CN1957302A - Toner, process for producing toner, two-component developer and image forming apparatus - Google Patents

Abstract

A toner produced by mixing, in a water base medium, at least a resin particle dispersion having resin particles dispersed therein, a colorant particle dispersion having colorant particles dispersed therein and a wax particle dispersion having wax particles dispersed therein together and thereafter conducting aggregation heating thereof, wherein the main component of a surfactant for use in the resin dispersion is a nonionic surfactant and further the main component of at least one surfactant selected from among the surfactant for use in the wax dispersion and the surfactant for use in the colorant dispersion is a nonionic surfactant. Thus, a toner of small particle diameter with a sharp particle size distribution can be prepared without the need to conduct classification. Further, oilless fixation can be realized, and the service life thereof can be prolonged without spending of toner components onto a carrier. Still further, image void and scattering at transfer can be avoided. Consequently, there can be provided a toner or two-component developer attaining high transfer efficiency.

Description

The manufacture method of toner, toner, two-component developing agent and image processing system

Technical field

The present invention relates to be used for the toner of the compounding machine of duplicating machine, laser printer, plain paper facsimile, colored PPC, color laser printer, colour facsimile apparatus and these machines, manufacture method, two-component developing agent and the image processing system of toner.

Background technology

In recent years, the purpose that electro-photography apparatus has used from office transfers the individual to be used, and requires to realize miniaturization, high speed, high image qualityization, non-maintaining etc. technology simultaneously.

When obtaining coloured image, produce set-off (offset) on the fixing roller surface owing to toner adheres to, so that must on fixing roller, be coated with a large amount of wet goods, this makes the structure complicated of process operation and device.Therefore, for miniaturization, non-maintainingization, the cost degradation that installs, when photographic fixing described later, require to realize not using the oilless fixing of oil.In order to realize this target, the scheme that release agents such as wax are added in the binder resin with remarkable pre-arcing characterisitics is actually used.

Yet there is following problems in the problem of utilizing this toner to constitute: because toner has the very strong characteristic of coherency, and the toner image disorder when therefore producing transfer printing more significantly and the tendency of transfer printing difference, thus be difficult to realize simultaneously transfer printing and photographic fixing.In addition when developing use as bi-component, because impact, friction between the particle, or physical shocks such as the impact between particle and developer, friction, by the heating that caused of friction, be easy to generate low melting point composition in the toner and adhere to consumption (spent) on the carrier surface, reduce the charged ability of carrier, and shortened the serviceable life of developer.

In following patent documentation 1, the carrier that a kind of organic siliconresin to overlay that is used for positively charged type toner has imported the fluorine substituted alkyl has been proposed.In addition, in following patent documentation 2, as development capability height in high speed processing, its also carrier of deterioration not in long-time, it discloses a kind of coating carrier that comprises conductive carbon and cross-linking type fluorine modified organic silicone resin.In the charged characteristic of the excellence of utilizing organic siliconresin, give features such as lubricity, fissility and hydrophobicity by the fluorine substituted alkyl, thereby being difficult to produce wear and tear, peel off, slight crack etc., can also prevent consumption; But, the requirement of aspects such as it can not satisfy wearing and tearing, peel off, slight crack, and, though can obtain appropriate carried charge in having the toner of positively charged, when use had the toner of electronegative property, carried charge was low excessively, generate the anti-electrical toner (toner) of band in large quantities with positively charged, produce the deterioration that photographic fog or toner disperse etc., thereby this toner is unsuitable for practical application.

In addition, in toner, in the pulverizing and progressive operation in existing mixing comminuting method,, consider that the actual particle diameter that can provide also can only reach about 8 μ m from economy and aspect of performance though be small particle diameterization.At present, considering to make the toner of small particle diameter by the whole bag of tricks.In addition, considering when the toner melting mixing, release agents such as wax are being added in the resin of the low property of softening and realize the method for oilless fixing.But, there is restriction in this method to the amount of the wax that can mix, and along with the increase of the addition of wax, can produce following harm: the flowability of toner reduces, the literal desalination (translocation Xie Zhong order け, transfer voids) during transfer printing increases, to the melt bonded increase of photoreceptor etc.

Therefore, studied the toner preparation method who has used the various polymerizations that are different from mixing comminuting method.For example, when preparing toner,, in most cases need further progressive operation even want to control the zone that the size-grade distribution of toner can not exceed mixing comminuting method with suspension polymerization.In addition, the toner that is obtained by these methods is because its shape is roughly spherical shape, thereby has this spatter property extreme difference and the infringement picture quality reliability problems that remains in the toner in the photoreceptor etc.

In addition, used the method for emulsion polymerization manufactured toner to prepare by following operation: in the dispersion liquid that makes resin particle disperse to form at least, form aggregated particle, and the operation of preparation aggregated particle dispersion liquid; Add to mix resin microparticle to be scattered in the aggregated particle dispersion liquid and the resin microparticle dispersion liquid that forms, thereby resin microparticle is attached on the aggregated particle and forms the operation of adhering to particle; And heating is adhered to particle and is made its melt bonded operation.

Following technology is disclosed in following patent documentation 3: have the colorant particle dispersion liquid that forms in the spreading agent of polarity by mixing at least resin particle to be dispersed in have the resin particle dispersion liquid that forms in the spreading agent of polarity and colorant particle is dispersed in, thereby the mixed liquor preparation section of preparation mixed liquor, and make spreading agent contained in the aforementioned mixed liquor have identical polarity, thus can be simply and easily prepare the high tone agent for developing electrostatic charge image of reliability of charging property and color emissivity excellence.

In addition, disclose following content in following patent documentation 4: it is that 12～30 higher alcohol and carbon number are at least a ester of forming of 12～30 higher fatty acid by carbon number that release agent contains a kind of at least, and this resin particle comprises at least two kinds of resin particles that molecular weight is different, prepares excellent toner such as fixation performance, color emissivity, the transparency and colour mixture thus.

But, when the dispersiveness of the release agent that is added reduces, during photographic fixing, in the toner image of fusion, have the tendency that is easy to generate color muddiness (dull color).Meanwhile also reduce dispersing of pigments, thereby the color emissivity of toner becomes not enough.In addition in operation subsequently, when resin particle further adheres on the surface of condensed matter, because the dispersiveness of this release agent etc. reduces, so the adhesion of resin particle is unsettled.And, in case separate with the release agent of resin cohesion, just free immediately in aqueous medium.Cohesion when mixing cohesion brings very big influence to the breaking up of the branch of release agent according to thermal characteristicss such as the polarity of the wax that uses etc., fusing points.In addition, do not use the oilless fixing of oil when being implemented in photographic fixing, add specific wax therefore in a large number.

Mixed a certain amount of with the system of waxing in, when forming particle by aggregation, particle diameter carry out thickization during heat treated, thereby is difficult to generate the small particle diameter particle with narrow size-grade distribution.

By using release agent, can realize oilless fixing simultaneously, reduce the photographic fog when developing and improve transfer efficiency, but, on the contrary during fabrication, the even mixing in aqueous medium of resin particle and pigment particles is condensed and is hindered, and has increase and participates in the existence of release agent cohesion, that suspend and increase influencing the tendency that particle is merged in the cohesion that produces thus in aqueous medium.

Patent documentation 1: No. 2801507 communique of Japan's special permission

Patent documentation 2: the spy opens the 2002-23429 communique

Patent documentation 3: the spy opens flat 10-198070 communique

Patent documentation 4: the spy opens flat 10-301332 communique

Summary of the invention

The invention provides the toner that does not need classification operation ground to make small particle diameter with sharp-pointed size-grade distribution, on fixing roller, do not use in the oilless fixing of oil, in toner, use release agents such as wax, thereby realize low-temperature fixing, high temperature bonding-miry capacity and storage-stable simultaneously, even when the toner with release agents such as the content of wax is used in combination, can not produce the deterioration that consumption causes yet, the long two-component developing agent of life-span that permanance is high, also provide the literal when preventing transfer printing to desalinate, disperse, and can obtain the image processing system of high transfer efficiency.

Toner of the present invention be by in aqueous medium to the major general disperseed resin particle resin particle dispersion liquid, disperseed the colorant particle dispersion liquid of colorant particle and disperseed the wax particle dispersion of wax particle to mix, and form by the cohesion heating, wherein, the major component that is used for the surfactant of described resin dispersion is a non-ionic surfactant, and the major component that is selected from the surfactant that is used for described wax dispenser and is used at least a surfactant among the surfactant of described colorant dispersion is a non-ionic surfactant.

The manufacture method of toner of the present invention is by disperseed the resin particle dispersion liquid of resin particle to the major general in aqueous medium, disperse the colorant particle dispersion liquid of colorant particle and disperseed the wax particle dispersion of wax particle to mix, and form toner by cohesion heating, the major component that wherein is used for the surfactant of described resin dispersion is a non-ionic surfactant, and the major component that is selected from the surfactant that is used for described wax dispenser and is used at least a surfactant among the surfactant of described colorant dispersion is a non-ionic surfactant; Described manufacture method comprises following operation:

Make the operation of the mixed dispersion liquid be the resin particle dispersion liquid that has disperseed described resin particle, the colorant particle dispersion liquid that has disperseed described colorant particle and the wax particle dispersion that disperseed described wax particle at least,

The pH of described mixed dispersion liquid is adjusted into 9.5-12.2 scope operation and

Add water-soluble inorganic salt, and carry out heat treated, thereby described resin particle, described colorant particle and described wax particle condense the operation of the aggregated particle that is melted with formation at least a portion.

Two-component developing agent of the present invention is made up of toner and carrier, the aforesaid toner parent of wherein said toner or be that the inorganic micro powder end of 6nm～200nm scope forms by the mean grain size of adding 1～6 weight portion scope with respect to this toner parent of 100 weight portions in the toner parent of aforesaid method manufacturing, and described carrier contains magnetic particle as core, and wherein the surface of core covers with the fluorine modified organic silicone resin that contains amino silicane coupling agent at least.

Description of drawings

Fig. 1 is the cut-open view of the structure of the imaging device that uses in the one embodiment of the invention.

Fig. 2 is the cut-open view of the structure of the fixation unit that uses in the one embodiment of the invention.

Fig. 3 is the dispersed with stirring schematic representation of apparatus of using in the one embodiment of the invention.

Fig. 4 is the vertical view of the dispersed with stirring device that uses in the one embodiment of the invention.

Fig. 5 is the dispersed with stirring schematic representation of apparatus of using in the one embodiment of the invention.

Fig. 6 is the vertical view of the dispersed with stirring device that uses in the one embodiment of the invention.

Fig. 7 is the change of size curve map of the toner that uses in the one embodiment of the invention.

Embodiment

The present invention can not need classification operation ground to make the toner of the small particle diameter with sharp-pointed size-grade distribution.

The inventive method is that the resin particle dispersion liquid that will disperse resin particle, the colorant particle dispersion liquid that has disperseed colorant particle and the wax particle dispersion that disperseed wax mix cohesion in aqueous medium, generate the toner parent by heating, can eliminate the existence of the wax particle of the suspension that in aqueous medium, does not participate in cohesion thus, but also can eliminate the existence of the colorant particle of suspension, the small particle diameter toner that can not need classification operation ground to make small particle diameter and in even and narrow scope, have sharp-pointed size-grade distribution.

The present invention does not need to be coated with unction and just can prevent bonding-miry capacity, photographic fixing at low temperatures in addition.Even and then when the toner with the release agent of content of wax etc. is used in combination, can produce the deterioration that consumption causes yet, thereby can realize having the two-component developing agent of permanance.

In addition, and a plurality of images with photoreceptor and development section of row arrangement form the station, on transfer article, carry out continuously the versicolor toner of transfer printing successively and implement in the tandem color processing of transfer printing process, literal desalination and oppositely transfer printing in the time of can preventing transfer printing, and can obtain higher transfer efficiency.

The present invention has carried out wholwe-hearted research to tone agent for developing electrostatic charge image and the two-component developing agent that a kind of small particle diameter is provided, this toner is an oilless fixing, have high-luster, high light transmittance, also have excellent charged characteristic and environmental factor dependence, spatter property, transfer printing, and have sharp-pointed size-grade distribution; And the present invention is also to providing a kind of image forming method to carry out wholwe-hearted research, and this method can toner disperse to have, the high-quality and high reliability ground of photographic fog etc. forms coloured image.

(1) polymerization

The preparation of resin particle dispersion liquid can be undertaken by following method: by ethene base system monomer is carried out emulsion polymerization or seeding polymerization etc. in surfactant, the homopolymer of ethene base system monomer or the resin particle of multipolymer (vinyl resin) are distributed in the surfactant, thereby form dispersion liquid.Device as the preparation resin particle dispersion liquid can list, and for example high speed rotating type emulsifier unit, high-pressure emulsification device, colloid type emulsifier unit, the bowl mill with medium, sand mill, ball mill (Dyno mill) wait itself known diverting device.

As polymerization initiator, can use 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azoisobutyronitrile, 1,1 '-azo two (cyclohexane-1-nitrile), 2,2 '-azo two-4-methoxyl-2, azo class such as 4-methyl pentane nitrile, azoisobutyronitrile or two azo class polymerization initiators and persulfate (potassium persulfate, ammonium persulfate etc.), azo compound (4,4 '-azo two 4-cyanopentanoic acids or its salt, 2,2 '-azo two (2-amidine propane) salt etc.), peroxide compound etc.

The dispersion liquid of colorant particle can be by adding colorant particle, using aforementioned diverting device that its dispersion is prepared in the water that has added surfactant.

The formation of preferred first manufacture method of the present invention is: in aqueous medium with the above-mentioned resin particle dispersion liquid that disperses resin particle, disperse the colorant particle dispersion liquid of colorant particle and disperseed the wax particle dispersion of wax particle to mix, be adjusted under the constant condition at pH aqueous medium, in the presence of water-soluble inorganic salt, aqueous medium is condensed heating certain hour (for example 1-6 hour) more than the glass transition temperature (Tg) of resin and/or under the temperature more than the fusing point of wax, thereby generate the toner parent particle of forming by the aggregated particle of partial melting (being also referred to as core particle sometimes) at least.This toner parent particle and external additive are carried out hybrid processing and generate toner.

In the formation of preferred first manufacture method of the present invention, the wax particle dispersion that has disperseed the resin particle dispersion liquid of resin particle, the colorant particle dispersion liquid that has disperseed colorant particle and mixing and emulsifying dispersion treatment to cross to the major general in aqueous medium mixes.This moment, preferred fabrication pH was the mixed dispersion liquid below 6.0.This is because when using persulfate such as potassium persulfate as polymerization initiator when polymerization generates the emulsion polymerization resin, its residual component when the heating cohesion process sometimes because thermal decomposition makes the pH reduction.Preferably behind the resin emulsion polymerization (being preferably more than 80 ℃) more than the uniform temperature in order fully to decompose residual component, carry out certain hour (preferably about 1-5 hour) heat treated.This moment, the pH of emulsion polymerization resin dispersion liquid was preferably below 4, more preferably below 1.8.

In above-mentioned, if the pH when making mixed dispersion liquid surpasses 6.0, when then adding thermosetting pigmentary resin particle, exist the residual component of the persulfate of polymerization initiator to decompose, pH fluctuation (pH reduces phenomenon) becomes greatly in the solution, adds heat-coagulation and the tendency of thickization takes place for the particle that obtains.

In this mixed dispersion liquid, add water-soluble inorganic salt, be heated more than the fusing point of the above and/or wax of the glass transition temperature (Tg) of resin, can generate aggregated particle with certain particle diameter.Preferably be adjusted into the pH of mixed dispersion liquid the scope of 9.5-12.2 before the adding of water-soluble inorganic salt and before the heating this moment.Can add 1N NaOH and adjust pH.If pH is lower than 9.5, then there is the tendency of thickization of particle that forms.In addition, if pH surpasses 12.2, then free wax becomes many and is difficult to inner wax equably.

After adjusting pH, add water-soluble inorganic salt, heat treated certain hour (for example 1-6 hour) while stirring, thereby resin particle, colorant particle and wax particle coacervation form the aggregated particle of predetermined volume average particle size (for example 3-6 μ m) at least, wherein at least a portion of aggregated particle fusing.When forming the aggregated particle of this predetermined volume average particle size, the scope by the pH with solution remains 7.0-9.5 can form the aggregated particle that free wax is few, included the narrow size-grade distribution of having of wax.The setting value of the pH of NaOH amount, polycoagulant kind and the amount that suitable selection adds, the pH of emulsion polymerization resin dispersion liquid, colorant dispersion, the pH of wax dispersion and heating-up temperature, time.If the pH of solution is lower than 7.0 when forming particle, then there is the tendency of thickization of aggregated particle.If pH above 9.5, then exists the bad and free wax of cohesion to become many inclining together.

The formation of preferred second manufacture method of the present invention is in the formation of above-mentioned first manufacture method, further preferably, further then pH to be adjusted into the scope of 2.2-6.8, heat treated certain hour (preferably about 1-5 hour) generation aggregated particle.By being adjusted into this scope and carrying out heat treated, can suppress aggregated particle secondary aggregation each other, and can promote the surface smoothing of shape of particle, and make size-grade distribution become more sharp-pointed.

The formation of preferred the 3rd manufacture method of the present invention is: in the aggregated particle dispersion liquid of the aggregated particle that will disperse first or second method to generate, add second resin particle dispersion liquid that has disperseed second resin particle, it is bonding to carry out heating and melting, thereby also can form the superficial layer of resin melt bonded.Can make permanance, storage-stable, the high temperature anti setoff properties of toner become better thus.

When make second resin attached to the aggregated particle surface on, and be heated more than the Tg of second resin and when forming the melt bonded layer of resin surface, need make second resin particle not free, and prevent the secondary aggregation of aggregated particle, thereby make it equably attached on the aggregated particle surface.

Therefore, preferably, second resin particle dispersion liquid that has disperseed second resin particle in adding, and after the pH that will add the aggregated particle dispersion liquid of this second resin particle dispersion liquid is adjusted into the scope of 2.2-6.8, under the temperature more than the glass transition temperature of second resin particle heat treated 0.5-5 hour.

Use this method, can be with second resin particle equably attached to also having suppressed suspended particles on the aggregated particle surface simultaneously.If pH is lower than 2.2, then exist and can not easily cause adhering to of second resin particle, thus the tendency that the free resin particle increases.If pH surpasses 6.8, then aggregated particle is easy to produce secondary aggregation each other.If processing time length is more than 5 hours, then there is the wide tendency of thickization of particle and size-grade distribution.

The formation of preferred the 4th manufacture method of the present invention is, after heat treated 0.5-5 hour, pH is adjusted into the scope of 5.2-8.8 in the 3rd manufacture method again, under the temperature more than the glass transition temperature of second resin particle heat treated 0.5-5 hour then.

Can the limit suppress thickization of particle, the limit makes size-grade distribution become sharp-pointed.Have and do not change shape, just can make particle surface produce the effect of flatness.

By this operation, can be with second resin particle equably attached to also having suppressed suspended particles on the core particle surface simultaneously.If pH is lower than 5.2, then form following tendency: be difficult to cause that second resin particle adheres to, thereby the free resin particle increases.If pH surpasses 8.8, then core particle is easy to produce secondary aggregation each other.If processing time length is more than 5 hours, then there is the wide tendency of thickization of particle and size-grade distribution.

The formation of preferred the 5th manufacture method of the present invention is, in the 4th manufacture method, then again pH is adjusted into the scope of 3.2-6.8, under the temperature more than the glass transition temperature of second resin particle heat treated 0.5-5 hour then, make second resin particle melt bonded on above-mentioned core particle.By this operation, can not can cause that core particle each other or second resin particle secondary aggregation each other, makes second resin particle melt bonded on core particle, thereby obtains the particle of narrow size-grade distribution.If pH is lower than 3.2, the particle that has then adhered to is free sometimes.If pH surpasses 6.8, then core particle is easy to produce secondary aggregation.

It is 0.5-2 μ m that the preferred core particle and second resin particle adhere to the difference that fusion sticks to the volume average particle size of the particle that forms on the core particle.If this difference is lower than 0.5 μ m, then the attachment state of second resin is bad, the undercapacity of the influence of moisture, second resin self.If should difference surpass 2 μ m, fixation performance, glossiness are descended.

In the present invention preferred first～the 5th constitutes, then, can obtain the toner parent through washing procedure, solid-liquid separation process and drying process arbitrarily.In this washing procedure,, preferably carry out displacement washing with ion exchange water fully from improving the viewpoint of charging property.As the separation method in the above-mentioned solid-liquid separation process, there is no particular limitation, from the viewpoint of throughput rate, preferably lists known filter methods such as suction filtration and pressure filtration method.As the drying means in the aforementioned drying process, there is no particular limitation, from the viewpoint of throughput rate, preferably lists known drying means such as dodging spray seasoning, the seasoning that flows and the mobile seasoning of oscillating mode.

As toner require further low-temperature fixingization and when the photographic fixing at high temperature the separation property, the high light transmittance of coloured image, the storage-stable under the condition of high temperature of anti setoff properties, paper and fixing roller in the oilless fixing of coating silicone oil etc. on fixing roller, must these satisfy simultaneously.

Therefore, preferably following formation: by according to the function difference of the wax that in toner, adds and mixed melting point forms different or a plurality of waxes that skeleton is different can realize having concurrently low-temperature fixingization and release agent.

But, when resin, colorant form aggregated particle together in these aqueous mediums, if the fusing point difference of wax, then a kind of wax melts and the acceleration cohesion in advance, and opposite, the aggregation of another kind of wax is slow, can not enter the wax particle and is easy to produce the suspension phenomenon.The wax of hydro carbons is the wax that is difficult to produce with resin the cohesion class from the fused property with resin in addition.Wax can not enter in the aggregated particle and exist the particle that suspends and aggregated particle not to condense and size-grade distribution broadens, thereby is difficult to bring into play the original developing property of toner.

In addition, if use anionic surfactant treatment wax, though then improved dispersion stabilization, aggregated particle when cohesion, thickization of particle diameter and be difficult to obtain the particle of sharp-pointed size-grade distribution.Especially the wax of hydro carbons and ester wax being mixed when making aggregated particle, be easy to occur this phenomenon.

Therefore constitute as the present invention preferred first, the formation of wax is preferably the formation that comprises first wax and second wax at least, described first wax contains by the DSC method measures the endothermic peak temperature obtain (be called fusing point Tmw1 (℃)) be 50～90 ℃ wax, described second wax contains by the DSC method measures the endothermic peak temperature that obtains (fusing point Tmw2 (℃)) than the also high 5-70 ℃ wax of the Tmw1 of above-mentioned first wax.

It has been generally acknowledged that first wax when adding heat-coagulation,, encouraged the cohesion of wax and resin, thereby wax can enter equably, prevents to exist suspended particles owing to carry out compatibilized with styrene acrylic resin.In addition, with respect to first wax, with having more dystectic second wax, can make the performance of second wax optimize the function of high temperature bonding-miry capacity, and can further improve low-temperature fixing by low-melting first wax by also.

The fusing point Tmw1 of first wax is preferably 50-90 ℃.More preferably 60-85 ℃, more preferably 65-80 ℃.If be lower than 50 ℃, then there is the tendency of the thermotolerance variation of toner.If surpass 90 ℃, then exist the coherency of wax to descend, UA free particle increases in aqueous medium, can not bring into play the tendency of above-mentioned effect.

The fusing point Tmw2 of second wax preferably has the fusing point also higher 5-70 ℃ than the fusing point Tmw1 of first wax.If the said temperature difference is for being lower than 5 ℃, then there is the tendency that can not bring into play the function of optimizing the high temperature bonding-miry capacity in the function that so can separate wax effectively.When the said temperature difference surpasses 70 ℃ in addition, the tendency that existence descends with the coherency of resin, the suspended particles of wax increase.

The fusing point Tmw2 of second wax is preferably 80-120 ℃, and more preferably 80-100 ℃, more preferably 85-95 ℃.If be lower than 80 ℃, then exist storage-stable poor, the tendency that the high temperature anti setoff properties descends.If surpass 120 ℃, then there is the tendency that can not improve low-temperature fixing and colorful light-permeable.

Total addition of wax is with respect to 100 weight portion binder resins, to be preferably the 5-30 weight portion.If be lower than 5 weight portions, then there is the tendency that to bring into play low-temperature fixing and release property effect.If greater than 30 weight portions, then there is the tendency of the particle be difficult to control small particle diameter.

Constitute as the present invention preferred second in addition, by using the wax of forming by second wax that contains aliphatic hydrocarbon and first wax that contains specific ester wax, the existence of the particle that can suppress aliphatic hydrocarbon not enter aggregated particle and suspend, and the size-grade distribution that suppresses aggregated particle broadens, and then relaxed when becoming shell that aggregated particle sharply produces secondary aggregation and particle carries out the phenomenon of thickization.

When in aqueous medium, forming aggregated particle with resin, colorant and aliphatic hydrocarbon wax, aliphatic hydrocarbon wax from the viewpoint of the fused property of resin, be the wax that is difficult to produce the cohesion class with resin.Particle that so exists wax can not enter in the aggregated particle and suspend and aggregated particle do not condense and size-grade distribution broadens easily.In addition, if in order to suppress these suspended particles and to prevent that size-grade distribution from broadening, and change the temperature and time of heat treated, then particle diameter carry out thickization.In addition as described later, when on the aggregated particle of this fusing, again resin particle being become shell, occur that aggregated particle sharply produces secondary aggregation and particle carries out the phenomenon of thickization.

