CN100576094C - The container of toner, developer, the toner of packing into, handle box, image processing system and image forming method - Google Patents

Abstract

The invention provides can good transfer printing and the spatter property of long term maintenance, and there is not the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, the toner of the excellent in stability that mobile and charging property secular variation is less and use the developer of this toner, container, handle box, image processing system and the image forming method of the toner of packing into.Described toner has the toner parent particle and forms different particulates with at least 2 kinds that are present in this toner parent particle surface, described toner parent particle comprises the toner materials that contains colorant, charged controlling agent and binder resin at least, above-mentioned toner contains secondary aggregate, and at least a and aggregate particle size that this secondary aggregate contains in the above-mentioned particulate is more than the 10 μ m.

Description

The container of toner, developer, the toner of packing into, handle box, image processing system and image forming method

Technical field

The present invention relates to be used for container, handle box, image processing system and the image forming method of toner that electrostatic image is developed in electrofax, electrostatic recording, xeroprinting etc. and the developer that uses this toner, the toner of packing into.

Background technology

In electro-photography apparatus or electrostatic recording apparatus etc., make toner attached on the electrostatic latent image that is formed on the photoreceptor, it is transferred on the recording medium, then, make its photographic fixing on this recording medium, thereby form toner image with heat.And, in general, it is to carry out the reproduction of color with 4 colour toners such as black, yellow, magenta and cyans that full-colour image forms, by developing to of all kinds, each toner layer is superimposed on recording medium, to the toner image heating that obtains, carry out photographic fixing simultaneously, thereby form full-color image.

, in general, if the user has got used to printing, the image in panchromatic duplicating machine can't reach satisfied level, satisfies high tractability, high resolving power for forcing photograph and printing, just requires high image qualityization more.In this case, the known high image qualityization that can effectively realize electrophotographic image with small particle diameter and the narrower toner of size distribution.

In the past, electric sub-image or magnetic sub-image were developed by toner.In general, being used for making the toner of this electrostatic image development is the colored particles that contains colorant, charged controlling agent and other adjuvants in binding resin.The manufacture method of this toner roughly has comminuting method and polymerization.As above-mentioned comminuting method, make colorant, charged controlling agent and anti-print through agent etc. dissolve mixing, and be dispersed in the thermoplastic resin, again the method for producing toner and toner that obtains is pulverized, make toner by classification.

According to above-mentioned comminuting method, have the toner of excellent specific property to a certain degree though can produce,, the used material of toner is selected restricted.For example, by dissolve mix the method for producing toner and toner obtain be must pulverize by operative installations at an easy rate, the composition of classification.Because this requirement, the method for producing toner and toner that dissolves mixing has to become very crisp.For this reason, in fact, when above-mentioned method for producing toner and toner is ground into particle, form large-scale size distribution easily, if want to obtain the copy image of good resolution and level, for example, must remove particle diameter at micro mist below the 5 μ m and the meal more than the 20 μ m by classification, just there is the productive rate low-down shortcoming that becomes in this.And as comminuting method, it is very difficult that adjuvants such as colorant and charged controlling agent are evenly spread in the thermoplastic resin.The inhomogeneous dispersion of such adjuvant brings harmful effect to the flowability of toner, development, permanance, image quality etc.

In recent years, in order to overcome the problem points in these comminuting methods, for example, obtain toner particle (spy opens flat 9-43909 communique) by suspension polymerization.But though the toner particle that obtains by this suspension polymerization is spherical, it has the shortcoming of spatter property difference.The transfer printing residual toner is few in lower development of image area rate and transfer printing, though do not clean problems such as bad, but, image area rate that photographic image is contour and the toner that forms because of the image of paper feeding not transfer printing such as bad remain on the photoreceptor as the transfer printing residual toner sometimes, if accumulation, the pollution that then can produce image.And, because of contaminated, make it can not bring into play original charged ability with charged roller of photoreceptor contact electrification etc.In addition, low-temperature fixing is also insufficient, and therefore, the photographic fixing energy needed just must increase.

On the other hand, a kind of method (No. 2537503 communique of patent) that makes the resin particle association that obtains by emulsion polymerization obtain atypic toner particle is disclosed.But, when the toner particle that utilizes this emulsion polymerization to obtain passes through the water washing operation, surfactant not only remains in the surface, and greater amount remain in particle inside, the charged environmental stability of toner suffers damage, and make carried charge distributed more widely, the image contamination that obtains becomes bad.And because remaining surfactant, photoreceptor and charged roller, developer roll etc. are polluted, and can not bring into play original charged ability.

And, in the photographic fixing operation that the employing Contact Heating mode that heater blocks such as using hot-rolling carries out is carried out, require toner particle that heater block is had release property (hereinafter referred to as anti-print through).Here, can exist release agent to improve heat-resisting print through by making surfaces of toner particles.To this, open in 2000-292973 communique and the Te Kai 2000-292978 communique the spy, propose a kind of method that improves anti-print through in the following way, promptly, not only make and contain resin particle in the toner particle, and this resin particle exists on the surface of toner particle unevenly.But in this motion, the photographic fixing lower limit temperature raises, and has low-temperature fixing, promptly economizing can the inadequate problem of fixation performance.

And, obtain in the method for atypic toner particle, produce problem as described below in that the resin particle that obtains by emulsion polymerization is associated.That is, for improving anti-print through, under the situation that the release agent particulate is associated, this release agent particulate enters into the inside of toner particle.As a result, can not fully seek the raising of anti-print through.Owing to the adhesions of fusion randomly such as making resin particle, release agent particulate, colorant particles constitutes toner particle, therefore between the toner particle that obtains, the molecular weight etc. of forming (constituent contain ratio) and constituting resin produces uneven (バ ラ Star キ).As a result, the character of surface difference between toner particle can not form image steady in a long-term.In addition, in requiring the low-temperature fixing system of low-temperature fixing, the problem that the photographic fixing that occurs causing in the inhomogeneous existence of toner surface because of resin particle encumbers and can not fully guarantee the fixing temperature scope.

In addition, a kind of method for making (No. 3141783 communique of patent) of dissolving suspension method that is called has been proposed.To form particle by monomer different with suspension polymerization or emulsion polymerization, and this method adopts by the polymkeric substance that is dissolved in the organic solvent etc. carries out process for granulating, have the advantage of the aspect such as controlled of resin choice expanded range, polarity.But, in this motion, shell (shell) structure is the layer of resin itself, purpose is in order to reduce pigment or wax exposing on the surface, design surface state especially, also need not become such structure (tor filial piety hero etc., " feature of new preparation method toner and in the future prospect " (the 4th Japanese iconology meeting, electrostatics can associating discussion (2000.7.29)).In above-mentioned motion, though become shell structure, toner surface is common resin, not special design, during for photographic fixing under low temperature more, heat-resisting keeping quality, environment charged stable aspect and insufficient.

And above-mentioned suspension polymerization, emulsion polymerization use the resin of styrene-propene acids usually, also can use the resin of polyesters.In addition, during for photographic fixing under low temperature more, have both fixation performance and heat-resisting keeping quality is conditional.

Therefore, be target with heat-resisting keeping quality and low-temperature fixing, proposed to use method (spy opens flat 11-133667 communique) by the polyester of urea key modification.But, in this motion, do not design toner surface especially, on this aspect of charged stability under the harsher environment of condition and insufficient.

Recently, in the electrofax field, studied high image qualityization from various angles, wherein, the pathization of toner and spheroidization are that extremely effectively such understanding improves.But along with the progress of toner pathization, transfer printing, fixation performance reduce, and find to become the tendency of poor image.And, can know, by the toner spheroidization, can improve transfer printing (spy opens flat 9-258474 communique).In this case, in color copy machine and color printer field, wish the high speed that image forms more.For high speed, " series system " is effective (spy opens flat 5-341617 communique).

Above-mentioned " series system " is that the superimposed successively transfer printing of image that will be formed by image formation unit is being transported on the single recording medium of transfer belt, thereby obtains the mode of full-colour image on recording medium.The coloured image of series system forms the characteristic that device has following excellence: the kind of operable recording medium is abundant, the quality of full-colour image is also high and can at full speed obtain full-colour image.Especially, the characteristic that can at full speed obtain full-colour image is not that the coloured image of other modes forms the peculiar character of device.

In addition, carry out the use spherical toner and sought high image qualityization, and reached the trial of high speed.For example, because the spherical toner that chemical toner is such is owing to form fine and close toner image on photoreceptor, transfer pressure when making transfer printing is applied on the toner layer equably, compare with the comminuting method toner, the transfer printings such as (image viod) that comes off of rare transferring rate, transferred image is unusual.But, when long-time the use, compare with crushed toner, toner transfer printing raising, and because the mobile modifier that adds outward in order to give flowability promptly is embedded in toner surface, so transfer printing, mobile variation become big.Particularly less at continuous output portrait area, it is situation of the less image of consumption of toner etc., because the external additive in the toner is passed and embedding in time, can not obtain the mobile effect that improves, therefore present situation is to have following problem: the transfer printing change perhaps results from this image significantly uneven.

Summary of the invention

Problem of the present invention is according to above-mentioned requirements, to solve problem in the past and realize following purpose.Promptly, the objective of the invention is to, provide a kind of excellent in stability toner, use the developer of this toner, container, handle box, image processing system and the image forming method of the toner of packing into, described toner can good transfer printing and the spatter property of long term maintenance, the change of image inequality is little, and it is, do not have the embedding of external additive, and very little through long-time variation mobile and charging property owing to stir developer in use.

As the method that solves above-mentioned problem, as described below.That is,

(1) a kind of toner, wherein containing toner parent particle and aggregate particle size is the secondary aggregate of the above particulate of 10 μ m, described toner parent particle comprises the toner materials that contains colorant and binder resin at least.

(2) above-mentioned (1) described toner, it comprises the toner parent particle and is present in the lip-deep at least 2 kinds of particulates that composition is different of this toner parent particle, this toner parent particle comprises the toner materials that contains colorant, charged controlling agent and binder resin at least, wherein, above-mentioned toner contains secondary aggregate, and the content of this secondary aggregate is 5/every gram toner～800/every gram toner, and it is more than the 10 μ m that described secondary aggregate contains in the above-mentioned particulate at least a kind and aggregate particle size.

(3) above-mentioned (1) or (2) described toner, wherein, the aggregate particle size of secondary aggregate is 10～50 μ m, and the content of this secondary aggregate is 5/every gram toner～200/every gram toner.

(4) each described toner in above-mentioned (1)～(3), wherein, it is the above and big particle diameter composition that be 30nm～200nm less than small particle diameter composition and the primary particle size of 30nm of 1nm that particulate contains primary particle size.

(5) each described toner in above-mentioned (1)～(4), wherein, it is the titanium oxide microparticle of 80～150nm that secondary aggregate contains 50% above primary particle size.

(6) each described toner in above-mentioned (1)～(5) wherein, makes solution or dispersion liquid emulsification or dispersion in water-medium of toner materials, with the toner granulation.

(7) above-mentioned (6) described toner, wherein, the solution or the dispersion liquid of toner materials contain organic solvent, and when granulation or after the granulation above-mentioned organic solvent are removed.

(8) above-mentioned (6) or (7) described toner, wherein, toner materials comprises compound that contains active hydrogen group and the polymkeric substance that can contain the compound reaction of active hydrogen group with this at least,

Granulation is carried out by the following method: make the above-mentioned compound that contains active hydrogen group generate the cementability matrix material with reacting with this polymkeric substance that contains the compound reaction of active hydrogen group, and contained the particle of this cementability matrix material at least.

(9) toner of record in above-mentioned (8) wherein, can contain modified polyester resin with the polymkeric substance of the compound reaction that contains active hydrogen group.

(10) each described toner in above-mentioned (1)～(9), wherein, the binder resin in the toner materials is a unmodified polyester resin.

(11) each described toner in above-mentioned (1)～(10), wherein, the average circularity of toner is 0.90～0.99.

(12) each described toner in above-mentioned (1)～(11), wherein, the shape coefficient SF-1 of the spherical degree of the expression toner of representing with following mathematical expression 1 is 100～150, and the shape coefficient SF-2 of the concavo-convex degree of the expression toner of representing with following mathematical expression 2 is 100～140.

[mathematical expression 1]

$\mathrm{SF}-1=\frac{{\left(\mathrm{MXLNG}\right)}^2}{\mathrm{AREA}}\×\frac{\mathrm{\π}}{4}\×100$ ... .. mathematical expression 1

Wherein, in the above-mentioned mathematical expression 1, MXLNG represents that toner projects on the two dimensional surface and the maximum length of the shape that obtains.AREA represents that toner projects on the two dimensional surface and the area of graph that obtains.

[mathematical expression 2]

$\mathrm{SF}-2=\frac{{\left(\mathrm{PERI}\right)}^2}{\mathrm{AREA}}\×\frac{1}{4\mathrm{\π}}\×100$ ... mathematical expression 2

Wherein, in above-mentioned mathematical expression 2, PERI represents toner is projected on the two dimensional surface and the girth of the figure that obtains.AREA represents toner is projected on the two dimensional surface and the area of graph that obtains.

(13) each described toner in above-mentioned (1)～(12), wherein, the weight average particle diameter (D of toner ₄) be 2～7 μ m, and this weight average particle diameter (D ₄) and number average particle diameter (D _n) ratio (D ₄/ D _n) be below 1.25.

(14) a kind of developer, it contains each described toner in above-mentioned (1)～(13).

(15) above-mentioned (14) described developer, this developer is any in monocomponent toner and the two-component developing agent.

(16) a kind of container of the toner of packing into, it has filled each described toner in above-mentioned (1)～(13).

(17) a kind of handle box wherein, comprises at least: electrostatic latent image carrier, use each described toner in above-mentioned (1)～(13) will be formed on the latent electrostatic image developing on this electrostatic latent image carrier and form the developing apparatus of visual image.

(18) a kind of image processing system, wherein, comprise at least: electrostatic latent image carrier, the electrostatic latent image that forms electrostatic latent image on this electrostatic latent image carrier form device, use each described toner in above-mentioned (1)～(13) above-mentioned latent electrostatic image developing is formed visual image developing apparatus, above-mentioned visual image is transferred to transfer device on the recording medium, makes the fixing device of the transferred image photographic fixing that is transferred on the recording medium.

(19) a kind of image forming method, wherein, comprise at least: the electrostatic latent image that forms electrostatic latent image on electrostatic latent image carrier forms operation, utilize each described toner in above-mentioned (1)～(13) above-mentioned latent electrostatic image developing is formed visual image developing procedure, above-mentioned visual image is transferred to transfer printing process on the recording medium, will be transferred to the photographic fixing operation of the transferred image photographic fixing on the recording medium.

Toner of the present invention is characterised in that, this toner has the toner parent particle and is the secondary aggregate of the particulate more than the 10.0 μ m at the lip-deep aggregate particle size of this toner parent particle, wherein, this toner parent particle comprises the toner materials that contains colorant and binder resin at least.

In addition, toner of the present invention is characterised in that, this toner contains the toner parent particle and the lip-deep aggregate particle size of this toner parent particle is the above secondary aggregates of 10 μ m, wherein, this toner parent particle comprises the toner materials that contains colorant and binder resin at least, and the content of this secondary aggregate is 5/g～800/g.

According to toner of the present invention, can good transfer printing and the spatter property of long term maintenance, and there is not the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, flowability and charging property change less between for a long time, excellent in stability can obtain flowability and charging property and change less images with high image quality between long-term.

Developer of the present invention comprises above-mentioned toner of the present invention.Therefore, when using this developer to carry out image formation by xerography, its result, can good transfer printing and the spatter property of long term maintenance, and there is not the change of image inequality, and, by stirring developer in use, do not have the embedding of external additive, can obtain flowability and charging property change less excellent in stability between for a long time images with high image quality.

The container of the toner of packing into of the present invention with above-mentioned toner storage of the present invention in container.Therefore, the toner that use is accommodated in the container of this toner of packing into carries out image when forming by xerography, as a result, can good transfer printing and the spatter property of long term maintenance, and do not have the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, flowability and charging property change less between for a long time, excellent in stability can obtain flowability and charging property change less and excellent in stability between for a long time images with high image quality.

The toner that handle box of the present invention has electrostatic latent image carrier at least, use the invention described above will be formed on the latent electrostatic image developing on this electrostatic latent image carrier and form the developing apparatus of visual image.This handle box can load and unload in image processing system, the convenience excellence, and, owing to use above-mentioned toner of the present invention, its result can good transfer printing and the spatter property of long term maintenance, and does not have the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, flowability and charging property all change less between for a long time, excellent in stability can obtain mobile and the less images with high image quality of charging property secular variation.

Image processing system of the present invention has electrostatic latent image carrier at least, electrostatic latent image forms device, developing apparatus, transfer device and fixing device.In this image processing system, above-mentioned electrostatic latent image forms device and form electrostatic latent image on above-mentioned electrostatic latent image carrier.Above-mentioned developing apparatus uses above-mentioned toner of the present invention that latent electrostatic image developing is formed visual image.Above-mentioned transfer device is transferred to above-mentioned visual image on the recording medium.Above-mentioned fixing device will be transferred to the transferred image photographic fixing on the aforementioned recording medium.Its result, can good transfer printing and the spatter property of long term maintenance, and there is not the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, flowability and charging property all change less between for a long time, excellent in stability can form the electrophotographic image mobile and high image quality that the charging property secular variation is less.

Image forming method of the present invention contains electrostatic latent image at least and forms operation, developing procedure, transfer printing process, photographic fixing operation.In this image forming method, it is to form electrostatic latent image on electrostatic latent image carrier that above-mentioned electrostatic latent image forms operation.Above-mentioned developing procedure is to use above-mentioned toner of the present invention that latent electrostatic image developing is formed visual image.Above-mentioned transfer printing process is that above-mentioned visual image is transferred on the recording medium.In above-mentioned photographic fixing operation, be transferred to transferred image on the aforementioned recording medium by photographic fixing.Its result, can good transfer printing and the spatter property of long term maintenance, and there is not the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, flowability and charging property all change less between for a long time, excellent in stability can form the electrophotographic image mobile and high image quality that the charging property secular variation is less.

According to the present invention, can solve problem in the past, can good transfer printing and the spatter property of long term maintenance, and there is not the change of image inequality, and, by stirring developer in use, there is not the embedding of external additive, the toner of mobile and the excellent in stability that the charging property secular variation is less can be provided and use the developer of this toner, container, handle box, image processing system and the image forming method of the toner of packing into.

Description of drawings

Fig. 1 is the summary construction diagram that an example of handle box of the present invention is shown.

Fig. 2 is the summary construction diagram that an example of image processing system of the present invention is shown.

Fig. 3 is another routine summary construction diagram that image processing system of the present invention is shown.

Fig. 4 is the part skeleton diagram that an example of tandem type image processing system of the present invention is shown.

Fig. 5 is another routine part skeleton diagram that tandem type image processing system of the present invention is shown.

Fig. 6 illustrates the diagrammatic illustration figure that implements an example of image forming method of the present invention by image processing system of the present invention (the tandem type coloured image forms device).

Fig. 7 is the part enlarged drawing of Fig. 6.

Embodiment

(toner)

Toner of the present invention has the toner parent particle, the lip-deep aggregate particle size of this toner parent particle is the secondary aggregate of the above particulate of 10 μ m, also contain other neccessary compositions as required, wherein, this toner parent particle comprises the toner materials that contains colorant and binder resin at least.

Above-mentioned toner contains secondary aggregate, this secondary aggregate comprises that at least a and aggregate particle size is more than the 10 μ m in the above-mentioned particulate, and the content of this secondary aggregate is 5/g～800/g, the offspring of secondary aggregate is preferably 10～50 μ m, and the content of this secondary aggregate is preferably 5/g～200/g.

If the aggregate particle size deficiency of above-mentioned secondary aggregate 10 μ m then can not good transfer printing and the spatter property of long term maintenance, it is unequal to produce image, can not obtain the toner mobile and excellent in stability that the charging property secular variation is few sometimes.

If the containing 5/g of quantity not sufficient and surpass 800/g of above-mentioned secondary aggregate, then can not good transfer printing and the spatter property of long term maintenance, it is unequal to produce image, can not obtain the toner mobile and excellent in stability that the charging property secular variation is few sometimes.

In addition, above-mentioned secondary aggregate preferably contains the titanium oxide microparticle (can carry out hydrophobization handles) of the primary particle size 80～150nm more than 50%, more preferably contains more than 70%.If the content of the titanium oxide microparticle of above-mentioned primary particle size 80～150nm is more than 50%, then can good transfer printing and the spatter property of long term maintenance, there is not the change of image inequality, and the developer when using stirs, do not have the external additive embedding, obtain mobile and the charging property secular variation is few and the toner of excellent in stability.

