameter of said a plurality of nozzles is in 3 to 35 mu m ranges.

10. an apparatus for producing toner is characterized by, and comprising:

The droplet treatment device periodically with toner composition liquid droplet treatment, and sprays the drop of this toner composition liquid from nozzle; And,

Micro-granulating device solidifies the drop by the said toner composition liquid of said droplet treatment device ejection, forms toner particle,

Wherein, said droplet treatment device possesses:

Film is formed with a plurality of said nozzles; With,

Vibration unit, by constituting with lower device:

Vibration generating arrangement is used for vibrating;

The amplitude multiplying arrangement has in the face of said film and the vibration plane parallel with said film, is used to amplify the amplitude of the vibration that said vibration generating arrangement takes place.

Said toner composition liquid is to be supplied to and also to contain resin and colorant between said film and the said vibration plane at least.

11. apparatus for producing toner according to claim 10 is characterized by, said droplet treatment device is formed, and the said vibration plane of said amplitude multiplying arrangement is greater than the faying face of said amplitude multiplying arrangement and said vibration generating arrangement be combined into.

12. apparatus for producing toner according to claim 11 is characterized by, said vibration plane in the said amplitude multiplying arrangement and faying face are rectangle, and the ratio of long limit and minor face is more than 2.0.

13. apparatus for producing toner according to claim 10 is characterized by, the said amplitude multiplying arrangement in the said droplet treatment device adopts horn shape.

14. apparatus for producing toner according to claim 10 is characterized by, said vibration unit is the fixing ten thousand bright type Vib.s of anchor pole.

15. apparatus for producing toner according to claim 10 is characterized by, in said droplet treatment device, the vibration frequency that said vibration generating arrangement produces is that 20kHz is above but less than 2.0MHz.

16. apparatus for producing toner according to claim 10 is characterized by, in the film of said droplet treatment device, the pressure that said toner composition liquid is paid is more than the 10kPa in the zone to the following scope of 500kPa, and said a plurality of nozzle is set.

17. apparatus for producing toner according to claim 10; It is characterized by; Be provided with in the film zone of a plurality of nozzles at said droplet treatment device; The ratio R that a plurality of nozzles are set at vibration of thin membrane direction displacement is 2.0 with in the interior zone, and wherein, R is the maximal value Δ Lmax of said displacement and the ratio of minimum value Δ Lmin.

18. apparatus for producing toner according to claim 10 is characterized by, in said droplet treatment device, said film is the metallic film formation of 5 to 500 μ m with thickness, and the opening diameter of said a plurality of nozzles is in 3 to 35 mu m ranges.

19. the toner that method for preparing toner according to claim 1 is made.

20. toner according to claim 19 is characterized by, and is in 1.00 to 1.15 scopes with the size-grade distribution that the weight average particle size diameter/the number mean particle diameter is represented.

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