Therefore, it has been generally acknowledged that first wax and resin carried out compatibilized when formation by above-mentioned second wax added heat-coagulation, and the second aliphatic hydrocarbon wax encourages the cohesion with resin, thereby can enter equably, prevented the existence of suspended particles.In addition, because the part has promoted first wax and the resin compatibleization, thereby there is the tendency that further improves low-temperature fixing.Yet, because the second aliphatic hydrocarbon wax does not carry out compatibilized with resin, so this second wax can be brought into play the function of optimizing the high temperature bonding-miry capacity.That is when, this first wax has the emulsification dispersion treatment of the second aliphatic hydrocarbon wax as the function of dispersing aid and as the function of low-temperature fixing auxiliary agent.

The fusing point Tmw1 of first wax is preferably 50-90 ℃.More preferably 60-85 ℃, more preferably 65-80 ℃.If be lower than 50 ℃, then there is the tendency of the thermotolerance variation of toner.If surpass 90 ℃, the tendency that then exist the coherency of wax to descend, UA free particle increases, can not bring into play above-mentioned effect in aqueous medium.

The fusing point Tmw2 of second wax is preferably 80-120 ℃, and more preferably 80-100 ℃, more preferably 85-95 ℃.If be lower than 80 ℃, then exist storage-stable poor, the tendency that the high temperature anti setoff properties descends.If surpass 120 ℃, then there is the tendency that can not improve low-temperature fixing, colorful light-permeable.

The fusing point Tmw2 of second wax preferably has the fusing point also higher 5-70 ℃ than the fusing point Tmw1 of first wax.If the said temperature difference is lower than 5 ℃, then there is the tendency that can not bring into play the function of optimizing the high temperature bonding-miry capacity in the function that so can separate wax effectively.When the said temperature difference surpasses 70 ℃ in addition, the tendency that existence descends with the coherency of resin, the suspended particles of wax increase.

Total addition of wax is preferably the 5-30 weight portion with respect to 100 weight portion binder resins.If be lower than 5 weight portions, then there is the tendency that to bring into play low-temperature fixing and release property effect.If surpass 30 weight portions, then there is the tendency of the particle that is difficult to control small particle diameter.

In addition when will being set at EW1 with respect to the part by weight of first wax of 100 weight portions of the wax in the wax particle dispersion, when the part by weight of second wax was set at TW2, TW2/EW1 was preferably the scope of 0.2-10.The scope of 1-9 more preferably.If be lower than 0.2, then exist to obtain the effect of high temperature bonding-miry capacity and the tendency of storage-stable variation.If surpass 10, then there is the tendency that can not realize low-temperature fixing and can not solve above-mentioned problem.

In addition, the wax particle dispersion preferably carries out the mixing and emulsifying dispersion treatment with first wax and second wax and makes.It is the method that first wax and second wax is heated emulsification treatment in the emulsification diverting device with certain mixing ratio.Can drop into respectively also and can drop into simultaneously, but preferably in the dispersion liquid that finally obtains, contain first wax, second wax with the state that mixes.If first wax, second wax are carried out the dispersion liquid that the emulsification dispersion treatment obtains respectively independently to be mixed with resin dispersion liquid and colorant dispersion, make it add heat-coagulation, then can not obtain above-mentioned effect, not enter in the fusing aggregated particle and exist suspended particles and aggregated particle not to condense and problem that size-grade distribution is easy to broaden thereby can not solve wax.When becoming shell in addition, can not solve aggregated particle fully and sharply produce secondary aggregation and the problem of thickization of particle.

In addition, during with anionic surfactant treatment wax, though improved dispersion stabilization, during the aggregated particle cohesion, thickization of particle diameter and be difficult to obtain the particle of sharp-pointed size-grade distribution.Therefore the wax particle dispersion preferably is the surfactant of major component in order to non-ionic surfactant, first wax and second wax is carried out the mixing and emulsifying dispersion treatment make.By being that the surfactant of major component mixes with ester wax and carries out dispersion treatment and make emulsified dispersed liquid in order to non-ionic surfactant, can suppress wax self cohesion and improve dispersion stabilization.So with these waxes and resin, when colorant dispersion makes aggregated particle, it is few to form free wax, the particle of the sharp-pointed size-grade distribution that particle diameter is little and narrow.

Owing to by surfactant, make the dispersed particle of wax, resin microparticle and many hydrones carry out hydration, particle is difficult to adhesion each other.By adding electrolyte the hydrone that carries out hydration is attracted by electrolyte, then particle is easy to adhesion.More particle is adhered each other, grows up to big particle.At this moment, if use the dispersion that forms by ionic surfactant, for example in resin dispersion, use the ionic species surfactant, in disperseing, uses by wax the anionic species surfactant, though then obtained aggregated particle, but when the hydrone that carries out hydration being attracted owing to the adding electrolyte, the particle that remaining wax particle repels, thus be easy to exist the wax of only independent suspension to condense the particle that forms.The existence that does not participate in the particle of this cohesion causes in film forming, image color decline and photographic fog increase when developing on the photoreceptor.The particle of these suspensions joins in the aggregated particle when the cohesion heating reaction process of certain hour in addition, still causes thickization of particle that obtains, the factor that broadens.

Relative therewith, in the wax dispersion that forms with non-ionic surfactant, the hydrone that carries out hydration is attracted by electrolyte by adding electrolyte, then particle is easy to adhesion.More particle is adhered each other, grows up to big particle.When the hydrone that carries out hydration being attracted by the adding electrolyte, owing to be non-ionic species surfactant, so the influence that the wax particle repels is little, the existence of the particle that the wax that can suppress only to suspend separately condenses can form and has sharp grain size distribution and particle uniformly.

Preferred form during as the formation aggregated particle, preferred constitute be: the major component of the surfactant that uses when making the resin particle dispersion of aggregated particle is a non-ionic surfactant, the major component that is used for the surfactant of colorant dispersion is a non-ionic surfactant, and the major component that is used for the surfactant of wax dispenser is a non-ionic surfactant." major component " described in above-mentioned refers to account for more than the 50wt% in the surfactant of use.

In addition, among the surfactant that is used for colorant dispersion and wax dispenser, preferred nonionic surfactants has 50-100wt% with respect to whole surfactant.More preferably has 60-100wt%.Constitute by this, can not exist in and not participate in the suspends colorants particle and the wax particle that condense in the aqueous medium, can form small particle diameter and have evenly and the core particle of the sharp-pointed size-grade distribution of narrow range.Also can obtain following effect: reduced by second resin particle that suspends, it has been adhered to equably be melted on the core particle, made sharp-pointed size-grade distribution.

The surfactant of the resin particle dispersion liquid that the resin particle when aggregated particle is generated disperses also is preferably the mixed system of non-ionic surfactant and ionic surfactant (being preferably anionic species), and preferred nonionic surfactants has 60-95wt% with respect to whole surfactant.Be preferably 65-90wt%, more preferably 70-90wt%.If less than 60wt%, then be difficult to obtain the aggregated particle of particle diameter unanimity.If greater than 95wt%, the dispersion instability of resin particle itself then.

In addition, as preferred form, also preferred following formation: be used for the glass or plastic containers of resin particle dispersion and the mixed style of ionic surfactant, and the major component that is used for the surfactant of wax dispenser only is a non-ionic surfactant.

In addition, as preferred form, also preferred following formation: be used for the glass or plastic containers of resin particle dispersion and the mixed form of ionic surfactant, the major component that is used for the surfactant of colorant dispersion only is a non-ionic surfactant, and the major component that is used for the surfactant of wax dispenser only is a non-ionic surfactant.When the mixed style of glass or plastic containers that is used for the resin particle dispersion and ionic surfactant, preferred nonionic surfactants has the amount of 60-95wt% with respect to whole surfactant.Be preferably 65-90wt%, more preferably 70-90wt%.If be lower than 60wt%, then be difficult to obtain the core particle of particle diameter unanimity.If surpass 95wt%, then there is the unsettled tendency of dispersion of resin particle itself.

In addition, in the formation of melt bonded again second resin particle in aggregated particle surface, the major component that is preferred for the surfactant of second resin dispersion is the formation of non-ionic surfactant.In addition, also be preferred for the formation of the mixing of the glass or plastic containers of second resin dispersion and ionic surfactant (being preferably the nonionic class), the formation of this moment preferably non-ionic surfactant has 50-95wt% with respect to whole surfactant.Be preferably 60-90wt%, more preferably 70-90wt%.If be lower than 50wt%, then be difficult to promote the second resin particle particulate attached on the core particle.If surpass 95wt%, then there is the unsettled tendency of dispersion of resin particle itself.

As the water-soluble inorganic salt that uses in the present embodiment, can list alkali metal salt and alkali earth metal salt.As alkaline metal, can list lithium, potassium, sodium etc., can list magnesium, calcium, strontium, barium etc. as alkaline-earth metal.Wherein, be preferably potassium, sodium, magnesium, calcium, barium.Counterion (constituting the negative ion of salt) as aforementioned bases metal or alkaline-earth metal can list chloride ion, bromide ion, iodide ion, carbonic acid ion, sulfate ion etc.

As non-ionic surfactant, can enumerate for example higher alcohol ethylene oxide adduct, the alkyl phenol ethylene oxide adduct, the fatty acid ethylene oxide adduct, the polyol fatty acid ester ethylene oxide adduct, the fatty acid amide ethylene oxide adduct, the ethylene oxide adduct of grease, polyethylene glycol type non-ionic surfactants such as polypropylene glycol ethylene oxide adduct, the fatty acid ester of glycerine, the fatty acid ester of pentaerythrite, the fatty acid ester of D-sorbite and sorbitan, the fatty acid ester of sucrose, the alkyl ether of other yuan alcohol, polyol-based non-ionic surfactants such as the fatty acid amide of alkane amine etc.

Can especially preferably use polyethylene glycol type non-ionic surfactants such as higher alcohol ethylene oxide adduct, alkyl phenol ethylene oxide adduct.

As aqueous medium, can list as water such as distilled water, ion exchange water, alcohols etc.They can use separately, also two or more can be used in combination.The content of aforementioned polar surfactant in aforementioned spreading agent with polarity can not be unified regulation, can suitably select according to purpose.

In addition, among the present invention, when also with non-ionic surfactant and ionic surfactant, as the polar surfactant, can list for example cationic surfactants such as anionic surfactants such as sulfuric ester salt, sulphonic acid ester salt, phosphates, soap class, amine salt type, quaternary etc.

As the object lesson of aforementioned anionic surfactant, can list neopelex, lauryl sodium sulfate, sodium alkyl naphthalene sulfonate, dialkyl sodium sulfosuccinate etc.

As the object lesson of aforementioned male ionic surface active agent, can list alkyl benzene alkyl dimethyl ammonium chloride, alkyl trimethyl ammonium chloride and distearyl ammonium chloride etc.They may be used alone, or two or more kinds may be used in combination.

(2) wax

As second wax, can suit to use fatty acid hydrocarbon waxs such as low-molecular-weight polypropylene wax, low molecular weight polyethylene wax, polypropylene-polyethylene and ethylene copolymers wax, microcrystalline wax, paraffin, the uncommon wax of Fei Xier-Top.

In addition, as second wax, the also preferred wax that uses the pure and mild unsaturated polybasic carboxylic acid of chain alkyl or its acid anhydrides and the reaction of Synthin wax to obtain.The carbon number of chain alkyl is preferably 4-30, and preferred acid number is 10-80mgKOH/g.

In addition, can also suit to use the wax that obtains by chain alkyl amine and unsaturated polybasic carboxylic acid or its acid anhydrides and the reaction of unsaturated hydro carbons wax; Perhaps by the pure and mild unsaturated polybasic carboxylic acid of long-chain fluoro-alkyl or its acid anhydrides and and the wax that obtains of unsaturated hydro carbons wax reaction.It is generally acknowledged that effect is as follows: promoted the demoulding effect that produces by chain alkyl; Make the dispersion phasic property that produces by ester group good with resin; By the permanance of vinyl generation, the optimization effect of bonding-miry capacity.

The acid number of preferred this wax is 10-80mgKOH/g, and fusing point is 80-120 ℃.More preferably acid number is 10-50mgKOH/g, and fusing point is 80-100 ℃, and further preferred acid number is 35-50mgKOH/g, and fusing point is 85-95 ℃.

Above-mentioned wax can show the high light transmittance of the non-bonding-miry capacity of oilless fixing and high-luster, OHP, can not reduce the high temperature keeping quality.When on thin paper, forming the image of 3 layers of color toner, effective especially aspect the separation property of the paper of raising and fixing roller or travelling belt.

In addition, can in spreading agent, make the finely dispersed small particle diameter particle of emulsification, and can evenly condense with resin pigment, not have the existence of suspension, suppress the color muddiness by mixing cohesion.Even be not coated with unction thus, also can prevent bonding-miry capacity, and the oilless fixing that realization has high-luster, light transmission under low-temperature fixing.

Wherein, if the carbon number of the chain alkyl of wax less than 4, then demoulding effect dies down, the non-bonding-miry capacity of separation property, high temperature reduces.If the carbon number of chain alkyl is greater than 30, then with the mixing coherency variation of resin, the dispersed reduction.If acid number less than 10mgKOH/g, then causes the reduction of the carried charge when toner uses for a long time.If acid number surpasses 80mgKOH/g, then moisture-proof reduces, and the photographic fog under the high humidity increases.If too high, the particle diameter of the generation particle when then being difficult to reduce the emulsified and dispersed particle generation.

If fusing point less than 80 ℃, then exists the storage-stable of toner to reduce the tendency of high temperature bonding-miry capacity variation.If fusing point is greater than 120 ℃, then low-temperature fixing dies down, the colorful light-permeable variation.The tendency that has the particle diameter of the generation particle when being difficult to reduce the emulsified and dispersed particle generation.

As alcohol, can use octanol (C ₈H ₁₇OH), dodecanol (C ₁₂H ₂₅OH), octadecanol (C ₁₈H ₃₇OH), nonacosanol (C ₂₉H ₅₉OH), pentadecanol (C ₁₅H ₃₁OH) etc. has the alcohol that carbon number is the alkyl chain of 4-30 scope.In addition, as amine, can suit to use the basic amine of N-methyl, nonyl amine, stearyl amine and 19 amine etc.As fluoroalkyl alcohol, can suit to use 1-methoxyl-(perfluoro-2-methyl isophthalic acid-propylene), Hexafluoro acetone and 3-perfluoro capryl-1,2-epoxypropane etc.

As unsaturated polybasic carboxylic acid or its acid anhydrides, can use in maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, the citraconic anhydride etc. more than a kind or 2 kinds.Wherein, more preferably maleic acid, maleic anhydride.As unsaturated hydro carbons wax, can suit to use ethene, propylene, alpha-olefin etc.

Use alcohol or amine to make unsaturated polybasic carboxylic acid or its acid anhydrides carry out polymerization, in the presence of dicumyl peroxide or tert-butyl hydroperoxide isopropyl monocarbonate etc., this polymkeric substance is added in the Synthin wax then and obtains.

As first wax, comprising at least a is the higher alcohol of 16-24 and at least a ester of forming of the higher fatty acid that carbon number is 16-24 by carbon number.By using this wax, the existence of the particle that can suppress aliphatic hydrocarbon wax not enter the fusing aggregated particle and suspend, the size-grade distribution that can also suppress aggregated particle broadens, and then can relax the phenomenon that aggregated particle sharply produces secondary aggregation and thickization of particle when becoming shell.Can also carry out low-temperature fixing.

As pure composition, except monohydroxy alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, what be fit to is ternary alcohols such as di-alcohols such as ethylene glycol, propylene glycol and polymer, glycerine and polyvalent alcohols such as polymer, pentaerythrite thereof, sorbitan, cholesterol etc.When these pure compositions were polyvalent alcohol, above-mentioned higher fatty acid can be the monobasic substituent, also can be polynary substituent.

Particularly, can suitably list stearyl stearate, cetyl palmitate, mountain Yu acid 20 diester, montanic acid octadecyl esters etc. are the ester class that the higher alcohol of 16-24 and higher fatty acid that carbon number is 16-24 are formed by carbon number, butyl stearate, mountain Yu acid isobutyl ester, the montanic acid propyl ester, oleic acid 2 one Octyl Nitrites etc. are the higher fatty acid of 16-24 and the ester class that low-grade monobasic alcohol is formed by carbon number, montanic acid monoethylene glycol ester, glycol distearate, glyceryl monostearate, one Glyceryl Behenate, tripalmitin, pentaerythrite one behenate, pentaerythrite dilinoleic acid ester, the pentaerythrite trioleate, pentaerythritol tetrastearates etc. are the higher fatty acid of 16-24 and the ester class that polyvalent alcohol is formed by carbon number, diethylene glycol one behenate, diethylene glycol two behenates, the dipropylene glycol monostearate, distearyl acid two glyceride, four glycerol stearates, six mountain Yu acid, four glyceride, ten stearic acid, ten glyceride etc. are the higher fatty acid of 16-24 and ester class that the polyvalent alcohol polymer is formed etc. by carbon number.These waxes can be used alone, and also can more than two kinds and use.

If the carbon number of pure composition and/or sour composition is lower than 16, then be difficult to bring into play function, and if, then be difficult to bring into play function as the low-temperature fixing auxiliary agent above 24 as dispersing aid.

As first wax, preferred to constitute be to comprise iodine number and be below 25, saponification number is the wax of 30-300.By also using second wax, can prevent thickization of granularity, the toner parent particle that can generate small particle diameter and have narrow size-grade distribution.Iodine number surpasses at 25 o'clock, and the suspension in aqueous medium increases, and can not evenly form aggregated particle with resin, colorant particle, and particle is easy to become thickization, wide size-grade distribution.When suspended particles remain in the toner in addition, be easy to film forming on photoreceptor etc.When the toner multilayer transfer of primary transfer, be difficult to relax repulsion by the charge effect generation of toner.The environment interdependence increases, and the charging property of material changes greatly when using continuously for a long time in addition, and has hindered the stability of image.Also be easy to produce the memory of developing in addition.If saponification number is lower than 30, then the existence of unsaponifiables, hydrocarbon increases, and is difficult to form the uniform aggregated particle of small particle diameter.The charging property of photoreceptor film forming, toner worsens, thereby charging property descends when causing using continuously.If saponification number is greater than 300, then the suspension in aqueous medium increases.Be difficult to relax repulsion by the charge effect generation of toner.Also can cause the increase of dispersing of photographic fog and toner.

This wax is preferably below the 8 weight % at the weight loss on heating under 220 ℃.If weight loss on heating greater than 8 weight %, then makes the glass transition temperature of toner reduce, damaged the storage-stable of toner.Bring bad influence for development, and produce photographic fog and photoreceptor film forming.The size-grade distribution of the toner that generates broadens.

For the molecular weight characteristics of this wax in gel permeation chromatography (GPC), preferably, number-average molecular weight is that 100-5000, weight-average molecular weight are 200～10000, the ratio of weight-average molecular weight and number-average molecular weight (weight-average molecular weight/number-average molecular weight) is 1.01～8, the ratio of Z-average molecular weight and number-average molecular weight (Z-average molecular weight/number-average molecular weight) is 1.02～10, and at molecular weight 5 * 10 ²～1 * 10 ⁴The zone in have a molecular weight peak-peak at least.More preferably, number-average molecular weight is 500-4500, weight-average molecular weight is 600～9000, the ratio of weight-average molecular weight and number-average molecular weight (weight-average molecular weight/number-average molecular weight) is 1.01～7, the ratio of Z-average molecular weight and number-average molecular weight (Z-average molecular weight/number-average molecular weight) is 1.02～9, further preferably, number-average molecular weight is 700-4000, weight-average molecular weight is 800～8000, the ratio of weight-average molecular weight and number-average molecular weight (weight-average molecular weight/number-average molecular weight) is 1.01～6, and the ratio of Z-average molecular weight and number-average molecular weight (Z-average molecular weight/number-average molecular weight) is 1.02～8.

If number-average molecular weight is less than 100, weight-average molecular weight is less than 200, and the molecular weight peak-peak also is positioned at less than 5 * 10 ²Scope, storage stability variation then.The operability that also exists in the developer descends, and hinders to keep the inhomogeneity tendency of toner concentration.Its result, toner is easy to produce the photoreceptor film forming.In addition, the tendency that broadens of the size-grade distribution of the toner that exist to generate.

If number-average molecular weight greater than 5000, weight-average molecular weight is greater than 10000, the ratio of weight-average molecular weight and number-average molecular weight (weight-average molecular weight/number-average molecular weight) is greater than 8, the ratio of Z-average molecular weight and number-average molecular weight (Z-average molecular weight/number-average molecular weight) is greater than 10, and the molecular weight peak-peak also is positioned at greater than 1 * 10 ⁴The zone, then exist the demoulding effect to die down, and the tendency of fixation performance function reduction such as fixation performance, anti setoff properties.The particle diameter of the generation particle the when emulsified particle that is difficult to reduce wax generates.

The endotherm peak temperature (fusing point Tmww) of preferably being measured by the DSC method and obtaining is 50-90 ℃ a material.Preferred 60-85 ℃ material, more preferably 65-80 ℃ material.If be lower than 50 ℃, then there is the tendency of the storage-stable difference of toner.If surpass 90 ℃, the particle diameter of the generation particle when then being difficult to reduce the emulsified particle generation.Exist the coherency of wax to descend, the tendency that UA free particle increases in aqueous medium.

As this wax, also preferred white awns caul-fat (meadowfoam oil) derivant, Brazil wax derivant, jojoba oil derivant, vegetable wax, beeswax, ceresine, Brazil wax, candelila wax, materials such as ceresin, rice wax, and also their derivant also is fit to use.Can only use a kind of wax, also can use the combination of two or more.

As white awns caul-fat derivant, the also preferred slaine of white awns caul-fat fatty acid, white awns caul-fat fatty acid, white awns caul-fat fatty acid ester, the white awns caul-fat of hydrogenation, white awns caul-fat three esters of using.Can make the emulsification dispersion of the uniform grain sizes distribution of small particle diameter.It is the preferable material of acquisition oilless fixing and long-life developer, transfer printing property improvement effect.These can use one or two or more kinds to be used in combination.

As white awns caul-fat fatty acid ester, for example be the ester of methyl, ethyl, butyl and glycerine, pentaerythrite, polypropylene glycol, trimethylolpropane etc., be preferably white awns caul-fat fatty acid pentaerythrite monoesters, white awns caul-fat fatty acid pentaerythrite three esters, white awns caul-fat fatty acid trihydroxy methyl propyl ester etc. especially.Anti setoff properties under the high temperature and cold-resistant bonding-miry capacity are all good.

The white awns caul-fat of hydrogenation is a dialogue awns caul-fat hydrogenation and make unsaturated link become the material of saturated bond.Anti setoff properties can be both improved, glossiness, light transmission can be improved again.

As the jojoba oil derivant, also preferred jojoba oil fatty acid, the slaine of jojoba oil fatty acid, jojoba oil fatty acid ester, hydrogenated jojoba oil, jojoba oil three esters, the maleic acid derivatives of epoxidation jojoba oil, the isocyanate polymer of jojoba oil polyol esters of fatty acids, the halogenation modification jojoba oil of using.Can make the emulsification dispersion of the uniform particle size distribution of small particle diameter.Resin and wax also can easily evenly mix dispersion.These materials are the preferable material that obtain oilless fixing and long-life developer, transfer printing property improvement effect.These can use one or two or more kinds to be used in combination.

As the jojoba oil fatty acid ester, for example be the ester of methyl, ethyl, butyl and glycerine, pentaerythrite, polypropylene glycol, trimethylolpropane etc., be preferably jojoba oil fatty acid pentaerythrite monoesters, jojoba oil fatty acid pentaerythrite three esters, jojoba oil fatty acid trihydroxy methyl propyl ester etc. especially.Anti setoff properties under the high temperature and cold-resistant bonding-miry capacity are all good.

Hydrogenated jojoba oil is to make unsaturated link become the material of saturated bond to the jojoba oil hydrogenation.Anti setoff properties can be both improved, glossiness, light transmission can be improved again.

Saponification number refers to the milligram number of the required potassium hydroxide of saponification 1 gram sample.And the summation that is equivalent to acid number and esterification number.Be to measure saponification number, in the alcoholic solution of the potassium hydroxide of about 0.5N, make the sample saponification, use the potassium hydroxide of the hydrochloric acid overtitration of 0.5N then.

Iodine number refers to when halogen acts on sample, and the amount of absorbed halogen is scaled iodine, with the value of representing with respect to the gram numbers of 100 gram samples.And be the gram number of absorbed iodine.This value is big more, and the degree of unsaturation of fatty acid is just high more in the expression sample.The alcoholic solution of iodine and mercuric chloride (II) or the glacial acetic acid solution of lodine chloride are added in the chloroform or carbon tetrachloride solution of sample, and carry out titration to placing back unreacted residual iodine, to calculate the iodine amount that absorbs with sodium thiosulfate standard solution.

By sample cell accurately being weighed into 0.1mg (W1mg), 10～15mg sample is placed this groove, and accurately be weighed into 0.1mg (W2mg), measure weight loss on heating thus.Sample cell is placed differential thermal balance, and the sensitivity of will weighing is set at 5mg and begins measurement.After measuring, according to chart, the loss in weight when specimen temperature reaches 220 ℃ reads 0.1mg (W3mg).Employed device is vacuum science and engineering system TGD-3000, and heating rate is 10 ℃/minute, and maximum temperature is 220 ℃, and the residence time is 1 minute, and the result is obtained by following formula: weight loss on heating (%)=W3/ (W2-W1) * 100.

