CN101301595B - Method of preparing powder and toner for electrophotography, and toner therefor - Google Patents

Abstract

A method of preparing a powder, including bombarding a spray gas to a liquid material through a spray nozzle to form an atomized liquid material; and solidifying the atomized liquid material, wherein 5 to 40% by weight of the spray gas are previously mixed with the liquid material to form a two-phase flow in a flow path of the spray nozzle, and 60 to 95% by weight of the spray gas is further discharged from a circumference of the flow path discharging the two-phase flow and bombarded thereto to uniformly atomize the liquid material.

Description

The manufacture method of powder, electrofax tinter and electrofax tinter

Technical field

The present invention relates to carry out each lattice field of mist projection granulating, chemical products for example, pharmaceuticals, food, the spray-drying of inorganic particle etc. and melt pelletization.The manufacture method that particularly relates to the toner of electrophotography.In detail, relate to solution, dispersion liquid, the liquid material of slurries etc. be with two fluid-type nozzle spray, and obtain the method for toner particle.

Background technology

In the past, this spray granulation plant was that the particle that will generate carries out the spray that various materials are carried out in dust trapping chamber inside, and then, finely particulate or Powdered thing with this material forms come the granular product of Zhi Zao Teeth.

For example, will in solvent, dissolve in advance or be separated into liquid dispersion, or the liquid material that forms with heating and melting, spray in the inside of granulation chamber with nozzle, and make the solvent drying in the inside of this granulation chamber, or make the fused mass cooling, thus form solids.

Such nozzle, the Games big at desired particle diameter closes, and for example surpasses the such Games of 100 μ m and closes, and can use the nozzle of ratary disk type, but obtains closing less than the Games of such small particle diameter of 100 μ m in expectation, use two fluid-type nozzles of external mix formula.

Among these, as the example of using in toner, for example patent documentation 1 and 2 is put down in writing to some extent.

The method of patent documentation 1 makes, the mixing thing that will contain the raw material of toner manufacturing usefulness with melting plant carry out after the fusion with and/or fusion on one side, on one side with this fused mass row to indoor, and spray, thereby obtain toner particle with the gases at high pressure nozzle.The method of patent documentation 2 is, the dispersed substance that will contain the raw material of toner manufacturing usefulness carries out in disperseing medium that differential looses and the dispersion liquid that obtains, make its corpusculed and spray with nozzle, on one side with its conveyance in solidified portion, be cured on one side and obtain shot-like particle.

But, in patent documentation 1 and 2, in the disclosed technology, closing with the Games that spray granulation plant carries out the manufacturing of particle from solution and slurries attitude material, the nozzle of raw material liq can produce blocking problem.

For example in the patent documentation 3, the supply of spraying in the inside of the granulation chamber of device body of the liquid material (ie in solution and slurries attitude raw material) of at least one side composition of the mixture that the technology that discloses is mixed with solid and liquid or the solution of solid dissolving, thereby make the prilling granulator of particle, its problem points is pointed out, is the problem of nozzle blockage.As Xie Decision method, in the hydraulic fluid side, be provided with and make nozzle carry out the pin of change in location of machinery, by pin the solids of jet expansion is removed.

But, in the example of patent documentation 3, Games in mechanical cleaning mechanism closes, do not set up and put pin, for example also need the liquid envelope locking mechanism of moving portion of week etc., therefore structure of nozzle has the problem of too complex, its objective is originally that how will stop up the nozzle that maybe will stop up was recovered as main purpose, so the scope of deviating to cure the symptoms, not the disease not.

As above such, though nozzle is a key element important among the spray granulation plant, but exist the big problem of spray nozzle clogging.

The obstruction of nozzle, to the particle diameter of the particle that generates and control that particle diameter distributes by very big influence.Take place as the obstruction of nozzle, the atomize confusion reigned of liquid, oversize grain takes place, drop directly distribute (particle diameter distribution) broaden.

Particularly require the Games of autofrettage of the toner of hi-vision weight to close, have following problem.For hi-vision weight, the particle diameter of toner distributes will be small particle diameter, and will make it narrow as much as possible.Thus, as the obstruction owing to nozzle oversize grain takes place, particle diameter distributes and to broaden, and in the manufacture method of the toner particle of mist projection granulating, is fatal problem.

The inventor advanced careful research, had obtained removing the obstruction of nozzle, made the invention that good toner particle obtains the manufacture method of toner.

[patent documentation 1] spy opens the 2005-258394 communique

[patent documentation 2] spy opens the 2004-226668 communique

[patent documentation 3] spy opens the 2000-312817 communique

[patent documentation 4] spy opens the 2003-001090 communique

[patent documentation 5] spy opens the 2000-254554 communique

Purpose of the present invention, providing a kind of can the manufacturing does not have nozzle blockage, can make liquid material stable, and supply with sprayer unit equably, has the mist projection granulating method of the toner of particle diameter distribution straitly.

The content of invention

In order to reach above-mentioned purpose, the present invention has following content.First, prilling process of the present invention, supply with the liquid material (spray liquid of spraying, be water and organic solvent and solution and slurries that these substance dissolves or dispersion are formed) and the part of spray gas be pre-mixed, after the two-phase fluid of the gas-liquid mixed of the part of fluent material and spray gas forms, the spray gas (main flow) on every side of the stream of this two-phase fluid and two-phase fluid ejection is conflicted mutually, thus the atomizing granulation.

As spray gas, mainly use air, but, also can use the inert gas of steam and nitrogen etc. according to the difference of operating.

As this method, with fluent material as two-phase fluid, before nozzle for liquid ejection, because liquid charging stock becomes two-phase fluid, thus fluid volumes increase, the essence of fluid the rate of outflow quicken, thus can be to the adhering to of spray nozzle inside, block given anti-.

Further, the spray gas (main flow) of coming out around the ejection stream of this two-phase fluid and two-phase fluid is conflicted, so among jet expansion, form gas stream wall, can adhere to fluent material dispersing around jet expansion thus, thereby can prevent jet expansion to pay the near obstruction of adhering to.