Here, as the assay method of the primary particle size of the particulate that forms secondary aggregate, for example with this microparticulate in water, measure its particle diameter.

As determinator, for example preferably use millimicro track (Na ノ ト ラ Star Network) the particle size distribution device UPA-EX150 of Nikkiso Company Limited.Particularly, in glass 100ml beaker, add 0.5ml electrolytic solution: ア イ ソ ト Application II (manufacturing of ベ Star Network マ Application コ one Le one company) and as the 10 weight % mixed liquors of the エ マ Le グ Application 109P (KAO. Corp. SA's manufacturing, polyoxyethylene lauryl ether, HLB:13.6) of spreading agent, add this an amount of particulate, with ultrasonic disperser (manufacturing of this polyelectron of W-113MK-II company) with its dispersion treatment 10 minutes.

Then, the dispersion liquid that obtains is suitably diluted, and use UPA-EX150 to obtain weight average particle diameter with ion exchange water.

In addition, to have or not aggregate particle size be the secondary aggregate of the above particulate of 10 μ m in affirmation as described below.

Make toner attached on the adhesive tape of electric conductivity two sides, evaporation platinum as required, and observe with the scanning electron microscope S-4200 type that Hitachi makes.Observing multiplying power is 1000 times, observes particle picture.Secondary aggregate is approved really with by further amplifying corresponding particle picture, is easily judged from its shape.

And the same SEM that adopts of the size of particle is obtained by the diameter of secondary aggregate.At this moment, during the remarkable separable spherical of the shape of aggregation, directly be aggregate particle size with major axis.

Here, as at least a and aggregate particle size that comprises in the above-mentioned particulate is the assay method of the content (number) of the secondary aggregate more than the 10 μ m, for example, the circle sieve of diameter 24mm is oppositely arranged, make the closed sieve cylindraceous (sieve of use is 635 orders) of thickness 7mm, and the toner of weighing 0.2g is placed in one.Toner is paved on sieve equably, and it is horizontally disposed with, from the suction of sieve downside, the screening secondary aggregate.Use swabbing pig (CV-TN96) with 5mmHg swabbing pressure suction air by using by Hitachi's toner of slide transformer (ス ラ イ ダ Star Network) adjustment swabbing pressure.Further aspirate on one side, on one side on said units height 160mm sentence and blow pressure 0.2MPa blow air 30 seconds, remove toner.With the swabbing pressure 20mmHg suction air of swabbing pig, remove toner again.Observe sieving remaining residue with 150 times by digital microscope (KEYENCE VHX-100).Counting remains in the number of the secondary aggregate on the sieve.It is measured 20 visuals field.Obtain several n at 20 detected aggregations more than 10 microns in the visual field.Obtain the shooting visual field area Va of microscope 1 picture in advance, the size of sieve is 4.5cm ², the content of the secondary aggregate in every 0.2g toner is by n * (4.5cm ²/ (20 * Va)) are obtained.This value is as the content of the secondary aggregate more than the 10 μ m in the toner.

As above-mentioned particulate, preferably contain primary particle size 1nm above and the small particle diameter composition of not enough 30nm and the big particle diameter composition of primary particle size 30nm～200nm.

Above-mentioned small particle diameter composition is preferably titanium oxide microparticle, silicon dioxide microparticle, fatty acid metal salts (for example zinc stearate, aluminium stearate etc.), metal oxide (titanium dioxide, aluminium oxide, tin oxide, antimony oxide etc.) or their hydrophobization handled thing etc.In addition, as above-mentioned big particle diameter composition, preferred titanium oxide microparticle, silicon dioxide microparticle, fatty acid metal salts (for example zinc stearate, aluminium stearate etc.), metal oxide (titanium dioxide, aluminium oxide, tin oxide, antimony oxide etc.) or their hydrophobization handled thing etc.

In the present invention, by using at least two kinds to form different particulates,, also can suppress rotatablely moving of toner even the shape of toner is essentially sphere, and can prevent toner overcompaction (packing), therefore can keep spatter property, transfer printing well.And, stir by long developer, can prevent the fine powder of small particle diameter in the embedding toner selectively, therefore can obtain stable flowability for a long time.Under this situation, if the primary particle size of big particle diameter composition is littler than 30nm, then can not get the inhibition effect that toner rotatablely moves, the compacting because toner container easily becomes becomes the reason of transfer printing inequality easily.On the other hand, if surpass 200nm, then be easy to generate the disengaging of particulate, and be easy to generate mobility variations over time.And, if the primary particle size of small particle diameter composition surpasses 30nm, then find to lack flowability, lose the stability of toner replenishing amount sometimes.

In these two kinds of micropowders, big particle diameter composition is fewer to the mobile effect that improves of toner.For example, in the toner of small particle diameter composition that adds equivalent respectively and big particle diameter composition, the situation of adding the small particle diameter composition obtains quite high flowability.But for being above-mentioned small particle diameter composition, through using after a while, additive-package is embedded in the toner, causes mobile low easily.

Relative therewith, by adding big particle diameter composition, though can suppress mobile reduction in time, but big particle diameter composition is many, when developer stirs, produce big particle diameter composition and from toner, break away from, even mix toner and big particle diameter composition, owing to there are unfavorable conditions such as big particle diameter composition adheres to inadequately in toner, so it is use the transfer printing change after a period of time to compare some improvement, but and insufficient with the situation of only using the small particle diameter composition.Particularly, under the situation of the image that the output image area is different, according to the mixing time of developer, the delay of toner in the developer, transfer printing change.This be because: if big particle diameter composition equally little by little is embedded in the toner with the small particle diameter composition in toner, at this moment, exist on the mixed uniformly big particle diameter uneven components of toner surface ground in advance, in toner surface a spot of concavo-convex, accumulate, can not show the desired effect of big particle diameter composition.

Among the present invention, mix in toner a little by the secondary aggregate that will come from big particle diameter composition, the toner during by use stirs new big particle diameter composition is supplied in the toner at leisure, thereby can further improve the stability of transfer printing.The aggregation of the big particle diameter composition in the toner is slowly pulverized according to the mixing time of developer, and attached to toner surface.Thus, the big particle diameter composition of embedding a little, because the flowability of toner changes, perhaps in toner, move, therefore supplying with particulate again in toner becomes to assign to replace for the inoperative big particle diameter composition of the performance of flowability, its result, but long term maintenance transfer printing, and can obtain uniform image and do not rely on the image area of output image.The size of this aggregation is preferably more than the 10 μ m.Thus, though these aggregations when developing attached to photoreceptor on, also can use easy cleaning mode such as scraper plate cleaning mode easily to clean, can not pollute live part etc., so preferably use.

As above-mentioned particulate, be not particularly limited, can use in order to give the mobile particulate that uses with giving charging property, for example except that oxide fine particle, can also use inorganic particles, hydrophobization to handle inorganic particles, the particulate that hydrophobization is handled is carried out on their surface simultaneously.、

As above-mentioned particulate, be not particularly limited, can from known particulate, suitably select according to purpose, for example can enumerate fatty acid metal salts (for example zinc stearate, aluminium stearate etc.), metal oxide (for example silicon dioxide, titanium dioxide, aluminium oxide, tin oxide, antimony oxide etc.) or their hydrophobization handled thing, fluoropolymer etc.

In the middle of these, the alumina particulate of the Titanium particles of the silicon dioxide granule of preferred especially silicon dioxide granule, hydrophobization, Titanium particles, hydrophobization, alumina particulate, hydrophobization etc.

As above-mentioned silicon dioxide microparticle, can use commercially available product, as this commercially available product, for example can enumerate HDK H2000, HDK H2000/4, HDK H2050EP, HVK21, HDK H1303 (more than be ヘ キ ス ト company make); R972, R974, RX200, RY200, R202, R805, R812 (more than be Japanese ア エ ロ ジ Le company make).

As above-mentioned titanium oxide microparticle, can use commercially available product, as this commercially available product, for example can enumerate P-25 (Japanese ア エ ロ ジ Le company make); STT-30, STT-65C-S (more than be チ Application industrial group make); TAF-140 (manufacturing of チ Application industrial group of Fuji), MT-150W, MT-500B, MT-600B, MT-150A (more than be テ イ カ company make) etc.

Titanium oxide microparticle as hydrophobization is handled can use commercially available product, as this commercially available product, for example can enumerate T-805 (Japanese ア エ ロ ジ Le company make); STT-30A, STT-65S-S (more than be チ Application industrial group make); TAF-500T, TAF-1500T (more than be チ Application industrial group of Fuji make), MT-100S, MT-100T (more than be テ イ カ company make), IT-S (the former industry corporate system of stone is made) etc.

In order to obtain the oxide fine particle that above-mentioned hydrophobization is handled, for example, silicon dioxide microparticle, titanium oxide microparticle, alumina particulate that hydrophobization is handled can and obtain with silane coupling agents such as methyltrimethoxy silane or methyl triethoxysilane, octyl group trimethoxy silane processing hydrophilic particulate.

And the silicone oil processing oxide fine particle, the inorganic particles that if necessary heat after silicone oil is handled inorganic particles also are suitable.

As above-mentioned silicone oil, for example can use dimethyl silicon oil, methyl phenyl silicone oil, chlorphenyl silicone oil, Methyl Hydrogen Polysiloxane Fluid, alkyl modified silicon oil, fluorine modified silicon oil, polyether modified silicon oil, pure modified silicon oil, amino-modified silicone oil, epoxide modified silicone oil, epoxidized polyether modified silicon oil, phenol modified silicon oil, carboxy-modified silicone oil, sulfhydryl modified silicone oil, acrylic acid modified silicone oil, methacrylic acid modified silicon oil, α-Jia Jibenyixi modified silicon oil etc.

As above-mentioned inorganic particles, for example can enumerate silicon dioxide, aluminium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, iron oxide, cupric oxide, zinc paste, tin oxide, silica sand, clay, mica, wollastonite, zeyssatite, chromium oxide, cerium oxide, iron oxide red, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit, silicon nitride etc.In the middle of these, preferred especially silicon dioxide and titania.The addition of above-mentioned inorganic particles is 0.1～5 quality % with respect to above-mentioned toner preferably, more preferably 0.3～3 quality %.

Other macromolecule based fine particles for example can be enumerated the polystyrene, methacrylate or the acrylate copolymer that are obtained by emulsifier-free emulsion polymerization or suspension polymerization, dispersin polymerization; System such as the polycondensation of polysiloxane, benzo guanamine, nylon etc., the polymer particle that obtains by thermoset resin.

Above-mentioned particulate can add outward by known dry type to be handled or known wet type is added outward and handled and attached to toner parent particle surface.

Toner of the present invention if its method for making and material satisfy above-mentioned condition, then is not particularly limited, can from known toner, suitably select according to purpose, for example, in order to export the high meticulous image of high image quality, the toner of preferred small particle diameter and subglobular.As the manufacture method of such toner, the crushing and classification method is arranged, in water-medium, make oil phase emulsification, suspension or cohesion and form suspension polymerization, emulsion polymerization, polymer suspension method of toner parent particle etc.

Above-mentioned comminuting method is for example by toner materials fusion or mixing, pulverizing, classification etc. being obtained the method for above-mentioned toner parent particle.In addition, under the situation of this comminuting method,, can also give mechanical impact force to the parent particle of the toner that obtains and control shape for the average circularity that makes above-mentioned toner is 0.97～1.0 scope.At this moment, above-mentioned mechanical impact force for example can use that mixer, mechanical fusion machine devices such as (mechanofusion) are applied on the parent particle of above-mentioned toner.

Above-mentioned suspension polymerization is that colorant, release agent etc. is dispersed in oil-soluble polymerization initiator, the polymerizable monomer, carries out emulsification by emulsion process described later then in the water-medium that comprises surfactant, other solid dispersion etc. and disperses.Carry out polyreaction then, after particlized, can carry out adhering to the wet processed of inorganic particles at surfaces of toner particles of the present invention.At this moment, the toner particle of preferably remaining surfactant etc. being removed in washing is implemented to handle.

As above-mentioned polymerizable monomer, for example, can import functional group at surfaces of toner particles by have amino acrylate, the methacrylate etc. that use acids, acrylamide, Methacrylamide, diacetone acrylamide or their methylol compound, vinylpyridine, vinyl pyrrolidone, vinyl imidazole, second such as part acrylic acid, methacrylic acid, alpha-cyanoacrylate, alpha-cyano methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride to embrace imines, dimethylaminoethyl acrylate methyl base ammonia ethyl ester etc.

And, by selecting to have the spreading agent of the material of acid groups or basic group, can make dispersant adsorption remain in particle surface, and import functional group as use.

As the above-mentioned emulsion polymerization, use surfactant in water with water-soluble polymerization initiator, polymerizable monomer emulsification, by common emulsion polymerisation process synthetic latex.Prepared in water-medium, to disperse the dispersion of colorant, release agent etc. in addition, agglomerated to toner-sized after the mixing, heating and melting and obtain toner.Then, can carry out the wet processed of inorganic particles described later.If use and the same material of monomer that can in suspension polymerization, use, then can import functional group at surfaces of toner particles.

Among the present invention, in the middle of these, as above-mentioned toner, be preferably as follows the toner of acquisition: make to comprise the compound that contains active hydrogen group, can with this contain active hydrogen group compound reaction polymkeric substance the toner materials dissolving or be distributed in the organic solvent, after the preparation toner solution, make this toner solution emulsification or dispersion in water-medium, the preparation dispersion liquid, in this water-medium, make the above-mentioned compound that contains active hydrogen group, can with the polymer reaction of the above-mentioned compound reaction that contains active hydrogen group, make the cementability matrix material generate the particle shape, remove above-mentioned organic solvent again, this be because, the resin choice height of these toners, low-temperature fixing is also high, and the granulation excellence, particle diameter, size-grade distribution, shape control easily.

As above-mentioned toner materials, at least comprise cementability matrix material etc., this cementability matrix material makes the compound that contains active hydrogen group, can obtain with this polymkeric substance, binder resin, charged controlling agent, colorant reaction that contains the compound reaction of active hydrogen group, as required, also comprise other compositions such as resin particle, release agent.

-cementability matrix material-

Above-mentioned cementability matrix material shows cementability for recording mediums such as paper, and comprise the cementability polymkeric substance at least, this cementability polymkeric substance makes the above-mentioned compound that contains active hydrogen group, can react in above-mentioned water-medium with this polymkeric substance that contains the compound reaction of active hydrogen group and obtain, and can also contain from the suitable binder resin of selection of known binder resin.

The weight-average molecular weight of above-mentioned cementability matrix material is not particularly limited, and can suitably select according to purpose, for example is preferably more than 1000 more preferably 2000～10000000, preferred especially 3000～1000000.

If above-mentioned weight-average molecular weight less than 1000, then anti-print through worsens sometimes.

The storage modulus of above-mentioned cementability matrix material is not particularly limited, and can suitably select according to purpose, for example, measuring under the frequency 20Hz, reaches 10000dyne/cm ²Temperature (TG ') be generally more than 100 ℃ preferred 110～200 ℃.Should (TG ') if 100 ℃ of less thaies, then heat-resisting print through worsens sometimes.

The viscosity of above-mentioned cementability matrix material is not particularly limited, and can suitably select according to purpose, for example, is measuring under the frequency 20Hz, and the temperature (T η) that reaches 1000 pools is generally below 180 ℃ preferred 90～160 ℃.Be somebody's turn to do (T η) if surpass 180 ℃, then low-temperature fixing worsens sometimes.

Therefore, from seeking to have both the viewpoint of heat-resisting print through and low-temperature fixing, preferably above-mentioned (TG ') than above-mentioned (T η) height.That is, poor (TG '-T η) of (TG ') and (T η) is preferably more than 0 ℃, more preferably more than 10 ℃, more preferably more than 20 ℃.This difference is the bigger the better.

In addition, from seeking to have both low-temperature fixing and heat-resisting conservatory viewpoint, above-mentioned (TG '-T η) be preferably 0～100 ℃, more preferably 10～90 ℃, further preferred 20～80 ℃.

Object lesson as above-mentioned cementability matrix material is not particularly limited, and can suitably select according to purpose, but especially preferably enumerate polyester resin etc.

As above-mentioned polyester resin, be not particularly limited, can suitably select according to purpose, but especially preferably enumerate for example urea-modified polyester resin etc.

Above-mentioned urea-modified polyester resin makes in above-mentioned water-medium as the above-mentioned amine (B) that contains the compound of active hydrogen group with as obtaining with this polyester prepolymer (A) reaction that contains isocyanate groups of polymkeric substance that contains the compound reaction of active hydrogen group.

Above-mentioned urea-modified polyester resin is except the urea key, can also contain urethane bond, under this situation, contain mol ratio (urea key/urethane bond) as this urea key and this urethane bond, be not particularly limited, can suitably select, but be preferably 100/0～10/90 according to purpose, more preferably 80/20～20/80, preferred especially 60/40～30/70.

If above-mentioned urea key less than 10, then heat-resisting print through worsens sometimes.

Preferred object lesson as above-mentioned urea-modified vibrin, can preferably enumerate following (1) to (10), promptly, (1) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with isophorone diamine and 2 moles of addition products of bisphenol-A epoxy ethane and m-phthalic acid, the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and m-phthalic acid and isophorone diisocyanate reaction obtain; (2) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with isophorone diamine and 2 moles of addition products of bisphenol-A epoxy ethane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and m-phthalic acid and isophorone diisocyanate reaction obtain; (3) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with isophorone diamine and 2 moles of addition products of bisphenol-A epoxy ethane/2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane/2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA) and isophorone diisocyanate reaction obtain; (4) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with isophorone diamine and 2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane/2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA) and isophorone diisocyanate reaction obtain; (5) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with hexamethylene diamine and 2 moles of addition products of bisphenol-A epoxy ethane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and terephthalic acid (TPA) and isophorone diisocyanate reaction obtain; (6) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with hexamethylene diamine and 2 moles of addition products of bisphenol-A epoxy ethane/2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and terephthalic acid (TPA) and isophorone diisocyanate reaction obtain; (7) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with ethylenediamine and 2 moles of addition products of bisphenol-A epoxy ethane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and terephthalic acid (TPA) and isophorone diisocyanate reaction obtain; (8) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with hexamethylene diamine and 2 moles of addition products of bisphenol-A epoxy ethane and m-phthalic acid, the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and m-phthalic acid and '-diphenylmethane diisocyanate reaction obtain; (9) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with hexamethylene diamine and 2 moles of addition products of bisphenol-A epoxy ethane/2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA), the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane/2 moles of addition products of bisphenol-A epoxy propane and terephthalic acid (TPA)/dodecenyl succinic anhydride and '-diphenylmethane diisocyanate reaction obtain; (10) potpourri of the condensed polymer of the material that the polyester prepolyer ureaization is obtained with hexamethylene diamine and 2 moles of addition products of bisphenol-A epoxy ethane and m-phthalic acid, the condensed polymer of 2 moles of addition products of described polyester prepolyer bisphenol-A epoxy ethane and m-phthalic acid and toluene diisocyanate reaction obtain.

-contain the compound of active hydrogen group-

The above-mentioned compound that contains the active hydrogen group chain extender as can carry out chain extending reaction, cross-linking reaction etc. with the above-mentioned polymkeric substance that contains the compound reaction of active hydrogen group time the, crosslinking chemical etc. in above-mentioned water-medium work.

As the above-mentioned compound that contains active hydrogen group, as long as have active hydrogen group, be not particularly limited, can suitably select according to purpose, for example, can be under the situation of the above-mentioned polyester prepolyer (A) that contains isocyanate groups with the polymkeric substance of the above-mentioned compound reaction that contains active hydrogen group, from can coming macromolecule to quantize this point by carrying out reactions such as chain extending reaction, cross-linking reaction with this polyester prepolyer (A) that contains isocyanate groups, preferred above-mentioned amine (B).

As above-mentioned active hydrogen group, be not particularly limited, can suitably select according to purpose, for example, can use hydroxyl (alcohol hydroxyl group or phenol hydroxyl), amino, carboxyl, sulfydryl etc.These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, especially preferably use alcohol hydroxyl group.

As above-mentioned amine (B), be not particularly limited, can suitably select according to purpose, for example, the material (B6) that can enumerate diamines (B1), the polyamines more than 3 yuan (B2), amino alcohol (B3), amineothiot (B4), amino acid (B5), the amino-terminated of above-mentioned B1～B5 is obtained.

These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, especially preferably use the potpourri of diamines (B1), diamines (B1) and a spot of polyamines (B2) more than 3 yuan.

As above-mentioned diamine (B1), for example can enumerate aromatic diamine, ester ring type diamines, aliphatic diamine etc.As this aromatic diamine, for example can enumerate phenylenediamine, diethyl toluene diamine, 4,4 '-diaminodiphenylmethane etc.As this ester ring type diamines, for example can enumerate 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride, cyclohexane diamine, isophorone diamine etc.As this aliphatic diamine, for example can enumerate ethylenediamine, tetra-methylenedimine, hexamethylene diamine etc.