The light transmission in the coloured image can be improved thus, the anti setoff properties of roller can be improved simultaneously.Can be suppressed in addition to produce on the carrier to consume also and can make the developer ILS.

In addition, as second wax, also the material of the derivant of preferred hydroxy stearic acid, fatty acid glyceride, glycol fatty acid ester, sorbitan fatty acid esters replaces above-mentioned ester type waxes, perhaps also uses.One or two or more kinds is used in combination also is effective.Can make the small particle diameter particle that uniformly emulsify disperses, by with second wax and usefulness, can prevent thickization of granularity, the toner parent that can generate small particle diameter and have narrow size-grade distribution.

Even be not coated with unction, also can prevent bonding-miry capacity, and the oilless fixing that realization has high-luster, light transmission under low-temperature fixing.In oilless fixing, can make the developer ILS in addition, can also keep the homogeneity in the developer, also can suppress the generation of developing and remembering.

As the hydroxy stearic acid derivant, preferable material is the 12-methyl hydroxystearate, 12-hydroxy stearic acid butyl ester, propylene glycol list 12-hydroxy stearic acid ester, glycerine list 12-hydroxy stearic acid ester and glycol monomethyl 12-hydroxy stearic acid ester etc.These materials have following effect: in oilless fixing, prevent to be wound up on the paper and prevent film forming.

As fatty acid glyceride, preferable material is stearine, glycerol distearate, tristearin, glycerine monopalmitate, dipalmitin, tripalmitin, Tridocosanoin, glycerine two behenates, glycerol tri-docosanoic acid ester, monomyristin, glycerine two myristinates, myristin etc.These materials have following effect: the cold bonding-miry capacity in oilless fixing during mixing low temp and prevent transfer printing decline.

As glycol fatty acid ester, preferable material is glycol fatty acid esters such as methyl glycol fatty acid esters such as propylene glycol monopalmitate, propylene glycol monostearate, and ethylene glycol monostearate and glycol monopalmitate.These materials have following effect: when improving oilless fixing, improve the lubricity in developing, and prevent to consume on carrier.

As sorbitan fatty acid esters, preferable material is sorbitan monopalmitate, sorbitan monostearate, sorbitan tripalmitate and sorbitan tristearate.Stearate, hexane diacid and the stearic acid of further preferred pentaerythrite or the materials such as mixed ester of oleic acid, these materials can use separately or two or more are used in combination.These materials have following effect: in oilless fixing, prevent to be wound on the paper and prevent film forming.

In order to make these waxes not break away from suspension when mixing cohesion, and wrap in equably in the resin, the fineness of dispersion distribution of wax, the composition of wax, the dissolution characteristics of wax also are affected.

Wax dispersion of nano-particles liquid can be by heating wax in ion exchange water, and fusion is distributed in the aqueous medium that has added surfactant, prepares thus.

The emulsified dispersion of wax this moment, make the dispersion particle diameter of wax from the small particle diameter side particle volume diameter cumulative distribution in when accumulative total, reach the following stated scope, promptly, disperseing particle diameter is that 16% particle diameter (PR16) is 20～200nm, 50% particle diameter (PR50) is 40～300nm, 84% particle diameter (PR84) is below the 400nm, and PR84/PR16 is 1.2～2.0.Preferably, the following particle of 200nm is more than the 65 volume %, and the particle that surpasses 500nm is below the 10 volume %.

Preferably, 16% particle diameter (PR16) the particle volume diameter cumulative distribution during from small particle diameter side accumulative total is 20～100nm, and 50% particle diameter (PR50) is 40～160nm, and 84% particle diameter (PR84) is below the 260nm, and PR84/PR16 is 1.2～1.8.The following particle of preferred 150nm is more than the 65 volume %, and the particle that surpasses 400nm is below the 10 volume %.

More preferably, 16% particle diameter (PR16) the particle volume diameter cumulative distribution during from small particle diameter side accumulative total is 20～60nm, and 50% particle diameter (PR50) is 40～120nm, and 84% particle diameter (PR84) is below the 220nm, and PR84/PR16 is 1.2～1.8.The following particle of preferred 130nm is more than the 65 volume %, and the particle that surpasses 300nm is below the 10 volume %.

Mix cohesion and when forming aggregated particle at resin particle dispersion liquid and colorant particle dispersion liquid and wax particle dispersion, by fine dispersion 50% particle diameter (PR50) is 20～200nm, wax enters between resin particle easily, can prevent the cohesion between the wax self, can disperse uniformly.Thereby the wax particle can enter in the resin particle, and the particle that is suspended in the water disappears.

In aqueous medium when heating aggregated particle and the aggregated particle that obtains melting, because capillary relation, the resin particle of fusing has surrounded the wax particle of fusing, forms the form that comprises, and release agent is easy to wrap in the resin in addition.

If PR16 greater than 160nm, 50% particle diameter (PR50) greater than 200nm, PR84 also greater than 300nm, PR84/PR16 also the particle greater than 2.0, below the 200nm surpass 65 volume %, surpass the particle of 500nm greater than 10 volume %, then wax is difficult to enter between resin particle, and more appearance is the situation of the cohesion between wax self only.In addition, also exist wax can't enter between resin particle, the tendency that the particle that suspends in water increases.When heating aggregated particle in aqueous medium and the aggregated particle that obtains melting, the resin particle of fusing is difficult to form the form of the wax particle that comprises fusing, and wax is difficult to be included in the resin.And then when adhere to merging resin, the quantitative change of exposing free wax on toner parent surface is many, to the film forming of photoreceptor, the consumption of carrier is increased, and the processing reduction during development, and be easy to generate the memory of developing.

If PR16 also less than 1.2, then is difficult to keep disperse state less than 40nm, PR84/PR16 less than 20nm, 50% particle diameter (PR50), wax produces cohesion again when placing, and the shelf-stability of size-grade distribution is bad.And it is big that the load during dispersion becomes, and it is big that heating becomes, and throughput rate reduces.

In addition, because 50% particle diameter (PR50) of the resin particle when 50% particle diameter (PR50) ratio in the particle volume diameter cumulative distribution during the small particle diameter side of the wax particle from be distributed to wax particle dispersion accumulative total forms aggregated particle is littler, wax enters between resin particle easily, can prevent the cohesion between the wax self, and can disperse uniformly.Wax can enter in the resin particle, thereby the particle that suspends in water disappears.Heat aggregated particle in aqueous medium, and when obtaining the cohesion set particle of fusion, because capillary relation, the resin particle of fusing forms the form of the wax particle that comprises fusing, wax is easy to be included in the resin.More preferably, 50% particle diameter (PR50) than resin particle is also little more than 20%.

Emulsification disperses with the effect of the wax concentration high shear force that rotary body was produced that is the wax fused solution that forms of the following fusion of 40wt% by becoming certain interval and high speed rotating with fixed body will to make aforementioned wax in the medium of the spreading agent under the temperature more than having added the fusing point that remains on wax, thus can be with the fine dispersion of wax particle.

In the groove of the constant volume shown in Fig. 3,4, in the gap that is provided with on the cell wall about 0.1mm～10mm, by make rotary body with more than the 30m/s, be preferably more than the 40m/s, the high speed rotating more than the 50m/s more preferably, water system is applied powerful shearing force, thereby obtain the emulsification dispersion of fine particle size.By the processing time be processing about 30s～5min, can form dispersion.

In addition, by the gap about 1～100 μ m is set with respect to the fixing fixed body shown in Fig. 5,6, and apply with more than the 30m/s, more than the preferred 40m/s, the more preferably strong shearing force effect of the rotary body of the rotation of the speed more than the 50m/s, make fine dispersion thus.

By the such decollator of homogenizer, also can make fine particle form narrower sharp-pointed size-grade distribution.And even long-time the placement, the particulate that forms dispersion can not condense yet again, can keep stable disperse state, improves the shelf-stability of size-grade distribution.

When the fusing point of wax is higher, can make the solution of fusion by heating under high pressure conditions.In addition, wax is dissolved in the oil-based solvent.Also can use the decollator shown in Fig. 3,4,5,6 that this solution and surfactant or polyelectrolyte are distributed in the water with the form of particulate together, afterwards, heating or decompression are evaporated this oil-based solvent and are obtained fine dispersion.

Granulometry can use the hole field boundary to make the laser diffraction granularity analyzer (LA920) of manufacturing, the laser diffraction granularity analyzer mensuration such as (SALD2100) of Shimadzu Seisakusho Ltd..

(3) resin

For example can list the thermoplastic bonded resin as the resin microparticle of the toner of the present embodiment.Particularly, can list styrene, to phenylethylenes such as chlorostyrene and α-Jia Jibenyixi; Acrylic monomers such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, lauryl acrylate, 2-EHA; Methacrylic monomers such as methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, lauryl methacrylate, methacrylic acid 2-Octyl Nitrite; Acrylic acid, methacrylic acid, maleic acid, fumaric acid etc. have carboxyl as the homopolymer such as unsaturated polybasic carboxylic acid class monomer of dissociation group, the multipolymer that making up more than 2 kinds of these monomers formed, or their potpourri etc.

The content of the aforementioned resin particle in resin particle dispersion liquid is generally 5～50 weight %, is preferably 10～30 weight %.The monodisperse polystyrene that can use several types is measured the molecular weight of resin, wax and toner as standard sample by gel permeation chromatography (GPC).

Device is the HPLC8120 series that TOSOH company makes, use TSK gel superHM-H H4000/H3000/H2000 (diameter 7.8mm, 150mm * 3) as analytical column, THF (tetrahydrofuran) is as eluent, its flow is 0.6ml/ minute, sample solution concentration is 0.1wt%, injection rate IR is 20 μ L, detecting device is RI, measuring temperature is 40 ℃, the mensuration pre-treatment is: with sample dissolution THF in, filter with the filtrator of 0.45 μ m afterwards, the resinous principle of the adjuvant of having removed silicon dioxide etc. is measured.Measuring condition is that the molecular weight distribution of target sample is comprised in the following scope, and described scope is that the logarithm value and the calculated value of the molecular weight in the analytic curve that is obtained by a plurality of monodisperse polystyrene standard specimens forms straight line.

The mensuration of the wax that obtains for reacting by long-chain alkyl alcohol, unsaturated polybasic carboxylic acid or its acid anhydride and Synthin wax, the GPC-150C that device is to use WATERS company to make, with Shodex HT-806M (8.0mmI.D.-30 cm x 2) as analytical column, use neighbour-dichloro-benzenes as eluent, its flow is 1.0mL/ minute, sample solution concentration is 0.3wt%, injection rate IR is 200 μ L, detecting device is RI, temperature is 130 ℃, the mensuration pre-treatment is: in solvent, the metal sintering filtrator with 0.5 μ m carries out filtration treatment then with sample dissolution.Measuring condition is that the molecular weight distribution of target sample is comprised in the following scope, and described scope is that the logarithm value and the calculated value of the molecular weight in the analytic curve that is obtained by a plurality of monodisperse polystyrene standard specimens forms straight line.

In addition, the permanent load extrusion type capillary rheometer (CFT-500) that can use Tianjin, island manufacturing company to make is measured the softening point of binder resin.To be about 9.8 * 10 ⁵N/m ²Load be applied to 1cm by plunger ³Sample on, simultaneously with 6 ℃/minute programming rate heating sample, make sample from mouthful mould of diameter 1mm and long 1mm, extrude.According in the throw of poston of this plunger and the temperature relation with the relation of intensification temperature characterisitic, the temperature that begins to rise when throw of poston begins temperature (Tfb) for flowing out, try to achieve minimum value and 1/2 of the difference that flows out end point at curve, then, with the minimum value addition of the value that obtains and curve and the temperature of the position of the point that obtains as the melt temperature in 1/2 method (softening point Tm).

In addition, the glass transition point of resin can be measured with differential scanning calorimeter (DSC-50 of Shimadzu Seisakusho Ltd.).Specimen temperature is risen to 100 ℃, after placing 3 minutes under this temperature, again with 10 ℃/minute cooling rate cool to room temperature, the sample that obtains is thus measured the hot resume of this sample with 10 ℃/minute programming rate intensification, at this moment, the extended line of the baseline below the glass transition point and expression peak value rising rising part are called glass transition point to the temperature of the point of crossing of the tangent line of the maximum inclination between the peak of peak value.

That can use that differential scanning calorimeter (Tianjin, island manufacturing company make DSC-50) measures wax measures the fusing point in endothermic peak that obtains by the DSC method, this method is to be warmed up to 200 ℃ with 5 ℃/minute programming rate, be incubated 5 minutes, be cooled fast to 10 ℃ again, place after 15 minutes, heat up with 5 ℃/minute speed, then, obtain fusing point by heat absorption (fusing) peak value.The sample size that drops in the sample cell is 10mg ± 2mg.

(4) pigment

As the colorant that uses in the present embodiment (pigment),, can preferably use the metal complex of carbon black, iron oxide black, graphite, nigrosine, azo dyes as black pigment.

As yellow uitramarine, what be fit to is by acetoacetate aromatic radical amide-type monoazo yellow pigments such as C.I. pigment yellow 1,3,74,97 and 98, C.I. pigment Yellow 12,13, acetoacetate aromatic radical amide-type two azophosphine pigment such as 14 and 17, C.I. solvent yellow 19,77 and 79, perhaps C.I. disperse yellow 164 mixes, and particularly preferably is the such benzimidazolone series pigments of C.I. pigment yellow 93,180 and 185.

As magenta pigment, can preferably use C.I. pigment red 48,49:1,53:1,57,57:1,81, red pigments such as 122 and 5, C.I. solvent red 49,52, orchils such as 58 and 8.

As green pigment, can preferably use the C.I. pigment blue 15: the blueness of 3 phthalocyanines such as grade and derivant thereof is dyed pigment.Addition is preferably, and is 3～8 weight portions with respect to per 100 weight portion binder resins.

The median particle diameter of each particle is generally below the 1 μ m, is preferably 0.01～1 μ m.When above-mentioned median particle diameter during greater than 1 μ m, the size distribution of the toner that the final electrostatic charge image developing that obtains is used broadens, and produces free particle, causes Performance And Reliability to reduce easily.On the other hand, when aforementioned median particle diameter is in above-mentioned scope, then there is not above-mentioned shortcoming, and the minimizing of the uneven distribution between the toner, improved the dispersion of pigment particles in toner, be favourable aspect the uneven reduction of performance or reliability.In addition, can use the hole field boundary to make the aforementioned median particle diameters of measurement such as laser diffraction granularity analyzer (LA920) of manufacturing.

(5) external additive

As the external additive in the present embodiment, can mix and add the inorganic micro powder end.As external additive, can use metal oxide micropowders such as silicon dioxide, aluminium oxide, titanium dioxide, zirconium dioxide, magnesium oxide, ferrite and magnetic iron ore, titanates such as barium titanate, calcium titanate, strontium titanates, zirconate or their potpourris such as barium zirconate, calcium zirconate, strontium zirconate.As required, external additive can be handled through hydrophobicity.

As the silicone oil material that external additive is handled, the material shown in the preferred Chemical formula 1.

(Chemical formula 1)

(in the formula, R ²The expression carbon number is 1～3 alkyl, R ³The expression carbon number is 1～3 alkyl, halogen modified alkyl, phenyl or substituted-phenyl, R ¹The expression carbon number is that 1～3 alkyl or carbon number are 1～3 alkoxy, and m and n represent 1 to 100 integer.)

The external additive that uses following at least a above silicone oil to handle can suit: dimethyl silicon oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, ring-type dimethyl silicon oil, epoxy radicals modified silicon oil, fluorine modified silicon oil, amino-modified silicone oil and chlorphenyl modified silicon oil.For example, can enumerate SH200, SH510, SF230, SH203, BY16-823 or the BY16-855B etc. that make by Toray-Dow Corning company.

This processing comprises following method: by the method for using Henschel mixer mixers such as (the system FM20B of Mitsui mine society) that materials such as external additive and silicone oil are mixed; And to the method for outside additive spray silicone oil material; With the silicone oil material dissolves or after being distributed in the solvent and external additive mix, remove the method for desolvating and being prepared etc. thereafter.With respect to 100 weight portion external additives, the silicone oil material preferably adds 1～20 weight portion.

As silane coupling agent, can suit to use dimethyldichlorosilane, trimethyl chlorosilane, allyldimethylcholrosilane, hexamethyldisilazane etc.Can wait by dry process or wet processed and carry out the silane coupling agent processing, in this dry process, make external additive form grey pulpous state by stirring to wait, and make silane coupling agent and its reaction of gasification; In this wet processed, be to be added drop-wise in the external additive and to react with being dispersed in silane coupling agent in the solvent.

It also is preferred handling aftertreatment silicone oil based material at silane coupling agent in addition.

Can utilize amino-modified silicone oil shown in amino silane, the following Chemical formula 2 or epoxy radicals modified silicon oil to handle external additive with positively charged.

(Chemical formula 2)

(wherein, R ¹And R ⁶Expression hydrogen, carbon number are alkyl, alkoxy or the aryl of 1-3, R ²The expression carbon number is alkylidene or the phenylene of 1-3, R ³Represent nitrogenous heterocyclic organic group, R ⁴And R ⁵Expression hydrogen, carbon number are alkyl or the aryl of 1-3, and m is the number more than 1, and n and q comprise 0 positive integer, and n+1 represents the positive number more than 1.)。

In addition, handle in order to improve hydrophobicity, also preferred compositions is used the processing that utilizes hexamethyldisilazane, dimethyldichlorosilane or other silicone oil to carry out.For example, preferably use in dimethyl silicon oil, methyl phenyl silicone oil or the alkyl modified silicon oil at least a with on handle.

Preferred formation is that with respect to the toner parent particle of 100 weight portions, outside interpolation 1～6 weight portion mean grain size is the external additive of 6nm～200nm.If mean grain size is less than 6nm, then be easy to generate suspended particles and to the photoreceptor film forming.Reverse transfer printing takes place when being difficult to avoid transfer printing.If mean grain size is greater than 200nm, then the flowability of toner reduces.If the external additive that is added is less than 1 weight portion, then the flowability of toner reduces, and reverse transfer printing takes place when being difficult to avoid transfer printing.If surpass 6 weight portions, then be easy to generate suspended particles and to the photoreceptor film forming.The non-bonding-miry capacity variation of high temperature.

In addition, also preferred formation is that with respect to the toner parent particle of 100 weight portions, outside interpolation 0.5～2.5 weight portion mean grain size is the external additive of 6nm～20nm; And with respect to the toner parent particle of 100 weight portions, outside at least to add 0.5～2.5 weight portion mean grain size be the external additive of 20nm～200nm.Utilize this formation, the external additive that functions of use is different can improve charged giving property, charged retentivity, and the reverse transfer printing during at transfer printing, literal desalination and toner disperse wideer surplus is provided.This moment, mean grain size was that the calcination loss of weight of the external additive of 6nm～20nm is preferably 0.5～20wt%, and the calcination loss of weight of the external additive of mean grain size 20nm～200nm is preferably 1.5～25wt%.Calcination loss of weight by making mean grain size 20nm～200nm is the calcination loss of weight of the external additive of 6nm～20nm greater than mean grain size, can bring into play charged retentivity, and the reverse transfer printing during simultaneously to transfer printing, literal desalination produce effect.

By the calcination loss of weight of designated external adjuvant, the desalination of the reverse transfer printing in the time of can guaranteeing transfer printing, literal provides wideer surplus with dispersing.And can improve the interior processing of developer, thereby increase the homogeneity of toner concentration.The generation of memory can also suppress to develop.

If mean grain size be the calcination loss of weight of 6nm～20nm less than 0.5wt%, then the transfer printing boundary to reverse transfer printing and literal desalination narrows down.If the calcination loss of weight is greater than 20wt%, surface treatment is inhomogeneous, produces charged inequality.The calcination loss of weight is preferably 1.5～17wt%, more preferably 4～10wt%.

If mean grain size be the calcination loss of weight of 20nm～200nm less than 1.5wt%, then the transfer printing boundary in oppositely transfer printing and literal desalination narrows down.If the calcination loss of weight is greater than 25wt%, surface treatment is inhomogeneous, produces charged inequality.The calcination loss of weight is preferably 2.5～20wt%, more preferably 5～15wt%.

In addition, also be preferably as follows formation: with respect to 100 weight portion toner parent particles, outside at least 0.5～2 weight portion mean grain size of adding is that 6nm～20nm, calcination loss of weight are that external additive, 0.5～3.5 weight portion mean grain size of 0.5～20wt% is that 20nm～100nm, calcination loss of weight are that external additive, 0.5～2.5 weight portion mean grain size of 1.5～25wt% is that 100nm～200nm, calcination loss of weight are the external additive of 0.1～10wt%.By specifying the formation of this mean grain size external additive different with the function of calcination loss of weight, can obtain following effect: improve charged giving property, charged retentivity, in reverse transfer printing when improving transfer printing, the literal desalination, remove the attachment of carrier surface.

In addition, the formation that also is preferably as follows: further with respect to 100 weight portion toner parent particles, adding 0.2～1.5 weight portion mean grain size from the outside is that 6nm～200nm, calcination loss of weight are the external additive with positively charged of 0.5～25wt%.

The effect of adding the external additive with positively charged is, excessive charged in the time of can restraining toner and use for a long time prolongs life-span of developer more.In addition, in the time of can also obtaining to be suppressed at transfer printing by the effect of dispersing of the excessive charged toner that causes.And, can stop the consumption on the carrier.If the external additive of the positively charged that is added then is difficult to obtain these effects less than 0.2 weight portion.If it is greater than 1.5 weight portions, then the photographic fog when developing increases.The calcination loss of weight is preferably 1.5～20wt%, more preferably 5～19wt%.

Dry loss of weight (%) can be determined according to following manner.In the container of drying, placement cooling, accurately weighing in advance, get about 1g sample, accurately weighing.With air drier (105 ℃ ± 1 ℃) dry 2 hours.In desiccator, place cooling after 30 minutes, accurate its weight of weighing, calculate dry loss of weight by following formula:

Dry loss of weight (%)=(loss of weight (the gram)/sample size (gram) that causes by drying) * 100.

The calcination loss of weight can be determined according to following manner.In the magnetic crucible of drying, placement cooling, accurately weighing in advance, get about 1g sample, accurately weighing.Calcination is 2 hours in being set at 500 ℃ electric furnace.In desiccator, place cooling after 1 hour, accurate its weight of weighing, calculate the calcination loss of weight by following formula:

Calcination loss of weight (%)=(loss of weight (the gram)/sample size (gram) that causes by calcination) * 100.

(6) Powder Physical of toner

In the present embodiment, contain binder resin, the volume average particle size of the toner parent particle of colorant and wax is 3～7 μ m, the content of toner parent particle that has the particle diameter of 2.52～4 μ m in number distributes is 10～75 number %, the toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is 25～75 volume %, the toner parent particle that has the particle diameter more than the 8 μ m in volume distributed median is below the 5 volume %, the volume % of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is set at V46, when the number % of toner parent particle that has the particle diameter of 4～6.06 μ m during number distributed is set at P46, P46/V46 is the scope of 0.5-1.5, the coefficient of variation of volume average particle size is 10-25%, and the coefficient of variation of number size distribution is 10-28%.

Preferably, the volume average particle size of toner parent particle is 3～6.5 μ m, the content of toner parent particle that has the particle diameter of 2.52～4 μ m in number distributes is 20～75 number %, the toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is 35～75 volume %, the toner parent particle that has the particle diameter more than the 8 μ m in volume distributed median is below the 3 volume %, the volume % of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is set at V46, when the number % of toner parent particle that has the particle diameter of 4～6.06 μ m during number distributed is set at P46, P46/V46 is the scope of 0.5-1.3, the coefficient of variation of volume average particle size is 10-20%, and the coefficient of variation of number size distribution is 10-23%.

More preferably, the volume average particle size of toner parent particle is 3～5 μ m, the content of toner parent particle that has the particle diameter of 2.52～4 μ m in number distributes is 40～75 number %, the toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is 45～75 volume %, the toner parent particle that has the particle diameter more than the 8 μ m in volume distributed median is below the 3 volume %, the volume % of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is set at V46, when the number % of toner parent particle that has the particle diameter of 4～6.06 μ m during number distributed is set at P46, P46/V46 is the scope of 0.5-0.9, the coefficient of variation of volume average particle size is 10-15%, and the coefficient of variation of number size distribution is 10-18%.

Toner parent particle with above-mentioned feature can take into account high-resolution picture quality so that prevent in the tandem transfer printing reverse transfer printing, prevent literal desalination and oilless fixing.Attritive powder can influence flowability, picture quality, storage-stable, the film forming on photoreceptor and developer roll, the transfer article, the time variability of toner, the multilayer transfer in the transfer printing, particularly tandem moor in the toner.In addition, also can influence non-bonding-miry capacity, glossiness and light transmission in the oilless fixing.Be combined with in order to realize oilless fixing in the toner of waxes such as wax, the amount of attritive powder can influence taking into account between oilless fixing and the tandem transfer printing.

If volume average particle size surpasses 7 μ m, then picture quality and transfer printing can not take into account simultaneously.If the treatment characteristic of the toner particle during volume average particle size less than 3 μ m, is then developed reduces.