At this moment the air that uses for two-phase fluid is formed utilizes the air that originally is used as spray gas and uses, so use extra air in order to form two-phase fluid with regard to there is no need.One one of the spray gas that spraying is used is used and is got final product.Form the weight ratio preferred 5 of the amount of the amount of gas of above-mentioned two-phase fluid and above-mentioned spray gas (main flow): 95-40: 60, more preferably 10: 90-30: 70, further preferred 10: 90-20: 80.In other words, two-phase fluid forms the spray gas amount of usefulness, preferably accounts for all 5-40 weight % of spray gas, more preferably 10-30 weight %, further preferred 10-20 weight %.Identical, ejection around the ejection stream of two-phase fluid and with the amount of the two-phase fluid and the spray gas of conflicting, preferred 95-60 weight %, more preferably 90-70 weight %, further preferred 90-80 weight %.At this,

Spray gas amount=spray gas (main flow) amount+two-phase fluid forms the gas flow of usefulness.

The too little Games of ratio that two-phase fluid forms the gas flow of usefulness closes, and not only can not form the two-phase fluid of homogeneous, and the gas flow of above-mentioned spray gas (main flow) is by substantial Xiao Minus, so the possibility of the micronize performance that can not get is suitably arranged.

The too big Games of ratio that two-phase fluid forms the gas flow of usefulness closes, and closes with the little Games of the ratio of gas flow with two-phase fluid formation and compares, can further micronize when two-phase fluid forms.But comparatively speaking, the spray gas quantitative change is little, and the micronize that spray gas (main flow) causes can step-down.Thus, spray gas just is difficult to have make has carried out the further micronized energy dispersive of micronized two-phase fluid to a certain degree, preferred relatively ratio, and micronize can step-down.

Nozzle arrangements of the present invention can exemplify as shown in Figure 1.

Fluent material is slurries attitude raw material for example, forms with gas and mixes with separate the two-phase fluid that forms from spray gas in nozzle interior, while once disperse and quicken quilt to the jet expansion conveyance.Further among jet expansion, owing to two-phase fluid forms the further acceleration that the expansion with gas brings, the spray gas (main flow) that sprays with the high speed that expands gradually is to conflicting, and by micronize.This spray gas stream, the outlet ejection that forms around the ejiction opening of two-phase fluid.

The two-phase fluid of nozzle interior forms with gas and mixes once and disperse, and fluid quickens, and can prevent the obstruction of nozzle interior thus.Further, around liquid among the jet expansion (two-phase fluid) ejiction opening, there is the wall of spray gas stream to exist, is suppressed so jet expansion is paid near adhering to also.

At this, the nozzle that uses in the existing spray granulation plant describes.

Two-phase fluid is formed, Pen Wu technology simultaneously, in general, known is the second fluid nozzle of internal mix formula.The general structure of nozzle that is called as the internal mix formula, as shown in Figure 6.For example raw slurry and spray gas are mixed the limit and are formed two-phase fluid in nozzle, and quicken on the limit, at jet expansion, and the further acceleration that brings to the acceleration that exports and owing to the expansion of spray gas, thus spray.Relative therewith, do not form two-phase fluid, and the nozzle of spraying with spray gas, be generally known as external mix formula nozzle, external mix formula structure of nozzle, as shown in Figure 7, for example raw slurry is near jet expansion, quicken to conflicting with the spray gas of ejection at a high speed on expansion limit, limit, thereby sprayed.In Fig. 7, spray gas also further is supplied to eddy current.

The second fluid nozzle of internal mix formula, because unlike the nozzle of external mix formula, the wall that has gas stream around liquid (two-phase fluid) ejiction opening closely is easy to the shortcoming stopped up so pay closely to adhere to and pay at jet expansion therefrom at jet expansion.

The nozzle of external mix formula, liquid charging stock pay near conveyance power at jet expansion, the faint attraction that forms for hydraulic pressure and suction pipe effect by the liquid feed pump apparatus, so extremely, in addition, the rate of outflow of liquid is also slow than internal mix formula, so by the shortcoming that is easy to stop up in nozzle interior.Particularly, the Games that the material of slurries attitude is used closes, and is subject to the precipitation and the aggegation of dispersate, and the influence of separation is easily blocked.

Fig. 6 of the example of prior art and 7 nozzle, because paying at jet expansion does not closely have gas stream wall to exist, or nozzle interior do not have the conveyance function of liquid material, so compare with nozzle of the present invention, close at the Games that is suitable for spray granulation plant, a little less than the outside and inner obstruction of nozzle.Promptly according to the mist projection granulating method of the nozzle that uses these, the particle diameter of the product pellet that obtains distributes wide, contains more thick grain example.

According to mist projection granulating method of the present invention,, do not contain the good particulate and the powder ， Teeth grain of thick grain because the above-mentioned nozzle that blocks of being difficult to like that can produce narrow diameter distribution.

The flow chart of the mist projection granulating method of the manufacture method of powder of the present invention also can be identical with existing method, and is for example shown in Figure 2.Raw material liq is supplied with to nozzle by pump installation from the raw material holding device.Simultaneously, at nozzle, spray gas is supplied to.Spray gas, temperature is adjusted as required.As nozzle, can use for example Fig. 1,3,4 nozzle.Inside raw material from nozzle towards dust trapping chamber is sprayed.The droplets of feed of being sprayed, the conveyance air-flow of being supplied with by other air-supply arrangement is sent to capturing device, is recovered as product.The temperature of this conveyance air-flow can be regulated as required.In addition, the drop of spraying as required, can carry out heat exchange with this conveyance air-flow, and volatile ingredient that also can this conveyance air-flow is emitted.

In addition, in the flow graph of Fig. 2, use Fig. 6, the Games of such nozzle of 7 closes and has represented to carry out the mist projection granulating method with existing method.

Structure as second is to use venturi (venturi), injector or annular nozzle in the formation method of above-mentioned two-phase fluid.Example as venturi shape structure is Fig. 3, is Fig. 4 as an example of injector shape structure.At this, be omitted with right figure, utilize annular nozzle, to have replaced that Games closes almost be identical with the two-phase fluid of Fig. 3 being formed stream with the stream of spray air and fluent material.

As this structure, by using injector, venturi, perhaps annular nozzle can form two-phase fluid dispersedly effectively, also can prevent simultaneously fluent material to the adverse current of gas of supplying tubing.