As above-mentioned polyamines (B2) more than 3 yuan, for example can enumerate diethylene triamine, trien etc.

As above-mentioned amino alcohol (B3), for example can enumerate monoethanolamine, carboxyethyl aniline etc.

As above-mentioned amineothiot (B4), for example can enumerate aminoethyl mercaptan, aminopropyl mercaptan etc.

As above-mentioned amino acid (B5), for example can enumerate alanine, aminocaproic acid etc.

As the material (B6) that the amino-terminated of above-mentioned B1～B5 obtained, for example can enumerate from above-mentioned (B 1) to (B5) any amine and ketimine compound, oxazoline (オ キ サ ゾ リ ゾ Application) compound of obtaining of ketone (acetone, MEK, hexone etc.) etc.

That is,, can use reaction to stop agent in order to make the above-mentioned compound that contains active hydrogen group and can to stop with the chain extending reaction of the polymkeric substance of the above-mentioned compound reaction that contains active hydrogen group, cross-linking reaction etc.If use this reaction to stop agent, in the scope that molecular weight of above-mentioned cementability matrix material etc. can be controlled at hope, be preferred on this aspect then.Stop agent as this reaction, can enumerate monoamine (diethylamine, dibutylamine, butylamine, lauryl amine) or compound (ketimine compound) that their end-blockings are obtained etc.

As above-mentioned amine (B) and the above-mentioned mixture ratio that contains the polyester prepolyer (A) of isocyanate groups, the isocyanate groups [NCO] in the above-mentioned prepolymer (A) that contains isocyanate groups and the mixing equivalent proportion ([NCO]/[NHx]) of the amino [NHx] in the above-mentioned amine (B) are preferably 1/3～3/1, more preferably 1/2～2/1, be preferably 1/1.5～1.5/1 especially.

If above-mentioned mixing equivalent proportion ([NCO]/[NHx]) less than 1/3, then low-temperature fixing reduces sometimes, if surpass 3/1, then the molecular weight of above-mentioned urea-modified vibrin reduces, and heat-resisting print through worsens sometimes.

-can with the polymkeric substance of the compound reaction that contains active hydrogen group-

As can with the polymkeric substance of the above-mentioned compound reaction that contains active hydrogen group (below be sometimes referred to as " prepolymer "), can get final product with the polymkeric substance at the position of the above-mentioned compound reaction that contains active hydrogen group so long as have at least, be not particularly limited, can from known resin, suitably select, for example, can enumerate polyol resin, polyacrylic acid resinoid, vibrin, epoxy resin, their derivatives resin etc.

These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, see special preferred polyester resin on the high fluidity when fusion, this aspect of the transparency.

As in the above-mentioned prepolymer can with the position of the above-mentioned compound reaction that contains active hydrogen group, be not particularly limited, can from known substituting group etc., suitably select, for example, can enumerate isocyanate groups, epoxide group, carboxylic acid, acid chloride groups etc.

These substituting groups can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, especially preferably use isocyanate groups.

In above-mentioned prepolymer, from being easy to regulate the molecular weight of macromolecule component, and can guarantee the nothing oil low-temperature fixing characteristic of dry toner, particularly even without under the situation of photographic fixing, also guaranteeing to see on this aspect of release property and fixation performance with the mechanism of heating medium coating form oil, especially preferably contain the vibrin (RMPE) of urea key generation group.

Generate group as above-mentioned urea key, for example can enumerate isocyanate groups etc.When above-mentioned this urea key that contains in the vibrin (RMPE) that the urea key generates group generates group for this isocyanate groups,, especially preferably list the above-mentioned polyester prepolyer (A) that contains isocyanate groups etc. as this vibrin (RMPE).

As the above-mentioned polyester prepolyer (A) that contains isocyanate groups, be not particularly limited, can suitably select according to purpose, for example can enumerate the condensed polymer of polyvalent alcohol (PO) and polycarboxylic acid (PC), and can make above-mentioned vibrin that contains active hydrogen group and polyisocyanates (PIC) reaction and obtain.

As above-mentioned polyvalent alcohol (PO), be not particularly limited, can suitably select according to purpose, for example can enumerate the potpourri of glycol (DIO), the polyvalent alcohol more than 3 yuan (TO), glycol (DIO) and the polyvalent alcohol more than 3 yuan (TO) etc.These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, preferred independent above-mentioned glycol (DIO), the potpourri of perhaps above-mentioned glycol (DIO) and a spot of above-mentioned polyvalent alcohol (TO) more than 3 yuan etc.

As above-mentioned glycol (DIO), for example can enumerate alkylene oxide adducts, the bisphenols of aklylene glycol, alkylene ether glycol, ester ring type glycol, ester ring type glycol, alkylene oxide adducts of bisphenols etc.

As above-mentioned aklylene glycol, the aklylene glycol of preferred carbon number 2～12 for example can be enumerated ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol etc.As above-mentioned alkylene ether glycol, for example can enumerate diglycol, triethylene glycol, dipropylene glycol, polyglycol, polypropylene glycol, polytetramethylene ether diol etc.As above-mentioned ester ring type glycol, for example can enumerate 1,4 cyclohexane dimethanol, hydrogenation bisphenol-A etc.As the alkylene oxide adducts of above-mentioned ester ring type glycol, for example can enumerate to the addition of above-mentioned ester ring type glycol the addition product of epoxyalkane such as oxirane, epoxypropane, epoxy butane etc.As above-mentioned bisphenols, for example can enumerate bisphenol-A, Bisphenol F, bisphenol S etc.As the alkylene oxide adducts of above-mentioned bisphenols, for example can enumerate to above-mentioned bisphenols addition the addition product of epoxyalkane such as oxirane, epoxypropane, epoxy butane.

Wherein, the aklylene glycol of preferred carbon number 2～12, the alkylene oxide adducts of bisphenols etc., the potpourri of the aklylene glycol of the alkylene oxide adducts of preferred especially bisphenols, the alkylene oxide adducts of bisphenols and carbon number 2～12.

As above-mentioned polyvalent alcohol (TO) more than 3 yuan, polyvalent alcohol that preferred 3～8 yuan or its are above for example, can be enumerated the alkylene oxide adducts of multi-alcohol more than 3 yuan, the Polyphenols more than 3 yuan, the Polyphenols more than 3 yuan etc.

As above-mentioned multi-alcohol more than 3 yuan, for example can enumerate glycerine, trimethylolethane, trimethylolpropane, pentaerythrite, D-sorbite etc.As above-mentioned Polyphenols more than 3 yuan, for example can enumerate trihydric phenol PA, phenol novolaks, cresols novolaks etc.As the alkylene oxide adducts of above-mentioned Polyphenols more than 3 yuan, for example can enumerate addition product to epoxyalkane such as above-mentioned Polyphenols addition of ethylene oxide, epoxypropane, epoxy butane more than 3 yuan.

In the potpourri of above-mentioned glycol (DIO) and above-mentioned polyvalent alcohol (TO) more than 3 yuan, as the mixing quality of above-mentioned glycol (DIO) and above-mentioned polyvalent alcohol (TO) more than 3 yuan than (DIO: TO), preferred 100: 0.01～100: 10, more preferably 100: 0.01～100: 1.

As above-mentioned polycarboxylic acid (PC), be not particularly limited, can suitably select according to purpose, for example can enumerate the potpourri of dicarboxylic acid (DIC), the polycarboxylic acid more than 3 yuan (TC), dicarboxylic acid (DIC) and the polycarboxylic acid more than 3 yuan (TC) etc.

These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, the preferred independent dicarboxylic acid (DIC) or the potpourri of DIC and a spot of polycarboxylic acid (TC) more than 3 yuan.

As above-mentioned dicarboxylic acid, for example can enumerate alkylene dicarboxylic acids, alkenylene dicarboxylic acid, aromatic dicarboxylic acid etc.

As above-mentioned alkylene dicarboxylic acids, for example can enumerate succinic acid, hexane diacid, decanedioic acid etc.As above-mentioned alkenylene dicarboxylic acid, the alkenylene dicarboxylic acid of preferred carbon number 4～20 for example can be enumerated maleic acid, fumaric acid etc.As above-mentioned aromatic dicarboxylic acid, the aromatic dicarboxylic acid of preferred carbon number 8～20 for example can be enumerated phthalic acid, m-phthalic acid, terephthalic acid (TPA) acid, naphthalene dicarboxylic acids etc.

Wherein, the alkenylene dicarboxylic acid of preferred carbon number 4～20, the aromatic dicarboxylic acid of carbon number 8～20.

As above-mentioned polycarboxylic acid (TC) more than 3 yuan, preferred 3～8 yuan or its above polycarboxylic acid for example can be enumerated aromatic multi-carboxy acid etc.

As above-mentioned aromatic multi-carboxy acid, the aromatic multi-carboxy acid of preferred carbon number 9～20 for example can enumerate trimellitic acid, pyromellitic acid etc.

As above-mentioned polycarboxylic acid (PC), can use from above-mentioned dicarboxylic acid (DIC), above-mentioned more than 3 yuan polycarboxylic acid (TC) and above-mentioned dicarboxylic acid (DIC) and above-mentioned polycarboxylic potpourri more than 3 yuan select any acid anhydrides or lower alkyl esters.As above-mentioned lower alkyl esters, for example can enumerate methyl esters, ethyl ester, isopropyl ester etc.

In the potpourri of above-mentioned dicarboxylic acid (DIC) and above-mentioned polycarboxylic acid (TC) more than 3 yuan, mixed mass ratio (DIC: TC) as above-mentioned dicarboxylic acid (DIC) and above-mentioned polycarboxylic acid (TC) more than 3 yuan, be not particularly limited, can suitably select according to purpose, for example, be preferably 100: 0.01～100: 10, more preferably 100: 0.01～100: 1.

Mixed ratio when making above-mentioned polyvalent alcohol (PO) and polycarboxylic acid (PC) polycondensation reaction, be not particularly limited, can suitably select according to purpose, for example, the equivalent proportion ([OH]/[COOH]) of hydroxyl [OH] in the above-mentioned polyvalent alcohol (PO) and the carboxyl [COOH] in the above-mentioned polycarboxylic acid (PC) is preferably 2/1～1/1 usually, more preferably 1.5/1～1/1, be preferably 1.3/1～1.02/1 especially.

The content of above-mentioned polyvalent alcohol (PO) in the above-mentioned polyester prepolyer (A) that contains isocyanate groups is not particularly limited, can suitably select according to purpose, for example, be preferably 0.5～40 quality %, more preferably 1～30 quality % is preferably 2～20 quality % especially.

If the above-mentioned quantity not sufficient 0.5 quality % that contains, heat-resisting print through worsens sometimes, is difficult to have both the heat-resisting keeping quality and the low-temperature fixing of toner sometimes, if surpass 40 quality %, then low-temperature fixing worsens sometimes.

As above-mentioned polyisocyanates (PIC), be not particularly limited, can suitably select according to purpose, for example can enumerate with aliphatic polyisocyante, ester ring type polyisocyanates, aromatic diisocyanate, aromatic-aliphatic diisocyanate, chlorinated isocyanurates class, they amphyl, oxime, caprolactam etc. carry out end-blocking and material of obtaining etc.

As above-mentioned aliphatic polyisocyante, for example can enumerate tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-two isocyanate group methyl caproates, eight methylene diisocyanates, decamethylene diisocyanate, ten dimethylene diisocyanates, ten tetramethylene diisocyanate, trimethyl cyclohexane diisocyanate, tetramethyl hexane diisocyanate etc.As above-mentioned ester ring type polyisocyanates, for example can enumerate isophorone diisocyanate, cyclohexyl-methane diisocyanate etc.As above-mentioned aromatic diisocyanate, for example can enumerate benzal diisocyanate, '-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, biphenylene-4,4 '-diisocyanate, 4,4 '-two isocyanate groups-3,3 '-dimethyl diphenyl, 3-methyldiphenyl methane-4,4 '-diisocyanate, diphenyl ether-4,4 '-diisocyanate etc.As above-mentioned aromatic-aliphatic diisocyanate, for example can enumerate α, α, α ', α '-tetramethylbenzene dimethyl diisocyanate.As above-mentioned chlorinated isocyanurates class, for example can enumerate three isocyanate group alkyl isocyanide urates (tris-isocyanatoalkyl-isocyanurate), three isocyanate group naphthenic base chlorinated isocyanurates (tris-isocyanatocycloalkyl-isocyanurate) etc.

These can use a kind separately, also can use simultaneously more than 2 kinds.

As above-mentioned polyisocyanates (PIC) and the above-mentioned vibrin that contains active hydrogen group (for example, mixed ratio when the vibrin that contains hydroxyl) reacting, the mixed equivalent proportion ([NCO]/[OH]) of the hydroxyl [OH] in the isocyanate groups [NCO] in this polyisocyanates (PIC) and this vibrin that contains hydroxyl is preferably 5/1～1/1 usually, more preferably 4/1～1.2/1, most preferably be 3/1～1.5/1.

If above-mentioned isocyanate groups [NCO] surpasses 5, then low-temperature fixing worsens sometimes, if less than 1, then anti-print through worsens sometimes.

As the content of above-mentioned polyisocyanates (PIC) in the above-mentioned polyester prepolyer (A) that contains isocyanate groups, be not particularly limited, can suitably select according to purpose, for example, be preferably 0.5～40 quality %, more preferably 1～30 quality %, more preferably 2～20 quality %.

If the above-mentioned quantity not sufficient 0.5 quality % that contains, then heat-resisting print through worsens sometimes, is difficult to have both heat-resisting keeping quality and low-temperature fixing, if surpass 40 quality %, then low-temperature fixing worsens sometimes.

Average as the isocyanate groups that contains in 1 molecule of the above-mentioned polyester prepolyer (A) that contains the polyisocyanates group is preferably more than 1, and more preferably 1.2～5, more preferably 1.5～4.

If the average less than 1 of above-mentioned isocyanate groups then generates the molecular weight step-down of the vibrin (RMPE) of basic modification with above-mentioned urea key, heat-resisting print through worsens sometimes.

As can with the weight-average molecular weight (Mw) of the polymkeric substance of the above-mentioned compound reaction that contains active hydrogen group, to adopt the molecular weight distribution of tetrahydrofuran (THF) soluble fraction that GPC (gel permeation chromatography) measures, be preferably 1,000～30,000, more preferably 1,500～15,000.If this weight-average molecular weight (M _W) less than 1,000, then heat-resisting keeping quality worsens sometimes, if surpass 30,000, then low-temperature fixing worsens sometimes.

For example following the carrying out of molecular weight distribution of adopting above-mentioned gel permeation chromatography (GPC) to measure.

That is, at first, in 40 ℃ thermal capacitance device, make post stable.Under this temperature, be of the speed circulation of post solvent with tetrahydrofuran (THF) with per minute 1ml, the adjustment sample solution concentration that injects 50～200 μ l is that the tetrahydrofuran sample solution of the resin of 0.05～0.6 quality % is measured.Molecule measuring in said sample regularly, the logarithm value of the typical curve that is made by the monodisperse polystyrene standard sample by several and the relation between counting calculate the molecular weight distribution of sample.As making the used polystyrene standard sample of above-mentioned typical curve, the molecular weight that uses Pressure Chemical Co. or eastern ソ one Co., Ltd. to make is 6 * 10 ², 2.1 * 10 ², 4 * 10 ², 1.75 * 10 ⁴, 1.1 * 10 ⁵, 3.9 * 10 ⁵, 8.6 * 10 ⁵, 2 * 10 ⁶, and 4.48 * 10 ⁶Sample, preferred use is the polystyrene standard sample about 10 at least.In addition, as above-mentioned detecting device, can use RI (refractive index) detecting device.

-binder resin-

As above-mentioned binder resin, be not particularly limited, can suitably select according to purpose, for example can enumerate vibrin etc., preferred especially unmodified polyester resin (vibrin that does not have modification).

If in above-mentioned toner, contain above-mentioned unmodified polyester resin, then can improve low-temperature fixing and glossiness.

As above-mentioned unmodified polyester resin, can enumerate with the above-mentioned urea key that contains and generate the basic identical resin of vibrin, that is, and the condensed polymer of polyvalent alcohol (PO) and polycarboxylic acid (PC) etc.Because the part of this unmodified polyester resin and above-mentionedly contain the urea key to generate the vibrin (RMPE) of base compatible, that is, having can compatible mutually similar structure, therefore, is preferred seeing aspect low-temperature fixing and the heat-resisting print through.

As the weight-average molecular weight (Mw) of above-mentioned unmodified polyester resin, to adopt the molecular weight distribution of the tetrahydrofuran soluble fraction that GPC (gel permeation chromatography) measures, be preferably 1,000～30,000, more preferably 1,500～15,000.If because this weight-average molecular weight (M _W) less than 1,000, then heat-resisting keeping quality worsens sometimes, and therefore, as mentioned above, the content of the composition of above-mentioned weight-average molecular weight (Mw) less than 1,000 is necessary for 8～28 quality %.On the other hand, if above-mentioned weight-average molecular weight (Mw) surpasses 30,000, then low-temperature fixing worsens sometimes.

As the glass transition temperature of above-mentioned unmodified polyester resin, be generally 30～70 ℃, more preferably 35～70 ℃, more preferably 35～50 ℃, be preferably 35～45 ℃ especially.If 30 ℃ of above-mentioned glass transition temperature less thaies, then the heat-resisting keeping quality of toner worsens sometimes, if surpass 70 ℃, then low-temperature fixing becomes insufficient sometimes.

As the hydroxyl value of above-mentioned unmodified vibrin, be preferably more than the 5mgKOH/g, more preferably 10～120mgKOH/g, more preferably 20～80mgKOH/g.If the not enough 5mgKOH/g of above-mentioned hydroxyl value then is difficult to have both heat-resisting keeping quality and low-temperature fixing sometimes.As the acid number of above-mentioned unmodified polyester resin, be preferably more than 1.0～50.0mgKOH/g, more preferably 1.0～45.0mgKOH/g, more preferably 15.0～45.0mgKOH/g.In general, by keeping the acid number of above-mentioned toner, make it be easy to become negative charging.

In making above-mentioned toner, contain under the situation of above-mentioned unmodified polyester resin, generate the mixing quality of basic vibrin (RMPE) and this unmodified polyester resin (PE) than (RMPE/PE) as the above-mentioned urea key that contains, be preferably 5/95～25/75, more preferably 10/90～25/75.

If the mixing quality of above-mentioned unmodified polyester resin (PE) is than surpassing 95, then heat-resisting print through deterioration is difficult to have both heat-resisting keeping quality and low-temperature fixing sometimes, if less than 25, then glossiness worsens sometimes.

As the content of the above-mentioned unmodified polyester resin in the above-mentioned binder resin, for example be preferably 50～100 quality %, more preferably 70～95 quality %, more preferably 80～90 quality %.If this contains quantity not sufficient 50 quality %, then the glossiness of low-temperature fixing and image worsens sometimes.

-other composition-

As above-mentioned other composition, be not particularly limited, can suitably select according to purpose, for example can enumerate colorant, release agent, charged controlling agent, inorganic particles, fluidity improving agent, spatter property improving agent, magnetic material, metallic soap etc.

As above-mentioned colorant, be not particularly limited, can from known dyestuff and pigment, suitably select according to purpose, for example, carbon black, aniline black byestuffs, iron black, Naphthol Yellow S, hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, the colour of loess, lead and yellow-collation, titan yellow, the polyazo Huang, oil yellow (oil yellow), hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Wu Erkang fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthracene Huang (anthracene yellow) BGL, the isoindolinone Huang, iron oxide red, red lead, plumbous red, cadmium red, cadmium mercury is red, antimony red, permanent red 4R, rose-red, fire red (fire red), p-chloro-o-nitroaniline red, lithol that fast red G, gorgeous fast red, bright fuchsin BS, permanent red (F2R, F4R, FRL, FRLL, F4RH), fast red VD, Vulcan Fast Rubine B, brilliant scarlet G G, lithol that rubine GX, permanent red F5R, bright fuchsin 6B, pigment red 3 B, purplish red 5B, everbright fast maroon, permanent purplish red F2K, He Liao bordeaux B L, purplish red 10B, nation is brown light red, the brown centre of nation is red, eosine lake, rhodamine color lake B, rhodamine color lake Y, alizarine lake, the red B of Di Aoyindige, thioindigoid maroons, oil red, quinacridone is red, pyrazolone red, polyazo is red, molybdate red, benzidine orange, pyrene orange (Perynone Orange), the oil orange, cobalt blue, peace is blue in the match fine jade, alkali blue lake, peacock blue lake, the Victoria blue color lake, metal-free phthalocyanine blue, phthalocyanine blue, fast blue, indanthrene blue (RS, BC), indigo, ultramarine, Prussian blue, anthraquinone blue, fast scarlet B, the methyl violet color lake, cobalt violet, manganese violet diox purple, the anthraquinone purple, chrome green, zinc green, chromium oxide, tie up sharp Dean pigment, emerald, pigment green B, the green B of Naphthol, the golden yellow diazonium class of green glow pigment, the acid green color lake, peacock green precipitation color lake, phthalocyanine green, anthraquinone green, titanium dioxide, zinc white, lithopone etc.