If the content of toner parent particle of particle diameter that has 2.52～4 μ m during number distributes is less than 10 number %, then picture quality and transfer printing can not take into account simultaneously.If it is greater than 75 number %, the processing difficulty of the toner parent particle in then developing.On photoreceptor, developer roll, transfer article, be easy to film forming in addition.In addition, because the stickability of micropowder and hot-rolling is big, so have the tendency that is easy to bonding-miry capacity.In addition in tandem, the cohesion of toner strengthens, and the transfer printing that is easy to produce second kind of color when multilayer transfer is bad.Need suitable scope.

Surpass 75 volume % if having the toner parent particle of the particle diameter of 4～6.06 μ m in the volume distributed median, then picture quality and transfer printing can not take into account simultaneously.If it is less than 30 volume %, then image quality decrease.

The toner parent particle that has the above particle diameter of 8 μ m in the volume distributed median surpasses 5 volume % and contains sometimes image quality decrease.And then become the bad reason of transfer printing.

The volume % of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is set at V46, when the number % of toner parent particle that has the particle diameter of 4～6.06 μ m during number distributed is set at P46, P46/V46 was less than 0.5 o'clock, the micropowder amount is too much, mobile decline, transfer printing is poor, the background fog variation.When greater than 1.5 the time, have a large amount of big particles, and size-grade distribution broadens, can not form high image quality.

The purpose of regulation P46/V46 is can be used for conduct to make the toner particle become small particle diameter, and the index that its distribution of particles is narrowed down.

Coefficient of variation is meant, the value that obtains divided by mean grain size with the standard deviation of toner particle diameter.This coefficient of variation is obtaining based on the particle diameter that uses Coulter counter (manufacturing of Coulter company) mensuration.Standard deviation is when the mensuration of the particle diameter that carries out n particle, by square trying to achieve divided by the square root of the value of (n-1) of the difference of the mean value of each measured value.

It is the expansion degree that coefficient of variation is represented size-grade distribution.If the coefficient of variation of volumetric particle size distribution is less than 10%, or the coefficient of variation of number size distribution then produces the difficulty that becomes less than 10%, becomes the reason that cost increases.If the coefficient of variation of volumetric particle size distribution is greater than 25%, perhaps the coefficient of variation of number size distribution is greater than 28%, then size-grade distribution broadens, the coherency grow of toner, and this may cause not good in film forming, transfer printing on the photoreceptor, residual in no cleaning toner to reclaim difficulty.

For the mensuration of size-grade distribution, can use Coulter counter TA-II type (manufacturing of Coulter company), connect the interface (day section's machine is made) and the personal computer that are used to export number distribution, volume distributed median, measure thus.Measure about will about 2mg and join in about 50ml electrolytic solution, added surfactant (lauryl sodium sulfate) in this electrolytic solution, so that concentration reaches 1wt% with toner.Use the ultrasonic dispersing device that the electrolytic solution of the sample that suspending is carried out about 3 minutes dispersion treatment, then, use the Coulter counter TA-II type of aperture 70 μ m to measure.In this 70 μ m aperture system, the measured zone of size-grade distribution is 1.26 μ m～50.8 μ m.But, be unsuitable for actual use less than the zone of 2.0 μ m because externally under the influence of noise etc. the repeatability of measuring accuracy or mensuration low.Therefore, measured zone is set to 2.0 μ m～50.8 μ m.

(7) carrier

The suitable use of the carrier of the present embodiment contained the carrier of magnetic particle as core, and wherein the surface of core covers with the fluorine modified organic silicone resin that contains amino silicane coupling agent.In addition, be composite magnetic particle at least with magnetic particle and adhesive resin, this magnetic particle surface of use preferably carrier of the resin covering of forming by the fluorine modified organic silicone resin that contains amino silicane coupling agent.

As the adhesive resin that constitutes this magnetic particle, preferred heat-curing resin.As heat-curing resin, phenolics, epoxy resin, polyamide, melamine resin, urea resin, unsaturated polyester resin, alkyd resin, xylene resin, acetylguanamine resin, furane resin, organic siliconresin, polyimide resin, urethane resin are arranged, these resins can use separately, also can mix use more than two kinds, preferably contain phenolics at least.

For complex particles of the present invention, preferably, mean grain size is preferably 10-50 μ m, 10-40 μ m more preferably, and 10-30 μ m more preferably most preferably is the spherical particle of 15-30 μ m.In addition its characteristic preferably, proportion is 2.5-4.5, especially is 2.5-4.0, and the BET specific surface area that is obtained by the absorption of the nitrogen of carrier is 0.03-0.3m ²/ g.When the mean grain size of carrier was lower than 10 μ m, because the atomic rate that exists uprises in the distribution of carrier particle, the magnetization of each carrier particle of these carrier particles reduced, thereby carrier is easy to develop on photoreceptor.In addition, if the mean grain size of carrier surpasses 50 μ m,, produce toner and disperse then because the specific surface area of carrier particle diminishes, and the toner confining force dies down.In addition, for comprising the panchromatic of many whole printings, the reproduction of whole printing is poor especially, so not preferred.

Be with regard to the carrier of core particle with in the past ferrite just, because proportion is greater than 5-6, particle diameter is also greater than 50-80 μ m in addition, so the BET specific surface area is little value, and a little less than the Combination when stirring with toner, charged rising during the supply toner is not enough and consumed a large amount of toners, when supplying a large amount of toners, often sees that a large amount of photographic fogs produce.In addition, when the concentration rate of toner and carrier is not controlled at narrower scope, be difficult to take into account simultaneously the reduction of dispersing of image color and photographic fog, toner.But by using the big carrier of specific surface area value, even the concentration rate of toner and carrier is controlled in the scope of broad, picture quality also is difficult to produce deterioration, can carry out the control of toner concentration roughly.

In addition, above-mentioned toner is formed be bordering on spherical shape, and the specific surface area value also approaches carrier.Can when stirring, mix more equably thus with toner.When supply during toner, have good charged rising, even the concentration rate of toner and carrier is controlled at wideer scope, picture quality also is difficult to variation, can take into account image color and photographic fog simultaneously, the reduction toner disperses.

At this moment, if the specific surface area value of toner is set at TS (m ²/ g), the specific surface area value of carrier is set at CS (m ²/ g), then, can make stable image quality by making TS/CS satisfy the relation of 2-110.Be preferably 2-50, more preferably 2-30.If less than 2, then be easy to take place adhering to of carrier.In addition greater than 110 o'clock, for take into account image color and photographic fog simultaneously, the reduction toner disperses and make the concentration rate of toner and carrier become narrow, picture quality is easy to variation.Be with regard to the carrier of core particle with in the past ferrite just, specific surface area is little value, shape instability concerning the toner of grinding mode in the past in addition, and the specific surface area value is big value.

Composite magnetic particle can be with following method manufacturing: in the presence of magnetic particle and base catalyst, stir phenols and aldehydes on the limit in aqueous medium, the limit makes phenols and aldehydes reaction and solidifies, and generates the composite magnetic particle that contains magnetic particle and phenolics.

The control of the mean grain size of the composite magnetic particle that obtains can be according to the water yield of using, and according to the mode of suitable shearing or compacting, the peripheral speed of the stirring vane by adjusting stirring apparatus is adjusted.

Use epoxy resin to make composite magnetic particle, can enumerate the inorganic compound particles powder that for example in aqueous medium, disperses bisphenols, epihalohydrins to carry out the oleophylic processing, and in the buck medium, make the method for their reactions as adhesive resin.

The magnetic particle of composite magnetic particle of the present invention and adhesive resin contain the proportional 1-20 of being preferably quality % adhesive resin and 80-99 quality % magnetic particle.When the content of magnetic particle was lower than 80wt%, saturation magnetisation value diminished, and when surpassing 99wt%, interparticle bonding being easy to of magnetic that is produced by phenolics dies down.If consider the intensity of composite magnetic particle, then be preferably below the 97wt%.

As fine magnetic-substance particle, can use ferrospinels such as magnetic iron ore, γ iron oxide, contain the magnet lead ore type ferrite such as ferrospinel, barium ferrite of the metal (Mn, Ni, Zn, Mg, Cu etc.) beyond one or two or more kinds iron, have the iron of oxide layer and the particulate powder of alloy on the surface.Its shape can be any of granular, spherical, needle-like.Especially requiring under the high magnetized situation, can use ferromagnetism particulate powder such as iron, but when considering chemical stability, the preferred ferromagnetism body particulate powder that uses magnet lead ore type ferrite such as the ferrospinel that contains magnetic iron ore, γ iron oxide and barium ferrite.Can obtain to have the complex particles of desirable saturated magnetization by suitably selecting the kind and the content of ferromagnetism body particulate powder.

In the measurement under the magnetic field of 1000 oersteds (79.57kA/m), preferably, magnetized intensity is 30-70Am ²/ kg is preferably 35-60Am ²/ kg, residual magnetization (σ r) is 0.1-20Am ²/ kg is preferably 0.1-10Am ²/ kg is 1 * 10 than resistance value ⁶-1 * 10 ¹⁴Ω cm is preferably 5 * 10 ⁶-5 * 10 ¹³Ω cm, more preferably 5 * 10 ⁶-5 * 10 ⁹Ω cm.

In the manufacture method of carrier of the present invention, can in aqueous medium, make phenols and aldehydes in the presence of base catalyst, by making magnetic particle, suspension stabilizer coexistence and reacting.

As use therein phenols, except phenol, the halogenation phenols that is partly or entirely replaced by chlorine atom or bromine atoms etc. that can enumerate induced by alkyl hydroxybenzene such as m-cresols, p-tert-butyl phenol, o-propylphenol, resorcinol, bisphenol-A and benzene nucleus or alkyl has the compound of phenol hydroxyl, wherein phenol most preferably.Compound beyond using phenol owing to be difficult to generate particle sometimes, also is an amorphous even generate particle sometimes during as phenols, so when considering shape, phenol most preferably.

In addition, the aldehydes that uses in the manufacture method as complex particles of the present invention can be enumerated the formaldehyde of any form of formalin or paraformaldehyde and furfural etc., preferred especially formaldehyde.

In addition, as the resin that uses in the resin overlay of the present invention, must be the fluorine modified organic silicone resin.The fluorine modified organic silicone resin of the bridging property that obtains of organo-silicon compound by containing perfluoroalkyl and the reaction between the polysiloxane preferably as this fluorine modified organic silicone resin.Polysiloxane and contain interpolation ratio between the organo-silicon compound of perfluoroalkyl, with respect to 100 weight portion polysiloxane, the organo-silicon compound that contain perfluoroalkyl are preferably 3 weight portions～20 weight portions.Compared with cover the ferrite core particle in the past, in gel-type resin, disperseed the magnetic particle and cohesive in the composite magnetic particle that forms strengthens, both improved electric conductivity described later, improved permanance again.

Polysiloxane preferably has at least one repetitive that is selected from following chemical formula 3 and the chemical formula 4.

(chemical formula 3)

(in the formula, R ¹, R ²Expression hydrogen atom, halogen atom, hydroxyl, methoxyl, carbon number are 1～4 alkyl or phenyl; R ³, R ⁴The expression carbon number is 1～4 alkyl or phenyl, and m is average degree of polymerization and is positive integer (preferably in 2～500 scope, more preferably in 5～200 scope)).

(chemical formula 4)

(in the formula, R ¹, R ²Be respectively that hydrogen atom, halogen atom, hydroxyl, methoxyl, carbon number are 1～4 alkyl or phenyl; R ³, R ⁴, R ⁵And R ⁶The expression carbon number is 1～4 alkyl or phenyl, and n represents average degree of polymerization and is positive integer (preferably in 2～500 scope, more preferably in 5～200 scope)).

As the example of the organo-silicon compound that contain perfluoroalkyl, can list CF ₃CH ₂CH ₂Si (OCH ₃) ₃, C ₄F ₉CH ₂CH ₂Si (CH ₃) (OCH ₃) ₂, C ₈F ₁₇CH ₂CH ₂Si (OCH ₃) ₃, C ₈F ₁₇CH ₂CH ₂Si (OC ₂H ₅) ₃(CF ₃) ₂CF (CF ₂) ₈CH ₂CH ₂Si (OCH ₃) ₃Deng.The compound that especially preferably contains trifluoro propyl.

In addition, in the present embodiment, in the application of resin layer, contain amino silicane coupling agent.As this amino silicane coupling agent, can use known material, for example can list γ-(2-amino-ethyl) TSL 8330, γ-(2-amino-ethyl) aminopropyl methyl dimethoxysilane, octadecyl methyl (3-(trimethoxysilyl) propyl group) ammonium chloride (from top, corresponding to trade name SH6020, the SZ6023 and the AY43-021 that make by Toray-dow coring company), and KBM602, KBM603, KBE903, KBM573 (Shin-EtsuChemical company makes trade name) etc.Preferred especially primary amine.Secondary amine or tertiary amine by replacements such as methyl, ethyl, phenyl have more weak polarity, and the charged rising of toner is not had effect.In addition, when amino partly forms amino methyl, amino-ethyl or aminophenyl, the end of silane coupling agent is a primary amine, and still, the amino from the extended straight chain organic group of silane is helpless to charged rising, on the contrary, when high humility owing to be subjected to the influence of moisture, though because the amino of top, the toner at initial stage is had charging ability, but charging ability reduces in anti-brush, and ultimate life shortens.

Therefore, by this amino silicane coupling agent and fluorine modified organic silicone resin are used in combination, can directly guarantee has sharp-pointed carried charge to distribute to toner, can give electronegative property, and the toner that replenishes there is very fast charged rising, can reduces the consumption of toner.In addition, amino silicane coupling agent also demonstrates the effect as the crosslinking chemical, raising is as the degree of crosslinking of the fluorine modified organic silicone resin layer of material resin, further improve by the hardness of film resin, can reduce wearing and tearing in long-term the use, peel off etc., improve anti-expendable, suppressing charging ability reduces, thereby realize charged stabilization, improve permanance.

In addition, in the formation of above-mentioned toner, add the toner surface of a certain amount of above low-melting wax and have only resin basically, so it is unsettled slightly an of charging property.For example, have charging property a little less than, and the slower situation of charged rising, this causes easily, and the homogeneity of photographic fog, whole printed images reduces and the literal when transfer printing disperses, the literal desalination.But, toner and this carrier combinations are used and can address the above problem, and improve toner property handled in developer, can reduce so-called development memory, that is: obtain the resume of leaving over behind whole the printed images.

As the usage ratio of amino silicane coupling agent, be 5～40 weight % with respect to resin, be preferably 10～30 weight %.When ratio during, do not observe the effect of amino silicane coupling agent less than 5 weight %.When greater than 40 weight %, the crosslinking degree of resin overlay is too high, is easy to generate the phenomenon that overcharges, and this will cause image deflects such as development property deficiency.

In addition, electrically conductive microparticle can also be contained so that charged stabilization and prevent to overcharge at the resin overlay.As electrically conductive microparticle, can list semiconductive oxide such as oil oven is black or acetylene black is such carbon black, titanium dioxide, zinc paste and with the powder such as titanium dioxide, zinc paste, barium sulphate, aluminium borate or potassium titanate on tin oxide, carbon black or metal coat surface.Its intrinsic resistance is preferably 10 ¹⁰Below the Ω cm.When using electrically conductive microparticle, its content is preferably 1～15 weight %.Electrically conductive microparticle can improve the hardness of resin overlay by the filler effect as long as contain some with respect to the resin overlay.But when content during greater than 15 weight %, electrically conductive microparticle can hinder resin-coated formation on the contrary, becomes the reason that reduces adaptation and hardness.In addition, the content of the electrically conductive microparticle of the surplus in the panchromatic developer becomes the reason that causes transfer printing and photographic fixing toner color dyes on paper.

The method that forms overlay on composite magnetic particle has no particular limits, and can use known coating method, is for example being formed with dipping in the solution by rete as the infusion process of the powder of composite magnetic particle; To be formed with the lip-deep spray-on process of solution spray by rete to composite magnetic particle; Under the state that composite magnetic particle is suspended, spraying is formed the fluidized bed process of using solution by rete; And in mediating coating machine, mix composite magnetic particle and formed and use solution by rete, and the wet type coating methods such as kneading rubbing method of removal solvent, except that inferior, can also use dry type coating method etc., described dry type coating method is: high-speed mixing powdery resin and composite magnetic particle, and by utilizing its heat of friction that the toner thawing is coated on the composite magnetic particle surface.These methods can suit to use, but in the coating of the fluorine modified organic silicone resin that contains amino silicane coupling agent of the present invention, especially preferably use the wet type coating method.

Overlay forms with the solvent that uses in the coating fluid, so long as can dissolve aforementioned coating resin just, there is no particular limitation, can choose according to suitable employed coating resin.As a rule, can use for example aromatic hydrocarbons such as toluene, dimethylbenzene, ketones such as acetone, methyl ethyl ketone, ethers such as tetrahydrofuran, diox.

With respect to composite magnetic particle, the resin coating amount is preferably 0.2～6.0 weight %, 0.5～5.0 weight % more preferably, and more preferably 0.6～4.0 weight % most preferably is 0.7～3 weight %.When the coating amount of resin during less than 0.2 weight %, can not form uniform overlay on the composite magnetic particle surface, the characteristic of composite magnetic particle is subjected to very big influence, and can not give full play of the effect of fluorine modified organic silicone resin of the present invention and amino silicane coupling agent.Greater than 6.0 weight % the time, overlay is too thick, produces composite magnetic particle granulation each other, has the tendency that can't obtain uniform composite magnetic particle.

So, after the fluorine modified organic silicone resin that will contain amino silicane coupling agent is coated on the composite magnetic particle surface, preferably carry out calcination process.Have no particular limits as the method that is used for calcination process, can use in external heating method or the inside heating method any one.For example, can use fixed or mobile electric furnace, rotary kiln formula electric furnace or combustion furnace, also can use microwave to come roasting.But, temperature for calcination process, in order effectively to show the effect of fluoridizing organic siliconresin of the anti-consumption performance that can improve so-called resin overlay, preferably under 200～350 ℃ high temperature, handle, more preferably under 220～280 ℃, handle.Processing time is preferably 1.5～2.5 hours.If treatment temperature is lower, then can reduce the hardness of application of resin itself, if treatment temperature is too high, then can cause the minimizing of electric charge.

(8) tandem color processing

In order to form coloured image at a high speed, the present embodiment has been used following transfer printing process: used a plurality of toner images of photoreceptor, charged mechanism and toner carrier that comprise to form the station; In primary transfer technology, image-carrier is contacted with the transfer article of annular, will be transferred on the aforementioned transfer article at the toner image that the latent electrostatic image developingization that forms on the above-mentioned image-carrier forms; Above-mentioned primary transfer technology is implemented successively continuously, thereby on aforementioned transfer article, form the multilayer transfer toner image, implement secondary transfer printing technology then, this secondary transfer printing technology is once to be transferred on the offset mediums such as paper or OHP at the multilayer toner image that forms on the transfer article aforementioned.In above-mentioned transfer printing process, the transfer position that satisfies following relation by employing constitutes, and can realize the miniaturization of machine and the raising of print speed printing speed simultaneously thus.Promptly when will being d1 (mm) from the distance setting between 2 primary transfer positions, the 1st primary transfer position to the, the peripheral speed of photoreceptor is set at v when (mm/ second), their satisfy relation: d1/v≤0.65.For the paper (A4) of per minute processing more than 20, and make machine dimensions little of the purpose that can be used as SOHO, the distance that forms between the station at a plurality of toner images must shorten, and processing speed must improve.In order to realize miniaturization and print speed printing speed simultaneously, it is minimum requirements that above-mentioned value is set at below 0.65.

But, when choosing the formation that shortens the spacing between this toner image formation station, for example, as the yellow tone agent of first kind of color by primary transfer after, extremely the adjustment of the magenta of second kind of color of conduct subsequently is very short by the time till the primary transfer, substantially do not produce the slowing down of electric charge of the charged toner that slows down or be transferred of transfer article, when the magenta adjustment is transferred in the yellow tone agent, it is subjected to the charge effect of yellow tone agent and is ostracised, and this may produce, and transfer efficiency descends and the problem of font desalination when transfer printing.To adjust when going up to the yellow of front and magenta as the cyan toner primary transfer of the third color again, produce obviously that the cyan toner disperses, transfer printing is not good and the literal desalination.After further reusing, the toner of specified particle diameter is optionally developed, and because the mobile difference of each toner particle is very big, the chance difference of frictional electrification, therefore produces the inhomogeneous of carried charge, causes making transfer printing further to reduce.

Therefore,, can stablize charged distribution, and restrain the excessive charged of toner, can suppress mobile fluctuation simultaneously by using the toner or the double component developing of the present embodiment.Therefore, can be under the situation of not sacrificing the photographic fixing characteristic, literal desalination and oppositely transfer printing when preventing transfer efficiency reduction, transfer printing.

(9) no greasepaint look photographic fixing

The toner of the present embodiment is suitable for following electro-photography apparatus: this device has the photographic fixing technology of the oilless fixing formation of not using oil in the mechanism of toner photographic fixing.From reducing the viewpoint of heat time heating time and energy savings, as its heating arrangements, preferred formation is an electromagnetic induction heating.Described oilless fixing constitutes, use magnetic field to produce mechanism and heating and pressurizing mechanism, this heating and pressurizing mechanism comprises rotation heater block and rotation pressure-producing part at least, described rotation heater block has heating layer and the release layer that forms by electromagnetic induction at least, described rotation pressure-producing part and described rotation heater block are formed with predetermined gap, wherein between described rotation heater block and described rotation pressure-producing part, make transfer printing the offset mediums such as copy paper of toner pass through, thereby carry out photographic fixing.As its feature, compare with the situation of present use Halogen lamp LED the heat time heating time of rotation heater block, demonstrated very fast rising characteristic.Therefore, just carry out copying operation under the state that the rotation pressure-producing part is not having fully to heat up, the result is to need toner to have the anti setoff properties of low-temperature fixing and wide region.

As formation, the also preferred formation of using the photographic fixing band that heater block and fixing member are separated.As this photographic fixing band, suitable use has the nickel electroforming band of thermotolerance and Free Transform or heat-resisting polyimide band.Silicon rubber, fluororubber, fluororesin can be used as superficial layer, to improve release property.

In these photographic fixing, up to the present, can be coated with form oil to prevent set-off.Just needn't be coated with form oil by the toner that does not use oil to have release property.But, then charged easily if be not coated with form oil, therefore when the toner image of not photographic fixing during near heater block or fixing member, because charged influence produces dispersing of toner sometimes.Especially under the condition of low temperature and low humidity degree, be easy to generate this dispersing.

Therefore,,, also can realize the anti setoff properties of low-temperature fixing and wide region, can obtain colored high light transmittance even do not use oil by using the toner of the present embodiment.In addition, the mistake charging property of toner can also be suppressed, and the caused toner dispersion of charged effect of heater block or fixing member can be suppressed.

Embodiment

(carrier core Production Example)

In 1 liter flask, phenol 52g, 37wt% formalin 75g, the mean grain size of packing into is spherical magnetic iron ore particle powder particle 400g, 28wt% ammoniacal liquor 15g, calcium fluoride 1.0g and the water 50g of 0.24 μ m, in 60 minutes, be warming up to 85 ℃ while stirring, under uniform temp, make its reaction then and solidified 120 minutes, thereby generate the composite magnetic particle of forming by phenolics and spherical magnetic iron ore particle.

Then, the content in the flask is cooled to 30 ℃,, removes supernatant afterwards, wash the sediment of lower floor again, carry out air-dry then to the water that wherein adds 0.5 liter.Then, with its under reduced pressure (5mmHg following), 50-60 ℃ dry down, thereby obtain composite magnetic particle (carrier core A).

In 1 liter flask, phenol 50g, 37wt% formalin 65g, the mean grain size of packing into is spherical magnetic iron ore particle powder particle 450g, 28wt% ammoniacal liquor 15g, calcium fluoride 1.0g and the water 50g of 0.24 μ m, in 60 minutes, be warming up to 85 ℃ while stirring, under uniform temp, make its reaction then and solidified 120 minutes, thereby generate the composite magnetic particle of forming by phenolics and spherical magnetic iron ore particle.

Then, the content in the flask is cooled to 30 ℃,, removes supernatant afterwards, wash the sediment of lower floor again, carry out air-dry then to the water that wherein adds 0.5 liter.Then, with its under reduced pressure (5mmHg following), 50-60 ℃ dry down, thereby obtain composite magnetic particle (carrier core B).

In 1 liter flask, phenol 47.5g, 37wt% formalin 62g, the mean grain size of packing into is spherical magnetic iron ore particle powder particle 480g, 28wt% ammoniacal liquor 15g, calcium fluoride 1.0g and the water 50g of 0.24 μ m, in 60 minutes, be warming up to 85 ℃ while stirring, under uniform temp, make its reaction then and solidified 120 minutes, thereby generate the composite magnetic particle of forming by phenolics and spherical magnetic iron ore particle.

Then, the content in the flask is cooled to 30 ℃,, removes supernatant afterwards, wash the sediment of lower floor again, carry out air-dry then to the water that wherein adds 0.5 liter.Then, with its under reduced pressure (5mmHg following), 50-60 ℃ dry down, thereby obtain composite magnetic particle (carrier core C).

Saturated magnetization is 65Am when as a comparative example, using mean grain size 80 μ m, externally-applied magnetic field as 238.74kA/m (3000 oersted) ²The core d of the ferrite particle of/kg.