In the two-phase fluid nozzle of internal mix formula and the such nozzle of the present invention, close as the Games that when two-phase fluid forms, the pressure of liquid flow path is not suitably controlled, for example to the supply pressure of spray gas (gas), the too small Games of the supply pressure of fluent material closes, and might produce the adverse current of fluent material to supplying tubing.But by with injector, when venturi or annular nozzle were used for the formation of two-phase fluid, the Games littler than gas pressure in supply pressure closed, and gas not only can not attract fluent material to the hydraulic fluid side adverse current on the contrary, with its effect to the outlet side conveyance.

Outside the method for above-mentioned venturi etc., liquid is the method for adverse current not, preferably can give the such method to the propulsive force of outlet, if form the method for two-phase fluid, can expect to have identical effect.

As other structure, the formation method of above-mentioned two-phase fluid is to use eddy current.For example the two-phase fluid of Fig. 1 is formed such off-centre, realization (Fig. 5 is the sectional view of the vertical direction in the figure ground of Fig. 1) therefrom with The Fig. 5 of mixing portion of spray gas stream and fluent material.As Fig. 5,, carry out two-phase fluid and form the supply of using spray gas, thereby two-phase fluid is formed with eddy current along the liquid flow path wall.

By two-phase fluid is formed with eddy current, adhere to and volume can be suppressed for the nozzle inner walls face, thereby, can prevent to block.

As other device that forms eddy current, for example be after the formation of two-phase fluid, pay device with configuration turning power on the stream of two-phase fluid before spray gas is conflicted.Pay device as turning power, can exemplify the plate of in stream, placing obstacles, use to flow to change, or on the wall of stream, form spiral goove etc. to certain orientation.As concrete form, such form of Fig. 9 for example.These parts are shown in Figure 10 at the example that nozzle interior is provided with.

As the 3rd structure, above-mentioned spray gas (main flow) is an eddy current.Among the existing spray granulation plant, also be preferred eddy current.But particularly among this method, making this spray gas is eddy current, can suppress the adhering to of jet expansion, thereby anti-clogging in advance, from but preferred.

Structure as the 4th is with the manufacture method of method of the present invention as electrophoto-graphic toner.The manufacture method of toner particle of the device of above-mentioned such structure important document is satisfied in use, to tailing off of the generation of the thick grain that adheres to and produced by the obstruction of nozzle of nozzle, so be a kind of good method.

The 5th structure is the electrophoto-graphic toner particle made from above-mentioned method.The toner particle that this law makes, it is few that the toner of existing mist projection granulating manufactured is compared oversize grain, and particle diameter distributes sharp-pointed, is good electron photograph toner.

The 6th structure is to form above-mentioned two-phase fluid flow path length, more than 4 times of garden conversion diameter D of the squit hole of two-phase fluid.Like this, stable phase fluid is sprayed from the hole, so stable with the conflict situation of spray gas, the result makes atomize become stable.

In other words, too short as the formation flow path length of above-mentioned two-phase fluid, will spray not steady just from the hole ejection before the formation of two-phase fluid is stable.The formation unstability of two-phase fluid, the non-persistent state of ejection state is the undercompounding of gas-liquid, the bubble in the two-phase fluid and the footpath of the drop fully little state that do not become, this moment, well afoot was cut apart in the dispersion of bubble and drop.

Thus, the flow path length that above-mentioned two-phase fluid forms is more than the 4D, and it is sharp-pointed that particle diameter is distributed.

Among Figure 11, represented that above-mentioned two-phase fluid forms the diameter D of the squit hole of flow path length and two-phase fluid.

The present invention provides a kind of nozzle can not block, and spraying of the stable homogeneous of liquid material can be made the mist projection granulating method of the toner with narrow particle diameter distribution.

Description of drawings

Fig. 1 is the skeleton diagram of the structure of nozzle that can use among the manufacture method of powder of the present invention.

Fig. 2 is the flow chart of mist projection granulating method of the manufacture method of powder of the present invention.

Fig. 3 is the skeleton diagram of another structure of nozzle of using among can the manufacture method of powder of the present invention.

Fig. 4 is the skeleton diagram of another structure of nozzle of using among can the manufacture method of powder of the present invention.

Fig. 5 is the sectional drawing of the vertical direction of Fig. 1.

The skeleton diagram of the structure of nozzle of using among the manufacture method of Fig. 6 for the powder of prior art.

The skeleton diagram of another structure of nozzle of using among the manufacture method of Fig. 7 for the powder of prior art.

Another flow chart of the mist projection granulating method that Fig. 8 carries out for the manufacture method of powder of the present invention.

Fig. 9 pays the structure skeleton diagram of device for the turning power in the nozzle that can use among the manufacture method of powder of the present invention.

Figure 10 is for can use the turning power in the nozzle to pay the skeleton diagram of the example that the position is set of device among the manufacture method of powder of the present invention.

Figure 11 forms the skeleton diagram of aperture D (garden conversion diameter) of the squit hole of the length at position and two-phase fluid for the two-phase fluid in the nozzle that uses among the manufacture method of powder of the present invention.

The specific embodiment

Below, this method is applied in the flow process that the Games of the spray granulation plant of electrophoto-graphic toner closes, describe according to Fig. 2.

For example, the raw material for toner that resin for toner and colouring agent and other toner constituent material are formed by from the raw material holding device, supplies to nozzle with the state of fusion or dissolving through pump installation, with spray gas together, in dust trapping chamber, spray.The particle of spraying flows the device conveyance that is captured with the air that supplies to dust trapping chamber in addition, is reclaimed.

Above-mentioned air stream carries out the temperature adjustment by temperature adjustment device, and it decides device (T1) meter side in the suction temperature side.In addition, delivery temperature, delivery temperature side are decided device T 2 sides.Also temperature adjustment device can be set to spray gas, the temperature of spray gas is by temperature adjustment device T3 meter side.

In another example, for example make the raw material for toner by the constituent material of toner resin, colouring agent and other toners is being dissolved under the state of solvent, supply nozzle, by nozzle with after the finely particulate spraying, carry out heat exchange with the air stream of heating, after the solvent evaporation, capture with trap.The heating-up temperature of air stream, preferred more than 30 ℃, more preferably more than 40 ℃, further preferred more than 40 ℃.In addition, with 50 ℃ less than serving as preferred, more preferably 100 ℃ less than.