They can use a kind separately, also can use simultaneously more than 2 kinds.

The content of above-mentioned colorant in above-mentioned toner has no particular limits, and can suitably select according to purpose, but preferred 1～15 quality % is more preferably 3～10 quality %.

If the above-mentioned quantity not sufficient 1 quality % that contains, then reducing appears in the colouring power of toner, if surpass 15 quality %, causes that sometimes the dispersion of pigment in toner is bad, causes colouring power to reduce, and the reduction of the electrical characteristics of toner.

Above-mentioned colorant can also be made the parent sizing material use with resin compoundedization.As this resin, be not particularly limited, can from known material, suitably select according to purpose, for example can enumerate the polymkeric substance of styrene or its substituent, styrene copolymer, polymethylmethacrylate, poly-n-butyl methacrylate, Polyvinylchloride, polyvinyl acetate, tygon, polypropylene, polyester, epoxy resin, the many alcohol resins of epoxy, polyurethane, polyamide, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, fragrance same clan petroleum resin, the chloroalkane hydrocarbon, paraffin etc.They can use a kind separately, also can use simultaneously more than 2 kinds.

As the polymkeric substance of above-mentioned styrene or its substituent, for example can enumerate vibrin, polystyrene, poly-to chlorostyrene, polyvinyl toluene etc.As above-mentioned styrene copolymer, for example can enumerate styrene-to chloro-styrene copolymer, the styrene-propene multipolymer, styrene-ethylene base toluene multipolymer, styrene-ethylene base naphthalenedicarboxylate copolymer, styrene-propene acid methyl terpolymer, styrene-propene acetoacetic ester multipolymer, the styrene-propene butyl acrylate copolymer, the misery ester copolymer of styrene-propene, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymer, styrene-alpha-chloro methylmethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-ethylene ylmethyl ketone multipolymer, Styrene-Butadiene, the styrene-isoprene multipolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer etc.

Above-mentioned parent sizing material can apply that high shear force mixes or mixing the manufacturing to above-mentioned parent sizing material with resin and above-mentioned colorant.At this moment, in order to improve the interaction of colorant and resin, preferably add organic solvent.In addition, so-called flash method also can directly use the wet cake of colorant, needn't dry this point, is preferred.

Above-mentioned flash method is that the moisture water paste of colorant and resin and organic solvent are mixed together or mixing, makes colorant move to resin side, removes the method for moisture and organic solvent composition.Above-mentioned mixing or mixing in, can preferably use for example high shear diverting device such as three roller attrition mills.

As above-mentioned charged controlling agent, have no particular limits, can from known material, suitably select according to purpose, but tone can change during owing to the use colored materials, therefore preferred colourless or near the material of white, for example can enumerate the slaine of the simple substance of the simple substance of triphenylmethane dye, molybdic acid chelating pigment, rhodamine class dyestuff, alcoxyl base class amine, quaternary ammonium salt (comprising the fluorine modified quaternary ammonium salt), alkylamide, phosphorus or its compound, tungsten or its compound, fluorine class activating agent, salicylic slaine, salicyclic acid derivatives etc.These can use a kind separately, also can use simultaneously more than 2 kinds.

Above-mentioned charged controlling agent can use commercially available product, as this commercially available product, for example can enumerate the ボ Application ト ロ Application P-51 of quaternary ammonium salt, the E-82 of hydroxyl naphthalene-carboxylic acid metalloid coordination compound, the E-84 of salicylic acid metal complex, the E-89 of phenolic condensate (more than, for オ リ エ Application ト chemical industrial company makes), the TP-302 of quaternary ammonium salt molybdenum complex, TP-415 (more than, for hodogaya chemical industrial group makes), the copy load PSYVP2038 of quaternary ammonium salt, the blue PR of the copy of triphenylmethane derivative, the copy load NEG VP2036 of quaternary ammonium salt, copy load NX VP434 (more than, for ヘ キ ス ト company makes), LRA-901, the LR-147 of boron coordination compound (Japanese カ one リ Star ト company make), quinoline a word used for translation ketone, azo class pigment, and has a sulfonic group, carboxyl, the macromolecule compound of functional groups such as quaternary ammonium salt etc.

Above-mentioned charged controlling agent can be behind above-mentioned parent sizing material melting mixing, dissolve or disperse, perhaps, also can when directly dissolving or be distributed in the above-mentioned organic solvent, add with each composition of above-mentioned toner, perhaps can also after making, toner particle be fixed on toner surface.

As the content of above-mentioned charged controlling agent in above-mentioned toner, according to the kind of above-mentioned binder resin, have additive-free, process for dispersing etc. different and different, can not decide without exception, for example, with respect to above-mentioned binder resin 100 mass parts, preferred 0.1～10 mass parts, more preferably 0.2～5 mass parts.If this content less than 0.1 mass parts, can not obtain sometimes charged controlled, if surpass 10 mass parts, the charging property of toner is excessive, the effect of master tape controling agent goes down, and with the electrostatic attraction increase of developer roll, causes the flowability reduction of developer or the reduction of image color sometimes.

As above-mentioned release agent, be not particularly limited, can from known material, suitably select according to purpose, for example can enumerate wax class etc.

As above-mentioned wax class, for example can enumerate the wax that contains carbonyl, polyolefin-wax, long chain hydrocarbon etc.They can use a kind separately, also can use simultaneously more than 2 kinds, preferably contain the wax of carbonyl among these.

As the above-mentioned wax that contains carbonyl, for example can enumerate polyalkane acid esters, polyalkane alcohol ester, polyalkane acid acid amides, poly-alkylamide, dialkyl ketone etc.As above-mentioned polyalkane acid esters, for example can enumerate Brazil wax, montan wax, trimethylolpropane tris behenic acid ester, pentaerythrite Si behenic acid ester, pentaerythrite oxalic acid Er behenic acid ester, Gan oil San behenic acid ester, 1,18-octacosanol distearate etc.As above-mentioned polyalkane alcohol ester, for example can enumerate tri trimellitate (octadecyl) ester, maleic acid two (octadecyl) ester etc.As above-mentioned polyalkane acid acid amides, for example can enumerate Er Shan Yu acid amides etc.As above-mentioned poly-alkylamide, for example can enumerate tri trimellitate stearmide etc.As above-mentioned dialkyl ketone, for example can enumerate two (octadecyl) ketone etc.These contain in the wax of carbonyl, preferred especially polyalkane acid esters.

As said polyolefins wax, for example can enumerate Tissuemat E, polypropylene wax etc.

As above-mentioned long chain hydrocarbon, for example can enumerate paraffin, Sa Suoer wax (Sasol wax) etc.

Fusing point as above-mentioned release agent is not particularly limited, can suitably select according to purpose, but preferred 40～160 ℃, be more preferably 50～120 ℃, preferred especially 60～90 ℃.

If 40 ℃ of above-mentioned fusing point less thaies then can be brought harmful effect to the heat-resisting keeping quality of wax,, then when low-temperature fixing, cause cold print through easily if surpass 160 ℃.

As the melt viscosity of above-mentioned release agent, as than the measured value under the high 20 ℃ temperature of the fusing point of this wax, be preferably 5～1000cps, be more preferably 10～100cps.

If the not enough 5cps of above-mentioned melt viscosity, then release property reduces sometimes, if surpass 1000cps, then can not obtain the raising effect of heat-resisting print through, low-temperature fixing sometimes.

As the content of above-mentioned release agent in above-mentioned toner, be not particularly limited, can suitably select according to purpose, but preferred 0～40 quality % is more preferably 3～30 quality %.

If above-mentioned content surpasses 40 quality %, then the flowability of toner worsens sometimes.

-resin particle-

As above-mentioned resin particle, get final product so long as can in water-medium, form the resin of aqueous liquid dispersion, have no particular limits, can from known resin, suitably select according to purpose, it can be thermoplastic resin, also can be thermoset resin, for example can enumerate vinyl-based resin, urethane resin, epoxy resin, vibrin, polyamide, polyimide resin, silicon resinoid, phenolics, melamine resin, Lauxite, anline resin, ionic polymer resin, polycarbonate resin etc.Among these, special preferred vinyl resinoid.

These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, on the aqueous liquid dispersion this point that obtains fine spherical resin particle easily, the preferred resin particle that forms by at least a resin that is selected from vinylite, urethane resin, epoxy resin and the vibrin.

In addition, above-mentioned vinylite is the polymkeric substance that vinyl monomer homopolymerization or copolymerization are obtained, and for example can enumerate styrene-(methyl) acrylate resin, Styrene-Butadiene, (methyl) acrylic acid-acrylate polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene-(methyl) acrylic copolymer etc.

In addition, as above-mentioned resin particle, can also use the multipolymer that contains the monomer formation that has 2 unsaturated groups at least.As the above-mentioned monomer that has 2 unsaturated groups at least, be not particularly limited, can suitably select according to purpose, for example can enumerate the sodium salt (" エ レ ミ ノ one Le RS-30 " of methacrylic acid ethylene oxide adduct sulfuric ester; Sanyo Chemical Industries, Ltd. makes), divinylbenzene, 1,6-hexanediol acrylate etc.

Above-mentioned resin particle can carry out polymerization by the known method of suitably selecting according to purpose and obtain, but preferably obtains the aqueous liquid dispersion of this resin particle.Preparation method as the aqueous liquid dispersion of this resin particle, can enumerate following method, for example, (1) under the situation of above-mentioned vinylite, with vinyl monomer as initial feed, by being selected from suspension polymerization, emulsion polymerization, any one polyreaction in seeding polymerization method and the dispersion copolymerization method is directly made the method for the aqueous liquid dispersion of resin particle, (2) above-mentioned vibrin, urethane resin, under addition polymerizations such as epoxy resin or the resinoid situation of condensation, in the presence of suitable spreading agent, with precursor (monomer, oligomer etc.) or after its solvent solution is dispersed in the aqueous medium, heating or interpolation hardening agent make it to solidify, make the method for the water-borne dispersions of resin particle, (3) above-mentioned vibrin, urethane resin, under addition polymerizations such as epoxy resin or the resinoid situation of polycondensation, at precursor (monomer, oligomer etc.) or its solvent solution (be preferably liquid.Also can be by heating liquid stateization) middle dissolve suitable emulsifying agent after, add entry and carry out the method for Phase inversion emulsification, (4) will (can be addition polymerization by polyreaction in advance, ring-opening polymerization, addition polymerization, addition condensation, any one polyreaction form such as polycondensation) Zhi Bei resin is pulverized with atomizers such as mechanical rotation formula or injecting types, then, after obtaining resin particle by classification, in the presence of suitable spreading agent, be distributed to the method in the water, (5) will (can be addition polymerization by polyreaction in advance, ring-opening polymerization, addition polymerization, addition condensation, any one polyreaction form such as polycondensation) Zhi Bei resin dissolves is in solvent, be vaporific with this resin solution spraying again, after obtaining resin particle thus, in the presence of suitable spreading agent, this resin particle is distributed to method in the water, (6) will (can be addition polymerization by polyreaction in advance, ring-opening polymerization, addition polymerization, addition condensation, any one polyreaction form such as polycondensation) Zhi Bei resin dissolves is in solvent, in this resin solution, add poor solvent, perhaps heating for dissolving is cooled off in the resin solution of solvent in advance, thus, separate out resin particle, after obtaining resin particle except that desolvating then, in the presence of suitable spreading agent, this resin particle is distributed to method in the water, (7) will (can be addition polymerization by polyreaction in advance, ring-opening polymerization, addition polymerization, addition condensation, any one polyreaction form such as polycondensation) Zhi Bei resin dissolves is in solvent, in the presence of suitable spreading agent, after being distributed to this resin solution in the aqueous medium, remove the method for desolvating by heating or decompression etc., (8) will (can be addition polymerization by polyreaction in advance, ring-opening polymerization, addition polymerization, addition condensation, any one polyreaction form such as polycondensation) Zhi Bei resin dissolves is in solvent, in this resin solution behind the suitable emulsifying agent of dissolving, add the method etc. that Phase inversion emulsification is carried out in entry.

As above-mentioned toner, for example can enumerate by known suspension polymerization, the emulsification coacervation, the toner that emulsification dispersion method etc. are made, but preferably enumerate, to contain the compound of active hydrogen group and can be dissolved in the organic solvent with this above-mentioned toner materials of polymkeric substance that contains the compound reaction of active hydrogen group, preparation toner solution, then, this toner solution is dispersed in the water-medium, the preparation dispersion liquid, in this water-medium, make compound that contains active hydrogen group and the polymer reaction that can contain the compound reaction of active hydrogen group with this, make the cementability matrix material become the particle shape, remove above-mentioned organic solvent and the toner that obtains.

-toner solution-

The preparation of above-mentioned toner solution can be carried out in the above-mentioned organic solvent by above-mentioned toner materials is dissolved in.

--organic solvent--

As above-mentioned organic solvent, so long as can dissolve or disperse the solvent of above-mentioned toner materials to get final product, be not particularly limited, can suitably select according to purpose, for example, removing this point easily, preferred boiling point is less than 150 ℃ volatile solvent, for example can enumerate toluene, dimethylbenzene, benzene, phenixin, methylene chloride, 1,2-ethylene dichloride, 1,1,2-trichloroethanes, triclene, chloroform, monochloro-benzene, 1,1-ethylene dichloride, methyl acetate, ethyl acetate, MEK, hexone etc.Among these, preferred toluene, dimethylbenzene, benzene, methylene chloride, 1,2-ethylene dichloride, chloroform, phenixin etc., special ethyl acetate.They can use a kind separately, also can use simultaneously more than 2 kinds.

Use amount as above-mentioned organic solvent is not particularly limited, can suitably select according to purpose, for example, and with respect to the above-mentioned toner materials of 100 mass parts, preferred 40～300 mass parts, more preferably 60～140 mass parts, further preferred 80～120 mass parts.

-dispersion liquid-

The preparation of above-mentioned dispersion liquid is undertaken by above-mentioned toner solution is distributed in the water-medium.

When being distributed to above-mentioned toner solution in the above-mentioned water-medium, in this water-medium, form the dispersion (oil droplet) that contains above-mentioned toner solution.

--water-medium--

As water-medium, be not particularly limited, can be from known water-medium suitably select, for example can enumerate water, the solvent that can mix with this water, their potpourri etc., among these, special preferred water.

Solvent as mixing with above-mentioned water as long as can mix with above-mentioned water, is not particularly limited, and for example can enumerate alcohol, dimethyl formamide, tetrahydrofuran, cellosolve class, rudimentary ketone etc.

As above-mentioned alcohol, for example can enumerate methyl alcohol, isopropyl alcohol, ethylene glycol etc.As above-mentioned rudimentary ketone, for example can enumerate acetone, MEK etc.

These can use a kind separately, also can use simultaneously more than 2 kinds.

Above-mentioned toner solution preferably disperses in above-mentioned water-medium while stirring.

Method as above-mentioned dispersion, be not particularly limited, known dispersion machine etc. be can suitably select to use,, low velocity shear formula dispersion machine, high speed shear formula dispersion machine, friction-type dispersion machine, high-pressure injection formula dispersion machine, ultrasonic dispersing machine etc. for example can be enumerated as this dispersion machine.Among these, see preferred high speed shear formula dispersion machine the particle diameter of above-mentioned dispersion (oil droplet) can being controlled on 2～20 μ m this point.

When using above-mentioned high speed shear formula dispersion machine, be not particularly limited, can suitably select according to purpose for conditions such as rotation number, jitter time, dispersion temperatures, for example, as above-mentioned rotating speed, be preferably 1000～30000rpm, more preferably 5000～20000rpm, as above-mentioned jitter time, under the situation of intermittent mode, be preferably 0.1～5 minute, as above-mentioned dispersion temperature, be preferably 0～150 ℃, more preferably 40～98 ℃ adding to depress.Usually disperse easily when in addition, above-mentioned dispersion temperature is high temperature.

As an example of the manufacture method of above-mentioned toner, illustrate below and make above-mentioned cementability matrix material become the method that the particle shape obtains toner.

Make above-mentioned cementability matrix material become the particle shape and with the toner process for granulating in, for example, carry out the preparation of the preparation of water-medium phase, the preparation of above-mentioned toner solution, above-mentioned dispersion liquid, the interpolation of above-mentioned water-medium, other (above-mentioned compound synthetic etc. that can contain active hydrogen group) with the polymkeric substance (prepolymer) of the compound reaction that contains active hydrogen group synthetic, above-mentioned.

The preparation of above-mentioned water-medium phase can be undertaken by for example above-mentioned resin particle being dispersed in the above-mentioned water-medium.As the addition of this resin particle in this water class medium, be not particularly limited, can suitably select for example preferred 0.5～10 quality % according to purpose.

The preparation of above-mentioned toner solution can or disperse above-mentioned the contain compound of active hydrogen group, above-mentioned can carrying out with toner materials such as the polymkeric substance of the compound reaction that contains active hydrogen group, above-mentioned colorant, above-mentioned release agent, above-mentioned charged controlling agent, above-mentioned unmodified polyester resins by dissolving in above-mentioned organic solvent.

In addition, in above-mentioned toner materials, except that above-mentioned can with the composition the polymkeric substance (prepolymer) of the compound reaction that contains active hydrogen group, in above-mentioned water-medium prepares mutually, can when being dispersed in above-mentioned resin particle in the above-mentioned water-medium, add and be mixed in this water-medium, perhaps, also can above-mentioned toner solution is added on above-mentioned water-medium mutually in the time, with this toner solution add to together above-mentioned water-medium mutually in.

The preparation of above-mentioned dispersion liquid can by previously prepared above-mentioned water-medium mutually in emulsification or disperse previously prepared above-mentioned toner solution to carry out.And this emulsification or when disperseing at the above-mentioned compound that contains active hydrogen group and above-mentioned can carry out chain extending reaction or cross-linking reaction with the polymkeric substance of the compound reaction that contains active hydrogen group the time, generates above-mentioned cementability matrix material.

Above-mentioned cementability matrix material (for example, above-mentioned urea-modified vibrin) can generate by the following method: for example, (1) will contain above-mentioned can with the polymkeric substance of the compound reaction that contains active hydrogen group (for example, the above-mentioned polyester prepolyer (A) that contains isocyanate groups) above-mentioned toner solution and the above-mentioned compound that contains active hydrogen group are (for example, above-mentioned amine (B)) together emulsification or be dispersed in above-mentioned water-medium mutually in, form dispersion, make the two carry out chain extending reaction or cross-linking reaction in mutually at this water-medium; (2) with above-mentioned toner emulsifying soln or be distributed to added the above-mentioned compound that contains active hydrogen group in advance above-mentioned water-medium mutually in, form dispersion, make the two carry out chain extending reaction or cross-linking reaction at this water-medium in mutually; Perhaps, (3) above-mentioned toner solution is added be mixed in the above-mentioned water-medium after, adds the above-mentioned compound that contains active hydrogen group, the formation dispersion makes the two carry out chain extending reaction or cross-linking reaction from particle interface at this water-medium in mutually.In addition, under the situation of above-mentioned (3), also can preferentially generate modified polyester resin, concentration gradient is set in toner particle in the toner surface that generates.

As the reaction conditions that generates above-mentioned cementability matrix material by above-mentioned emulsification or dispersion, be not particularly limited, can can suitably select with the polymkeric substance and the above-mentioned combination of compounds that contains active hydrogen group of the compound reaction that contains active hydrogen group according to above-mentioned, as the reaction time, preferred 10 minutes～40 hours, more preferably 2 hours～24 hours, as temperature of reaction, preferred 0～150 ℃, be more preferably 40～98 ℃.

Above-mentioned water-medium mutually in, as stably form contain above-mentioned can with the polymkeric substance of the compound reaction that contains active hydrogen group (for example, the method of the above-mentioned dispersion above-mentioned polyester prepolyer (A) that contains isocyanate group), can enumerate following method, for example, to in above-mentioned organic solvent, dissolve or disperse above-mentioned can with the polymkeric substance of the compound reaction that contains active hydrogen group (for example, the above-mentioned polyester prepolyer (A) that contains isocyanate groups), above-mentioned colorant, above-mentioned release agent, above-mentioned charged controlling agent, toner materials such as above-mentioned unmodified polyester resin and the above-mentioned toner solution for preparing add to above-mentioned water-medium mutually in, and the method for disperseing by shearing force etc.In addition, the detailed description of the method for above-mentioned dispersion as mentioned above.