(carrier Production Example 1)

Then, with polysiloxane and the 21 gram CFs of 250 grams by following chemical formula 5 and 6 expressions of following chemical formula ₃CH ₂CH ₂Si (OCH ₃) ₃Reaction prepares the fluorine modified organic silicone resin, wherein, and R in chemical formula (5) ₁, R ₂Be methyl, i.e. (CH ₃) ₂SiO _2/2The unit is 15.4 moles of %, R in chemical formula (6) ₃Be methyl, i.e. CH ₃SiO _3/2The unit is 84.6 moles of %.Then, convert in solid state component, weighing 100 above-mentioned fluorine modified organic silicone resins of gram and 10 gram amino silicane coupling agents (γ-An Jibingjisanyiyangjiguiwan), and be dissolved in 300cm ³In the toluene solvant.

(chemical formula 5)

(in the formula, R ¹, R ², R ³And R ⁴Be methyl, m is average degree of polymerization and is 100).

(chemical formula 6)

(in the formula, R ¹, R ², R ³, R ⁴, R ⁵And R ⁶Be methyl, n is average degree of polymerization and is 80).

With respect to the above-mentioned carrier core of 10kg A, use soaked with liquid dry type applying device, by above-mentioned application of resin solution stirring was applied in 20 minutes.Then 260 ℃ of following roastings 1 hour, thereby obtain carrier A 1.

Carrier A 1 is that the content of spherical magnetic iron ore particle is the spherical particle of 80.4 quality %, and mean grain size is 30 μ m, and proportion is 3.05, and magnetization value is 61Am ²/ kg, volume intrinsic resistance are 3 * 10 ⁹Ω cm, specific surface area is 0.098m ²/ g.

(carrier Production Example 2)

Except use carrier core B in Production Example 1, and with CF ₃CH ₂CH ₂Si (OCH ₃) ₃Be transformed to C ₈F ₁₇CH ₂CH ₂Si (OCH ₃) ₃In addition, obtain carrier B 1 according to the operation identical with Production Example 1.

Carrier B 1 is that the content of spherical magnetic iron ore particle is the spherical particle of 88.4 quality %, and mean grain size is 45 μ m, and proportion is 3.56, and magnetization value is 65Am ²/ kg, volume intrinsic resistance are 8 * 10 ¹⁰Ω cm, specific surface area is 0.057m ²/ g.

(carrier Production Example 3)

Except in Production Example 1, using carrier core C, and with the bowl mill disperse phase for the resin solid composition be 5wt% conductive carbon (Ketjenblack International Corporation corporate system EC) in addition, make support C 1 according to the operation identical with Production Example 1.

Support C 1 is that the content of spherical magnetic iron ore particle is the spherical particle of 92.5 quality %, and mean grain size is 48 μ m, and proportion is 3.98, and magnetization value is 69Am ²/ kg, volume intrinsic resistance are 2 * 10 ⁷Ω cm, specific surface area is 0.043m ²/ g.

(carrier Production Example 4)

Except in Production Example 1, the addition of amino silicane coupling agent being changed into 30g, obtain carrier A 2 according to the operation identical with Production Example 1.

Carrier A 2 is that the content of spherical magnetic iron ore particle is the spherical particle of 80.4 quality %, and mean grain size is 30 μ m, and proportion is 3.05, and magnetization value is 61Am ²/ kg, volume intrinsic resistance are 2 * 10 ¹⁰Ω cm, specific surface area is 0.01m ²/ g.

(carrier Production Example 5)

Except the addition of amino silicane coupling agent being changed into 50g, make core according to the operation identical with Production Example 1, apply, obtain carrier a1.

(carrier Production Example 6)

Convert in solid state component, the pure organic siliconresin (DowCorning Toray Silicone Co.Ltd. makes SR-2411) that weighing 100 restrains as application of resin, and be dissolved in 300cm ³In the toluene solvant.With respect to 10kg ferrite particle d, use soaked with liquid dry type applying device, by above-mentioned application of resin solution stirring was applied in 20 minutes.Then 210 ℃ of following roastings 1 hour, thereby obtain carrier d2.Mean grain size is 80 μ m, and proportion is 6, and magnetization value is 75Am ²/ kg, volume intrinsic resistance are 2 * 10 ¹²Ω cm, specific surface area is 0.024m ²/ g.

(carrier Production Example 7)

Convert in solid state component, weighing 100 restrains the acryl-modified silicone resin resin (the system KR-9706 of chemistry society of SHIN-ETSU HANTOTAI) as application of resin, and is dissolved in 300cm ³In the toluene solvant.With respect to above-mentioned 10kg ferrite particle d, use soaked with liquid dry type applying device, by above-mentioned application of resin solution stirring was applied in 20 minutes.Then 210 ℃ of following roastings 1 hour, thereby obtain carrier d3.Mean grain size is 80 μ m, and proportion is 6, and magnetization value is 75Am ²/ kg, volume intrinsic resistance are 2 * 10 ¹¹Ω cm, specific surface area is 0.022m ²/ g.

(embodiment 1)

Then the embodiment to toner of the present invention describes, but the present invention is not subjected to any qualification of these embodiment.

(making of resin dispersion)

The characteristic of employed resin has been shown in (table 1).Mn represents number-average molecular weight, and Mw represents weight-average molecular weight, and Mz represents Z-average molecular weight, and Mp represents the peak value of molecular weight, Tm (℃) the expression softening point, Tg (℃) the expression glass transition point.Styrene, n-butyl acrylate, acrylic acid are represented its addition (g).The nonionic amount (g) of the surfactant that uses in each resin dispersion and anion amount (g) and the nonionic amount ratio with respect to whole amount of surfactant has been shown in (table 2).

(table 1)

	Mn(×10 4)	Mw(×10 4)	Mz(×10 4)	Wm＝Mw/Mn	Wz＝Mz/Mn	Mp(×10 4)	Tg℃	Tm℃
									RL1	0.37	1.12	3.88	3.03	10.49	0.81	42	110
RL2	0.62	6.24	26.9	10.06	43.39	0.81	56	127
									RL3	0.28	1.88	9.54	6.71	34.07	0.37	47	105
RH4	4.45	27.3	58.1	6.13	13.06	18.2	78	199
									RH5	4.09	25.2	57.8	6.16	14.13	15.4	76	194

(table 2)

	Nonionic amount (g)	Anion amount (g)	Nonionic amount ratio
				RL1	2.5	1	71.4％
RL2	5	1	83.3％
				RL3	5.5	0.5	91.7％
RH4	2.5	0.5	83.3％
				RH5	2.5	0.5	83.3％

(1) preparation of resin particle dispersion liquid RL1

NEOGEN RK), 6g lauryl mercaptan, 1.2g carbon tetrabromide will be distributed to by the monomer solution that 96g styrene, 24g n-butyl acrylate, 3.6g acrylic acid form in the 180g ion exchange water (the 1st industrial drugmaker makes: to use 2.5g nonionic surfactant (Sanyo changes into company and makes: NONIPOL 400), 1g anionic surfactant, add the 1.2g potassium persulfate therein, under 70 ℃, carry out emulsion polymerization in 6 hours.And then under 90 ℃, carry out 3 hours maturation process, make resin particle dispersion liquid RL1 thus, disperseed in this resin particle dispersion liquid that Mn is 3700, Mw is 11200, Mz is 38800, Mp is 8100, Tm is that 110 ℃, Tg are that 42 ℃, median particle diameter are the resin particle of 0.12 μ m.

(2) preparation of resin particle dispersion liquid RL2

(Sanyo changes into company and makes: ELEMINOLNA400), (the 1st industrial drugmaker makes the 1g anionic surfactant: NEOGENRK), 6g lauryl mercaptan, 1.2g carbon tetrabromide will be distributed to by the monomer solution that 204g styrene, 36g n-butyl acrylate, 3.6g acrylic acid form in the 360g ion exchange water to use the 5g nonionic surfactant, add the 2.4g potassium persulfate therein, under 70 ℃, carry out emulsion polymerization in 5 hours.And then under 90 ℃, carry out 5 hours maturation process, make resin particle dispersion liquid RL2 thus, disperseed in this resin particle dispersion liquid that Mn is 6200, Mw is 62400, Mz is 269000, Mp is 8100, Tm is that 127 ℃, Tg are that 56 ℃, median particle diameter are the resin particle of 0.18 μ m.

(3) preparation of resin particle dispersion liquid RL3

(Sanyo changes into company and makes: ELEMINOLNA400), (the 1st industrial drugmaker makes the 0.5g anionic surfactant: NEOGENRK), 12g lauryl mercaptan, 2.4g carbon tetrabromide will be distributed to by the monomer solution that 204g styrene, 36g n-butyl acrylate, 3.6g acrylic acid form in the 360g ion exchange water to use the 5.5g nonionic surfactant, add the 2.4g potassium persulfate therein, under 70 ℃, carry out emulsion polymerization in 5 hours.And then under 90 ℃, carry out 2 hours maturation process, make resin particle dispersion liquid RL3 thus, disperseed in this resin particle dispersion liquid that Mn is 2800, Mw is 18800, Mz is 95400, Mp is 3700, Tm is that 105 ℃, Tg are that 47 ℃, median particle diameter are the resin particle of 0.18 μ m.

(4) preparation of resin particle dispersion liquid RH4

NEOGEN RK), 0g lauryl mercaptan, 0g carbon tetrabromide will be distributed to by the monomer solution that 102g styrene, 18g n-butyl acrylate, 1.8g acrylic acid form in the 180g ion exchange water (the 1st industrial drugmaker makes: to use 2.5g nonionic surfactant (Sanyo changes into company and makes: NONIPOL 400), 0.5g anionic surfactant, add the 1.2g potassium persulfate therein, under 75 ℃, carry out emulsion polymerization in 5 hours.And then under 90 ℃, carry out 2 hours maturation process, make resin particle dispersion liquid RH4 thus, disperseed in this resin particle dispersion liquid that Mn is 44500, Mw is 273000, Mz is 581000, Mp is 182000, Tm is that 199 ℃, Tg are that 78 ℃, median particle diameter are the resin particle of 0.12 μ m.

(5) preparation of resin particle dispersion liquid RH5

(Sanyo changes into company and makes: ELEMINOLNA400), (the 1st industrial drugmaker makes the 0.5g anionic surfactant: NEOGENRK), 0g lauryl mercaptan, 0g carbon tetrabromide will be distributed to by the monomer solution that 102g styrene, 18g n-butyl acrylate, 1.8g acrylic acid form in the 180g ion exchange water to use the 2.5g nonionic surfactant, add the 1.2g potassium persulfate therein, under 70 ℃, carry out emulsion polymerization in 5 hours.And then under 90 ℃, carry out 2 hours maturation process, make resin particle dispersion liquid RH5 thus, disperseed in this resin particle dispersion liquid that Mn is 40900, Mw is 252000, Mz is 578000, Mp is 154000, Tm is that 194 ℃, Tg are that 76 ℃, median particle diameter are the resin particle of 0.22 μ m.

(embodiment 2)

(manufacturing of pigment dispersion)

The pigment that uses has been shown in (table 3).The nonionic amount (g) of the surfactant that uses in the pigment dispersion and anion amount (g) and the nonionic amount ratio with respect to whole amount of surfactant has been shown in (table 4).

(table 3)

PM1	The PERMANENT RUBINE F6B that Clariant company makes
		PC1	The KETBLUE111 that big Japanese ink company makes
PY1	The PY74 that adret pigment company makes
		PB1	The MA100S that Mitsubishi Chemical Ind makes

(table 4)

	Ma pigment (g)	Nonionic amount (g)	Anion amount (g)	Nonionic amount ratio
					PM1	20	2	0	100.0％
PM2	20	1.5	1.2	55.6％
					pm3	20	1.2	1.4	46.2％
pm4	20	0	2	0.0％

(1) preparation of colorant particle dispersion liquid PM1

ELEMINOL NA400) and the mixing of 78g ion exchange water (Sanyo changes into company and makes: with 20g magenta pigment (Clariant company make PERMANENT RUBINE F6B), 2g nonionic surfactant, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid PM1 of the colorant particle of 0.12 μ m.

(2) preparation of colorant particle dispersion liquid PC1

ELEMINOL NA400) and the mixing of 78g ion exchange water (Sanyo changes into company and makes: with 20g green pigment (big Japanese ink company make KETBLUE111), 2g nonionic surfactant, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid PC1 of the colorant particle of 0.12 μ m.

(3) preparation of colorant particle dispersion liquid PY1

ELEMINOL NA400) and the mixing of 78g ion exchange water (Sanyo changes into company and makes: with 20g yellow uitramarine (adret pigment company make PY74), 2g nonionic surfactant, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid PY1 of the colorant particle of 0.12 μ m.

(4) preparation of colorant particle dispersion liquid PB1

ELEMINOL NA400) and the mixing of 78g ion exchange water (Sanyo changes into company and makes: with 20g black pigment (Mitsubishi Chemical Ind make MA100S), 2g nonionic surfactant, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid PB1 of the colorant particle of 0.12 μ m.

(5) preparation of colorant particle dispersion liquid PM2

With 20g magenta pigment (Clariant company make PERMANENT RUBINE F6B), 1.5g nonionic surfactant (Sanyo changes into company and makes: NONIPOL 400), (Sanyo changes into company and makes the 6g anionic surfactant: S20-F, the 20wt% concentration of aqueous solution) and the 78g ion exchange water mix, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid PM2 of the colorant particle of 0.12 μ m.

(6) preparation of colorant particle dispersion liquid pm3

With 20g magenta pigment (Clariant company make PERMANENT RUBINE F6B), 1.2g nonionic surfactant (Sanyo changes into company and makes: NONIPOL 400), (Sanyo changes into company and makes the 7g anionic surfactant: S20-F, the 20wt% concentration of aqueous solution) and the 78g ion exchange water mix, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid pm3 of the colorant particle of 0.12 μ m.

(7) preparation of colorant particle dispersion liquid pm4

(Sanyo changes into company's manufacturing: S20-F with 20g magenta pigment (the PERMANENT RUBINE F6B that Clariant company makes), 10g anionic surfactant, the 20wt% concentration of aqueous solution) and the 78g ion exchange water mix, use ultrasonic disperser, under vibration frequency 30kHz, disperseed 20 minutes, and made thus that to have disperseed median particle diameter be the colorant particle dispersion liquid pm4 of the colorant particle of 0.12 μ m.

(embodiment 3)

(manufacturing of wax dispenser)

The characteristic of employed wax and this wax has been shown in (table 5), (table 6), (table 7), (table 8), (table 9), (table 10), (table 11), (table 12).

The characteristic of (table 5), (table 6) expression first wax, the characteristic of (table 7) expression second wax.Tmw1 (℃) the expression fusing point, Ck (wt%) represents weight loss on heating.

The molecular weight characteristics of (table 8) expression wax.Mnr represents number-average molecular weight, and Mwr represents weight-average molecular weight, and Mzr represents Z-average molecular weight, and Mpr represents the peak value of molecular weight.

The particle volume diameter cumulative distribution when having illustrated from the small particle diameter side of dispersion accumulative total in (table 9), (table 10), PR16 is 16% particle diameter, and PR 50 is 50% particle diameter, and PR 84 is 84% particle diameter.The adding proportion of the numeric representation wax in (table 9), (table 10) bracket.The nonionic amount (g) of the surfactant that uses in the wax dispenser and anion amount (g) and the nonionic amount ratio with respect to whole amount of surfactant has been shown in (table 11), (table 12).

(table 5)

Wax	Material	Fusing point Tmw1 (℃)	Weight loss on heating Ck (wt%)	Iodine number 1)	Saponification number 2)
						W-1	The deep hydrogenation jojoba oil	68	2.8	2	95.7
W-2	Candelila wax	72	2.4	15	62
						W-3	The white awns caul-fat of deep hydrogenation (meadowfoam oil)	71	2.5	2	90
W-4	Brazil wax	84	1.5	8	88
						W-5	Jojoba oil fatty acid pentaerythrite monoesters	84	3.4	2	120

The unit of (remarks 1) iodine number is g/100g.Iodine number refers to when halogen acts on sample, and the amount of absorbed halogen is scaled iodine, with the value of representing with respect to the gram numbers of 100 gram samples.

The unit of (remarks 2) saponification number is mgKOH/g.Saponification number refers to the milligram number of the required potassium hydroxide of saponification 1 gram sample.

(table 6)

Wax	Material	Fusing point Tmw1 (℃)	Weight loss on heating Ck (wt%)
				W-6	Stearyl stearate	58	2
W-7	Glycerol stearate	63	1.5
				W-8	Pentaerythritol tetrastearate	70	0.9
W-9	Mountain Yu acid 20 diester	74	1.2
				W-10	Triglyceride (curing castor oil)	85	1.9

(table 7)

		Fusing point Tmw2 (℃)	Acid number	Pen.
					W-11	Saturated, hydrocarbon wax (FNP0090, Japanese smart wax company makes)	90.2		1
W-12	Polypropylene/maleic anhydride/carbon number is that 30 end is the wax/tert-butyl hydroperoxide isopropyl monocarbonate of pure type: 100/20/8/4 weight portion	98	45	1
					W-13	Thermal decomposition type low density polyethylene wax (NL200, Mitsui Chemicals company makes)	104		1

(table 8)

	Mnr	Mwr	Mzr	Mwr/Mnr	Mzr/Mnr	Mpr
							W-1	1009	1072	1118	1.06	1.11	1.02×10 3
W-3	1015	1078	1124	1.06	1.11	1.03×10 3
							W-8	1100	1980	3050	1.80	2.77	3.5×10 3
W-10	1050	1120	1290	1.07	1.23	3.1×10 3
							W-12	1240	2100	2760	1.69	2.23	1.4×10 3

(table 9)

Dispersion	First wax	Second wax	PR16(nm)	PR50(nm)	PR84(nm)	PR84/PR16
							WA1	W-1(1)	W-11(5)	94	128	162	1.72
WA2	W-2(1)	W-12(2)	105	155	205	1.95
							WA3	W-3(1)	W-13(1)	186	267	348	1.87
WA4	W-4(1)	W-11(2)	88	106	124	1.41
							WA5	W-5(1)	W-12(4)	194	273	352	1.81
WA6	W-1(1)	W-13(5)	188	279	370	1.97
							WA7	W-2(1)	W-11(9)	184	276	368	2.00
WA8	W-3(1)	W-12(7)	128	176	224	1.75
							WA9	W-4(1)	W-13(1)	182	272	362	1.99
WA10	W-5(1)	W-11(5)	124	176	228	1.84
							WA11	W-6(1)	W-11(5)	112	168	224	2.00
WA12	W-7(1)	W-12(3)	125	187	249	1.99
							WA13	W-8(1)	W-13(1.2)	186	267	348	1.87
WA14	W-9(1)	W-11(1)	112	158	204	1.82
							WA15	W-10(1)	W-12(1.5)	184	266	348	1.89
WA16	W-6(1)	W-13(1)	186	277	368	1.98
							WA17	W-7(1)	W-11(4)	204	297	390	1.91
WA18	W-8(1)	W-12(8)	182	273	364	2.00
							WA19	W-9(1)	W-13(1)	204	296	388	1.90

(table 10)

Dispersion	First wax	Second wax	PR16(nm)	PR50(nm)	PR84(nm)	PR84/PR16
							wa21	W-4(1.5)	W-11(1)	189	289	389	2.06
wa22	W-6(1)	W-11(5)	132	199.5	267	2.02
							wa23	W-6(1)	W-11(5)	119	208.5	298	2.50
wa24	W-1(1)		112	155	198	1.77
							wa25	W-2(1)		109	155	201	1.84
wa26	W-6(1)		168	236	304	1.81
							wa27	W-7(1)		148	213	278	1.88
wa28	W-11(1)		188	278	368	1.96
							wa29	W-12(1)		148	219	290	1.96
wa30	W-13(1)		168	240	312	1.86
							wa31	W-11(1)		268	418	568	2.12
wa32	W-12(1)		284	503	722	2.54
							wa33	W-13(1)		246	515	784	3.19
wa34	W-1(1)		162	284	406	2.51
							wa35	W-2(1)		146	314	482	3.30
wa36	W-6(1)		168	276	384	2.29
							wa37	W-7(1)		148	245	342	2.31

(table 11)

Dispersion	Nonionic amount (g)	Anion amount (g)	Nonionic amount ratio	The first wax amount (g)	The second wax amount (g)
						WA1	2	1	67％	5	25
WA2	3	0	100％	10	20
						WA3	2.5	0.5	83％	15	15
WA4	3	0	100％	10	20
						WA5	3	0	100％	6	24
WA6	3	0	100％	5	25
						WA7	3	0	100％	3	27
WA8	3	0	100％	3.75	26.25
						WA9	3	0	100％	15	15
WA10	3	0	100％	5	25
						WA11	2	1	67％	5	25
WA12	3	0	100％	8	24
						WA13	2.8	0.5	85％	15	18
WA14	3	0	100％	15	15
						WA15	3	0	100％	12	18
WA16	3	0	100％	15	15
						WA17	3.1	0	100％	6	24
WA18	3	0	100％	3.5	28
						WA19	3	0	100％	15	15

(table 12)

Dispersion	Nonionic amount (g)	Anion amount (g)	Nonionic amount ratio	The first wax amount (g)	The second wax amount (g)
						wa21	3	0	100％	18	12
wa22	1.4	1.6	47％	5	25
						wa23	0	3	0％	5	25
wa24	3	0	100％	30
						wa25	1.8	1.2	60％	30
wa26	3	0	100％	30
						wa27	3	0	100％	30
wa28	3	0	100％	30
						wa29	3	0	100％	30
wa30	3	0	100％	30
						wa31	0	3	0％	30
wa32	0	3	0％	30
						wa33	0	3	0％	30
wa34	0	3	0％	30
						wa35	0	3	0％	30
wa36	0	3	0％	30
						wa37	0	3	0％	30

(1) preparation of wax particle dispersion WA1

Fig. 3 represents the dispersed with stirring schematic representation of apparatus, and Fig. 4 represents vertical view.The 801st, water jacket, chilled water are injected into its inside from 808, and discharge from 807.The 802nd, block the weir plate of processed liquid, have the hole at central portion, treating fluid is successively by 805 from here, and is discharged to the outside.The 803rd, the rotary body of high speed rotating, and be fixed on the axle 806, can high speed rotating.Have the hole about 1～5mm in the side of rotary body, processed liquid can move.Groove is 120ml, and the input amount of processed liquid reaches about 1/2 of groove.The speed maximum of rotary body can reach 50m/s.The diameter of rotary body is 52mm, and the internal diameter of groove is 56mm.The 44th, the raw material inlet when handling continuously seals when HIGH PRESSURE TREATMENT and batch processing.

In groove, be forced under the state of 0.4MPa, ELEMINOL NA400), 1g anionic surfactant (Sanyo changes into industrial group and makes SCF), 5g first wax (W-1) and 25g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 2g nonionic surfactant, rotating speed at rotary body is to handle 5 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes.Thereby form wax particle dispersion WA1.

(2) preparation of wax particle dispersion WA2

Under the condition identical with (1), ELEMINOL NA400), 10g first wax (W-2) and 20g second wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, rotating speed at rotary body is to handle 3 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion WA2.

(3) preparation of wax particle dispersion WA3

Under the condition identical with (1), add 100g ion exchange water, 2.5g nonionic surfactant (the Japanese emulsifying agent manufacturing Newcol 565C of company), 0.5g anionic surfactant (Sanyo changes into industrial group and makes SCF), 15g first wax (W-3) and 15g second wax (W-13), rotating speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 2 minutes, thereby form wax particle dispersion WA3.

(4) preparation of wax particle dispersion WA4

Under the condition identical with (1), ELEMINOL NA400), 10g first wax (W-4) and 20g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, rotating speed at rotary body is to handle 3 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion WA4.

(5) preparation of wax particle dispersion WA5

Fig. 5 represents the dispersed with stirring schematic representation of apparatus, and Fig. 6 represents vertical view.This device is 850 for the raw material input port, and 852 is fixed body, and has floating structure.Live by the extruding of 851 spring, and the last thrust that produced of the high speed rotating power by rotary body 853, form the slit of about 1 μ m～10 μ m.The 854th, the axle that links to each other with motor (not shown).Between the slit between fixed body and the rotary body, be subjected to strong shearing force from 850 raw materials that drop into, in liquid, be separated into minuteness particle.Treated material liquid is discharged from 856.Fig. 6 represents vertical view.The material liquid 855 of discharging disperses with radial, and it is recovered in the closed container.The external diameter of rotary body is 100mm.

Material liquid forms as follows: wax and surfactant is pre-dispersed in the aqueous medium that pressurizes in advance and heat, it to be injected from inlet 80, and moment is handled by miniaturization.In supply is that 1kg/ hour, the speed of rotary body are to the maximum under the 100m/s and rotate.

ELEMINOL NA400), 6g first wax (W-5) and 24g second wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is that 100m/s, supply are to handle under 1kg/ hour, thereby forms wax particle dispersion WA5.

(6) preparation of wax particle dispersion WA6

Under the condition identical with (1), ELEMINOL NA400), 5g first wax (W-1) and 25g second wax (W-13) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 4 minutes, thereby form wax particle dispersion WA6.

(7) preparation of wax particle dispersion WA7

Under the condition identical with (1), ELEMINOL NA400), 3g first wax (W-2) and 27g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion WA7.

(8) preparation of wax particle dispersion WA8

Under the condition identical with (5), ELEMINOL NA400), 3.75g first wax (W-3) and 26.25g second wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is that 100m/s, supply are to handle under 1kg/ hour, thereby forms wax particle dispersion WA8.