In the another one example, for example will for example make the raw material for toner by the constituent material of toner resin, colouring agent and other toners be dissolved under the state of solvent, supply nozzle, by nozzle with after the finely particulate spraying, with be cooled to 60 less than, preferred 25 ℃ less than, more preferably 10 ℃ less than the cooling air carry out heat exchange, order captures with trap after but solidifying.

The preferred 90-350 of the temperature of nozzle ℃, more preferably 150-320 ℃.

In another example, raw material for toner disperses in the dispersion solvent of water and organic solvent etc. and the slurry supply nozzle that obtains, be sprayed into particulate by nozzle after, carry out heat exchange with the air stream of heating, solvent evaporation back is captured with capturing device.The heating-up temperature of air stream is preferred more than 30 ℃, more preferably more than 40 ℃, further more preferably more than 45 ℃.In addition, preferred 150 ℃ less than, more preferably 130 ℃ less than, further preferred 100 ℃ less than.

Microdispersed size, preferred middle linear diameter is below the 5 μ m, more preferably below the 1 μ m, more preferably below the 0.5 μ m.At this, the value that the mensuration of middle linear diameter is to use the laser diffraction formula particle size distribution measuring instrument SALD-2000 of Shimadzu Seisakusho Ltd.'s system to measure.

The above-mentioned resin for toner that this method can be used, for example such styrene of polystyrene, poly-p-chlorostyrene, polyvinyl dimethylbenzene and his replacement homopolymers; Styrene p-chlorostyrene co-polymer, styrene ethylene base dimethylbenzene co-polymer, styrene ethylene base naphthalene co-polymer, styrene acrylic acid esters co-polymer, styrene methacrylic acid acid esters co-polymer, styrene α-chloromethyl propylene acid methyl ester co-polymer, the styrene-acrylonitrile co-polymer, styrene ethylene ylmethyl ether co-polymer, styrene ethylene benzyl ethyl ether co-polymer, styrene ethylene ylmethyl ketone co-polymer, the styrene butadiene co-polymer, the phenylethylene co-polymer that styrene-acrylonitrile indenes co-polymer is such; Polychlorostyrene is for ethene; Phenolic resins; Natural sex change phenolic resins; Natural resin sex change maleic acid resin; Acrylic resin; Methacrylic resin; Poly-jealous woman acid vinyl; Silicones; Mylar; Poly-urethane; Polyamide; Furane resins; Epoxy resin; Polyvinyl butyrate; Terpene resin; Coumarone indeneresin; Petroleum line resin etc.Preferred bonding material is phenylethylene co-polymer or mylar.These resins can use separately, and use also can combine more than 2 Ge.

Use as above-mentioned colouring agent has no particular limits.Can suit to select normally used resin.Carbon black for example, aniline dyes, Tie, naphthol yellow S, hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, loess, Huang , titan yellow, poly-azophosphine, oil yellow, hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), the Wu Erkang fast yellow (5G, R), quinoline yellow lake, isoindoline ketone Huang, red Zhu of iron oxide red ， , cadmium red, cadmium mercury is red, crimson antimony, permanent red 4R, para is red, and is red as fire, para chloropharin and nitre aniline red, lithol that fast scarlet G, bright fast scarlet, permanent red (F2R, F4R, FRL, FRLL, F4RH), fast scarlet VD, brilliant scarlet G G, lithol that rubine GX, permanent red F5R, brilliant carmine 6B, pigment scarlet 3B, purplish red 5B, toluidines is dark brown, permanent purplish red F2K, He Liao bordeaux B L, purplish red 10B, nation is brown red, the brown red メ ニ ア system of nation, eosine lake, rhodamine color lake B, rhodamine color lake Y, alizarine lake, thioindigo red B, thioindigo is dark brown, oil red, quinoline mouth+bifurcation ketone is red, pyrazolone red, poly-azophloxine, chrome vermilion, benzidine orange, the oil orange, palladium indigo plant, cerulean blue, alkali is blue to form sediment, peacock blue lake, Victoria blue color lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, and indanthrene blue (RS, BC), indigo, ultramarine, Cyanosis green grass or young crops, anthraquinone blue, Fast violet B, the crystal violet color lake, palladium purple, manganese violet, two (mouth+evil) alkane purple, the anthraquinone purple, chromium chlorine, zinc chlorine, chromium oxide, tie up sharp Dean pigment, jewel chlorine, pigment chlorine B, naphthols chlorine B, the chlorine gold, acid chlorine color lake, peacock chlorine color lake, phthalocyanine chlorine, anthraquinone chlorine, titanium oxide, Xin , lithopone and they mixture etc.

The amount in toner (below, also claim image to form particle) of painted drug has no particular limits, and can have more the selection that purpose is illustrated, but preferred 1-15 weight %, more preferably 3-10 weight %.

This amount 1 weight % less than occasion, the tinting strength, tinting power that image forms particle is low, as surpassing 15 weight %, it is bad that image forms the dispersion of the face material in the particle, it is low that the low and image of tinting strength, tinting power forms the particle electrology characteristic.

Further, as raw material for toner, can contain the wax of releasing agent effect, it can exemplify vegetable waxs such as candelila wax, palm wax, rice wax; Mineral wax such as montan wax, ceresine; The pertroleum wax of paraffin, vaseline etc., the hydrogenation wax of the synthetic hydrocarbon of polypropylene, polyethylene etc., hardened castor oil and hardened castor oil derivative etc.; The derivative of fatty acid of alcohol, ester, acid amides, imines, ketone, metallic soap etc. etc.These materials can use the use that also can combine more than 2 kinds separately.

As the melting point of wax, not special system limit can be selected aptly according to purpose.But preferred 40-160 ℃, more preferably 50-120 ℃, preferred 60-90 ℃ especially.As 40 ℃ of melting points less than, wax has badly heat-resisting keeping quality to be influenced, and surpasses 160 ℃, is easy to take place cold skew during the photographic fixing of low temperature, and the problem that the volume of matter is paid also can take place in addition.

The amount in image formation particle kind of wax, not special system limit can be selected aptly according to purpose.Image is formed particle 100 weight portions, preferred 0-40 weight portion, more preferably 3-30 weight portion.Above-mentioned amount is as surpassing 40 weight portions, and obstruction and deterioration of image quality (Guang swamp that low-temperature fixing can take place are spent height).

Further, as the raw material of toner, preferably contain charge control material.