In the preparation of above-mentioned dispersion liquid, as required, can make above-mentioned dispersion (oil droplet that contains above-mentioned toner solution) stabilization, from shape that obtains expecting and the viewpoint that makes size distribution narrow, preferably use spreading agent.

As above-mentioned spreading agent, be not particularly limited, can suitably select according to purpose, for example can enumerate surfactant, be insoluble in mineral compound spreading agent, high score subclass protecting colloid of water etc.They can use a kind separately, also can use simultaneously more than 2 kinds.Among these, preferred surfactant.

As above-mentioned surfactant, for example can enumerate anionic surfactant, cationic surfactant, non-ionic surfactant, amphoteric surfactant etc.

As above-mentioned anionic surfactant, for example can enumerate alkyl benzene sulfonate, alpha-alkene sulfonate, phosphate etc., preferably have the anionic surfactant of fluoroalkyl.Have the anionic surface active agent of fluoroalkyl as this, for example can enumerate carbon number and be 2～10 fluoroalkyl carboxylic acid or its slaine, PFO sulphonyl disodium glutamate, 3-[ω-fluoro-alkyl (carbon number 6～11) oxygen base]-1-alkyl (carbon number 3～4) sodium sulfonate, 3-[ω-fluoro alkanol (carbon number 6～8)-N-ethylamino]-1-propane sulfonic acid sodium, fluoroalkyl (carbon number 11～20) carboxylic acid or its slaine, perfluoro carboxylic acid (carbon number 7～13) or its slaine, perfluoroalkyl (carbon number 4～12) sulfonic acid or its slaine, the Perfluorooctane sulfonates diglycollic amide, N-propyl group-N-(2-hydroxyethyl) PFO sulfonamide, perfluoroalkyl (carbon number 6～10) sulfonamide oxypropyl trimethyl ammonium salt, perfluoroalkyl (carbon number 6～10)-N-second sulphonyl glutamate, one perfluoroalkyl (carbon number 6～16) ethyl phosphonic acid ester etc.Have the commercially available product of the surfactant of fluoroalkyl as this, for example can enumerate サ one Off ロ Application S-111, S-112, S-113 (Asahi Glass Co., Ltd's manufacturing); Off ロ one ラ De FC-93, FC-95, FC-98, FC-129 (manufacturing of Sumitomo 3M Co., Ltd.); ユ ニ ダ イ Application DS-101, DS-102 (manufacturing of ダ イ キ Application Industrial Co., Ltd); メ ガ Off ア Star Network F-110, F-120, F-113, F-191, F-812, F-833 (big Japanese イ Application キ chemical industry Co., Ltd. make); エ Network ト Star プ EF-102,103,104,105,112,123A, 123B, 306A, 501,201,204 (manufacturing of ト one ケ system プ ロ ダ Network Star company); Off one ジ エ Application ト F-100, F150 (manufacturing of ネ オ ス company) etc.

As above-mentioned cationic surfactant, for example can enumerate amine salt type surfactant, quaternary ammonium salt cationic surfactant etc.As above-mentioned amine salt type surfactant, for example can enumerate alkylamine salt, amino alcohol fatty acid derivatives, polyamine derivative of fatty acid, imidazoline etc.As above-mentioned quaternary ammonium salt cationic surfactant, for example can enumerate alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt, pyridiniujm, alkyl isoquinolinium salt, benzethonium chloride etc.In this cationic surfactant, can enumerate aliphatics primary, the second month in a season or tertiary amine acid with fluoroalkyl, perfluoroalkyl (aliphatic quaternary ammonium salt, zephiran salt, benzethonium chloride, pyridiniujm, the imidazoline salt etc. such as sulfonamide oxypropyl trimethyl ammonium salt of C6～C10).As the commercially available product of this cationic surfactant, for example can enumerate サ one Off ロ Application S-121 (Asahi Glass Co., Ltd's manufacturing), Off ロ ラ one De FC-135 (manufacturing of Sumitomo 3M Co., Ltd.), ユ ニ ダ イ Application DS-202 (manufacturing of ダ イ キ Application Industrial Co., Ltd), メ ガ Off ア Star Network F-150, F-824 (big Japanese イ Application キ chemical industry Co., Ltd. make), エ Network ト Star プ EF-132 (manufacturing of ト one ケ system プ ロ ダ Network Star company), Off one ジ エ Application ト F-300 (manufacturing of ネ オ ス company) etc.

As above-mentioned non-ionic surfactant, for example can enumerate fat amide derivant, polyol derivative etc.

As above-mentioned amphoteric surfactant, for example can enumerate alanine, dodecyl two (aminoethyl) glycocoll, two (octyl group aminoethyl) glycocoll, N-alkyl-N, N-Dimethyl Ammonium betaine etc.

As the mineral compound spreading agent that is insoluble in water, for example can enumerate tricalcium phosphate, lime carbonate, titanium dioxide, cataloid, hydroxyapatite etc.

As above-mentioned high score subclass protecting colloid, for example can enumerate acids, contain (methyl) acrylic monomer, vinyl alcohol of hydroxyl or with ethers, the vinyl alcohol of vinyl alcohol with contain ester class, amide compound or their methylol compound, the chloride-based of the compound of carboxyl, the homopolymer of material etc. or multipolymer, polyoxyethylene, cellulose family etc. with nitrogen-atoms or its heterocycle.

As above-mentioned acids, for example can enumerate acrylic acid, methacrylic acid, alpha-cyanoacrylate, alpha-cyano methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride etc.As above-mentioned (methyl) acrylic monomer that contains hydroxyl, for example can enumerate propenoic acid beta-hydroxy base ethyl ester, methacrylic acid beta-hydroxy ethyl ester, propenoic acid beta-hydroxy base propyl ester, methacrylic acid beta-hydroxy propyl ester, acrylic acid γ-hydroxy propyl ester, methacrylic acid γ-hydroxy propyl ester, acrylic acid 3-chloro-2-hydroxy propyl ester, methacrylic acid 3-chloro-2-hydroxy propyl ester, diglycol monotertiary acrylate, diglycol monotertiary methacrylate, glycerine mono acrylic ester, glycerin monomethyl acrylic ester, N hydroxymethyl acrylamide, N-methylol methacrylamide etc.As above-mentioned vinyl alcohol or with the ethers of vinyl alcohol, for example can enumerate vinyl methyl ether, EVE, vinyl propyl ether etc.As above-mentioned vinyl alcohol and the ester class that contains the compound of carboxyl, for example can enumerate vinyl acetate, propionate, vinyl butyrate etc.As above-mentioned amide compound or their methylol compound, for example can enumerate acrylamide, Methacrylamide, diacetone acrylamide or their methylol compound etc.As above-mentioned chloride-based, for example can enumerate acryloyl chloride, methacrylic chloride etc.As the homopolymer or the multipolymer of above-mentioned material etc., for example can enumerate vinylpyridine, vinyl pyrrolidone, vinyl imidazole, second and embrace imines etc. with nitrogen-atoms or its heterocycle.As above-mentioned polyoxyethylene, for example can enumerate polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl amine, polyoxypropylene alkyl amine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylplenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene octadecyl phenylester, polyoxyethylene nonyl phenylester etc.As above-mentioned cellulose family, for example can enumerate methylcellulose, hydroxyethyl cellulose, hydroxypropyl cellulose etc.

In the preparation of above-mentioned dispersion liquid, can use dispersion stabilizer as required.

As this dispersion stabilizer, for example can enumerate synthos etc. and can be dissolved in material of acid, alkali etc.

When using this dispersion stabilizer, can be by with after the sour dissolving phosphoric acid calcium salts such as hydrochloric acid, the method for washing, by zymolytic method etc. thus, can be removed synthos from particulate.

In the preparation of above-mentioned dispersion liquid, can use the catalyzer of above-mentioned chain extending reaction or above-mentioned cross-linking reaction.As this catalyzer, for example can enumerate dibutyl tin laurate, dioctyltin laurate etc.

From the dispersion liquid (emulsion paste) that obtains, remove organic solvent.Removing of this organic solvent, can enumerate following method: (1) makes the whole slowly intensification of reaction system, above-mentioned organic solvent in the above-mentioned oil droplet is evaporated method, (2) of removing fully to be injected in the emulsification dispersion in the dry atmosphere, water-insoluble organic solvent in the oil droplet is removed fully, form toner particle, the method for water system spreading agent etc. is removed in evaporation simultaneously.

If carry out removing of above-mentioned organic solvent, then can form toner particle.To this toner particle can wash, drying etc., then, can carry out classification etc. according to expectation again.This classification for example can be removed particulate by cyclone separator, decanter, centrifuging etc. and partly carried out in liquid, can also carry out progressive operation after drying obtains powder again.

Like this, particle mixed together such as toner particle that obtains and above-mentioned colorant, release agent, above-mentioned charged controlling agent perhaps apply mechanical impact force again, can prevent that thus particle such as this release agent breaks away from from this surfaces of toner particles.

As the method that applies above-mentioned mechanical impact force, the blade that for example can enumerate by high speed rotating applies the method for impulsive force, potpourri is dropped in the high velocity air quicken potpourri, makes between the particle or the method for the particle of compoundization and suitable impingement plate collision etc.As the device that uses in this method, for example can enumerate and transform オ Application グ attrition mill (manufacturings of ホ ソ カ ワ ミ Network ロ Application company), I formula attrition mill (Japanese ニ ユ one マ チ Star Network company make) is transformed and reduced the device of pulverizing air pressure, vibration commingled system (Ha イ Block リ ダ イ ゼ イ シ ヨ Application シ ス テ system) (nara machinery is made company of institute and made), broken (Network リ プ ト ロ Application) system's (Kawasaki Heavy Industries Ltd.'s system), automatic mortar etc.

Above-mentioned toner preferably has weight average particle diameter (D as described below ₄), weight average particle diameter (D ₄)/number average particle diameter (D _n), average circularity, shape coefficient SF-1 and SF-2 etc.

Weight average particle diameter (D as above-mentioned toner ₄), for example, be preferably 2～7 μ m, more preferably 4～7 μ m, more preferably 5～6 μ m.

Weight average particle diameter D to above-mentioned toner ₄Assay method describe.

[weight average particle diameter of toner]

Mensuration machine: Coulter Multitizer II (manufacturing of Beckman Coulter company)

Aperture: 100 μ m

Analysis software: Coulter Multitizer Acucomp Ver.1.19 (manufacturing of Beckman Coulter company)

Electrolytic solution: Isoton II (manufacturing of Beckman Coulter company)

Dispersion liquid: (KAO. Corp. SA makes Emulgen 109P, polyoxyethylene lauryl ether, HLB:13.6) 5% electrolytic solution

Dispersion condition: in the dispersion liquid of 5ml, add the mensuration sample of 10mg, disperseed 1 minute, then, add the electrolytic solution of 25ml, utilize ultrasonic dispersing machine to disperse again 1 minute with ultrasonic dispersing machine.

Condition determination: in beaker, add electrolytic solution 100ml and dispersion liquid, utilize the concentration that to measure the particle diameter of 30,000 particles at 20 seconds, measure 30,000 particles, obtain weight average particle diameter from this size-grade distribution.

If above-mentioned weight average particle diameter less than 2 μ m, in two-component developing agent, when the medium-term and long-term stirring of developer, the molten surface that is bonded at carrier of toner, reduce the charged ability of carrier sometimes, in addition, in monocomponent toner, in order to make toner film forming or with toner thin layerization on developer roll, toner taking place sometimes easily glue to the molten of parts such as scraper plate, when surpassing 7 μ m, is difficult to obtain images with high image quality with high exploring, when carrying out the balance of the toner in the developer, it is big that the change of toner particle diameter sometimes becomes.

As the weight average particle diameter (D in the above-mentioned toner ₄) and the ratio (D of number average particle diameter (Dn) ₄/ Dn), for example, be preferably below 1.25 more preferably 1.00～1.20, more preferably 1.10～1.20.

Ratio (the D of above-mentioned weight average particle diameter and number average particle diameter ₄/ Dn) be 1.25 when following, the size-grade distribution of above-mentioned toner is narrow, fixation performance improves, but during less than 1.00, in two-component developing agent, when the medium-term and long-term stirring of developer, the molten surface that is bonded at carrier of toner, reduce the charged ability of carrier sometimes, spatter property is worsened, in addition, in monocomponent toner, in order to make toner film forming on developer roll, or with toner thin layerization, toner taking place sometimes easily glue to the molten of parts such as scraper plate, if surpass 1.20, then is difficult to obtain images with high image quality with high exploring, when carrying out the balance of the toner in the developer, it is big that the change of toner particle diameter sometimes becomes.

Ratio (the D of above-mentioned weight average particle diameter and above-mentioned weight average particle diameter and number average particle diameter ₄/ granulometry the device " Multisizer II " that Dn) can utilize aforesaid Beckman Coulter company to make is with the D of toner ₄Measure and similarly measure.

Above-mentioned average circularity is to be equivalent to the value of the girth of the circle that equates with the shape projected area of above-mentioned toner divided by the girth of actual particle, for example, is preferably 0.900～0.99, is more preferably 0.940～0.98.

If above-mentioned average circularity less than 0.900, then toner is to depart from spherical atypic shape, sometimes can not obtain the satisfied transfer printing and the high image quality image of free from smutting during, above 0.99 o'clock, in adopting the image formation system of scraper plate cleaning etc., take place on the photoreceptor and the cleaning of transfer belt etc. bad, pollution on the image, for example, when the high image of image area rates such as photograph image forms, because the bad grade of paper feeding has formed not the toner of the image of transfer printing become the transfer printing remaining toner and be accumulated on the photoreceptor, level image takes place sometimes to be polluted, perhaps, pollution makes the charged roller of photoreceptor contact electrification etc., can not give play to original charged ability.

Above-mentioned average circularity can be by the optical detection band method etc. measure, for example, the suspending liquid that will contain toner detects band by the image pickup part on the flat board, optically detect, analyze particle picture with the CCD camera, for example, can use flow-type particle picture analytical equipment FPIA-2100 (manufacturing of シ ス メ Star Network ス company) etc. to measure.

The shape coefficient SF-1 of the spherical degree of the expression toner of representing with following mathematical expression 1 is 100～150, and the shape coefficient SF-2 of the concavo-convex degree of the expression toner of representing with following mathematical expression 2 is 100～140.

Here, above-mentioned shape coefficient SF-1 and SF-2 be 300 SEM images by the toner of FE-SEM (S-4200) mensuration of Hitachi's manufacturing of grab sample for example, and import to this image information in the image analysis apparatus (Luzex AP) that ニ レ コ company makes and analyze by interface, and the value that obtains with following mathematical expression 1 and mathematical expression 2 calculating defines shape coefficient SF-1 and SF-2.In addition, the value of SF-1 and SF-2 is preferably obtained by Luzex, still, as long as can obtain same analysis result, then is not defined as above-mentioned FE-SEM device, image analysis apparatus especially.

[mathematical expression 1]

$\mathrm{SF}-1=\frac{{\left(\mathrm{MXLNG}\right)}^2}{\mathrm{AREA}}\×\frac{\mathrm{\π}}{4}\×100$ ... .. mathematical expression 1

In above-mentioned mathematical expression 1, MXLNG represents that toner projects on the two dimensional surface and the maximum length of the shape that obtains.AREA represents that toner projects on the two dimensional surface and the graphics area that obtains.

[mathematical expression 2]

$\mathrm{SF}-2=\frac{{\left(\mathrm{PERI}\right)}^2}{\mathrm{AREA}}\×\frac{1}{4\mathrm{\π}}\×100$ ... mathematical expression 2

In above-mentioned mathematical expression 2, PERI represents toner is projected on the two dimensional surface and the girth of the figure that obtains.AREA represents toner is projected on the two dimensional surface and the area of graph that obtains.

Here, in above-mentioned mathematical expression 1 and mathematical expression 2, L represents the absolute maximum length of toner, and A represents the projected area of toner, and P represents the maximum perimeter of toner.

And toner is if ball, then SF-1 and SF-2 each all be 100, just become unsetting along with becoming than 100 big values from sphere.And particularly, SF-1 represents the global shape (ellipse and ball etc.) of toner, and SF-2 is the shape coefficient of the concavo-convex degree of presentation surface.

Painted as above-mentioned toner, be not particularly limited, can suitably select according to purpose, for example, can be for being selected from least a in black toner, cyan toner, pinkish red toner and the Yellow toner, though toner of all kinds can obtain by the kind of the above-mentioned colorant of suitable selection,, preferred color toner.

(developer)

Developer of the present invention contains above-mentioned toner of the present invention at least, and contains other compositions that carrier etc. is suitably selected.As this developer, can be monocomponent toner, also can be two-component developing agent, but in being used in high-speed printer (HSP) corresponding to the raising of in recent years information processing rate etc. the time, see preferred above-mentioned two-component developing agent at aspects such as life-span raisings.

Under the situation of the above-mentioned monocomponent toner that has used above-mentioned toner of the present invention, even carry out the balance of toner, the change of toner particle diameter is also few, toner can not take place to molten sticking to the parts such as scraper plate that are used to make toner thin layerization of the film forming of developer roll or toner, even when using (stirring) for a long time, also can obtain good and stable development and image at developer.In addition, under the situation of the above-mentioned two-component developing agent that has used above-mentioned toner of the present invention, even carry out the balance of long-term toner, the change of the toner particle diameter in the developer is also few, even during the long-term stirring in developer, also can obtain good and stable development.

As above-mentioned carrier, be not particularly limited, can suitably select according to purpose, but preferably have core and coat the carrier of the resin bed of this core.

Material as above-mentioned core, be not particularly limited, can from material known, suitably select, for example, manganese-strontium of preferred 50～90emu/g (Mn-Sr) class material, manganese-magnesium (Mn-Mg) class materials etc. are being guaranteed on the image color this point, preferred iron powder (more than the 100emu/g), magnetic iron ore (75～120emu/g) contour Magnetized Materials.In addition, from weakening toner stand upright to presenting the wheat head collision (working as り) of photoreceptor of (fringe founds Chi) state and the viewpoint favourable to high image qualityization, (30～80emu/g) wait the weakly magnetization materials to preferably copper-zinc (Cu-Zn) class.These can use a kind separately, also can use simultaneously more than 2 kinds.

As the particle diameter of above-mentioned core, with mean grain size (weight average particle diameter (D ₅₀)) meter, preferred 10～200 μ m.Be more preferably 40～100 μ m.

If above-mentioned mean grain size (weight average particle diameter (D ₅₀)) less than 10 μ m, then in the distribution of carrier particle, it is many that the micro mist class becomes, and the magnetization of per 1 particle reduces, and produces carrier sometimes and disperses, if surpass 200 μ m, then specific surface area reduces, and produces dispersing of toner sometimes, in the full color that part is many on the spot, particularly, the reproduction variation sometimes of part on the spot sometimes.

Material as above-mentioned resin bed, be not particularly limited, can from known resin, suitably select according to purpose, for example can enumerate amino resin, polythylene resin, polystyrene resins, the alkenyl halide resin, polyester resin, polycarbonate resin, polyvinyl resin, polyfluoroethylene resin, polyvinylidene fluoride resin, poly-trifluoro-ethylene resin, the polyhexafluoropropylene resin, the multipolymer of vinylidene and acrylic monomers, the multipolymer of vinylidene and fluorothene, the fluorine-containing terpolymers such as terpolymer of tetrafluoroethene and vinylidene and non-fluorine monomer, silicones etc.These can use a kind separately, also can use simultaneously more than 2 kinds.

As above-mentioned amino resin, for example can enumerate urea-formaldehyde resin, melamine resin, benzo guanamine resin, Lauxite, polyamide, epoxy resin etc.As above-mentioned polythylene resin, for example can enumerate acryl resin, plexiglass, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin etc.As above-mentioned polystyrene resin, for example can enumerate polystyrene resin, styrene-propene acid copolymer resins etc.As above-mentioned alkenyl halide resin, for example can enumerate Corvic etc.As above-mentioned polyester resin, for example can enumerate pet resin, polybutylene terephthalate resin etc.

As required, can also make above-mentioned resin bed contain conducting powder etc.,, for example can enumerate metal powder, carbon black, titanium dioxide, tin oxide, zinc paste etc. as this conducting powder.As the mean grain size of these conducting powder, be preferably below the 1 μ m.If above-mentioned mean grain size surpasses 1 μ m, then the control of resistance becomes difficult sometimes.