(9) preparation of wax particle dispersion WA9

Under the condition identical with (1), ELEMINOL NA400), 15g first wax (W-4) and 15g second wax (W-13) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 3 minutes, thereby form wax particle dispersion WA9.

(10) preparation of wax particle dispersion WA10

Under the condition identical with (1), ELEMINOL NA400), 5g first wax (W-5) and 25g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion WA10.

(11) preparation of wax particle dispersion WA11

Fig. 3 represents the dispersed with stirring schematic representation of apparatus, and Fig. 4 represents vertical view.The 801st, water jacket, chilled water are injected into its inside from 808, and discharge from 807.The 802nd, block the weir plate of processed liquid and have the hole at central portion, treating fluid passes through 805 successively from here, and is discharged to the outside.The 803rd, the rotary body of high speed rotating, and be fixed on the axle 806, can high speed rotating.Have the hole about 1～5mm in the side of rotary body, processed liquid can move.Groove is 120ml, and the input amount of processed liquid reaches about 1/2 of groove.The speed maximum of rotary body can reach 50m/s.The diameter of rotary body is 52mm, and the internal diameter of groove is 56mm.The 44th, the raw material inlet when handling continuously seals when HIGH PRESSURE TREATMENT and batch processing.

In groove, be forced under the state of 0.4MPa, ELEMINOL NA400), 1g anionic surfactant (Sanyo changes into industrial group and makes SCF), 5g first wax (W-6) and 25g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 2g nonionic surfactant, rotating speed at rotary body is to handle 5 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes.Thereby form wax particle dispersion WA11.

(12) preparation of wax particle dispersion WA12

Under the condition identical with (1), ELEMINOL NA400), 8g first wax (W-7) and 24g second wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3.2g nonionic surfactant, rotating speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion WA12.

(13) preparation of wax particle dispersion WA13

Under the condition identical with (1), add 100g ion exchange water, 2.8g nonionic surfactant (the Japanese emulsifying agent manufacturing Newcol 565C of company), 0.5g anionic surfactant (Sanyo changes into industrial group and makes SCF), 15g first wax (W-8) and 18g second wax (W-13), rotating speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 2 minutes, thereby form wax particle dispersion WA13.

(14) preparation of wax particle dispersion WA14

Under the condition identical with (1), ELEMINOL NA400), 15g first wax (W-9) and 15g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, rotating speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 1 minute, thereby form wax particle dispersion WA14.

(15) preparation of wax particle dispersion WA15

Fig. 5 represents the dispersed with stirring schematic representation of apparatus, and Fig. 6 represents vertical view.This device is 850 for the raw material input port, and 852 is fixed body, and has floating structure.Live by the extruding of 851 spring, and the last thrust that produced of the high speed rotating power by rotary body 853, form the slit of about 1 μ m～10 μ m.The 854th, the axle that links to each other with motor (not shown).Between the slit between fixed body and the rotary body, be subjected to strong shearing force from 850 raw materials that drop into, in liquid, be separated into minuteness particle.Treated material liquid is discharged from 856.Fig. 6 represents vertical view.The material liquid 855 of discharging disperses with radial, and it is recovered in the closed container.The external diameter of rotary body is 100mm.

Material liquid forms as follows: wax and surfactant is pre-dispersed in the aqueous medium that pressurizes in advance and heat, it to be injected from inlet 80, and moment is handled by miniaturization.In supply is that 1kg/ hour, the speed of rotary body are to the maximum under the 100m/s and rotate.

ELEMINOL NA400), 12g first wax (W-10) and 18g second wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is that 100m/s, supply are to handle under 1kg/ hour, thereby forms wax particle dispersion WA15.

(16) preparation of wax particle dispersion WA16

Under the condition identical with (1), ELEMINOL NA400), 15g first wax (W-6) and 15g second wax (W-13) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 4 minutes, thereby form wax particle dispersion WA16.

(17) preparation of wax particle dispersion WA17

Under the condition identical with (1), ELEMINOL NA400), 6g first wax (W-7) and 24g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 4 minutes, thereby form wax particle dispersion WA17.

(18) preparation of wax particle dispersion WA18

Under the condition identical with (5), ELEMINOL NA400), 3.5g first wax (W-8) and 28g second wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3.1g nonionic surfactant, speed at rotary body is that 100m/s, supply are to handle under 1kg/ hour, forms wax particle dispersion WA18.

(19) preparation of wax particle dispersion WA19

Under the condition identical with (1), ELEMINOL NA400), 15g first wax (W-9) and 15g second wax (W-13) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 4 minutes, thereby form wax particle dispersion WA19.

(20) preparation of wax particle dispersion wa21

Under the condition identical with (4), ELEMINOL NA400), 18g first wax (W-4) and 12g second wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa21.

(21) preparation of wax particle dispersion wa22

Under the condition identical with (6), ELEMINOL NA400), (Sanyo changes into industrial group and makes the 8g anionic surfactant: S20-F (Sanyo changes into company and makes: to add 100g ion exchange water, 1.4g nonionic surfactant, the 20wt% concentration of aqueous solution), 5g first wax (W-6) and 25g second wax (W-11), speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa22.

(22) preparation of wax particle dispersion wa23

Under the condition identical with (6), (Sanyo changes into industrial group's manufacturing: S20-F for adding 100g ion exchange water, 15g anionic surfactant, the 20wt% concentration of aqueous solution), 5g first wax (W-6) and 25g second wax (W-11), speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa23.

(23) preparation of wax particle dispersion wa24

Under the condition identical with (1), ELEMINOL NA400), 30g wax (W-1) (Sanyo changes into company and makes: to add 100g ion exchange water and 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 2 minutes, thereby form wax particle dispersion wa24.

(24) preparation of wax particle dispersion wa25

Under the condition identical with (1), ELEMINOL NA400), (Sanyo changes into industrial group and makes the 6g anionic surfactant: S20-F (Sanyo changes into company and makes: to add 100g ion exchange water, 1.8g nonionic surfactant, the 20wt% concentration of aqueous solution), 30g wax (W-2), speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 45m/s, handled 2 minutes, thereby form wax particle dispersion wa25.

(25) preparation of wax particle dispersion wa26

Under the condition identical with (1), ELEMINOL NA400), 30g wax (W-6) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa26.

(26) preparation of wax particle dispersion wa27

Under the condition identical with (1), ELEMINOL NA400), 30g wax (W-7) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 30m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa27.

(27) preparation of wax particle dispersion wa28

Under the condition identical with (1), ELEMINOL NA400), 30g wax (W-11) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa28.

(28) preparation of wax particle dispersion wa29

Except being forced in the groove the state of 0.4MPa, under the condition identical with (1), ELEMINOL NA400), 30g wax (W-12) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa29.

(29) preparation of wax particle dispersion wa30

Except being forced in the groove the state of 0.4MPa, under the condition identical with (1), ELEMINOL NA400), 30g wax (W-13) (Sanyo changes into company and makes: to add 100g ion exchange water, 3g nonionic surfactant, speed at rotary body is to handle 3 minutes under the 20m/s, afterwards rotating speed is elevated to 50m/s, handled 2 minutes, thereby form wax particle dispersion wa30.

(30) preparation of wax particle dispersion wa31

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-11), handled 30 minutes, thereby form wax particle dispersion wa31 with homogenizer.

(31) preparation of wax particle dispersion wa32

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-12), handled 30 minutes, thereby form wax particle dispersion wa32 with homogenizer.

(32) preparation of wax particle dispersion wa33

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-13), handled 30 minutes, thereby form wax particle dispersion wa33 with homogenizer.

(33) preparation of wax particle dispersion wa34

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-1), handled 30 minutes, thereby form wax particle dispersion wa34 with homogenizer.

(34) preparation of wax particle dispersion wa35

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-2), handled 30 minutes, thereby form wax particle dispersion wa35 with homogenizer.

(35) preparation of wax particle dispersion wa36

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-6), handled 30 minutes, thereby form wax particle dispersion wa36 with homogenizer.

(36) preparation of wax particle dispersion wa37

Add 100g ion exchange water, 3g anionic surfactant (Sanyo changes into company and makes SCF), 30g wax (W-7), handled 30 minutes, thereby form wax particle dispersion wa37 with homogenizer.

(embodiment 4)

(manufacturing of toner parent)

The composition of the toner of making is shown in (table 13), (table 14).

The volume average particle size of d50 (μ m) expression toner parent particle, P2 represents that number has the number % amount that contains of toner parent particle of the particle diameter of 2.52-4 μ m in distributing, V46 represents to have in the volume distributed median volume % amount that contains of toner parent particle of the particle diameter of 4-6.06 μ m, P46 represents that number has the number % amount that contains of toner parent particle of the particle diameter of 4-6.06 μ m in distributing, and P8 represents to have in the volume distributed median volume % amount that contains of the toner parent particle of the above particle diameter of 8 μ m.

(table 13)

Toner	First resin dispersion	Wax dispenser	Wax dispenser	Pigment dispersion	First resin dispersion	d50 (μm)	P2 (pop％)	V46 (vol％)	P46 (pop％)	V8 (vol％)	P46/V46	The volume reference coefficient of variation
													M1	RL2	WA1		PM1	RH4	4.2	73.4	26.8	39.8	0.9	1.49	17.8
M2	RL2	WA2		PM1	RH4	6.5	13.4	66.2	67	1.2	1.01	17.9
													M3	RL2	WA3		PM1	RH4	4.9	40.1	52.9	70.2	1.2	1.33	18.9
M4	RL1	WA4		PM1	RH4	4.4	65.8	39.8	59.8	1.3	1.50	19.2
													M5	RL3	WA5		PM1	RH4	6.7	13.1	70.4	54.9	2.8	0.78	16.8
M6	RL1	WA6		PM1	RH4	5.2	44.1	56.8	61	2.5	1.07	18.2
													M7	RL3	WA7		PM1	RH5	4.6	58.9	42.8	62.8	2.4	1.47	16.8
M8	RL3	WA8		PM1	RH5	4.1	71.4	26.9	39.7	1.8	1.48	20.8
													M9	RL2	WA9		PM1	RH4	5.1	40.9	59.8	62.1	2.6	1.04	17.1
M10	RL2	WA10		PM1	RH4	5.3	42.1	55.8	63.1	2.8	1.13	19.8
													M11	RL2	WA11		PM1	RH4	4.4	73	26.8	39.1	2.1	1.46	18.8
M12	RL2	WA12		PM1	RH4	6.3	12.4	66.1	66.1	1.1	1.00	18.3
													M13	RL2	WA13		PM1	RH4	5	39.8	53.1	70.1	1.9	1.32	17.5
M14	RL1	WA14		PM1	RH4	4.4	55.8	57.9	66.2	1.3	1.14	19.2
													M15	RL3	WA15		PM1	RH4	6.6	12.9	71.5	55.9	2.9	0.78	17.9
M16	RL1	WA16		PM1	RH4	5.1	43.5	57.6	60.8	2.9	1.06	18.9
													M17	RL3	WA17		PM1	RH5	4.8	43.8	61.8	69.8	2.4	1.13	16.8
M18	RL3	WA18		PM1	RH5	3.9	71.2	28.9	38.4	1.2	1.33	21.5
													M19	RL2	WA19		PM1	RH4	5.1	40.9	59.8	62.1	2.6	1.04	17.1
M20	RL3	WA7		PM2	RH5	4.8	71.1	27.1	39.2	1.8	1.45	20.1

(table 14)

Toner	First resin dispersion	Wax dispenser	Wax dispenser	Pigment dispersion	Second resin dispersion	d50 (μm)	P2 (pop％)	V46 (vol％)	P46 (pop％)	V8 (vol％)	P46 /V46	The volume reference coefficient of variation
													m31	RL1	wa21		PM1	RH5	7.4						23.8
m32	RL2	wa22		PM1	RH4	8.4						24.8
													m33	RL2	wa23		PM1	RH4	10.9						31.8
m34	RL1	wa24(1)	wa28(5)	PM1	RH4	5.8						42.8
													m35	RL1	wa25(1)	wa29(2)	PM1	RH4	4.8						41.8
m36	RL1	wa26(1)	wa30(1)	PM1	RH5	7.8						45.8
													m37	RL2	wa27(1)	wa28(5)	PM1	RH4	8.2						41.8
m38	RL2	wa31		PM1	RH4	12.8	6.8	9.1	19.8	19.8	2.18	24.8
													m39	RL2	wa32		PM1	RH4	18.1	3.4	5.9	19.2	22.4	3.25	33.7
m40	RL2	wa33		PM1	RH4	20.7	5.8	4.9	13.5	23.1	2.76	36.8
													m41	RL1	wa34		PM1	RH4	22.4	2.2	6	18.1	19.8	3.02	33.7
m42	RL3	wa35		PM1	RH4	20.8	3.5	4.9	14.1	22.9	2.88	30.8
													m43	RL1	wa36		PM1	RH4	18.4	2.4	6.1	18.2	19.9	2.98	34.7
m44	RL3	wa37		PM1	RH4	19.2	3.6	4.8	13.8	23.4	2.88	31.2
													m45	RL2	WA7		pm3	RH4	8.2						26.8
m46	RL2	WA7		pm4	RH4	11.4						33.9

(1) manufacturing of toner parent M1

In 4 mouthfuls of flasks that have thermometer, condenser pipe, stirring rod, pH meter of 2000ml, add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion WA1, drop into the 200ml ion exchange water, mix in the same manner with above-mentioned (1), make the stuff and other stuff dispersion liquid.The pH of the mixed dispersion liquid of gained is 2.7.

Add 1N NaOH then in the mixed dispersion liquid of gained, making pH is 11.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 80 ℃ then, heat treated 2 hours.The pH of the dispersion liquid that obtains is 9.2.Then, add 1NHCl, to make pH be 6.6 and temperature is warming up to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 6.6, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filtration product (toner parent) is with ion-exchange water washing 3 times.Afterwards, the toner parent that obtains was descended dry 6 hours at 40 ℃ in the flow-type exsiccator, obtaining volume average particle size is that 4.2 μ m, coefficient of variation are 17.8 toner parent M1.

Before adjust adding water-soluble inorganic salt and during the pH of the mixed dispersion liquid before the heating, if be lower than 9.5, thickization of core particle of Xing Chenging then.And pH is set at 12.5 o'clock, free wax becomes many, and bag wax in being difficult to equably.The pH of the solution when forming core particle condensed not good and free wax and becomes many greater than 9.5 o'clock.

In addition, be warming up to 70 ℃ with the speed of 5 ℃/min from 22 ℃, then 80 ℃ of following heat treated after 2 hours, when not adjusting pH, even perhaps adjust when also carrying out heat treated with pH greater than 6.8 value, particle exists and becomes big tendency a little.If pH is lower than 2.2, then there are the effect disappearance of surfactant and the tendency of thickization of particle diameter.

If the pH that will add behind second resin particle dispersion liquid (being RH4 in the present embodiment) is set at 3.0 o'clock, second resin particle is difficult to attached on the core particle, thereby free resin increases.And if pH is set at 7.0 o'clock, then core particle produces secondary aggregation each other, thickization of particle.

(2) manufacturing of toner parent M2

In the flask identical with toner parent M1 (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,65g wax particle dispersion WA2, drop into the 200ml ion exchange water, with toner parent M1 (1) the same terms under mix, make the stuff and other stuff dispersion liquid.The pH of the mixed dispersion liquid of gained is 1.8.

Add 1N NaOH then in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 80 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 7.2.And then temperature is elevated to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃ in addition, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, with toner parent M1 (1) the same terms under filter, wash, drying, obtaining volume average particle size is that 6.5 μ m, coefficient of variation are 17.9 toner parent M2.

(3) manufacturing of toner parent M3

In the flask identical with toner (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,60g wax particle dispersion WA3, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 4.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.4.And then add 1N HCl, and to make pH be 5.4 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 4.9 μ m, coefficient of variation are 18.9 toner parent M3.

(4) manufacturing of toner parent M4

In the flask identical with toner (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,60g wax particle dispersion WA4, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.9, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 80 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 9.3.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 4.4 μ m, coefficient of variation are 19.2 toner parent M4.

(5) manufacturing of toner parent M5

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,55g wax particle dispersion WA5, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 7.And then temperature is elevated to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃ in addition, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 6.7 μ m, coefficient of variation are 16.8 toner parent M5.

(6) manufacturing of toner parent M6

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,70g wax particle dispersion WA6, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 10.5, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 7.9.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 5.2 μ m, coefficient of variation are 18.2 toner parent M6.

(7) manufacturing of toner parent M7

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,85g wax particle dispersion WA7, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 1.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.2, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.6.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH5, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 4.6 μ m, coefficient of variation are 16.8 toner parent M7.

(8) manufacturing of toner parent M8

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,90g wax particle dispersion WA8, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.1.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.6, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.9.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH5, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 4.1 μ m, coefficient of variation are 20.8 toner parent M8.

(9) manufacturing of toner parent M9

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,70g wax particle dispersion WA9, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 10.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.1.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 5.1 μ m, coefficient of variation are 17.1 toner parent M9.

(10) manufacturing of toner parent M10

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,70g wax particle dispersion WA10, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 1.9.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 10.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 7.9.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 5.3 μ m, coefficient of variation are 19.8 toner parent M10.

(11) manufacturing of toner parent M11

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion WA11, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 5.7.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 80 ℃ then, heat treated 2 hours.The pH of the dispersion liquid that obtains is 9.2.And then add 1NHCl, and to make pH be 6.6 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 6.6, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is that 4.4 μ m, coefficient of variation are 18.8 toner parent M11.

Before adjust adding water-soluble inorganic salt and during the pH of the mixed dispersion liquid before the heating, if be lower than 9.5, thickization of core particle of Xing Chenging then.And pH is set at 12.5 o'clock, free wax becomes many, and bag wax in being difficult to equably.The pH of the solution when forming core particle is greater than 9.5 the time, and it is many condense not good and feasible free wax change.

In addition, be warming up to 70 ℃ with the speed of 5 ℃/min from 22 ℃, then 80 ℃ of following heat treated after 2 hours, when not adjusting pH, even perhaps adjust when also carrying out heat treated with pH greater than 6.8 value, there is the tendency of thickization in particle.If pH is reduced to less than 2.2, then there are the effect disappearance of surfactant and the tendency of particle diameter rugosityization.

If the pH that will add behind second resin particle dispersion liquid (being RH4 or RH5 in the present embodiment) is set at 3.0 o'clock, be difficult to cause that second resin particle is attached on the core particle, thereby free resin increases.In addition, if pH is set at 7.0 o'clock, then core particle produces secondary aggregation each other, thus thickization of particle.

(12) manufacturing of toner parent M12

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,65g wax particle dispersion WA12, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 80 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 7.2.And then temperature is elevated to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃ in addition, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, volume average particle size is 6.3 μ m, and coefficient of variation is 18.3.Thereby obtain toner parent M12.

(13) manufacturing of toner parent M13

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,60g wax particle dispersion WA13, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 4.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.2, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.5.And then add 1N HCl, and to make pH be 5.4 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5.0, is heat treated 2 hours under 95 ℃ the condition in water temperature, then pH is adjusted into 8.6 and heat treated 1 hour, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, volume average particle size is 5 μ m, and coefficient of variation is 17.5.Thereby obtain toner parent M13.

(14) manufacturing of toner parent M14

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL 1,20g colorant particle dispersion liquid PM1,60g wax particle dispersion WA14, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 5.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.9, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 80 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 9.3.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 4.4 μ m, and coefficient of variation is 19.2 toner parent M14.

(15) manufacturing of toner parent M15

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,55g wax particle dispersion WA15, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 7.0.And then temperature is elevated to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃ in addition, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 2 hours under 90 ℃ the condition in water temperature, then pH is adjusted into 5.4 and heat treated 1 hour, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 6.6 μ m, and coefficient of variation is 17.9 toner parent M15.

(16) manufacturing of toner parent M16

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,70g wax particle dispersion WA16, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.2, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.3.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 5.1 μ m, and coefficient of variation is 18.9 toner parent M16.

(17) manufacturing of toner parent M17

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,85g wax particle dispersion WA17, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 4.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.2, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.6.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, add 43g second shell resin particle dispersion liquid RH5, making pH is 3.4, it in water temperature heat treated 2 hours under 90 ℃ the condition, then pH is adjusted into 5.4 and heat treated 1 hour, then pH is adjusted into 2.4 and heat treated 1 hour, thereby obtains the melt bonded particle of resin.

Then, after cooling, under the condition identical, filter, wash with toner (1), drying, obtaining volume average particle size is 4.8 μ m, coefficient of variation is that 16.8 particle surface almost be can't see the concavo-convex toner parent M17 that is in quite level and smooth state.In addition in the table 16, expression adds pH, temperature and the volume average particle size (d50) after 2 hours, after 1 hour and after 1 hour behind the shell resin.

(18) manufacturing of toner parent M18

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,90g wax particle dispersion WA18, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 4.3.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.6, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.9.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH5, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 3.9 μ m, and coefficient of variation is 21.5 toner parent M18.

(19) manufacturing of toner parent M19

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,70g wax particle dispersion WA19, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.2, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 8.5.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, add 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, it in water temperature heat treated 2 hours under 90 ℃ the condition, then pH is adjusted into 5.4 and heat treated 1 hour, then pH is adjusted into 6.6 and heat treated 1 hour, thereby obtains the melt bonded particle of resin.

Then, after cooling, under the condition identical, filter, wash with toner (1), drying, obtaining volume average particle size is 5.1 μ m, coefficient of variation is 17.1 and almost can't see the concavo-convex toner parent M19 that is in quite level and smooth state at particle surface.In addition in the table 16, expression adds pH, temperature and the volume average particle size (d50) after 2 hours, after 1 hour and after 1 hour behind the shell resin.

(20) manufacturing of toner parent M20

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM2,85g wax particle dispersion WA7, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.6.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 20 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is elevated to 85 ℃ then, obtained core particle in 2 hours thereby handle.The pH of the core particle dispersion liquid that obtains is 9.2.And then add 1N HCl, and to make pH be 3.2 and temperature is elevated to 90 ℃, heat treated 2 hours, thus obtain core particle.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH5, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 4.8 μ m, and coefficient of variation is 20.1 toner parent M20.

(21) manufacturing of toner parent m31

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,40g wax particle dispersion wa21, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.1.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH5, making pH is 5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 7.4 μ m, and coefficient of variation is 23.8 and the toner parent m31 that broadens a little of size-grade distribution.

(22) manufacturing of toner parent m32

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion wa22, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.2.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 8.4 μ m, and coefficient of variation is 24.8 and the toner parent m32 that broadens a little of size-grade distribution.Residual a little adularescent muddiness in the part of aqueous medium.

(23) manufacturing of toner parent m33

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion wa23, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.2.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 8.5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 10.8 μ m, and coefficient of variation is 31.8 and the toner parent m33 that broadens of size-grade distribution.Residual adularescent muddiness in the part of aqueous medium.

(24) manufacturing of toner parent m34

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,14.2g wax particle dispersion wa24 and 71g wax particle dispersion wa28, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.5.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.2.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 5.8 μ m, and coefficient of variation is 42.8 and the toner parent m34 that broadens of size-grade distribution.Because of there being the residual adularescent muddiness of wax particle that suspends.

(25) manufacturing of toner parent m35

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,21.7g wax particle dispersion wa25 and 43.4g wax particle dispersion wa29, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 7.2.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 4.8 μ m, and coefficient of variation is 41.8 and the toner parent m35 that broadens of size-grade distribution.Because of there being the residual adularescent muddiness of wax particle that suspends.

(26) manufacturing of toner parent m36

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,32.5g wax particle dispersion wa26 and 32.5g wax particle dispersion wa30, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.9.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.1, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 8.5.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH5, making pH is 5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 7.8 μ m, and coefficient of variation is 45.8 and the toner parent m36 that broadens of size-grade distribution.Because of there being the residual adularescent muddiness of wax particle that suspends.

(27) manufacturing of toner parent m37

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,8.3g wax particle dispersion wa27 and 41.5g wax particle dispersion wa28, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.9.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.8, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.2.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 7.0, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 8.2 μ m, and coefficient of variation is 41.8 and the toner parent m37 that broadens of size-grade distribution.Because of there being the residual adularescent muddiness of wax particle that suspends.

(28) manufacturing of toner parent m38

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion wa31, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.7.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 80 ℃ then, heat treated 2 hours.The pH of the dispersion liquid that obtains is 6.8.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 12.8 μ m, and coefficient of variation is 24.8 toner parent m38.

(29) manufacturing of toner parent m39

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion wa32, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 80 ℃ then, heat treated 2 hours, thus obtain core particle.The pH of the core particle dispersion liquid that obtains is 6.9.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃ in addition, adds 43g second shell resin particle dispersion liquid RH4, making pH is 3.4, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, volume average particle size is 18.1 μ m, and coefficient of variation is 33.7.Thereby obtain toner parent m39.

(30) manufacturing of toner parent m40

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,20g colorant particle dispersion liquid PM1,50g wax particle dispersion wa33, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 80 ℃ then, heat treated 2 hours, thus obtain core particle.The pH of the core particle dispersion liquid that obtains is 7.0.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5.0, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, volume average particle size is 20.7 μ m, and coefficient of variation is 36.8.Thereby obtain toner parent m40.

(31) manufacturing of toner parent m41

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,50g wax particle dispersion wa34, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 80 ℃ then, handled 2 hours, thereby obtain core particle.The pH of the core particle dispersion liquid that obtains is 6.8.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 22.4 μ m, and coefficient of variation is 33.7 toner parent m41.