As this charge control agent, have no particular limits, can from known material, suit to select according to purpose.Use colored materials can make tone variations, so preferably use colourless and even be bordering on the material of white, for example the slaine of the monomer of Buddhist nun's lattice dyestuff, kiton colors, the simple substance that contains chromium metal complex, molybdic acid acid chelate face material, rhodamine, alcoxyl class amine, quaternary ammonium salt (quaternary ammonium salt of fluorine-containing modification), alkylamide, phosphorus or its compound, tungsten or its compound, the active drug of fluorine, salicylic slaine, salicyclic acid derivatives etc.Wherein, the slaine of preferred salicylic slaine, salicylic derivative.They can use separately, also can use by And more than two kinds.

Metal as slaine has no particular limits.Can suit to select for example aluminium, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. according to purpose.

Above-mentioned charged controlling agent, can use the commodity in market, commodity on this market can exemplify Peng Taolong (the ボ Application ト ロ Application) P-51 of quaternary ammonium salt, the E-82 of chomene acids metal complex, the E-84 of salicylic acid metal complexes, the E-89 of phenol condensation product (more than, Orient chemical industrial company system), the TP-302 of quaternary ammonium salt molybdenum match, TP-415 (more than, hodogaya chemical industrial group system), the COPYCHARGEP SY VP 2038 of quaternary ammonium salt, the COPYBLUP R of triphenyl methane derivative, the COPYCHARGE NEG VP 2036 of quaternary ammonium salt, COPYCHARGE NX VP 434 (more than, Hai Kesite (ヘ キ ス ト) corporate system), LRA-901, boron complexes LR-147 (time special (カ one リ Star ト) corporate system in the Japan card), quinoline mouth+bifurcation ketone, azo class face material and other have a sulfonic group, carboxyl, the functional group's of quaternary ammonium salt etc. macromolecule compound etc.

【0036】

Above-mentioned charged controlling agent can with the masterbatch melting mixing after, dissolve and even disperse, perhaps each composition that forms particle with above-mentioned image directly is added in the solvent in dissolving and even when disperseing.Perhaps after forming the particle manufacturing, image is fixed on the surface that image forms particle.

【0037】

The above-mentioned image of above-mentioned charged controlling agent forms the amount in the particle, according to the difference of the having or not of the kind of binding resin, additive, process for dispersing etc. and difference cannot treat different things as the same.But, for example to binding resin 100 weight portions, preferred 0.1-10 weight portion, more preferably 1-5 weight portion.This amount 0.1 weight portion less than the time, image forms the variation of the charged characteristic of particle, as surpassing 10 weight portions, the charging property of image formation particle is too high, the Xiao Guo Minus of master tape controling agent moves back, increase with the attraction of the static of developer roll, can cause the mobile step-down of developer and the step-down of image color.

【0038】

As the organic solvent that can be used for this method, there is no particular limitation, so long as can dissolve or disperse the solvent of above-mentioned toner materials to get final product, can get final product according to suitable selection of purpose, for example, from the viewpoint that is easy to remove, preferred boiling point be 150 ℃ less than volatile material.Specifically, methylol, ethyl alcohol, modification ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, the second month in a season-butyl alcohol, uncle-amyl group alcohol, 3-amylalcohol, octanol, benzyl alcohol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerine, the alcohols of diethylene glycol (DEG) etc.; Methyl cellosolve, cellosolve, ispropyl cellosolve, butyl cellosolve, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diglycol monotertiary methyl ether, the ether alcohol of carbiphene etc.; Hexane, octane, benzinum, cyclohexane, benzene, toluene, the hydro carbons of dimethylbenzene etc.; Carbon tetrachloride, trichloro-ethylene, the halogenated hydrocarbons of tetrabromoethane etc.; Ethylether, trioxane, the ethers of oxolane etc.; Formaldehyde, the aldehydes of acetaldehyde etc.; Acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the ketone of cyclohexane etc.; The formic acid butyl ester, acetate butyl ester, propionic acid ethyl ester, the ester class of cellosolve acetic acid esters etc.; Formic acid, acetate, the acids of propionic acid etc.; Nitropropane, nitrobenzene, dimethyl amine, MEA, pyridine, dimethyl methyl acid amides, the organic compound class of the sulfur-bearing of dimethyl formamide etc., nitrogen; Wherein preferred toluene, dimethylbenzene, benzene, carbon tetrachloride, protochloride methyl, 1,2-dichloroethanes, 1,1,2-trichloroethanes, trichloro-ethylene, chloroform, monochloro benzene, 1,1-dichloroethanes, acetate methyl, acetate ethyl, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Further preferred toluene, dimethylbenzene, methyl ethyl ketone etc.Preferred especially acetate ethyl ester.These may be used alone, two or more kinds can also be used.

【0039】

As the use amount of above-mentioned organic solvent, there is no particular limitation, can get final product according to suitable selection of purpose, preference is as to above-mentioned toner materials 100 weight portions, preferred 100-2000 weight portion, more preferably 200-1500 weight portion, further more preferably 300-1000 weight portion.

【0040】

The evaluation of the particle diameter of toner can be used the value that can your his counting method obtains.

As use can you he the side that distributes of the particle diameter of toner particle of counting method decide device, can exemplify can you he count TA-II and can you he MultisizerII (any also can that he corporate system).The following offside method of deciding describes.At first, in electrolytic aqueous solution 100-150ml, add surfactant (polyoxyethylene alkyl ether) 0.1-5ml as dispersant.At this, electrolyte uses the about 1%NaCl aqueous solution of 1 grade sodium chloride preparation, for example can use ISOTON-II (can that he corporate system).Further add side and decide sample 2-20mg.With the outstanding turbid electrolyte of sample, with the about 1-3 of ultrasonic disperser minute dispersion treatment, then, decide device with above-mentioned side, the aperture of 100 μ m, to the volume of toner particle or toner, it is fixed that number is carried out side, calculates volume distributed median and number and distribute.From the distribution that obtains, can calculate the weight average particle diameter (DV) of toner, number average particle diameter (DN).