Above-mentioned resin bed can form by the following method, for example, above-mentioned silicones etc. is dissolved in the solvent, behind the preparation coating solution, by known coating process this coating solution is coated on above-mentioned core surface equably, carries out sintering after the drying and forms.As above-mentioned coating process, for example can enumerate infusion process, spraying process, spread coating etc.

As above-mentioned solvent, be not particularly limited, can suitably select according to purpose, for example can enumerate toluene, dimethylbenzene, MEK, hexone, cellosolve, butyl acetate etc.

As above-mentioned sintering, be not particularly limited, can be the external heating mode, also can be inner type of heating, for example can enumerate the method for using fixed electric furnace, flow-type electric furnace, rotary electric furnace, combustion furnace etc., the method for using microwave etc.

As the amount of above-mentioned resin bed in above-mentioned carrier, be preferably 0.01～5.0 quality %.If above-mentioned quantity not sufficient 0.01 quality % then can not form uniform above-mentioned resin bed on above-mentioned core surface sometimes, if surpass 5.0 quality %, then above-mentioned resin bed is blocked up, and granulation takes place between the carrier, can not obtain uniform carrier particle sometimes.

When above-mentioned developer is above-mentioned two-component developing agent,, be not particularly limited, can suitably select, for example, be preferably 90～98 quality %, more preferably 93～97 quality % according to purpose as the content of above-mentioned carrier in this two-component developing agent.

The toner of bi-component class developer and the blending ratio of carrier are usually with respect to 100 mass parts carriers, and toner is 1～10.0 mass parts.

Developer of the present invention can good transfer printing and the spatter property of long term maintenance, there is not the change of image inequality, and the developer when using does not stir the embedding that produces external additive, and contain of the present invention above-mentioned the toner mobile and excellent in stability that the charging property secular variation is few, therefore can stably form the high resolution image of excellent distinctness.

Developer of the present invention can preferably be used in the image that is undertaken by known various electrophotographic methods such as method of magnetic one-component development, non-magnetic mono-component developing method, bi-component developing methods and form, and especially preferably is used in container, handle box, image processing system and the image forming method of the following toner of packing into of the present invention.

(container of the toner of packing into)

The container of the toner of packing into of the present invention is contained in above-mentioned toner of the present invention or above-mentioned developer collecting in the container and forms.

As said vesse, be not particularly limited, can be from known container suitably select, for example, can preferably enumerate container with toner container main body and lid etc.

As above-mentioned toner container main body, its size, shape, structure, material etc. are not particularly limited, can suitably select according to purpose, for example, as above-mentioned shape, preferably drum shape etc., form particularly preferably in inner peripheral surface spiral helicine concavo-convex, by the rotation, can will transfer to the discharge oral-lateral as the toner of content, and part or all of this spire has the shape of crease function etc.

Material as above-mentioned toner container main body, be not particularly limited, the high person of preferred size precision, for example can preferably enumerate resin, wherein, can preferably enumerate, for example, vibrin, polyvinyl resin, acrylic resin, polystyrene resin, Corvic, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin etc.

The tank capacity preservation of the toner of packing into of the present invention, conveying etc., and operability excellence are removably mounted in handle box of the present invention described later, the image processing system etc., and can be used for the supply of toner.

(handle box)

Handle box of the present invention has the electrostatic latent image carrier of load electrostatic latent image at least and uses toner will load on the latent electrostatic image developing on this electrostatic latent image carrier and form the developing apparatus of visual image, and other devices such as the Charging system of suitably selecting as required, exposure device, developing apparatus, transfer device, cleaning device, neutralizer.

As above-mentioned developing apparatus, at least have the developer receptacle container and the load of taking in above-mentioned toner of the present invention or above-mentioned developer and carry and be accommodated in the interior toner of this developer receptacle container or the electrostatic latent image carrier of developer, the layer thickness control parts etc. that can also have in addition, the toner layer thickness that is used for control load.

Handle box of the present invention can be dismantled and be mounted freely in various electro-photography apparatus, facsimile recorder, the printer, and preferred dismounting is mounted freely in the image processing system of the present invention described later.

Here, above-mentioned handle box is built-in with photoreceptor 101 for example as shown in Figure 1, and comprises Charging system 102, developing apparatus 104, transfer device 108, cleaning device 107, also has other parts as required.103 is exposure by exposure device among Fig. 1, the light source that use can write with high resolving power.105 expression recording mediums.

As above-mentioned photoreceptor 101, can use the photoreceptor identical with image processing system described later.Above-mentioned Charging system 102 can use live part arbitrarily.

Then, the image formation process that is undertaken by handle box shown in Figure 1 is shown, photoreceptor 101 rotates along the direction of arrow, and the exposure 103 charged, that undertaken by the exposure device (not shown) by being undertaken by Charging system 102 simultaneously forms the electrostatic latent image corresponding to exposure image on its surface.This electrostatic latent image carries out toner development by developing apparatus 104, and this toner development is transferred on the recording medium 105 by transfer device 108, prints output.Then, the photosensitive surface after the image transfer printing cleans by cleaning device 107, removes electricity by the neutralizer (not shown) again, repeats above operation then.

As image processing system of the present invention, be combined as a whole as handle box and constitute by above-mentioned electrostatic latent image carrier and inscapes such as developer, clearer, for apparatus main body, these parts can be dismantled freely and constitute.In addition, at least one of charged device, developer, transfer printing device and clearer is with the electrostatic latent image carrier integrated support and form handle box, as dismantle single part freely on apparatus main body, guide pieces such as track that also can the operative installations main body are made and are dismantled structure freely.

(image processing system and image forming method)

Image processing system of the present invention has electrostatic latent image carrier at least, electrostatic latent image forms device, developing apparatus, transfer device and fixing device, as required, other devices that also have suitable selection, for example, neutralizer, cleaning device, re-use device, control device etc.

Image forming method of the present invention comprises that at least electrostatic latent image forms engineering, developing procedure, transfer printing process and photographic fixing operation, as required, other operations that also comprise suitable selection for example, are removed electrician's preface, cleaning process, are utilized operation, control operation etc. again.

Image forming method of the present invention can preferably be implemented by image processing system of the present invention, above-mentioned electrostatic latent image forms operation and can be undertaken by above-mentioned electrostatic latent image formation device, above-mentioned developing procedure can be undertaken by above-mentioned developing apparatus, above-mentioned transfer printing process can be undertaken by above-mentioned transfer device, above-mentioned photographic fixing operation can be undertaken by above-mentioned fixing device, and above-mentioned other operations can be undertaken by above-mentioned other devices.

-electrostatic latent image formation operation and electrostatic latent image formation device-

It is the operation that forms electrostatic latent image on electrostatic latent image carrier that above-mentioned electrostatic latent image forms operation.

As above-mentioned electrostatic latent image carrier (being sometimes referred to as " Electrophtography photosensor " " photoreceptor "), be not particularly limited for its material, shape, structure, size etc., can from known carrier, suitably select, as its shape, preferably enumerate the cylinder shape, as its material, for example can enumerate inorganic photoreceptor such as amorphous silicon, selenium, polysilane, phthalein polymethine Organophotoreceptors such as (phthalopolymethine) etc.Wherein, on the long-life this point, see preferred amorphous silicon etc.

As above-mentioned amorphous silicon photoreceptor, can use the photoreceptor that for example has the optical conductive layer that constitutes by a-Si (below, be called " a-Si class photoreceptor "), the described optical conductive layer that is made of a-Si is that support is heated to 50 ℃～400 ℃, and becomes embrane method to form by vacuum vapour deposition, sputtering method, ion plating method, hot CVD method, optical cvd method, plasma CVD method etc. on this support.Wherein, preferable methods is a plasma CVD method, that is, by direct current or high frequency or microwave glow discharge unstrpped gas is decomposed, and forms the method for a-Si accumulating film on support.

The formation of above-mentioned electrostatic latent image can for example with the surface of above-mentioned electrostatic latent image carrier same charged after, undertaken by exposing into image, and can form device by above-mentioned electrostatic latent image and carry out.Above-mentioned electrostatic latent image forms device and possesses the same charged charged device in the surface that for example makes above-mentioned electrostatic latent image carrier becomes image with the face exposure with above-mentioned electrostatic latent image carrier exposer at least.

Above-mentioned charged can being undertaken by for example using above-mentioned charged device that the surface of above-mentioned electrostatic latent image carrier is applied voltage.

As above-mentioned charged device, be not particularly limited, can suitably select according to purpose, for example can enumerate the roller that possesses electric conductivity or semiconduction, brush, film, rubber flap etc. itself known contact zones electrical equipment, utilized corona tube (コ ロ ト ロ Application), the corona charged device of noncontact etc. of electricity corona discharges such as (ス コ ロ ト ロ Application) unexpectedly.

As the shape of above-mentioned live part, except that roller, can also take forms such as magnetic brush, skin brush, the form or the form that also can be fit to electro-photography apparatus are selected.When using magnetic brush, magnetic brush for example uses various ferrite particles such as Zn-Cu ferrite as live part, by the non magnetic conducting sleeve that is used to support magnetic brush, in the magnetic roller that wraps in wherein constitute.In addition, when using brush, for example, as the material of skin brush, use the skin that has carried out conductive processing by carbon, copper sulfide, metal or metal oxide, and it is intervolved or be fitted on the mandrel of metal or other conductive processing, make charged device.

Above-mentioned charged device obviously is not limited to the charged device of above-mentioned contact, but since the image processing system of the ozone that produces by charged device of can being reduced, the therefore preferred charged device that uses contact.

Above-mentioned exposure can become image to carry out the face exposure of above-mentioned electrostatic latent image carrier by for example using above-mentioned exposer.

As above-mentioned exposer, as long as can expose to the image that form by the surface of the charged above-mentioned electrostatic latent image carrier of above-mentioned charged device, be not particularly limited, can suitably select according to purpose, for example can enumerate various exposers such as duplicating optics system, dolly camera group system (rod lens array system), laser optics system, liquid crystal optical shutter system.

In addition, in the present invention, can adopt the light back side mode of exposing into image from the rear side of above-mentioned electrostatic latent image carrier.

-developing procedure and developing apparatus-

Above-mentioned developing procedure is to use above-mentioned toner of the present invention or above-mentioned developer above-mentioned latent electrostatic image developing to be formed the operation of visual image.

The formation of above-mentioned visual image can be used above-mentioned toner of the present invention or above-mentioned developer that above-mentioned latent electrostatic image developing is carried out, and can use above-mentioned developing apparatus to carry out by for example.

As long as above-mentioned developing apparatus for example can use above-mentioned toner of the present invention or above-mentioned developer to develop, be not particularly limited, can from known device, suitably select, can preferably enumerate, for example, at least have and taken in above-mentioned toner of the present invention or developer, and can contact or non-contactly this toner or this developer be given the developer device of above-mentioned electrostatic latent image, more preferably possess the developer etc. of the container of the above-mentioned toner of packing into of the present invention.

Above-mentioned developer can be the developer of dry process development mode, it also can be the developer of wet developing mode, in addition, it can be the monochromatic developer of using, it also can be the polychrome developer, can preferably enumerate, for example, have and make above-mentioned toner or above-mentioned developer friction stir and charged stirrer and developer of rotatable magnetic roller etc.

In above-mentioned developer, for example, mix to stir above-mentioned toner and above-mentioned carrier, the friction by this moment makes this toner charged, and remains on the surface of the magnetic roller of rotation with the wheat head state of standing upright, and forms magnetic brush.Because this magnetic roller is configured near the above-mentioned electrostatic latent image carrier (photoreceptor), the part of above-mentioned toner of the above-mentioned magnetic brush of formation that is formed on this magnetic roller surface is because electric attractive force moves to the surface of this electrostatic latent image carrier (photoreceptor).Its result, above-mentioned electrostatic latent image passes through this toner development, and forms the visual image that is produced by this toner on the surface of this electrostatic latent image carrier (photoreceptor).

The developer that is accommodated in the above-mentioned developer is the developer that contains above-mentioned toner of the present invention, but as this developer, can be monocomponent toner, also can be two-component developing agent.Contained toner is an above-mentioned toner of the present invention in this developer.

-transfer printing process and transfer device-

Above-mentioned transfer printing process is that above-mentioned visual image is transferred to operation on the recording medium, preferred use the intermediate transfer body with the visual image primary transfer to this intermediate transfer body, and then with the mode of this visual image secondary transfer printing on the aforementioned recording medium, more preferably use more than two looks, preferred full-color toner is as above-mentioned toner, and comprise with visual image be transferred to form compound transferred image on the intermediate transfer body the first time transfer printing process and will this compound transferred image transfer printing on recording medium the second time transfer printing process mode.

Above-mentioned transfer printing can be used transfer belt electrical equipment to make charged the carrying out of above-mentioned electrostatic latent image carrier (photoreceptor) above-mentioned visual image, and can be undertaken by above-mentioned transfer device by for example.As above-mentioned transfer device, preferably have with visual image be transferred on the intermediate transfer body form compound transferred image the first time transfer device and will this compound transferred image transfer printing on recording medium the second time transfer device mode.

In addition,, be not particularly limited, can from known transfer article, suitably select, for example can preferably enumerate transfer belt etc. according to purpose as above-mentioned intermediate transfer body.

The coefficient of static friction of above-mentioned intermediate transfer body is preferred 0.1～0.6, is more preferably 0.3～0.5.The preferred a few Ω cm of the volume resistance of intermediate transfer body～10 ³Ω cm.By volume resistance being set at a few Ω cm～10 ³Ω cm, when preventing that intermediate transfer body self is charged, the electric charge of giving by the electric charge applicator is difficult for remaining on this intermediate transfer body, therefore, the transfer printing inequality in the time of can preventing secondary transfer printing.In addition, applying of the transfer bias in the time of can easily carrying out secondary transfer printing.

The material of above-mentioned intermediate transfer body is not particularly limited, can from material known, suitably select according to purpose, for example, (1) uses the high material of Young modulus (tensile modulus of elasticity) as single belt, can enumerate PC (polycarbonate), PVDF (Kynoar), the composite material of PAT (polyalkylene terephthalates), PC (polycarbonate)/PAT (polyalkylene terephthalates), the composite material of ETFE (ethylene-tetrafluoroethylene copolymer)/PC, ETFE/PAT, PC/PAT, the Thermocurable polyimide of carbon black dispersion etc.The deflection that the single belt that these Young moduluss are high has the stress when forming for image is few, particularly has the advantage that is difficult to produce positioning runout (レ ジ ズ レ) when coloured image forms.(2) be band that above-mentioned Young modulus is high as basic unit, and on its periphery, added the band of the 2～3-tier architecture in superficial layer or middle layer, the band of these 2～3-tier architectures has the performance that comes off that the hardness that can prevent owing to single belt causes line image.(3) be to use rubber and the lower band of elastomeric Young modulus, these bands have because of its flexibility can produce the advantage that line image comes off hardly.In addition, the width by making band is than driven roller and draw that to establish roller big, and utilizes the elasticity by the outstanding band ear of roller to prevent to crawl, thereby does not need to prevent flange (リ Block) and the device that crawls, thereby can realize low cost.

Above-mentioned intermediate transfer belt can use existing fluorine-type resin, polycarbonate resin, polyimide resin etc., in recent years, has used all layers that make band or a part of being with to become the elastic webbing of elastomeric element.Use the transfer printing of the coloured image of resin strip to have following problem.Coloured image normally with 4 looks colour toners form.In 1 coloured image, form 1 layer to 4 layers toner layer.By toner layer is born pressure through 1 transfer printing (transfer printing from the photoreceptor to the intermediate transfer belt), 2 transfer printings (transfer printing from middle transfer belt to thin slice), improve the cohesiveness between the toner.If the cohesiveness between the toner improves, coming off or the phenomenon that comes off of the image border of image section on the spot of literal then taken place easily.Because resin strip hardness height can not be out of shape for toner layer, so toner layer is compressed and takes place easily the obscission of literal easily.

In addition, recently for full-colour image being formed on various paper, the requirement that for example image is formed on having of Japan paper or design of the concavo-convex paper improves constantly.But the paper of flatness difference is easy and toner generation space when transfer printing, and the transfer printing deinking takes place easily.If improve the transfer pressure of 2 transfer sections in order to improve adaptation, the condensing power of toner layer improves, thereby coming off of aforesaid literal taken place.

Elastic webbing is used for following purpose.Elastic webbing in transfer printing portion corresponding to toner layer, the relatively poor paper distortion of flatness.That is,, can excessively not improve, can obtain the transferred image of excellent in uniformity to the paper of planarity difference yet even can obtain good adaptation and not have literal to come off for the transfer pressure of toner layer owing to elastic webbing is followed the tracks of local fluctuating and is out of shape.

Resin as above-mentioned elastic webbing, for example can enumerate polycarbonate, fluorine-type resin (ETFE, PVDF), polystyrene resin, the chloro polystyrene resin, the poly alpha methylstyrene resin, Styrene-Butadiene, styrene-vinyl chloride copolymer, styrene-acetate ethylene copolymer, styrene-maleic acid copolymer, copolymer in cinnamic acrylic ester (for example, styrene-propene acid methyl terpolymer, styrene-propene acetoacetic ester multipolymer, the styrene-propene butyl acrylate copolymer, misery ester copolymer of styrene-propene and styrene-propene acid phenenyl ester multipolymer etc.), styrene-methacrylate copolymer (for example, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-phenyl methacrylate multipolymer etc.), styrene-methyl multipolymer, styrene resins such as styrene-acrylonitrile-acrylate copolymer (homopolymer or the multipolymer that comprise styrene or styrene substituent), polymethyl methacrylate resin, the butyl methacrylate resin, the ethyl acrylate resin, the butyl acrylate resin, acrylic resin modified (for example, polysiloxane-modified acryl resin, vestolit is acrylic resin modified, acrylic/polyurethane resin etc.), vestolit, styrene-acetate ethylene copolymer, vinyl chloride-vinyl acetate copolymer, Abietyl modified maleic acid resin, phenolics, epoxy resin, vibrin, polyester polyurethane resin, tygon, polypropylene, polybutadiene, Vingon, ionomer resin, urethane resin, silicones, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin and polyvinyl butyral resin, polyamide, modified polyphenylene ether resin etc.

As above-mentioned elastic caoutchouc or elastic body, for example can enumerate butyl rubber, fluorine class rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene (ABS) rubber, natural rubber, isoprene rubber, styrene butadiene rubbers, butadiene rubber, ethylene-propylene rubber, the ethylene-propylene terpolymer, neoprene, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1, the 2-polybutadiene, chloropropylene oxide class rubber, silicon rubber, fluororubber, polysulfide rubber, poly-norbornene rubber, hydrogenated nitrile rubber, thermoplastic elastomer (polystyrene type for example, polyolefins, polyvinyl chloride, polyurethanes, polyamide-based, polyureas, polyesters, fluorine type resin) etc.

As the resistance value adjusting conductive agent, be not particularly limited, can suitably select according to purpose, for example, metal powders such as carbon black, graphite, aluminium or nickel, tin oxide, titanium dioxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxides (ATO), indium oxide-tin oxide composite oxides conductive metal oxides such as (ITO), conductive metal oxide can also be the material that has coated insulating fine particles such as barium sulphate, magnesium silicate, lime carbonate.

Skin-material, top layer require to prevent the pollution to photoreceptor that caused by resilient material, and reduce the surface friction drag to the transfer belt surface, and the adhesion that reduces toner is to improve cleaning, 2 transfer printings.The combination more than a kind or 2 kinds that can use for example polyurethane, polyester, epoxy resin etc. is to reduce surface energy and to improve the material of lubricity, for example, can with in powder, the particles such as fluororesin, fluorine compounds, fluorocarbons, titania, silicon carbide more than a kind or 2 kinds or make the combination of these different powder of particle diameter, particle disperse to use.In addition, can use the layer that is rich in fluorine element in surface formation by as fluorine class elastomeric material, heat-treating, thereby reduce the material of surface energy.

The manufacture method of band there is no special qualification, can enumerate, for example, injecting material immerses the infusion process of taking out then in the solution of material, is injected into casting in internal mold, the external mold, composition is twisted on the columnar mould with the centrifugal casting that forms band, spraying liquid coating with the spraying rubbing method that forms film, with columnar mould in the columnar model of rotation, add sulphur abrasive method etc., but being not limited to these methods, also is the method for using always by making up multiple manufacture method with the method for making band.

As the method for the stretching that prevents elastic webbing, be included in the few core body resin bed of elongation and form the method for rubber layer, in core layer, add the method that prevents the material that extends etc., but be not limited to these specific method for makings.

Constitute the material prevent the core layer that extends, can use to be selected from for example natural fibers such as cotton, thin,tough silk; Synthon such as dacron, nylon fiber, Dralon, polyolein fiber, vinal, polyvinyl chloride fibre, Saran, polyurethane fiber, polyacetal fibre, polyvinyl fluoride fibre, phenolic fibre; Inorganic fibres such as carbon fiber, glass fibre, boron fibre; The combination more than a kind or 2 kinds in the metal fibres such as iron fiber, copper fiber can also be used weaving cloth shape or thread material.