(32) manufacturing of toner parent m42

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,55g wax particle dispersion WA35, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.0, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 80 ℃ then, handled 2 hours, thereby obtain core particle.The pH of the core particle dispersion liquid that obtains is 6.0.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 5, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 20.8 μ m, and coefficient of variation is 30.8 toner parent m42.

(33) manufacturing of toner parent m43

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL1,20g colorant particle dispersion liquid PM1,50g wax particle dispersion Wa36, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 5.8.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.7, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 80 ℃ then, handled 2 hours, thereby obtain core particle.The pH of the core particle dispersion liquid that obtains is 6.8.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 2.0, is heat treated 3 hours under 95 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 18.4 μ m, and coefficient of variation is 34.7 toner parent m43.

(34) manufacturing of toner parent m44

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL3,20g colorant particle dispersion liquid PM1,55g wax particle dispersion WA37, drop into the 200ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 2.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 9.0, and afterwards, interpolation 200g concentration is 30% magnesium sulfate solution, stirs 10 minutes.Afterwards, be warmed up to 70 ℃ from 22 ℃ with 5 ℃/minute speed, afterwards, 70 ℃ of heating 2 hours down.Temperature is increased to 85 ℃ then, handled 5 hours, thereby obtain core particle.The pH of the core particle dispersion liquid that obtains is 6.0.And then temperature is increased to 90 ℃, and heat treated 2 hours, thus core particle obtained.

Water temperature is set at 60 ℃, adds 43g second shell resin particle dispersion liquid RH4, making pH is 2.0, is heat treated 3 hours under 90 ℃ the condition in water temperature, thus the melt bonded particle of acquisition resin.

Then, after cooling, filter under the condition identical with toner (1), wash, drying, obtaining volume average particle size is 19.2 μ m, and coefficient of variation is 31.2 toner parent m44.

(35) manufacturing of toner parent m45

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,30g colorant particle dispersion liquid pm3,50g wax particle dispersion WA7, drop into the 300ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.7, and afterwards, adding 281g concentration is the magnesium sulfate solution of 23wt%, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.2.And then be under 90 ℃ the state in water temperature, add 43g with the rate of addition of 5g/min pH be adjusted into 5 the second resin particle dispersion liquid RH4, drip finish after, heat treated is 2 hours under 95 ℃ condition, obtains the melt bonded particle of second resin particle.Then, under the condition identical, filter, wash, drying, obtain volume average particle size and be 8.2 μ m, coefficient of variation and be 26.8 and the toner parent m45 that broadens a little of size-grade distribution with toner (1).

(36) manufacturing of toner parent m46

In the flask identical with toner parent (1), add the 204g first resin particle dispersion liquid RL2,30g colorant particle dispersion liquid pm4,50g wax particle dispersion WA7, drop into the 300ml ion exchange water, under the condition identical, mix, make the stuff and other stuff dispersion liquid with toner (1).The pH of the mixed dispersion liquid of gained is 3.2.

Then, add 1N NaOH in the mixed dispersion liquid of gained, making pH is 11.7, and afterwards, adding 281g concentration is the magnesium sulfate solution of 23wt%, stirs 10 minutes.Afterwards, be warmed up to 90 ℃ from 20 ℃ with 1 ℃/minute speed, afterwards, heat treated 3 hours, thus core particle obtained.The pH of the core particle dispersion liquid that obtains is 9.2.

And then be under 90 ℃ the state in water temperature, rate of addition adding 43g with 5g/min is adjusted into pH 5 the second resin particle dispersion liquid RH4, after drip finishing, heat treated is 2 hours under 95 ℃ condition, has obtained the particle of second resin particle melt bonded.Then, under the condition identical, filter, wash, drying, obtain volume average particle size and be 12.1 μ m, coefficient of variation and be 32.6 and the toner parent m46 that broadens of size-grade distribution with toner (1).

Illustrated in (table 15) (table 16) (table 17) with respect to the pH in the aqueous medium in processing time, temperature, volume average particle size (d50 (μ m)).The variation of the particle diameter of toner parent M2, M4, m39, m40, m42 with respect to the processing time has been shown among Fig. 7 in addition.The change of size of M2, M4 is more stable, and the tendency of thickization of particle diameter appears after when the melt bonded reaction of the latter half of shell resin of handling in m39, m40, m42.

(table 15)

The toner parent particle	Processing time (h)	0	1	2	3	4	5	6	7	8	9
												M1	pH	11.8				9.2	6.6		6.6
Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
											d50(μm)			2.46	2.71	2.88	3.01	3.04	3.08	4.11	4.17	4.21
M2	pH	9.7				7.2			3.4
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		3.57	4.08	4.28	4.58	5.27	5.41	6.38	6.48												6.51
											M3	pH	11				8.4	5.4		5
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	95℃	95℃	95℃
												d50(μm)		2.89	3.42	3.68	3.78	3.81	3.98	4.82	4.89	4.92
M4	pH	11.9				9.3	3.2		3.4
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		2.28	2.68	3.07	3.17	3.28	3.37	4.24	4.31												4.44
											M5	pH	9.7				7			3.4
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		4.08	4.58	4.75	4.87	5.59	5.67	6.57	6.64	6.72
M6	pH	10.5				7.9	3.2		3.4
											Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
	d50(μm)		3.42	3.68	3.98	4.08	4.18	4.19	5.18	5.21												5.24
											M7	pH	11.2				8.6	3.2		3.4
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		2.89	3.08	3.29	3.38	3.45	3.49	4.58	4.62	4.63
M8	pH	11.6				8.9	3.2		3.4
											Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
	d50(μm)		2.38	2.61	2.67	2.68	2.78	2.81	3.88	3.98												4.1
											M9	pH	10.8				8.1	3.2		3.4
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		3.21	3.58	3.62	3.62	3.87	3.99	5.09	5.11	5.12
M10	pH	10.7				7.9	3.2		3.4
											Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
	d50(μm)		3.18	3.48	3.88	3.89	4.08	4.18	5.18	5.31												5.32

(table 16)

The toner parent particle	Processing time (h)	0	1	2	3	4	5	6	7	8	9
												M11	pH	11.8				9.2	6.6		6.6
Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
											d50(μm)			2.56	2.68	2.89	3.01	3.24	3.34	4.32	435	4.41
M12	pH	9.7				7.2			3.4
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		3.28	3.34	3.87	3.98	4.89	5.27	6.19	6.28												6.32
											M13	pH	11.2				8.5	5.4		5
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	95℃	95℃	95℃
												d50(μm)		2.87	3.42	3.54	3.67	3.78	3.82	4.81	4.89	5.01
M14	pH	11.9				9.3	3.2		3.4
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		2.04	2.57	2.67	2.89	3.02	3.18	4.3	434												4.42
											M15	pH	9.7				7			3.4
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		3.07	4.08	4.27	4.57	5.29	5.37	6.48	6.56	6.64
M16	pH	11.2				8.3	3.2		3.4
											Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
	d50(μm)		2.04	2.57	2.67	2.89	3.02	3.18	4.3	4.34												4.42
											M17	pH	11.2				8.6	3.2		3.4
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		2.35	2.84	2.98	3.08	337	3.47	4.67	4.78	4.82
M18	pH	11.6				8.9	3.2		3.4
											Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
	d50(μm)		2.07	2.28	2.34	2.48	2.57	2.68	3.75	3.78												3.9
											M19	pH	11.2				8.5	3.2		3.4
Temperature (℃)		70℃	70℃	85℃	85℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		2.64	2.98	3.34	3.48	3.75	3.89	5.01	5.03	5.13

(table 17)

The toner parent particle	Processing time (h)	0	1	2	3	4	5	6	7	8	9
												m38	pH	9.7				6.8			3.4
Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	90℃	90℃	90℃
											d50(μm)			3.08	4.25	5.38	5.68	7.89	8.24	9.57	10.87	12.83
m39	pH	9.7				6.9			3.4
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		3.57	5.48	6.08	6.48	8.57	10.28	13.78	16.48												18.12
											m40	pH	9.7				7			5
Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
												d50(μm)		3.98	5.48	6.24	6.42	8.08	8.98	14.89	17.8	20.73
m41	pH	9.7				6.8			2
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		3.98	5.07	6.08	6.48	8.28	8.97	15.47	18.97												22.4
											m42	pH	9				6			2
Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		4.28	5.89	6.28	7.08	8.48	9.78	14.82	17.89	20.81
m43	pH	9.7				6.8			2
											Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	95℃	95℃	95℃
	d50(μm)		3.67	5.08	5.48	5.89	7.28	7.89	13.27	16.78												18.44
											m44	pH	9				6			2
Temperature (℃)		70℃	70℃	80℃	80℃	90℃	90℃	90℃	90℃	90℃
												d50(μm)		3.27	4.98	5.67	6.08	8.38	8.79	12.67	15.87	19.23

The external additive that uses in the present embodiment has been shown in (table 18).Its carried charge by and not between the ferrite carrier of coating (blow-off) method that dispels of electrification by friction measure.Under 25 ℃, the environment of 45RH%, in the polyethylene can of 100ml with mixing such as 50g carrier and 0.1g silicon dioxide, with 100min ^-1Speed vertically rotate, stir after 5 minutes, 30 minutes, gather 0.3g, with 1.96 * 10 ⁴(Pa) nitrogen blew 1 minute.

(table 18)

The inorganic micro powder end	Raw material	Handle materials A	Handle material B	Particle diameter (nm)	Methyl alcohol titration (%)	Water absorbing capacity	Calcination loss of weight (wt%)	Dry loss of weight (wt%)	5 minutes values (μ C/g)	30 minutes values (μ C/g)	/ 30 minutes values of 5 minutes values
												S1	Silicon dioxide	The silicon dioxide that dimethyl silicone polymer was handled		6	88	0.1	10.5	0.2	-820	-710	86.6
S2	Silicon dioxide	The silicon dioxide that methylhydrogenpolysi,oxane was handled		16	88	0.1	5.5	0.2	-560	-450	80.4
												S3	Silicon dioxide	Methylhydrogenpolysi,oxane (1)		40	88	0.1	10.8	0.2	-580	-480	82.8
S4	Silicon dioxide	Dimethyl silicone polymer (20)	Aluminium distearate (2)	40	84	0.09	24.5	0.2	-740	-580	78.4
												S5	Silicon dioxide	First is hydrogen polysiloxanes (1)	Stearic amide (1)	40	88	0.1	10.8	0.2	-580	-480	82.8
S6	Silicon dioxide	Dimethyl silicone polymer (2)	Stearic acid pentaerythrite monoesters (1)	80	88	0.12	15.8	0.2	-620	-475	76.6
												S7	Silicon dioxide	Methylhydrogenpolysi,oxane (1)		150	89	0.10	6.8	0.2	-580	-480	82.8
S8	Titanium dioxide	Poly-diphenyl siloxane (10)	Odium stearate (1)	80	88	0.1	18.5	0.2	-750	-650	86.7
												S9	Silicon dioxide	The silicon dioxide that hexamethyldisilazane was handled		16	68	0.60	1.6	0.2	-800	-620	77.5

For electronegative, 5 minutes value is preferably-100～-800 μ C/g, and 30 minutes value is preferably-50～-600 μ C/g.The silicon dioxide of high-band electric weight can have been given play to function with less addition.

The composition of the toner material that uses in the present embodiment has been shown in (table 19), (table 20).Other black toner, cyan toner, yellow tone agent can also be used PB1, PC1, PY1 pigment, and the composition of other toner is identical with the composition that magenta is adjusted.

(table 19)

Toner	The toner parent	External additive A	External additive B	External additive C
					TM1	M1	S1(0.6)	S3(2.5)
TM2	M2	S2(1.8)	S4(1.5)
					TM3	M3	S1(1.8)	S5(1.2)
TM4	M4	S2(2.5)
					TM5	M5	S12.0)	S6(2.0)
TM6	M6	S2(1.8)	S7(3.5)
					TM7	M7	S1(0.6)	S8(2.0)
TM8	M8	S1(0.6)	S7(3.5)
					TM9	M9	S2(1.0)	S8(2.5)
TM10	M10	S2(1.0)	S8(2.5)	S7(1.5)
					TM11	M11	S1(0.6)	S3(2.5)
TM12	M12	S2(1.8)	S4(1.5)
					TM13	M13	S1(1.8)	S5(1.2)
TM14	M14	S2(2.5)
					TM15	M15	S12.0)	S6(2.0)
TM16	M16	S2(1.8)	S7(3.5)
					TM17	M17	S1(0.6)	S8(2.0)
TM18	M18	S1(0.6)	S7(3.5)
					TM19	M19	S2(1.0)	S8(2.5)
TM20	M20	S1(0.6)	S8(2.0)

(table 20)

Toner	The toner parent	External additive A
			tm31	m31	S1(1.0)
tm32	m32	S2(1.0)
			tm33	m33	S9(1.0)
tm38	m38	S9(0.5)
			tm39	m39	S9(0.5)
tm40	m40	S9(0.5)
			tm41	m41	S9(0.5)
tm42	m42	S9(0.5)
			tm43	m43	S9(0.5)
tm44	m44	S9(0.5)

Fig. 1 represents that the full-colour image that uses in the present embodiment forms the cut-open view with the structure of image processing system.In Fig. 1, omitted the housing of color xerographic printing machine.Transfer belt unit 17 comprises: transfer belt 12, the 1st kind of color (yellow) the transfer roll 10Y that forms by elastic body, the 2nd kind of color (magenta) transfer roll 10M, the 3rd kind of color (cyan) transfer roll 10C, the 4th kind of color (black) transfer roll 10K, the driven roller 11 that forms by the aluminium roller, the 2nd transfer roll 14 that forms by elastic body, the 2nd transfer printing driven voller 13, be used to clean the driving-belt clearance blade 16 of the toner image that remains on the transfer belt 12, and with the relative position of clearance blade on the roller 15 that is provided with.At this moment, from the distance of the 1st kind of color (Y) 2 kinds of colors of transfer position to the (M) transfer position is that 70mm is (from the distance of the 2nd kind of color (M) 3 kinds of colors of transfer position to the (C) transfer position, and also identical from the distance of the 3rd kind of color (C) 4 kinds of colors of transfer position to the (K) transfer position), the peripheral speed of photoreceptor is 125mm/s.

Transfer belt 12 is used following substances: at 95 weight portions as the polycarbonate resin of insulative resin (for example, Mitsubishi's aerochemistry is made, European Z300) in, adds 5 weight portion conductive carbon and (for example, KETJENBLACK) carry out mixing and employing extruder formation film.And, fluorine resin coating from the teeth outwards also, the thickness of gained film is about 100 μ m, and volume resistance is 10 ⁷～10 ¹²Ω cm, surface resistance is 10 ⁷～10 ¹²Ω/.Can also be used for improving the some repeatability.If volume resistance is less than 10 ⁷Ω cm then is easy to generate transfer printing again, if greater than 10 ¹²Ω cm, then transfer efficiency variation.

The 1st transfer roll is that external diameter is the electric conductivity polyurathamc roller that contains carbon of 8mm, and resistance value is 10 ²～10 ⁶Ω.When carrying out the 1st transfer operation, the 1st transfer roll 10 is crimped onto on the photoreceptor 1 by the extruding force of transfer belt 12 with 1.0～9.8 (N), and the toner on the photoreceptor is transferred on the transfer belt.If resistance value is less than 10 ²Ω then is easy to generate transfer printing once more.If greater than 10 ⁶Ω, it is not good then to be easy to generate transfer printing.If less than 1.0 (N), it is not good then to produce transfer printing, if greater than 9.8 (N), then produces the desalination of transfer printing literal.

The 2nd transfer roll 14 is that external diameter is the electric conductivity polyurathamc roller that contains carbon of 10mm, and resistance value is 10 ²～10 ⁶Ω.The 2nd transfer roll 14 is crimped onto on the transfer roll 13 by transfer belt 12 and offset mediums such as paper, OHP 19.This transfer roll 13 is to follow the structure that transfer belt 12 is rotated motion.The 2nd transfer roll 14 of the 2nd transfer printing and the extruding force crimping of relative transfer roll 13 with 5.0～21.8 (N) are transferred to toner on the recording mediums 19 such as paper from transfer belt.If resistance value is less than 10 ²Ω then is easy to generate transfer printing once more.If greater than 10 ⁶Ω, it is not good then to be easy to generate transfer printing.If less than 5.0 (N), it is not good then to produce transfer printing, if greater than 21.8 (N), then load increases, and is easy to generate image jitter.

Versicolor 4 groups of image formation unit 18Y, the 18M, 18C, the 18K that are used to form yellow (Y), pinkish red (M), cyan (C) and black (B) dispose with the series connection shape as shown in the figure like that.

Among each image formation unit 18Y, 18M, 18C, the 18K except the developer that adds, constitute by identical structure member respectively, so for simple declaration, only the image formation unit 18Y that the Y color is used describes, and omits the explanation of the unit of other color use.

Image formation unit constitutes according to mode as described as follows.The 1st, photoreceptor, the 3rd, pixel laser signal light, the 4th, developer roll, this developer roll is that the aluminium of 1200 Gausses' magnet constitutes by have magnetic force in inside, external diameter is 10mm, and faces mutually across the gap of 0.3mm with photoreceptor, rotates along the direction of arrow.The 6th, agitating roller stirs toner and carrier in the developer, and is supplied to developer roll.The interpolation of reading carrier and toner by the magnetic susceptibility sensor is supplied toner than (not shown) from toner loading hopper (not shown) in good time.The 5th, metal magnetic scraper, and the magnetic brush layer of developer is limited on the developer roll.The amount of the developer that adds is 150g.The gap is 0.4mm.Though power supply has been omitted, on developer roll 4, applied-DC voltage and 1.5kV (p-p), the frequency of 500V is the alternating voltage of 6kHz.Peripheral speed ratio between photoreceptor and the developer roll is 1: 1.6.In addition, the mixing ratio of toner and carrier is 93: 7, and the amount of the developer in the developer is 150g.

The 2nd, the external diameter that is formed by epichlorohydrin rubber is the charged roller of 10mm, and has applied-Dc bias of 1.2kv.Photoreceptor 1 surface charging is-600V.The 8th, clearer, the 9th, discarded toner case, the 7th, developer.

It is that carry below from transferring member 17 that paper is carried, and by paper feed rolls (not shown) paper 19 is transported to the nip (nip) that transfer belt 12 and 14 crimping of the 2nd transfer roll form, thereby forms the paper conveying circuit.

By being applied on the 2nd transfer roll 14+1000V, toner on the transfer belt 12 is transferred on the paper 19, and be transported to the photographic fixing portion that constitutes by fixing roller 201, backer roll 202, photographic fixing band 203, heating medium roller 204, electric induction heater 205, photographic fixing herein.

This photographic fixing technology of expression among Fig. 2.Between fixing roller 201 and hot-rolling 204, driving-belt 203 is set.Between fixing roller 201 and backer roll 202, apply the load of regulation, between transfer belt 203 and backer roll 202, form nip.The induction heater 205 that the exterior circumferential setting of hot-rolling 204 is formed by ferrite core 206 and coil 207, the surface configuration temperature sensor 208 outside.

Transfer belt is following structure: the Ni with 30 μ m is a matrix, the silicon rubber of stacked thereon 150 μ m, the PFA pipe of overlapping thereon again 30 μ m.

Backer roll 202 is pushed down fixing roller 201 by pressing spring 209.Recording materials 19 with toner 210 move along guide plate 211.

Is that 250mm, external diameter are that 14mm, thickness are on the surface of aluminum hollow roller core metal 213 of 1mm elastic layer 214 to be set as the fixing roller 201 of fixing member in length, elastic layer 214 is to be that the silicon rubber of 20 degree form by the rubber hardness (JIS-A) according to the JIS specification, and thickness is 3mm.Form the thick silastic-layer of 3mm 215 thereon, so the external diameter of fixing roller 201 is about 20mm.Be subjected to driving force, with the speed rotation of 125mm/s from the not shown drive motor that comes out.

Hot-rolling 204 is formed by the hollow tube of wall thickness 1mm, external diameter 20mm.Using thermal resistor is 170 ℃ with the surface temperature control of photographic fixing band.

Length as the backer roll 202 of pressure-producing part is that 250mm, external diameter are 20mm.This backer roll is that 16mm, thickness are that the surface of the hollow roller core metal 216 that forms of the aluminium of 1mm is provided with elastic layer 217 at external diameter, and this elastic layer 217 is to be that the silicon rubber of 55 degree form by the rubber hardness (JIS-A) according to the JIS specification, and thickness is 2mm.This backer roll 202 is set to and can rotates, and utilizes one-sided load to form the wide nip of 5.0mm that is for the loading spring 209 of 147N between backer roll 202 and fixing roller 201.

Below, operation is described.Under panchromatic mode, Y, M, the first whole transfer roll 10 of C, K are promoted, and push the photoreceptor 1 of image formation units by transfer belt 12.At this moment, on first transfer roll, apply+Dc bias of 800V.Picture signal is carried by laser 3, incides by charged roller 2 in the photoreceptor 1 of surface charging, forms electrostatic latent image.Toner on the developer roll 4 that contacts with photoreceptor 1 and rotate develops the electrostatic latent image that forms on the photoreceptor 1.

The image of the image formation unit 18Y of this moment forms speed (equate with the peripheral speed of photoreceptor, be 125mm/s) and the translational speed of transfer belt 12 is set to, and makes photoreceptor speed than transfer belt speed slow 0.5～1.5%.

Form operation by image, the flashlight 3Y of Y is input to image formation unit 18Y, forms image by the Y toner.And when forming image, by the effect of the 1st transfer roll 10Y, the Y toner image is transferred on the transfer belt 12 from photoreceptor 1Y.At this moment, on the 1st transfer roll 10Y, apply+DC voltage of 800V.

Between the transfer printing first time of the transfer printing first time of the 1st kind of color (Y) and the 2nd kind of color (M), has time delay, the flashlight 3M of M inputs to image formation unit 18M, form image by the M toner, when forming image, by the effect of the 1st transfer roll 10M, the M toner image is transferred on the transfer belt 12 from photoreceptor 1M.At this moment, transfer printing M toner on first kind of color (Y) toner that forms.Similarly, form image, when forming image,, on transfer belt 12, form the YMCK toner image by the effect of the 1st transfer roll 10C, 10B by C (cyan), K (black) toner.This mode is called the time delay mode.

The toner image position that forms on transfer belt 12 4 kinds of colors stacks the coloured image that forms with overlapping.After last B toner image transfer printing, the effect of the 2nd transfer roll 14 that passes through is transferred to the toner image of 4 kinds of colors on the paper of sending from paper feeding box (not shown) 19 under the situation about being complementary in the time in the lump.At this moment, transfer roll 13 ground connection apply on the 2nd transfer roll 14+DC voltage of 1kV.Be transferred to toner image on the paper by fixing roller to 201,202 photographic fixing.Paper is discharged to outside the device (not shown) through distributing roller thereafter.The residual toner of transfer printing that remains on the intermediate transfer belt 12 is cleaned in effect by clearance blade 16.

(table 21), (table 22) expression forms the result of image by the electro-photography apparatus of Fig. 1.Express following aspect: the film forming on photoreceptor; Image color before and after durable test changes; Be illustrated in non-image area and adhere to the state of photographic fog of the degree of toner; Homogeneity on whole during printed images; The full-colour image Chinese words part of overlapping magenta, cyan, yellow these 3 kinds of colors dispersing and local not transfer printing and remain in the state of the so-called literal desalination on the photoreceptor when transfer printing; After transfer printing yellow or magenta are adjusted, then when transfer printing magenta, cyan or black toner transfer printing yellow or magenta adjust the state that oppositely adheres to the reverse seal of getting back on the photoreceptor.

(table 21)

Developer	Toner	Carrier	Film forming on photoreceptor	After the test of image color (ID) initial stage	Photographic fog	Whole printed images homogeneity	Literal during transfer printing disperses	Reverse seal	Literal desalination in the transfer printing
										DM11	TM1	A1	Do not take place	1.43 1.42	○	○	○	○	○
DM12	TM2	B1	Do not take place	1.47 1.49	○	○	○	○	○
										DM13	TM3	C1	Do not take place	1.44 1.46	○	○	○	○	○
DM14	TM4	A2	Do not take place	1.32 1.31	○	○	○	○	○
										DM15	TM5	A1	Do not take place	1.43 1.41	○	○	○	○	○
DM16	TM6	B1	Do not take place	1.48 1.42	○	○	○	○	○
										DM17	TM7	C1	Do not take place	1.49 1.43	○	○	○	○	○
DM18	TM8	A2	Do not take place	1.38 1.32	○	○	○	○	○
										DM19	TM9	A2	Do not take place	1.37 1.32	○	○	○	○	○
DM20	TM10	A1	Do not take place	1.45 1.42	○	○	○	○	○
										DM11	TM11	A1	Do not take place	1.45 1.44	○	○	○	○	○
DM12	TM12	B1	Do not take place	1.43 1.48	○	○	○	○	○
										DM13	TM13	C1	Do not take place	1.41 1.42	○	○	○	○	○
DM14	TM14	A2	Do not take place	1.31 1.33	○	○	○	○	○
										DM15	TM15	A1	Do not take place	1.41 1.44	○	○	○	○	○
DM16	TM16	B1	Do not take place	1.46 1.43	○	○	○	○	○
										DM17	TM17	C1	Do not take place	1.48 1.52	○	○	○	○	○
DM18	TM18	A2	Do not take place	1.32 1.35	○	○	○	○	○
										DM19	TM19	A2	Do not take place	1.34 1.31	○	○	○	○	○
DM20	TM20	A1	Do not take place	1.44 1.40	○	○	○	○	○

(table 22)

Developer	Toner	Carrier	Film forming on photoreceptor	After the test of image color (ID) initial stage	Photographic fog	Whole printed images homogeneity	Literal during transfer printing disperses	Reverse seal	Literal desalination in the transfer printing
										cm31	tm31	B1	Take place	1.48 1.45	×	×	×	×	×
cm32	tm32	C1	Take place	1.50 1.52	×	×	×	×	×
										cm33	tm33	A2	Take place	1.35 1.32	×	×	×	×	×
cm38	tm38	a1	Do not take place	1.12 1.17	○	×	×	×	×
										cm39	tm39	d2	Do not take place	1.45 1.21	×	×	×	×	×
cm40	tm40	d3	Do not take place	1.39 1.19	×	×	×	×	×
										cm41	tm41	a1	Do not take place	1.29 1.12	○	×	×	×	×
cm42	tm42	d2	Do not take place	1.39 1.11	×	×	×	×	×
										cm43	tm43	a1	Do not take place	1.28 1.15	○	×	×	×	×
cm44	tm44	d2	Do not take place	1.38 1.12	×	×	×	×	×

Carried charge is by measuring with the method that dispels of ferrite carrier electrification by friction.Under 25 ℃, the environment of relative humidity 45%RH, gather 0.3g durability evaluation sample, 1.96 * 10 ⁴(Pa) blew under the nitrogen 1 minute.