【0041】

With particle diameter 2.00 μ m-40.30 μ m less than particle decide object as side, it is 13 that side is decided section, be specially 2.00-2.52 μ m less than; 2.52-3.17 μ m less than; 3.17-4.00 μ m less than; 4.00-5.04 μ m less than; 5.04-6.35 μ m less than; 6.35-8.00 μ m less than; 8.00-10.08 μ m less than; 10.08-12.70 μ m less than; 12.70-16.00 μ m less than; 16.00-20.20 μ m less than; 20.20-25.40 μ m less than; 25.40-32.00 μ m less than; 32.00-40.30 μ m less than.

Embodiment

【0042】

[embodiment A]

The spray granulation plant that uses Fig. 8 to represent, limit change spraying initial conditions (structure of nozzle), use the raw material for toner (mixture of solution state and dispersion slurries attitude) of following dissolving that toner particle is made, to particle diameter distribution (DV, DN) carry out side and decide, obtain DV/DN, and estimate.

Preferred DV/DN is the smaller the better, is that the toner particle as in recent years hi-vision weight correspondence uses, require at least DV/DN be 1.35 less than.Condition beyond the nozzle is identical.

【0043】

Among this evaluation method,, can obtain the narrow product particulate that particle diameter distributes more with the stable more homogeneous of spraying that the spray nozzle part that is provided with in the spray granulation plant carries out.Thus, preferably can make the spraying of the stable homogeneous that the value of above-mentioned DV/DN becomes littler.

【0043】

Among this evaluation method, can obtain just can stabilizing the narrow product particulate of particle diameter distribution of uniform spraying with the spray nozzle part that is provided with in the spray granulation plant.Thus, the value of preferred above-mentioned DV/DN is little of stabilizing the degree of spraying equably.

DV/DN value small particle size distribution more is narrow more, and this manufacture method as toner is preferred.In addition, so narrow particle diameter distributes, and is good as toner particle particularly.In addition, for identical actual use amount, the value of DV is more little, more can be high efficiency obtain particulate, this is preferred as manufacture method.

【0044】

The preparation of-toner solution-

--synthesizing of low molecular weight polycaprolactone ester--

In reactive tank with cooling tube, mixer and nitrogen ingress pipe, 2 moles of addition product 220 weight portions of ethylene oxide that add bisphenol-A, 3 moles of addition product 561 weight portions of third alkylene oxide of bisphenol-A, terephthalic acid (TPA) 218 weight portions, adipic acid 48 weight portions and dibutyl tin oxide 2 weight portions, 230 ℃ of normal pressures, carry out reaction in 8 hours.Then, this reactant liquor is depressed at 10-15mmHg De Minus, after carrying out reacting in 5 hours, added trimellitic anhydride 45 weight portions in reaction vessel, following 180 ℃ of normal pressure carries out reaction in 2 hours, thus synthetic low molecular weight polycaprolactone ester.

Several mean molecule quantities (Mn) of the low molecular weight polycaprolactone ester that obtains are 2,500, and weight average molecular weight (Mw) is 6,700, and vitrification point (Tg) is 43 ℃, and acid number is 25.

【0045】

--preparation of masterbatch (MB)--

As colouring agent De Copper phthalocyanine face material (" LIONOL BLUE FG-7351 ” ， East imported oil China ink is made the strain formula can corporate system) 50 weight portions, mylar (" RS801 "; Sanyo changes into industrial group's system, acid number=10, weight average molecular weight (Mw)=20,000, vitrification point (Tg)=64 ℃) 50 weight portions and water 30 weight portions mix with Henschel blender (Mitsui mine corporate system).With this mixture with two rollers 130 ℃ carry out 45 minutes mixing after, calendering cooling is pulverized the masterbatch that obtains diameter 1mm with pulverizer (Hosokawa corporate system).

【0046】

--preparation of toner predissolve liquid--

In reaction vessel with stirring rod and thermometer, add above-mentioned unmodified polyester 119.88 weight portions, (this dispersant comprises that the styrene acrylic butyl ester co-polymer of using 70 parts is grafted to Tissuemat E (products of 30 weight portions) to the dispersing agent for wax of palm wax 20.0 weight portions and 12.0 weight portions, CCA (" salicylic acid metal complex E-84 ", Orient chemical industrial company system) 4.0 weight portions, above-mentioned masterbatch 20.0 weight portions, above-mentioned acetate ethyl ester 200.0 weight portions as organic solvent, under agitation be warmed up to 80 ℃, 80 ℃ maintenances after 5 hours, be cooled to 30 ℃ with 1 hour, the raw material dissolving obtains dispersion liquid.

The raw material dissolving dispersion liquid that obtains is ground (Ultra Visco Mill with pearl, the IMECS corporate system) under dish circular velocity 6m/ second and 0.5mm zirconium oxide bead filling 80 volume %, by 3 times, carry out the dispersion of Shang Shu Copper phthalocyanine face material and palm wax, obtain the lysate that gives of toner.The dispersion particle diameter of palm wax is 0.3 μ m for (middle linear diameter).

【0047】

--synthesizing of heavy polymer--

In the reaction vessel that cooling tube, mixer and nitrogen ingress pipe are housed, add 2 moles of addition product 682 weight portions of bisphenol-A ethylene oxide, 2 moles of addition product 81 weight portions of bisphenol-A propylene oxide, terephthalic acid (TPA) 283 weight portions, trimellitic anhydride 22 weight portions and dibutyl tin oxide 2 weight portions, under normal pressure, 230 ℃, carry out reaction in 8 hours.Then, depress, carry out reaction in 5 hours, the synthetic intermediate polyester at 10-15mHg De Minus.The number-average molecular weight (Mn) of the intermediate polyester that obtains is 2,100, and weight average molecular weight (Mw) is 9,500, and vitrification point (Tg) is 55 ℃, and acid number is 0.5, hydroxyl value 51.

Then, in the reaction vessel that cooling tube, mixer and nitrogen ingress pipe are housed, add above-mentioned intermediate polyester 410 weight portions, IPDI 89 weight portions and acetate ethyl ester 500 weight portions, carry out reaction in 5 hours at 100 ℃, the synthetic polymers (the reactive hydrogen base contains compound and the possible polymer of reaction) that gives.

The cyanate amount that advances to divorce that gives polymers that obtains is 1.53 weight %.