Silk is formed by the twisting of 1 or multifilament, and can be that single twisted filament, many twisted filaments, mariages etc. are any adds twisted filament.In addition, the fiber that also can blending for example be selected from the material in the above-mentioned material.Certainly, also can carry out using after the suitable conductive processing to silk.On the other hand, weave cotton cloth and both can use weaving cloth as woven cloth etc., can certainly use the weaving cloth of blending, can also carry out conductive processing certainly.

As the manufacture method that above-mentioned core layer is set, be not particularly limited, can suitably select according to purpose, for example can enumerate the weaving cloth that will be woven into tubular covers on metal die etc., be provided with thereon then clad method, be immersed in aqueous rubber etc. by the weaving cloth that will be woven into tubular, on the one side of core layer or two faces, be provided with clad method, silk is wrapped on the metal die with spacing helically arbitrarily, the method for clad etc. is set then thereon.

Though the thickness of elastic layer also depends on the hardness of elastic layer, if blocked up, then Biao Mian flexible change is big, and the top layer is easy to generate be full of cracks.In addition, because flexible quantitative change is big, it is big etc. that image flexible also can become, therefore preferably not blocked up (more than about 1mm's).

Above-mentioned transfer device (above-mentioned first transfer device, above-mentioned second transfer device) preferably has at least makes the above-mentioned visual image that is formed on the above-mentioned electrostatic latent image carrier (photoreceptor) the transfer printing device to aforementioned recording medium side stripping charge.Above-mentioned transfer device can be 1, also can be more than 2.As above-mentioned transfer printing device, for example can enumerate corona transfer device, transfer belt, transfer roll, pressure transfer roll, the transfer printing device etc. of adhering by corona discharge.

In addition, as recording medium, representational is common paper, but if the medium of the uncertain image after can transfer printing developing then has no particular limits, can suitably select according to purpose, also can use PET tape base (ベ one ス) that OHP uses etc.

Above-mentioned photographic fixing operation is to use the operation of fixing device with the visual image photographic fixing of transfer printing on recording medium, can successively toner of all kinds be transferred on the aforementioned recording medium, also can each colour toners once be carried out simultaneously with the state with its lamination.

As above-mentioned fixing device, have no particular limits, can suitably select preferred known heating and pressurizing device according to purpose.As above-mentioned heating and pressurizing device, can enumerate combination, warm-up mill and the backer roll of warm-up mill and backer roll and the combination of endless belt etc.

Preferred 80 ℃～200 ℃ usually of the heating of above-mentioned heating and pressurizing device.

In addition, in the present invention, can use above-mentioned photographic fixing operation and fixing device simultaneously, perhaps can also use for example known smooth fuser to replace them according to purpose.

The above-mentioned electrician's preface of removing is that above-mentioned electrostatic latent image carrier is applied the operation of removing electricity except that electrical bias, can suitably carry out by neutralizer.

As above-mentioned neutralizer, have no particular limits, get final product so long as can apply except that electrical bias above-mentioned electrostatic latent image carrier, can suitably select from known removing the electrical equipment, for example can preferably enumerate except that electric light etc.

Above-mentioned cleaning process is to remove the operation that remains in the above-mentioned electrofax tinter on the above-mentioned electrostatic latent image carrier, is preferably undertaken by cleaning device.

As above-mentioned cleaning device, have no particular limits, as long as can remove the above-mentioned electrofax tinter that remains on the above-mentioned electrostatic latent image carrier, can from known clearer, suitably select, for example can preferably enumerate magnetic brush clearer, static bruss clearer, magnetic roller clearer, scraper plate clearer, brush clearer, netted (ウ エ Block) clearer etc.

The above-mentioned operation of utilizing again is that the above-mentioned electrophoto-graphic toner that will remove by above-mentioned cleaning process uses the operation in the above-mentioned developing apparatus again, is more preferably by re-use device and is undertaken.

As above-mentioned re-use device, have no particular limits, can enumerate known conveying device etc.

Above-mentioned control device is the operation of above-mentioned each operation of control, is preferably undertaken by control device.

As above-mentioned control device, as long as can control above-mentioned each device operation, have no particular limits, can suitably select according to purpose, for example can enumerate machines such as sequencer, computing machine.

Then, with reference to Fig. 2 a mode implementing image forming method of the present invention by image processing system of the present invention is described.Image processing system 100 shown in Figure 2 comprises: as the photoconductor drum 10 (hereinafter referred to as " photoreceptor 10 ") of above-mentioned electrostatic latent image carrier, as the charged roller 20 of above-mentioned Charging system, as the exposure device 30 of above-mentioned exposure device, as above-mentioned developing apparatus developer 40, intermediate transfer body 50, as cleaning device 60, remove electric light 70 as above-mentioned neutralizer with above-mentioned cleaning device of cleaning balde.

Intermediate transfer body 50 is the endless belt, and being designed to can be by setting within it side and draw 3 rollers establishing 51 to move along the direction of arrow it.The part of 3 rollers 51 also can be used as the transfer bias roller performance function that middle transfer article 50 is applied the transfer bias (primary transfer bias voltage) of regulation.On intermediate transfer body 50, configuration has the cleaning device 90 of cleaning balde in its vicinity, in addition, be oppositely arranged as applying and be used for developed image (toner image) transfer printing (secondary transfer printing) to transfer roll 80 as the above-mentioned transfer device of the transfer bias on the recording medium 95 of final transfer materials.Around intermediate transfer body 50, be used for giving corona charging device 58 to the toner image on the intermediate transfer body 50 with electric charge, on the sense of rotation of this intermediate transfer body 50, be configured between the contact site of the contact site of photoreceptor 10 and intermediate transfer body 50 and intermediate transfer body 50 and recording medium 95.

Developer 40 is by constituting as the strip-like developing pipe 41 of above-mentioned developer carrier, black developing cell 45K, yellow developing cell 45Y, pinkish red developing cell 45M and the cyan developing cell 45C that is set up in parallel around strip-like developing pipe 41.In addition, black developing cell 45K possesses the 42K of developer receptacle portion and developer supply roller 43K and developer roll 44K, yellow developing cell 45Y possesses the 42Y of developer receptacle portion and developer supply roller 43Y and developer roll 44Y, magenta developing cell 45M possesses the 42M of developer receptacle portion and developer supply roller 43M and developer roll 44M, and cyan developing cell 45C possesses the 42C of developer receptacle portion and developer supply roller 43C and developer roll 44C.In addition, strip-like developing pipe 41 is the endless belt, can draw rotatably to be located on a plurality of band rollers, and its part contacts with photoreceptor 10.

In image processing system shown in Figure 2 100, for example, charged roller 20 makes photoconductor drum 10 similarly charged.Exposure device 30 exposes into image on photosensitive drums 10, form electrostatic latent image.Supply with toner from developer 40,, form toner image the latent electrostatic image developing that is formed on the photosensitive drums 10.To intermediate transfer body 50, transfer printing again (secondary transfer printing) is to recording medium 95 by the voltage transfer printing (primary transfer) that applies from roller 51 for this toner image.Its result forms transferred image on recording medium 95.In addition, the device 60 that is cleaned of the remaining toner on the photoreceptor 10 is removed, and charged on the photoreceptor 10 once removed by removing electric light 70.

With reference to Fig. 3 the another kind of mode of implementing image forming method of the present invention by image processing system of the present invention is described.Image processing system 100 shown in Figure 3, except in image processing system shown in Figure 2 100, not possessing strip-like developing pipe 41, but around photoreceptor 10, directly relatively be provided with beyond black developing cell 45K, yellow developing cell 45Y, pinkish red developing cell 45M and the cyan developing cell 45C, have the structure same, and demonstrate same action effect with image processing system shown in Figure 2 100.In addition, in Fig. 3, represent with prosign with device identical among Fig. 2.

In the electro-photography apparatus of the tandem type of implementing image forming method of the present invention by image processing system of the present invention, have as shown in Figure 4 pass through transfer device 2 with the image on each photoreceptor 1 be transferred to successively on the paper s that paper conveying belt 3 carries direct transfer printing mode and as shown in Figure 5 with the image on each photoreceptor 1 by after 1 temporary transient successively transfer printing of transfer device 2 is on intermediate transfer body 4, again the image on the intermediate transfer body 4 is transferred to indirect transfer printing mode on the paper s together by 2 transfer devices 5.Transfer device 5 is transfer printing conveying belt, but also can be roll shape and mode.

When directly transfer printing mode and indirect transfer printing mode are compared, the former must be provided with paper feed 6 at the upstream side with photoreceptor 1 tandem type image processing system T arranged side by side, fixing device 7 is set in the downstream, therefore has the shortcoming that on the direction that paper is carried, maximizes.In contrast, the latter can more freely be provided with the position of 2 transfer printings.Can be with paper feed 6 and fixing device 7 and the overlapping setting of tandem type image processing system T, have can miniaturization advantage.

In addition, the former will dispose fixing device 7 in order not maximize on the paper throughput direction near tandem type image processing system T ground.Therefore, there is following shortcoming: paper s is had crooked abundant enough and to spare to dispose fixing device, collision when the front end of paper s enters fixing device 7 (particularly ground paper highly significant) or because the paper transporting velocity of the transporting velocity of the paper when the fixing device 7 and transfer printing conveying belt poor, fixing device 7 forms for easily the images of upstream side and brings influence.In contrast, the latter makes paper s crooked abundant enough and to spare dispose fixing device 7 owing to having, so fixing device 7 can bring influence to image formation hardly.

From as can be known above, the device of the particularly indirect transfer printing mode in the tandem type electronic photographic means gets most of the attention recently.

And, in this color electronic camera, as shown in Figure 5, remove the transfer printing remaining toner that remains in after 1 transfer printing on the photoreceptor 1 with photoreceptor cleaning device 8, cleaning photoreceptor 1 surface, the image of preparing once more forms.In addition, remove the transfer printing remaining toner that remains on the intermediate transfer body 4 after 2 transfer printings with intermediate transfer body cleaning device 9 and clean intermediate transfer body 4 surfaces, the image of preparing once more forms.

Series connection image processing system 100 shown in Figure 6 is that the tandem type coloured image forms device.Series connection image processing system 120 comprises copy device main body 150, feedboard for paper 200, scanner 300, master copy automatic conveying device (ADF) 400.

In copy device main body 150, endless belt-shaped intermediate transfer body 50 is arranged on central portion.And intermediate transfer body 50 draws and is located on support roller 14,15 and 16, among Fig. 6, and can be by turning clockwise.The intermediate transfer body cleaning device 17 that is used to remove the remaining toner on the intermediate transfer body 50 near the configuration support roller 15.Drawing by support roller 14 and support roller 15 on the intermediate transfer body of establishing 50, be set up in parallel tandem type developers 120 yellow, blue or green, pinkish red, black 4 image processing systems 18 relatively along its throughput direction configuration.Exposure device 21 is set near tandem type developer 120.Configuration secondary transfer printing device 22 on the opposite side of the side with having disposed tandem type developer 120 of intermediate transfer device 50.In secondary transfer printing device 22, on pair of rolls 23, draw the secondary transfer printing band of establishing as the endless belt 24, recording medium and the intermediate transfer body 50 carried on secondary transfer printing band 24 can contact with each other.Fixing device 25 is set near secondary transfer printing device 22.

In addition, in series connection image processing system 100, being used to of carrying out near the two sides that is provided for secondary transfer printing device 22 and the fixing device 25 at recording medium that image forms the reverse paper inversion set 28 of this recording medium.

Then, the formation (color photocopying) to the full-colour image that uses tandem type developer 120 describes.That is, at first, original copy is placed on the document board 130 of master copy automatic conveying device (ADF) 400, perhaps opens master copy automatic conveying device 400, original copy is placed on the contact glass 32 of scanner 300, close master copy automatic conveying device 400.

When pressing starting switch (not shown), when being placed on original copy on the master copy automatic conveying device 400, after original copy is transferred and moves on the contact glass 32, on the other hand, driven sweep instrument 300, the 1 moving bodys 33 and the 2nd moving body 34 move immediately when directly being placed on original copy on the contact glass 32.At this moment, in by the light of the 1st moving body 33 irradiations from light source, with the reflected light of the mirror reflects in the 2nd moving body 34 from the original copy face, by imaging len 35, accept light with read sensor 36, colored original (coloured image) is read, and becomes black, yellow, pinkish red and blue or green image information.

And, black, yellow, pinkish red and each blue or green image information be communicated to respectively each image processing system 18 in the tandem type developer 120 (black with image processing system, yellow with image processing system, magenta with image processing system and cyan image processing system), in each image processing system, form black, yellow, pinkish red and each blue or green toner image.Promptly, each image processing system 18 (black image processing system in the tandem type developer 120, the yellow image processing system of using, magenta image processing system and cyan image processing system) as shown in figure 17, has photoreceptor 10 (black photoreceptor 10K respectively, the yellow photoreceptor 10Y that uses, pinkish red with photoreceptor 10M and cyan photoreceptor 10C), with the same charged charged device 60 of this photoreceptor, based on each color image information according to the above-mentioned photoreceptor of the image exposure of each coloured image correspondence (among Fig. 7, L), and on this photoreceptor, form the exposer of the electrostatic latent image corresponding with each coloured image, use various color toner (black toners, Yellow toner, pinkish red toner and cyan toner) this latent electrostatic image developing formed the developer 61 of the toner image that produces by each color toner, be used for this toner image is transferred to transfer belt electrical equipment 62 on the intermediate transfer body 50, photoreceptor cleaning device 63, with remove electrical equipment 64, can form the image (black image of various monochromes based on each color image information, yellow image, magenta color image and cyan image).This black image of Xing Chenging, this yellow image, this magenta color image and this cyan image like this, on the intermediate transfer body 50 that moves by support roller 14,15 and 16 rotations, respectively transfer printing successively (primary transfer) be formed on black with the black image on the photoreceptor 10K, be formed on yellow with the yellow image on the photoreceptor 10Y, be formed on magenta with the magenta color image on the photoreceptor 10M, be formed on the cyan image of cyan on the photoreceptor 10C.And on intermediate transfer body 50, above-mentioned black image, above-mentioned yellow image, pinkish red image and cyan image overlap, and form combined color image (colour transfer image).

On the other hand, on feedboard for paper 200, optionally rotate in the paper feed roller 142, in one from paper storehouse 143 in the paper feeding cassette 144 of multilayer paper (recording chart) is extracted out, be separated into individual with separate roller 145, deliver in the paper supply passage 146, carry and import to paper supply passage 148 in the duplicating machine main body 150, bump against by 49 on roller and stop with conveying roller 147.Perhaps, rotation paper feed roller 142 is extracted the paper (recording chart) on the manual paper disc 54 out, is separated into individual with separate roller 52, sends into manual paper supply passage 53, similarly, bumps against by 49 on roller and stops.In addition, use by roller 49 common ground connection, but also can under the state that applies bias voltage for the paper powder of removing paper, use.And, rotate by roller 49 with the time of the combined color image (colour transfer image) that on intermediate transfer body 50, synthesizes with matching, between intermediate transfer body 50 and secondary transfer printing device 22, send paper (recording chart), by secondary transfer printing device 22 with this combined color image (colour transfer image) transfer printing (secondary transfer printing) on this paper (recording chart), thus, go up transfer printing and form coloured image at this paper (recording chart).In addition, the remaining toner on the intermediate transfer body 50 after the image transfer printing is removed by intermediate transfer body cleaning device 17.

Transfer printing and the above-mentioned paper (recording chart) that forms coloured image are transferred by secondary transfer printing device 22, and deliver to fixing device 25, in fixing device 25, by heat and pressure with above-mentioned combined color image (coloured image) photographic fixing on this paper (recording chart).Then, this paper (recording chart) switches and passes through distributing roller 56 discharges with switching pawl 55, on the row's of being stacked on paper disc 57, perhaps switch and pass through 28 counter-rotatings of paper inversion set with switching pawl 55, import to transfer position once more, also behind the document image, discharge by distributing roller 56, on the row's of being stacked on paper disc 57 overleaf.

In image forming method of the present invention and image processing system, because having used can good transfer printing and the spatter property of long term maintenance, there is not the change of image inequality, and, by stirring developer in use, do not have the embedding of external additive, flowability and charging property all change the toner of the present invention of less excellent in stability between long-term, so can form images with high image quality effectively.

Embodiment

Below, embodiments of the invention are described, but the present invention is not subjected to any qualification of following embodiment.In addition, in following example, " part " and " % " short of specified otherwise then is a quality criteria.

(Production Example 1)

-organic fine particles latex synthetic-

In the reaction vessel that stirring rod and thermometer are installed, sodium salt (the エ レ ミ ノ one Le RS-30 that adds 683 parts of water, 11 parts of methacrylic acid ethylene oxide adduct sulfuric esters, Sanyo Chemical Industries, Ltd.'s manufacturing), 166 parts of methacrylic acids, 110 parts of butyl acrylates and 1 part of ammonium persulfate, with 3800 rev/mins of stirrings 30 minutes, obtain white emulsion.Be heated and make the internal system temperature rise to 75 ℃ and reacted 4 hours.The ammonium persulfate aqueous solution that adds 30 part 1% again 75 ℃ of following slakings 6 hours, obtains the aqueous liquid dispersion of vinyl resins (multipolymer of the sodium salt of methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfuric ester).With it as [particle dispersion liquid 1].The weight average particle diameter that the Na ノ ト ラ Star Network particle size distribution device UPA-EX150 of employing Nikkiso Company Limited measures the particulate that contains in [particle dispersion liquid 1] that obtains is 110nm.In addition, the part of [particle dispersion liquid 1] is dry, the separation resin composition.The glass transition temperature of this resinous principle (Tg) is 58 ℃, and weight-average molecular weight (Mw) is 130,000.

The preparation of-water-

With 990 parts of water, 83 parts [particle dispersion liquid 1], 37 part 48.3% dodecyl diphenyl ether sodium disulfonate aqueous solution (エ レ レ ミ ノ one Le MON-7, Sanyo Chemical Industries, Ltd. makes) and 90 parts of ethyl acetate mixing stirrings, milky liquid obtained.With it as [water 1].

-low molecular weight polycaprolactone ester synthetic-

In the reaction vessel that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 229 parts of bisphenol-A epoxy ethane, 2 moles of addition products of 529 parts of bisphenol-A epoxy propane, 208 parts of terephthalic acid (TPA)s, 46 parts of hexane diacids and 2 parts of dibutyltin oxides, under normal pressure, reacted 7 hours in 230 ℃.Then, after 5 hours, add 44 parts of trimellitic anhydrides in reaction under the decompression of 10～15mmHg in reaction vessel, reaction is 3 hours under 180 ℃, normal pressure, obtains [low molecular weight polycaprolactone ester 1].

The glass transition temperature (Tg) of [the low molecular weight polycaprolactone ester 1] that obtains is 43 ℃, and weight-average molecular weight (Mw) is 6700, number-average molecular weight is 2300, and acid number is 25.

-prepolymer synthetic-

In the reaction vessel that cooling tube, stirring machine and nitrogen ingress pipe are installed, add 2 moles of addition products of 682 parts of bisphenol-A epoxy ethane, 2 moles of addition products of 81 parts of bisphenol-A epoxy propane, 283 parts of terephthalic acid (TPA)s, 22 parts of trimellitic anhydrides and 2 parts of dibutyltin oxides and add, normal pressure, 230 ℃ of following reactions 7 hours.Reacted 5 hours down in the decompression of 10～15mmHg again, obtain [intermediate polyester 1].

Several mean molecular weight of [the intermediate polyester 1] that obtains are 2200, and weight-average molecular weight (Mw) is 9700, and glass transition temperature (Tg) is 54 ℃, and acid number is 0.5, and hydroxyl value is 52.

Then, in the reaction vessel that cooling tube, stirring machine and nitrogen ingress pipe are installed, add 410 parts [intermediate polyester 1], 89 parts of isophorone diisocyanate, 500 parts of ethyl acetate, reacted 5 hours down, obtain [prepolymer 1] at 100 ℃.

The free isocyanate quality % of [prepolymer 1] that obtains is 1.53%.

-ketimide synthetic-

In the reaction vessel that has stirring rod and thermometer, add 170 parts of isophorone diamine, 75 parts of MEKs, reacted 4 hours half down at 50 ℃, obtain [ketimine compound 1].The amine value of [ketimine compound 1] that obtains is 417.

The preparation of-parent sizing material (MB)-

Add 1200 parts of water, 540 parts of carbon black (Printex35, デ グ サ company makes) [DBP oil absorption=42ml/100mg, pH=9.5], (Sanyo Chemical Industries, Ltd. makes, and RS801), uses Henschel mixer (manufacturing of Mitsui mine company) to mix for 1200 parts of vibrin.Under 110 ℃ the potpourri that obtains after mixing 1 hour, being rolled cooling and also uses flour mill to pulverize, obtain carbon black parent sizing material with 2 roller machines.With it as [parent sizing material 1].

The preparation of-oil phase-

In the reaction vessel that stirring rod and thermometer are installed, add 378 parts [low molecular weight polycaprolactone esters 1], 100 parts of Brazil waxs and 947 parts of ethyl acetate, be warming up to 80 ℃ under stirring, after keeping 5 hours under 80 ℃, be cooled to 30 ℃ through 1 hour.Then, in container, add 500 parts of [parent sizing material 1] and 500 parts of ethyl acetate, mixed 1 hour, obtain dissolved matter, with it as [raw material lysate 1].

Then, 1324 parts [raw material lysates 1] are transferred in the reaction vessel, use ball mill (ウ Le ト ラ PVC ス コ ミ Le, ア イ メ Star Network ス company makes), with the loading of the zirconium oxide bead of the 0.5mm of 1kg/ hour liquor charging speed, the 6m/ disk circular velocity of second, 80 volume %, carry out carrying out the dispersion of carbon black, wax under 3 times the condition.

Then, add 65% the ethyl acetate solution of 1324 parts [low molecular weight polycaprolactone esters 1], use the ball mill of condition same as described above to carry out 2 times, obtain dispersion liquid.With it as [pigment and wax dispersion 1].

The solid concentration (130 ℃, 30 minutes) of [pigment and the wax dispersion 1] that obtains is 50%.

-emulsification-

In reaction vessel, add 749 parts [pigment and wax dispersions 1], 115 parts [prepolymer 1] and 2.9 parts [ketimine compound 1], use TK homogenizer (special machine company make), under 5000rpm, mixed 2 minutes.Then, in reaction vessel, add 1200 parts [water 1], use the TK homogenizer under 13000rpm, to mix 25 minutes, obtain the water-medium dispersion liquid.With it as [emulsification slurry 1].

-Tuo organic solvent-

In the reaction vessel that stirring machine and thermometer are installed, drop in [emulsification slurry 1], after 8 hours, under 40 ℃, carry out slaking in 4 hours at 30 ℃ of following desolventizings, obtain having heated up in a steamer the dispersion liquid of organic solvent.With it as [dispersed paste 1].

-washing and drying-

After 100 parts of [dispersed paste 1] filtration under diminished pressure, wash and drying according to following steps.

(1) in filter cake, add 100 parts of ion exchange waters, mix (carrying out under the rotating speed 12000rpm 10 minutes) with the TK homogenizer after, filtration.

(2) in the filter cake of (1), add 100 part 10% sodium hydrate aqueous solution, use the TK homogenizer to mix (under rotating speed 12000rpm, carrying out 30 minutes), filtration under diminished pressure then.

(3) in the filter cake of (2), add 100 part 10% hydrochloric acid, use the TK homogenizer to mix (carrying out under the rotating speed 12000rpm 10 minutes) after, filter.

(4) in the filter cake of (3), add 100 parts of ion exchange waters, and add and to have dissolved that to be equivalent to the cake solid content be that the fluorine of 0.1% the charged controlling agent of conduct is the aqueous solution of surfactant, after using the TK homogenizer to mix (carrying out under the rotating speed 12000rpm 10 minutes), filter.

(5) in the filter cake of (4), add 300 parts of ion exchange waters, after use TK homogenizer mixes (carrying out under the rotating speed 12000rpm 10 minutes), filter, this operation is carried out 2 times, make filter cake.

Then, use the recirculating air dryer under 45 ℃ with the filtration cakes torrefaction that obtains 48 hours, and screen with the screen cloth of mesh 75 μ m, obtain the toner parent particle.With it as [toner parent particle 1].

For [the toner parent particle 1] that obtain, gravimetry mean grain size (D as described below ₄), size-grade distribution (D ₄/ Dn), average circularity, shape coefficient SF-1 and SF-2.Volume average particle size (D ₄) be 5.8 μ m, size-grade distribution (D ₄/ Dn) being 1.15, average circularity is 0.950, shape coefficient SF-1 is 110, shape coefficient SF-2 is 115.

＜weight average particle diameter (D ₄) and size-grade distribution (D ₄/ Dn) 〉

The weight average particle diameter of toner and size-grade distribution are used granulometry device (Coulter-counter TAII; Coulter Electronics,c. makes), be to measure under the condition of 100 μ m in the aperture.Calculate (weight average particle diameter/number average particle diameter) by these results.

＜average circularity 〉

The average circularity of toner uses flow-type particle picture analytical equipment (" FPIA-2100 ", シ ス メ Star Network ス Co., Ltd. makes) to measure.Particularly, in the 100～150ml water of having removed solid impurity in advance in container, add the surfactant (alkyl benzene sulfonate) of 0.1～0.5ml, add the various toners of 0.1～0.5g again and make it and disperse as spreading agent.Use ultrasonic disperser (manufacturing of ホ Application ダ エ レ Network ト ロ ニ Network ス company) that the dispersion liquid that obtains is carried out about 1～3 minute dispersion treatment, disperseing concentration is 3000～10,000/μ l, measures the shape and the distribution of toner.Calculate average circularity by these measurement results.

＜shape coefficient SF-1 and SF-2 〉

By the photo of scanning electron microscope (S-800, the Hitachi makes) shooting toner, it is imported to image analysis apparatus (LUSEX3, ニ レ コ company makes), and analyze, calculate by following mathematical expression 1 and mathematical expression 2.

(mathematical expression 1)

$\mathrm{SF}-1=\frac{{\left(\mathrm{MXLNG}\right)}^2}{\mathrm{AREA}}\×\frac{\mathrm{\π}}{4}\×100$ ... mathematical expression 1

In the above-mentioned mathematical expression 1, MXLNG represents that toner projects on the two dimensional surface and the maximum length of the shape that obtains, and AREA represents that toner projects on the two dimensional surface and the area of graph that obtains,

[mathematical expression 2]

$\mathrm{SF}-2=\frac{{\left(\mathrm{PERI}\right)}^2}{\mathrm{AREA}}\×\frac{1}{4\mathrm{\π}}\×100$ ... mathematical expression 2

In above-mentioned mathematical expression 2, PERI represents toner is projected on the two dimensional surface and the girth of the figure that obtains, and AREA represents toner is projected on the two dimensional surface and the area of graph that obtains.

The manufacturing of-carrier-

(SR2400 East レ ダ ウ コ one ニ Application グ シ リ コ one Application Co., Ltd. makes with 200 parts of toluene, 200 parts of silicones with stirrer, nonvolatile component 50%), 7 parts of amino silanes (manufacturing of SH6020 East レ ダ ウ コ one ニ Application グ シ リ コ one Application Co., Ltd.) and 4 parts of carbon black dispersion 10 minutes, the preparation coating fluid.

The coating fluid that obtains and 5000 parts of Mn ferrite particles as core (weight average particle diameter is 35 μ m) are put into the limit that is provided with rotary chassis and stirrer paddle in thermopnore form in the apparatus for coating that the eddy flow limit is coated with, this coating fluid is coated on the above-mentioned core.With the coating thing that obtains in electric furnace in 250 ℃ of sintering 2 hours, the preparation carrier.

The preparation of-external additive-

Shown in following table 1, preparation has been carried out surface-treated external additive A～C by surface conditioning agent.

(table 1)

The manufacturing of-secondary aggregate-

With 10 especially additive B (table 1) be distributed in 100 parts of methyl alcohol, after the stirring, make external additive B precipitation by centrifuging.Again that this sediment is air-dry, the dry thing that obtains is put in the bowl mill that has added the 10mm steel ball, pulverize.With 400 eye mesh screens this crushed material is sieved and collects, as secondary aggregate.With it as external additive D.

By the particle diameter of this secondary aggregate of electron microscope observation, when being confirmed by fluorescent x-ray, major component is a titanium oxide microparticle, and the aggregate particle size of secondary aggregate is 22 μ m, and it is the ferric oxide particles of 80～150nm that secondary aggregate contains 60% primary particle size.

(embodiment 1～5 and comparative example 1)

The manufacturing of-toner-

For 100 parts of [toner parent particles 1] that obtain, formula ratio interpolation external additive 1～3 and secondary aggregate with table 2 record mix with the Henschel mixer.Make the mesh of mixed powder, remove oversize grain, make toner A～H by mesh 100 μ m.

(table 2)

	External additive 1	Adjuvant (part)	External additive 2	Adjuvant (part)	External additive 3	Adjuvant (part)	Aggregation	Adjuvant (part)
									Toner A	A	0.5	B	0.5	C	0.5	D	0.05
Toner B	A	1.5	B	0.75	C	1	D	0.1
									Toner C	A	1.5	B	0.5	C	0.5	D	0.1
Toner D	A	1.5	B	0.5	C	0.5	D	0.2
									Toner E	A	1.5	B	0.75	C	0.5	D	0.2
Toner F	A	1.5	B	0.75	C	0.5	D	0.5
									Toner G	A	1.5	B	0.75	C	1.2	D	0
Toner H	A	1.5	B	0.75	C	0.6	D	0.6

Then, as described below for each toner of embodiment 1～5 that obtains and comparative example 1～2, the number of the secondary aggregate in the mensuration toner.The result is as shown in table 3.

(number of secondary aggregate is measured)

Here, as at least a and aggregate particle size that comprises in the above-mentioned particulate is the assay method of the content (number) of the secondary aggregate more than the 10 μ m, for example, the circle sieve of diameter 24mm is oppositely arranged, make the closed sieve cylindraceous (sieve of use is 635 orders) of thickness 7mm, and weighing 0.2g toner is placed in one.Use swabbing pig (CV-TN96) with 5mmHg swabbing pressure suction air by Hitachi's toner that use is adjusted swabbing pressure by slide transformer.Further aspirate on one side, on one side on said units height 160mm sentence and blow pressure 0.2MPa blow air, remove toner after, with the swabbing pressure 20mmHg suction air of swabbing pig, remove toner again.In addition, toner is removed when incomplete, carries out these operations continuously, removes toner.Observe sieving remaining residue with 150 times by digital microscope (KEYENCEVHX-100).Counting remains in the number of the secondary aggregate on the sieve.It is measured 20 visuals field, obtain the content of the secondary aggregation body that in toner, contains.Obtain the number of the secondary aggregation body that contains in the toner.

(table 3)

	Toner	The number of secondary aggregate (individual/g)
			Embodiment 1	Toner A	20
Embodiment 2	Toner B	94
			Embodiment 3	Toner C	38
Embodiment 4	Toner D	180
			Embodiment 5	Toner E	320
Embodiment 6	Toner F	740
			Comparative example 1	Toner G	0

The preparation of-developer-

Use container to rotate and each toner and 100 parts of above-mentioned carriers of the barrel mixer (tumbler mixer) of whipped form will obtain 7 parts of embodiment 1～6 and comparative example 1 evenly mix, and make it charged, make developer.

The developer that obtains is filled in the image processing system (Ricoh Co., Ltd makes, IPSiO Color8100), and output image is estimated according to following.The result is as shown in table 4.

＜image color 〉

Recording medium (Ricoh Co., Ltd makes, model 6200) in common paper is gone up the 0.3 ± 0.1mg/cm of output as low adhesion amount ²The image on the spot of adhesion amount after, measure image color by X-Rite (manufacturing of X-Rite company), estimate with following benchmark.

[metewand]

Zero: image color is more than 1.4;

△: image color is more than 1.2 and less than 1.4;

*: image color less than 1.2.

＜fixation performance (heat-resisting print through, low-temperature fixing) 〉

Carry out taking away from image processing system (Ricoh Co., Ltd makes, IPSIO Color 8100) transformation of photographic fixing oil coater unit, the temperature that changes the photographic fixing band is carried out the photographic fixing test.Will the ceiling temperature of heat penetration seal can not take place as the photographic fixing ceiling temperature on common paper.In addition, on ground paper, measure the photographic fixing lower limit temperature.The photographic fixing lower limit temperature is that the image color survival rate after the photographic fixing image that will obtain with thin (pad) wiping of notepaper is that fixing roller temperature more than 70% is as the photographic fixing lower limit temperature.Expectation photographic fixing ceiling temperature is more than 200 ℃, and the photographic fixing lower limit temperature is below 140 ℃.

Go up with image on the spot with 1.0 ± 0.1mg/cm at the recording medium of common paper and ground paper (Ricoh Co., Ltd makes, duplicating printing＜135 that model 6200 and NBS Ricoh make 〉) ²Toner adhesion amount evaluation map picture.

[metewand]

Zero: the photographic fixing lower limit temperature is less than 130 ℃;

△: the photographic fixing lower limit temperature is more than 130 ℃ and less than 140 ℃;

*: the photographic fixing lower limit temperature is more than 140 ℃.

＜spatter property 〉

Behind the recording chart of 1000 image area rates 95% of output, to transfer on the blank sheet of paper by the transfer printing remaining toner on the photoreceptor of cleaning operation with pressure zone (Scotch tape) (manufacturing of Sumitomo 3M Co., Ltd.), with wheat Jan Quast reflection of the concentration RD514 type it is measured, estimate by following benchmark.

[metewand]

◎: and blank poor less than 0.005;

Zero: and blank difference is 0.005～0.010;

△: and blank difference is 0.011～0.02;

*: and blank difference surpasses 0.02.

＜transfer printing 〉

The recording chart of image area rate 20% is transferred on the paper from photoreceptor, transfer printing remaining toner on the photoreceptor before using pressure zone (manufacturing of Sumitomo 3M Co., Ltd.) to clean is then transferred on the blank sheet of paper, with wheat Jan Quast reflection of the concentration RD514 type it is measured, estimate by following benchmark.

[metewand]

◎: and blank poor less than 0.005;

Zero: and blank difference is 0.005～0.010;

△: and blank difference is 0.011～0.02;

*: and blank difference surpasses 0.02.

＜image graininess, distinctiveness 〉

Carry out the output of photographic image with monochrome, by visual degree according to following benchmark evaluation graininess and distinctiveness.

[metewand]

◎: be equal to offset printing;

Zero: than the poor slightly degree of offset printing;

△: than offset printing degree far short of what is expected;

*: be electrophotographic image degree in the past, non-constant.

＜fog 〉

Under the environment of 10 ℃ of temperature, humidity 15%RH, (Ricoh Co., Ltd makes with image processing system in use, IPSiO Color 8100) is transformed into the adjusted evaluation machine of oilless fixing mode, observes in the toner contamination degree of using the recording medium upper surface part of various toners after implementing continuously endurancing that 100000 image area rates of output are 5% recording chart by range estimation (magnifier).

[metewand]

◎: do not observe pollution fully, be good state;

Zero: observe the degree of pollution a little, be out of question;

△: the degree of observing a small amount of pollution;

*: outside the scope of permission, there is severe contamination and becomes problem.

＜toner disperses 〉

Under the environment of 40 ℃ of temperature, humidity 90%RH, (Ricoh Co., Ltd makes with image processing system in use, IPSiO Color 8100) is transformed into the adjusted evaluation machine of oilless fixing mode, observe toner contamination state in using the image processing system of various toners after implementing continuously long duration test that 100,000 image area rates of output are 5% recording chart by range estimation (magnifier), estimate according to following benchmark.

[metewand]

◎: do not observe toner contamination fully, be good state;

Zero: observe the degree of pollution a little, be out of question;

△: the degree of observing a small amount of pollution;

*: outside the scope of permission, there is severe contamination and becomes problem.

＜environment keeping quality (anti-adhesive) 〉

Weighing is the toner of 10g for every part, puts into the glass container of 20ml, and the vial 100 times of vibrating is gently placed in the calibration cell in being arranged on hot and humid (55 ℃, 80%RH) environment after 24 hours then, uses penetrometer to measure pen..In addition, to (10 ℃, 15%RH) toner preserved down of environment is also estimated pen. in the same manner, adopts the value of pen. littler under hot and humid, the low temperature and low humidity environment to estimate at low temperature and low humidity.

[metewand]

◎: more than the 20mm

Zero: more than the 15mm and less than 20mm

More than △: the 10mm and less than 15mm

*: less than 10mm

＜charged stability 〉

Use each toner, use the character image pattern of image area rate 12%, implement the long duration test of 100,000 of outputs continuously, estimate the variation of the carried charge of this moment.Take a small amount of developer from sleeve, obtain the carried charge variation, estimate according to following benchmark by blowing out method.

[metewand]

Zero: the variation of carried charge is less than 5 μ c/g;

△: carried charge be changed to 5 μ c/g～10 μ c/g;

*: the variation of carried charge surpasses 10 μ c/g.

(table 4)

Toner of the present invention can good transfer printing and the spatter property of long term maintenance, does not have the change of image inequality, and, stir the embedding that developer does not have external additive during by use, flowability and charging property secular variation are few, and therefore excellent in stability is applicable to that high quality images forms.

Use container, handle box, image processing system and the image forming method of the developer of the present invention of toner of the present invention, the toner of packing into to be applicable to that high quality images forms.

Claims (14)

1. toner, wherein containing toner parent particle and aggregate particle size is the secondary aggregate of the above particulate of 10 μ m, described toner parent particle comprises the toner materials that contains colorant and binder resin at least,

Wherein the content of this secondary aggregate is 5/g～800/g, and

Wherein to contain primary particle size be the above and big particle diameter composition that be 30nm～200nm less than small particle diameter composition and the primary particle size of 30nm of 1nm to particulate.

2. the described toner of claim 1, wherein, the aggregate particle size of secondary aggregate is 10～50 μ m, and the content of this secondary aggregate is 5/g～200/g.

3. the described toner of claim 1, wherein, secondary aggregate contains the titanium oxide microparticle of the primary particle size 80～150nm more than 50%.

4. the described toner of claim 1 wherein, makes solution or dispersion liquid emulsification or dispersion in water-medium of toner materials, with the toner granulation.

5. the described toner of claim 4, wherein, the solution or the dispersion liquid of toner materials contain organic solvent, and when granulation or after the granulation organic solvent are removed.

6. the described toner of claim 4, wherein, toner materials comprise at least the compound that contains active hydrogen group and can with the polymkeric substance of the compound reaction that contains active hydrogen group, and,

Granulation is carried out by the following method: make the above-mentioned compound and the generation cementability matrix material that can react with the polymkeric substance that this compound that contains active hydrogen group reacts that contains active hydrogen group, and contained the particle of this cementability matrix material at least.

7. the described toner of claim 6 wherein, can comprise modified polyester resin with the polymkeric substance of the compound reaction that contains active hydrogen group.

8. the described toner of claim 1, wherein, the binder resin in the toner materials is a unmodified polyester resin.

9. the described toner of claim 1, wherein, the average circularity of toner is 0.90～0.99.

10. the described toner of claim 1, wherein, the shape coefficient SF-1 of the spherical degree of the expression toner of representing with following mathematical expression 1 is 100～150, and the shape coefficient SF-2 of the concavo-convex degree of the expression toner of representing with following mathematical expression 2 is 100～140

[mathematical expression 1]

$\mathrm{SF}-1=\frac{{\left(\mathrm{MXLNG}\right)}^2}{\mathrm{AREA}}\×\frac{\mathrm{\π}}{4}\×100$ ... mathematical expression 1

In the above-mentioned mathematical expression 1, MXLNG represents that toner projects on the two dimensional surface and the maximum length of the shape that obtains, and AREA represents that toner projects on the two dimensional surface and the area of graph that obtains,

[mathematical expression 2]

$\mathrm{SF}-2=\frac{{\left(\mathrm{PERI}\right)}^2}{\mathrm{AREA}}\×\frac{1}{4\mathrm{\π}}\×100$ ... mathematical expression 2

In above-mentioned mathematical expression 2, PERI represents toner is projected on the two dimensional surface and the girth of the figure that obtains, and AREA represents toner is projected on the two dimensional surface and the area of graph that obtains.

11. the described toner of claim 1, wherein, the weight average particle diameter D of toner ₄Be 2～7 μ m, and this weight average particle diameter D ₄Ratio D with number average particle diameter Dn ₄/ Dn is below 1.25.

12. a developer, it contains the described toner of claim 1.

13. the described developer of claim 12, this developer are any in monocomponent toner and the two-component developing agent.

14. image forming method, wherein, comprise at least: form operation at the electrostatic latent image that forms electrostatic latent image on the electrostatic latent image carrier, use the described toner of claim 1 above-mentioned latent electrostatic image developing is formed visual image developing procedure, above-mentioned visual image is transferred to transfer printing process on the recording medium, will be transferred to the photographic fixing operation of the transferred image photographic fixing on the recording medium.

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