【0048】

--synthesizing of ketimide (compound that contains above-mentioned reactive hydrogen base)--

In the reaction vessel that stirring rod and thermometer are housed, add IPD 170 weight portions and methyl ethyl ketone 75 weight portions, carry out reaction in 5 hours at 50 ℃, synthetic ketimine compound (compound that contains above-mentioned reactive hydrogen base).The amine value of the ketimine compound that obtains (compound that contains above-mentioned reactive hydrogen machine) is 418.

【0049】

--preparation of toner dissolving dispersion liquid--

When carrying out emulsification at once, in above-mentioned toner predissolve liquid, add ethyl acetate, make solid constituent become 50 weight %.In reaction vessel, add this organic solvent phase (1) 187.94 weight portion, above-mentioned polymers 11.46 weight portions and above-mentioned ketimine compound 0.6 weight portion of giving, with TK formula uniform mixer (special machine corporate system) 5,000rpm, carry out mixing in 1 minute, further add ethyl acetate, make these solid constituent become 10 weight portions, use TK formula uniform mixer (special machine corporate system) 5,000rpm carries out mixing in 1 minute, preparation toner dissolving dispersion liquid.

【0050】

--spraying engineering--

Above-mentioned toner dissolving dispersion liquid (below, claim " liquid material ") is sprayed with the device of Fig. 8.

Above-mentioned liquid material is supplied to nozzle with the pipe pump, with the spray gas of other supply to dust trapping chamber's internal spraying.In the dust trapping chamber, the conveyance gas that will be set in 80 ℃ is in addition supplied with air-supply arrangement and temperature adjustment device, carry out heat exchange with this conveyance gas limit, conveyance is carried out with redrying device [dodging spray jet drying and (the strain formula meeting セ イ シ of company Application enterprise system)] in the limit, captures with capturing device (cyclone).The solvent composition containing ratio of the toner particle that obtains with the fixed value of gas-chromatography side be 300ppm less than.

Among the above-mentioned spraying engineering, the various conditions of the nozzle of embodiment and comparative example are illustrated in the table 1, and among all spray conditions, different only is the gas supply mode of nozzle, actual use amount, the gap and the shape of liquid flow path outlet and spray gas (main flow) ejiction opening are identical.In addition, the ratio of spray gas use amount in the table 1 and two-phase fluid formation gas use amount is a weight ratio.At this, each nozzle of use is as follows.

【0051】

Comparative example 1

As the nozzle of general internal mix type, used the spraying of Spraying System Co., Ltd. that (Set-up) number SU 12A (liquid caps PF2050, liquid caps PA73160) is installed.From the structure of nozzle of above-mentioned Spraying System Co., Ltd. that the goods catalogue of spraying system is quoted as shown in Figure 6.

Comparative example 2

As the nozzle of general external mix type, except the AM 45S that has used Atomax Co. company, other are identical with comparative example 1.Structure detailed content about the AM 45S of Atomax Co. company is documented in the patent documentation 4,5.The structure chart of quoting from patent documentation 5 as shown in Figure 7.

Comparative example 3:

Except the liquid stream of the AM 45S that will use in above-mentioned comparative example 2 is transformed, only two-phase fluid is formed with gas and sneak into to form outside the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1.

【0052】

Embodiment 1:

Transform except the liquid stream of the AM 45S that will use at above-mentioned comparative example 2, only two-phase fluid is formed and sneak into gas, form outside the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1.

Embodiment 2:

Transform except the liquid stream of the AM 45S that will use at above-mentioned comparative example 2, with eddy current gas is sneaked into, to form beyond the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1 and Fig. 5.

【0053】

Embodiment 3

Except the liquid stream of the AM 45S that will use in above-mentioned comparative example 2 is transformed, in the venturi mode gas to be sneaked into to form outside the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 3.

Embodiment 4

Except the liquid stream of the AM 45S that will use at above-mentioned comparative example 2 is transformed, in the injector mode gas to be sneaked into to form beyond the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 4.

Embodiment 5:

Identical with the nozzle of the foregoing description 2.

Table 1

-result--

DV, DN, the evaluation result of DV/DN is listed in table 2.

From table 2, can know that embodiment compares with comparative example, the value of DV/DN is little, has demonstrated the good numerical value as toner particle.In addition, embodiment not only DV/DN is little, and the value of DV is identical also little, even the actual use amount that the toner of the narrow distribution of small particle diameter uses and existing thing is same also can obtain, energy efficiency might as well.

The form of the nozzle of comparative example 3 is identical with embodiment 1, has the two-phase fluid as the operating condition of nozzle to form the use amount of gas than bad, so DV/DN does not improve.But embodiment 2 and 5 because two-phase fluid forms the use amount of gas than in preferable range, compares with comparative example and has obtained sufficient improvement.Individual embodiment in the embodiment is compared, and the DV ガ of the two-phase fluid of usefulness venturi and injector formation in this example is little, can make small particle size toner with higher efficient.The two-phase fluid that forms with eddy current has littler DV/DN, and it is narrow to distribute, but its difference is very little.Can learn that any embodiment is to having demonstrated good performance.

【0056】

Table 2

	Dv(μm)	Dn(μm)	Dv/Dn
				Comparing embodiment 1	6.81	4.66	1.46
Comparing embodiment 2	7.13	4.99	1.43
				Comparing embodiment 3	7.19	4.96	1.45
Embodiment 1	6.38	4.95	1.29
				Embodiment 2	6.33	5.36	1.18
Embodiment 3	6.15	5.04	1.22
				Embodiment 4	6.19	5.20	1.19

Embodiment 5

6.37

5.54

1.15

[Embodiment B]

【0057】

The preparation of spray granulation plant and toner solution is identical with embodiment A, and the condition of nozzle is following condition, does with this understanding further relatively.

Comparative example 4

Except transforming by the liquid stream of the AM 45S of use in the above-mentioned comparative example 2, only two-phase fluid is formed and sneak into gas, form beyond the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1.Above-mentioned two-phase fluid forms flow path length, 10 times of the garden conversion diameter D of the squit hole of two-phase fluid.

Comparative example 5

Use the nozzle identical with comparative example 4.

【0058】

Embodiment 6

Transformed except the liquid stream of AM 45S that above-mentioned comparative example 2 is used, only two-phase fluid is formed and sneak into gas, form beyond the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1 and Fig. 5.The length of the formation stream of above-mentioned two-phase fluid is 10 times of garden conversion diameter D of the squit hole of two-phase fluid.

Embodiment 7

Except the liquid stream of the AM 45S that will be in the above-mentioned comparative example 2 uses be transformed, with eddy current gas to be sneaked into and to form beyond the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1 and Fig. 5.The length that above-mentioned two-phase fluid forms stream is 10 times of garden conversion diameter D of the squit hole of two-phase fluid.

【0059】

Embodiment 8

Except the liquid stream of AM 45S that above-mentioned comparative example 2 is used is transformed, and in the venturi mode gas is sneaked into and to form outside the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 3.The length that above-mentioned two-phase fluid forms stream is 10 times of garden conversion diameter D of the squit hole of two-phase fluid.

Embodiment 9

Except the liquid stream of AM 45S that above-mentioned comparative example 2 is used is transformed, and in the injector mode gas is sneaked into and to form beyond the two-phase fluid, other are identical with comparative example 2.The form of internal structure Fig. 4.Equally, above-mentioned two-phase fluid forms 10 times of garden conversion diameter D that flow path length is the squit hole of two-phase fluid.

Embodiment 10

Use the nozzle identical with the foregoing description 7.

Embodiment 11

With the inside of the foregoing description 8 same nozzle, will go into as such member Inserted that the turning power of two-phase fluid is paid Fig. 9 of device, using becomes eddy current spraying nozzle with two-phase fluid.

【0060】

Embodiment 12:

Except the liquid stream of AM 45S that above-mentioned comparative example 2 is used is transformed, and only two-phase fluid is formed to sneak into gas and form outside the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1.The formation flow path length of above-mentioned two-phase fluid is 3.5 times of the garden conversion diameter D of the squit hole of two-phase fluid.

Embodiment 13:

Except the liquid stream of AM 45S that above-mentioned comparative example 2 is used is transformed, and only two-phase fluid is formed to sneak into gas and form beyond the two-phase fluid, other are identical with comparative example 2.Internal structure is the form of Fig. 1.The formation flow path length of above-mentioned two-phase fluid is 4.5 times of garden conversion diameter D of the squit hole of two-phase fluid.

Embodiment 14:

Use and the foregoing description 6 structure same nozzle structures.

Table 3

	Two-mutually flow the formation method	The tolerance ratio that is used to spray	The tolerance ratio that is used for two-phase flow
				Comparing embodiment 4	The simple mixing	0.5	0.5
Relatively	The simple mixing	0.97	0.03

Embodiment 5
				Embodiment 6	The simple mixing	0.9	0.1
Embodiment 7	Eddy current	0.9	0.1
				Embodiment 8	Venturi	0.9	0.1
Embodiment 9	Spray	0.9	0.1
				Embodiment 10	Eddy current	0.7	0.3
Embodiment 11	Eddy current+turning power	0.7	0.3
				Embodiment 12	Simple mix (3.5D)	0.9	0.1
Embodiment 13	Simple mix (4.5D)	0.9	0.1
				Embodiment 14	The simple mixing	0.7	0.3

DV, DN, evaluation result such as the table 4 of DV/DN.

From table 4, can learn that embodiment compares with comparative example, the value of DV/DN is little, has good numerical value as toner particle.In addition, not only the DV/DN of embodiment is little, and the value of DV is too little, and the toner of small particle diameter and narrow distribution can obtain by the same actual use amount of use with prior art, and energy efficiency might as well.

The form of the nozzle of comparative example 4,5 is identical with embodiment 6, but forms the use amount of gas than bad, so do not see the improvement of DV/DN as the two-phase fluid of the operating condition of nozzle.But embodiment 7,10 and 14, and the use amount that can learn two-phase fluid formation gas is compared with comparative example, can be improved fully than in preferred range.As the words that in embodiment, compare, the two-phase fluid DV that is formed by venturi and injector in this example is little, efficient that can be higher is made small particle size toner, the DV/DN of the two-phase fluid that is formed by eddy current is littler, it is narrower to distribute, but its difference is small, and any one all demonstrates measured performance.In addition, by embodiment 6,12,13, two-phase fluid forms the Games of length more than 4D and closes, with 4D less than comparing, DV is that particle diameter is can further Shao You Minus few, DV/DN be particle diameter distribute and become sharp-pointed.

【0063】

Table 4

Dv(μm)

Dn(μm)

Dv/Dn

Comparing embodiment 4	7.19	4.96	1.45
				Comparing embodiment 5	7.15	4.93	1.45
Embodiment 6	6.38	4.95	1.29
				Embodiment 7	6.33	5.36	1.18
Embodiment 8	6.15	5.04	1.22
				Embodiment 9	6.19	5.20	1.19
Embodiment 10	6.37	5.54	1.15
				Embodiment 11	6.13	5.42	1.13
Embodiment 12	6.54	4.95	1.32
				Embodiment 13	6.40	4.96	1.29
Embodiment 14	6.42	5.10	1.26

Claims (9)

1. a manufacturing method of power comprises,

The micronize step makes the liquid material micronize; And

The solidification step is solidified micronized liquid material,

Wherein, in described micronize step; the spray gas and the liquid material that account for 5 all weight %-40 weight % of spray gas are pre-mixed; after the gas-liquid mixed two-phase fluid that comprises liquid material and spray gas forms in the stream in nozzle; further, around the ejection stream of this two-phase fluid, make the spray gas ejection that accounts for 95 whole weight %-60 weight % of spray gas; it is conflicted mutually with this two-phase fluid, thereby make the even micronize of liquid material.

2. according to the process of claim 1 wherein, form described two-phase fluid by the venturi mode.

3. according to the process of claim 1 wherein, form described two-phase fluid by the injector mode.

4. according to the process of claim 1 wherein, form described two-phase fluid by the annular nozzle mode.

5. according to the process of claim 1 wherein, form described two-phase fluid by the eddy current mode.

6. according to the process of claim 1 wherein, the spray gas of conflicting with two-phase fluid is an eddy current.

7. according to the process of claim 1 wherein, dispose in the stream of the two-phase fluid before two-phase fluid forms the back spray gas and two-phase fluid conflicts and carry out the device that turning power is paid.

8. according to the process of claim 1 wherein that the flow path length that forms two-phase fluid is, two-phase fluid squit hole De Yuan Change calculates more than 4 times of diameter D.

9. the manufacture method of a toner, wherein toner is to use and makes according to each the method for claim 1-8.

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