When using developer to form image, under high image density, can not produce background fog yet, can not produce dispersing of toner etc., can obtain to high resolving power image color and be the high concentration image more than 1.3 in non-image part.In addition, in the long durability test of 100,000 A4 paper, variation mobile, image color is also less, demonstrates stable properties.In addition, when developing, the homogeneity when forming whole printed images is also good.Can not produce the memory of developing yet.

When using continuously, can not produce the unusual image of vertical stripes yet.Also can produce the consumption of toner composition on carrier hardly.Can also reduce the carrier changes in resistance, and the reduction that reduces carried charge, the charged rising the during rapid recharge of toner is also good, under high humidity environment, does not find the phenomenon that photographic fog increases.

In addition, when long-term the use, can keep high saturated zone electric weight for a long time.Under low temperature and low humidity, the variation of carried charge does not almost take place yet.Even the mixture ratio of toner and carrier is changed to 5-20wt% in addition, the variation of picture qualities such as image color, background fog is also few, can control wide toner concentration.

In addition, in transfer printing, the literal desalination also is no problem level in practicality, and transfer efficiency is shown as about 95%.In addition, toner also is the practical no problem level that to the film forming of photoreceptor, transfer belt.The not good problem of cleaning of transfer belt does not take place yet.In addition, when photographic fixing, almost there are not the disorder of toner and dispersing of toner yet.In addition, overlapping in the full-colour image of 3 kinds of colors, it is not good not produce transfer printing, when photographic fixing, does not produce the coiling of paper to the photographic fixing band yet.

For cm31-33, cm38-44, charged rising takes place, photographic fog increases.In addition, forming continuously whole printed images by two-component developing agent, and then during the rapid recharge toner, carried charge reduces, photographic fog increases.Under high humidity environment, this phenomenon is poor especially.Even the mixture ratio of toner and carrier changes in the 5-8wt% concentration range, picture qualities such as image color, background fog change also few, if but during less than the value of this scope, image color descends, and if during greater than the value of this scope, photographic fog increases.Producing during transfer printing disperses around literal and produce the transfer printing literal desalinates.

Having illustrated adhesive capacity in (table 23), (table 24) is 1.2mg/cm ²Whole printed images with processing speed 125mm/s, use the not fixing device that is shown in Fig. 2 of the transfer belt of dope, estimate temperature that OHP transmitance (160 ℃ of fixing temperatures), minimum fixing temperature (not producing the dirty temperature of residual cold bonding on the photographic fixing band when toner does not melt), high temperature produces bonding-miry capacity down, preserve 5 hours storage-stable down, the result of the coiling of paper on the photographic fixing band during in photographic fixing at 60 ℃.

(table 23)

Toner	OHP transmitance (%)	Minimum fixing temperature (℃)	The temperature of high temperature generation set-off (℃)	The storage-stable test	Coiling on the photographic fixing band	Toner disorder during photographic fixing
							TM1	86.7	135	210	○	Do not take place	Do not take place
TM2	82.7	140	215	○	Do not take place	Do not take place
							TM3	83.7	135	210	○	Do not take place	Do not take place
TM4	87.9	135	220	○	Do not take place	Do not take place
							TM5	86.1	135	215	○	Do not take place	Do not take place
TM6	83.4	125	210	○	Do not take place	Do not take place
							TM7	88.4	130	215	○	Do not take place	Do not take place
TM8	87.6	130	210	○	Do not take place	Do not take place
							TM9	90.1	130	210	○	Do not take place	Do not take place
TM10	84.9	130	210	○	Do not take place	Do not take place
							TM11	86.8	135	210	○	Do not take place	Do not take place
TM12	82.1	140	215	○	Do not take place	Do not take place
							TM13	84.6	135	210	○	Do not take place	Do not take place
TM14	88.7	135	220	○	Do not take place	Do not take place
							TM15	82.1	135	215	○	Do not take place	Do not take place
TM16	84.1	125	210	○	Do not take place	Do not take place
							TM17	89.8	130	215	○	Do not take place	Do not take place
TM18	88.7	130	210	○	Do not take place	Do not take place
												Do not take place	Do not take place

(table 24)

Toner	OHP transmitance (%)	Minimum fixing temperature (℃)	The temperature of high temperature generation set-off (℃)	The storage-stable test	Coiling on the photographic fixing band	Toner disorder during photographic fixing
							tm31	90.2	140	180	○	Do not take place	Do not take place
tm32	83.2	140	210	×	Do not take place	Do not take place
							tm33	81.8	140	210	×	Do not take place	Do not take place
tm38	50.1	170	190	○	Take place	The generation toner disperses
							tm39	49.8	170	190	○	Take place	The generation toner disperses
tm40	45.6	170	190	○	Take place	The generation toner disperses
							tm41	90.8	140	150	×	Take place	The generation toner disperses
tm42	91.8	140	150	×	Take place	The generation toner disperses
							tm43	87.9	140	160	○	Take place	The generation toner disperses
tm44	83.2	140	160	○	Take place	The generation toner disperses

The OHP transmitance is measured the transmitance of the light of 700nm by spectrophotometer U-3200 (Hitachi's manufacturing).Storage-stable is illustrated in 60 ℃ of results that place down after 5 hours.

For the TM1-TM19 toner, the obstruction that the fixing nip part does not produce OHP.For whole printing of common paper green image, set-off does not all take place on 200,000 paper.Even dope on silicones or fluorine class photographic fixing band is not found the surperficial variation phenomenon of transfer belt yet.The OHP light transmission is shown as more than 80%, and in the photographic fixing band that does not use oil, also can obtain the non-set-off temperature range than broad.In addition, in the storage-stable test, almost do not find to have cohesion (being expressed as zero grade) yet.

The temperature that tm31, tm41, tm42, tm43, tm44 toner at high temperature produce bonding-miry capacity is low, and the set-off boundary narrows down.Tm32, tm33, tm41, tm42 toner it is generally acknowledged that the minimum fixing temperature height and the photographic fixing amplitude of tm38, tm39, tm40 toner are narrow to the residual influential storage-stable equal difference of wax on the toner particle surface.

The present invention also is applicable to directly to adhere to the toner that is added with conductive material in the mode of printing on the paper and on substrate as the mode of printing of Wiring pattern etc. except being applicable to the electrofax mode that has adopted photoreceptor.

Claims (53)

1. toner, its be by in aqueous medium to the major general disperseed resin particle resin particle dispersion liquid, disperseed the colorant particle dispersion liquid of colorant particle and disperseed the wax particle dispersion of wax particle to mix, and form by the cohesion heating, wherein, the major component that is used for the surfactant of described resin dispersion is a non-ionic surfactant, and the major component that is selected from the surfactant that is used for described wax dispenser and is used at least a surfactant among the surfactant of described colorant dispersion is a non-ionic surfactant.

2. according to the toner of claim 1 record, the major component that wherein is used for the surfactant of described wax dispenser only is a non-ionic surfactant, and is used for the glass or plastic containers of described resin dispersion and the potpourri of ionic surfactant.

3. according to the toner of claim 1 record, the major component that wherein is used for the surfactant of described colorant dispersion only is a non-ionic surfactant, and is used for the glass or plastic containers of described resin dispersion and the potpourri of ionic surfactant.

4. according to the toner of claim 1 record, wherein said wax comprises first wax and second wax at least, described first wax contains by the DSC method measures the endothermic peak temperature obtain (be called fusing point Tmw1 (℃)) be 50～90 ℃ wax, described second wax contains by the DSC method measures the endothermic peak temperature that obtains (fusing point Tmw2 (℃)) than the also high 5-70 ℃ wax of the Tmw1 of described first wax.

5. according to the toner of claim 1 record, wherein said wax comprises first wax and second wax at least, and described first wax contains that iodine number is below 25, saponification number is the wax of 30-300, and described second wax contains aliphatic hydrocarbon wax.

6. according to the toner of claim 1 record, wherein said wax comprises first wax and second wax at least, it is at least a ester type waxes of forming among the higher alcohol of 16-24 and the higher fatty acid that carbon number is 16-24 that described first wax contains by carbon number, and described second wax contains aliphatic hydrocarbon wax.

7. according to the toner of claim 5 or 6 records, wherein the endothermic peak temperature that is obtained by DSC method mensuration of first wax is 50～90 ℃.

8. according to the toner of claim 5 or 6 records, wherein the endothermic peak temperature that is obtained by DSC method mensuration of second wax is 80～120 ℃.

9. according to the toner of any one record of claim 4-6, wherein when will being set at EW1 with respect to the part by weight of first wax of 100 weight portions of the wax in the wax particle dispersion, when the part by weight of second wax was set at TW2, TW2/EW1 was 0.2-10.

10. according to the toner of claim 9 record, wherein when will being set at EW1 with respect to the part by weight of first wax of 100 weight portions of the wax in the wax particle dispersion, when the part by weight of second wax was set at TW2, TW2/EW1 was 1-9.

11. according to the toner of any one record of claim 4-6, wherein the wax particle dispersion prepares by described first wax and described second wax are carried out the mixing and emulsifying dispersion treatment.

12. according to the toner of any one record of claim 4-6, wherein the wax particle dispersion is by being that the surfactant of major component carries out the mixing and emulsifying dispersion treatment with described first wax and described second wax and prepares in order to non-ionic surfactant.

13. toner according to any one record of claim 4-6, the major component that wherein is used for the surfactant of resin dispersion is a non-ionic surfactant, and the major component that is used for the surfactant of colorant dispersion is non-ionic surfactant, and the major component that is used for the surfactant of wax dispenser is a non-ionic surfactant.

14. toner according to claim 13 record, wherein be used for the glass or plastic containers of described resin dispersion and the mixing of ionic surfactant, its blending ratio is that non-ionic surfactant is more than the 60wt% with respect to whole surfactant.

15. according to the toner of claim 13 record, wherein being used for the major component of surfactant of described colorant dispersion and the major component that is used for the surfactant of described wax dispenser only is non-ionic surfactant.

16. toner according to claim 1, any one record of 4-6, wherein the volume average particle size of toner is 3～7 μ m, the content of toner parent particle that has the particle diameter of 2.52～4 μ m in number distributes is 10～75 number %, the content of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is 25～75 volume %, and the content that has the toner parent particle of the particle diameter more than the 8 μ m in volume distributed median is below the 5 volume %; The volume % of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is set at V46, when the number % of toner parent particle that has the particle diameter of 4～6.06 μ m during number distributed was set at P46, P46/V46 was the scope of 0.5-1.5.

17. the manufacture method of toner, it is by disperseed the resin particle dispersion liquid of resin particle to the major general in aqueous medium, disperse the colorant particle dispersion liquid of colorant particle and disperseed the wax particle dispersion of wax particle to mix, and form toner by cohesion heating, the major component that wherein is used for the surfactant of described resin dispersion is a non-ionic surfactant, and the major component that is selected from least a surfactant among surfactant that is used for described wax dispenser and the surfactant that is used for described colorant dispersion is a non-ionic surfactant

Described manufacture method comprises following operation:

Make the operation of the mixed dispersion liquid be the resin particle dispersion liquid that has disperseed described resin particle, the colorant particle dispersion liquid that has disperseed described colorant particle and the wax particle dispersion that disperseed described wax particle at least,

The pH of described mixed dispersion liquid is adjusted into 9.5-12.2 scope operation and

Add water-soluble inorganic salt, and carry out heat treated, thereby described resin particle, described colorant particle and described wax particle condense the operation of the aggregated particle that is melted with formation at least a portion.

18. manufacture method according to the toner of claim 17 record, the major component that wherein is used for the surfactant of described wax dispenser only is a non-ionic surfactant, and is used for the glass or plastic containers of described resin dispersion and the potpourri of ionic surfactant.

19. manufacture method according to the toner of claim 17 record, the major component that wherein is used for the surfactant of described colorant dispersion only is a non-ionic surfactant, and is used for the glass or plastic containers of described resin dispersion and the potpourri of ionic surfactant.

20. according to the manufacture method of the toner of claim 17 record, the major component that wherein is used for the surfactant of described resin dispersion, described wax dispenser and described colorant dispersion is a non-ionic surfactant.

21. according to the manufacture method of the toner of claim 17 record, the pH when wherein forming described particle is the scope of 7.0-9.5, and then pH is adjusted into the scope of 2.2-6.8 and carries out heat treated to form the aggregated particle that at least a portion is melted.

22. according to the manufacture method of the toner of any one record of claim 17-21, it comprises following operation: in having disperseed the aggregated particle dispersion liquid of described aggregated particle, add the operation of second resin particle dispersion liquid that has disperseed second resin particle again; The pH that has disperseed the aggregated particle dispersion liquid of described aggregated particle is adjusted into the operation of the scope of 2.2-6.8; In having disperseed the aggregated particle dispersion liquid of described aggregated particle, add second resin particle dispersion liquid that has disperseed second resin particle, under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, pH is adjusted into the operation of the scope of 5.2-8.8; And under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, thereby on described aggregated particle the operation of melt bonded described second resin particle.

23. according to the manufacture method of the toner of any one record of claim 17-22, it comprises following operation: in having disperseed the aggregated particle dispersion liquid of described aggregated particle, add the operation of second resin particle dispersion liquid that has disperseed second resin particle again; The pH that has disperseed the aggregated particle dispersion liquid of described aggregated particle is adjusted into the operation of the scope of 2.2-6.8; In having disperseed the aggregated particle dispersion liquid of described aggregated particle, add second resin particle dispersion liquid that has disperseed second resin particle, under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, pH is adjusted into the operation of the scope of 5.2-8.8; Under the temperature more than the glass transition temperature of described second resin particle, carry out the operation of heat treated; PH is adjusted into the operation of the scope of 2.2-6.8; And further under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, thereby on described aggregated particle the operation of melt bonded described second resin particle.

24. manufacture method according to the toner of any one record of claim 17-23, wherein said wax particle dispersion prepares by using surfactant to major general's first wax and second wax to carry out the mixing and emulsifying dispersion treatment, described first wax contains by the DSC method measures the endothermic peak temperature obtain (be called fusing point Tmw1 (℃)) be 50～90 ℃ wax, described second wax contains by the DSC method measures the endothermic peak temperature that obtains (be called fusing point Tmw2 (℃)) than the also high 5-70 ℃ wax of the Tmw1 of described first wax.

25. manufacture method according to the toner of any one record of claim 17-24, wherein wherein said wax prepares by using surfactant to major general's first wax and second wax to carry out the mixing and emulsifying dispersion treatment, described first wax contains that iodine number is below 25, saponification number is the wax of 30-300, and described second wax contains aliphatic hydrocarbon wax.

26. manufacture method according to the toner of any one record of claim 17-25, wherein said wax prepares by using surfactant to major general's first wax and second wax to carry out the mixing and emulsifying dispersion treatment, it is at least a ester type waxes of forming among the higher alcohol of 16-24 and the higher fatty acid that carbon number is 16-24 that described first wax contains by carbon number, and described second wax contains aliphatic hydrocarbon wax.

27. according to the manufacture method of the toner of any one record of claim 24-26, it comprises following operation: making is the operation of resin particle dispersion liquid, colorant particle dispersion liquid that has disperseed colorant particle that has disperseed resin particle and the mixed dispersion liquid of the wax particle dispersion that has disperseed the wax particle at least; The pH of described mixed dispersion liquid is adjusted into the operation of the scope of 9.5-12.2; And the interpolation water-soluble inorganic salt, carry out heat treated, thereby described resin particle, colorant particle and described wax particle condense the operation of the aggregated particle that is melted with formation at least a portion.

28. according to the manufacture method of the toner of any one record of claim 24-27, it comprises following operation: making is the operation of resin particle dispersion liquid, colorant particle dispersion liquid that has disperseed colorant particle that has disperseed resin particle and the mixed dispersion liquid of the wax particle dispersion that has disperseed the wax particle at least; The pH of described mixed dispersion liquid is adjusted into the operation of the scope of 9.5-12.2; Add water-soluble inorganic salt, carry out the operation of heat treated; And the scope that afterwards pH is adjusted into 2.2-6.8, carry out heat treated, thereby described resin particle, described colorant particle and described wax particle condense the operation of the particle that is melted with formation at least a portion.

29. according to the manufacture method of the toner of any one record of claim 24-28, it comprises following operation: in having disperseed the aggregated particle dispersion liquid of described aggregated particle, add the operation of second resin particle dispersion liquid that has disperseed second resin particle again; The pH that has disperseed the aggregated particle dispersion liquid of described aggregated particle is adjusted into the operation of the scope of 2.2-6.8; And in having disperseed the aggregated particle dispersion liquid of described aggregated particle, add second resin particle dispersion liquid disperseed second resin particle, under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, thus on described aggregated particle the operation of melt bonded described second resin particle.

30. according to the manufacture method of the toner of any one record of claim 24-29, it comprises following operation: in having disperseed the aggregated particle dispersion liquid of described aggregated particle, add the operation of second resin particle dispersion liquid that has disperseed second resin particle again; The pH that has disperseed the aggregated particle dispersion liquid of described aggregated particle is adjusted into the operation of the scope of 2.2-6.8; In having disperseed the aggregated particle dispersion liquid of described aggregated particle, add second resin particle dispersion liquid that has disperseed second resin particle, under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, again pH is adjusted into the operation of the scope of 5.2-8.8; And under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, thereby on described aggregated particle the operation of melt bonded described second resin particle.

31. according to the manufacture method of the toner of any one record of claim 24-30, it comprises following operation: in having disperseed the aggregated particle dispersion liquid of described aggregated particle, add the operation of second resin particle dispersion liquid that has disperseed second resin particle again; The pH that has disperseed the aggregated particle dispersion liquid of described aggregated particle is adjusted into the operation of the scope of 2.2-6.8; In having disperseed the aggregated particle dispersion liquid of described aggregated particle, add second resin particle dispersion liquid that has disperseed second resin particle, under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, again pH is adjusted into the operation of the scope of 5.2-8.8; Under the temperature more than the glass transition temperature of described second resin particle, carry out the operation of heat treated; PH is adjusted into the operation of the scope of 2.2-6.8; And further under the temperature more than the glass transition temperature of described second resin particle, carry out heat treated, thereby on described aggregated particle the operation of melt bonded described second resin particle.

32. according to the manufacture method of the toner of any one record of claim 24-31, wherein first wax to measure the endothermic peak temperature that obtains by the DSC method be 50～90 ℃.

33. according to the manufacture method of the toner of any one record of claim 24-31, wherein second wax to measure the endothermic peak temperature that obtains by the DSC method be 80～120 ℃.

34. manufacture method according to the toner of any one record of claim 24-31, wherein when being set at EW1 with respect to the part by weight of first wax of 100 weight portions of the wax in the wax particle dispersion, when the part by weight of second wax was set at TW2, TW2/EW1 was 0.2-10.

35. according to the manufacture method of the toner of claim 34 record, wherein when will being set at EW1 with respect to the part by weight of first wax of 100 weight portions of the wax in the wax particle dispersion, when the part by weight of second wax was set at TW2, TW2/EW1 was 1-9.

36. according to the manufacture method of the toner of any one record of claim 24-31, wherein the wax particle dispersion is by being that the surfactant of major component carries out the mixing and emulsifying dispersion treatment with described first wax and described second wax and prepares in order to non-ionic surfactant.

37. manufacture method according to the toner of any one record of claim 24-31, the major component that wherein is used for the surfactant of resin dispersion is a non-ionic surfactant, and the major component that is used for the surfactant of colorant dispersion is non-ionic surfactant, and the major component that is used for the surfactant of wax dispenser is a non-ionic surfactant.

38. manufacture method according to the toner of claim 37 record, wherein be used for the glass or plastic containers of described resin dispersion and the mixing of ionic surfactant, its blending ratio is that non-ionic surfactant is more than the 60wt% with respect to whole surfactant.

39. according to the manufacture method of the toner of claim 37 record, the major component that wherein is used for the surfactant of described colorant dispersion only is a non-ionic surfactant.

40. according to the manufacture method of the toner of claim 37 record, the major component that wherein is used for the surfactant of described wax dispenser only is a non-ionic surfactant.

41. manufacture method according to the toner of any one record of claim 24-31, wherein the volume average particle size of toner is 3～7 μ m, the content of toner parent particle that has the particle diameter of 2.52～4 μ m in number distributes is 10～75 number %, the content of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is 25～75 volume %, and the content that has the toner parent particle of the particle diameter more than the 8 μ m in volume distributed median is below the 5 volume %; The volume % of toner parent particle that has the particle diameter of 4～6.06 μ m in volume distributed median is set at V46, when the number % of toner parent particle that has the particle diameter of 4～6.06 μ m during number distributed was set at P46, P46/V46 was the scope of 0.5-1.5.

42. two-component developing agent, it is made up of toner and carrier, wherein said toner is that the mean grain size of adding 1～6 weight portion scope with respect to this toner parent of 100 weight portions at the toner parent of any one record of claim 1-16 or in by the toner parent of the method manufacturing of any one record of claim 17-41 is that the inorganic micro powder end of 6nm～200nm scope forms, and described carrier contains magnetic particle as core, and wherein the surface of core covers with the fluorine modified organic silicone resin that contains amino silicane coupling agent at least.

43. two-component developing agent according to claim 42 record, wherein magnetic particle is made up of adhesive resin and fine magnetic-substance particle, the phenolics that described adhesive resin solidifies by making the reaction of aldehydes and phenols is formed, the content of described fine magnetic-substance particle is 80-99wt%, and number average bead diameter is 10-60 μ m.

44. two-component developing agent according to claim 42 or 43 records, wherein with respect to 100 weight portion toner parents, the mean grain size of adding 0.5～2.5 weight portion is the inorganic micro powder end of 6nm～20nm, and the mean grain size of adding 0.5～3.5 weight portion is the inorganic micro powder end of 20nm～200nm.

45. two-component developing agent according to claim 42 or 43 records, wherein with respect to 100 weight portion toner parents, the mean grain size of adding 0.5～2.5 weight portion is that 6nm～20nm, burning decrement are the inorganic micro powder end of 0.5-20wt%, and the mean grain size of adding 0.5～3.5 weight portion is that 20nm～200nm, burning decrement are the inorganic micro powder end of 1.5-25wt%.

46. the two-component developing agent according to claim 42 or 43 records wherein in the application of resin of carrier, contains 5-40 weight portion amino silicane coupling agent with respect to 100 weight portion application of resin.

47. the two-component developing agent according to claim 42 or 43 records wherein in the application of resin layer, contains 1-15 weight portion conductive powders with respect to 100 weight portion application of resin.

48. according to the two-component developing agent of claim 42 or 43 records, wherein said application of resin is the 0.1-5.0 weight portion with respect to 100 weight portion carrier cores.

49. according to the two-component developing agents of claim 42 or 43 records, wherein said fluorine modified organic silicone resin is that the organo-silicon compound that make 100 weight portion polysiloxane and 3 weight portions～20 weight portions contain perfluoroalkyl react and the bridging property fluorine modified organic silicone resin that obtains.

50. according to the two-component developing agent of claim 49 record, the organo-silicon compound that wherein contain perfluoroalkyl are to be selected from CF ₃CH ₂CH ₂Si (OCH ₃) ₃, C ₄F ₉CH ₂CH ₂Si (CH ₃) (OCH ₃) ₂, C ₈F ₁₇CH ₂CH ₂Si (OCH ₃) ₃, C ₈F ₁₇CH ₂CH ₂Si (OC ₂H ₅) ₃(CF ₃) ₂CF (CF ₂) ₈CH ₂CH ₂Si (OCH ₃) ₃Among at least a.

51. according to the two-component developing agent of claim 49 record, wherein said polysiloxane is at least one that is selected from following Chemical formula 1 and the Chemical formula 2,

(Chemical formula 1)

In the formula, R ¹, R ²Expression hydrogen atom, halogen atom, hydroxyl, methoxyl, carbon number are 1～4 alkyl or phenyl; R ³, R ⁴The expression carbon number is 1～4 alkyl or phenyl, and m is average degree of polymerization and is positive integer,

(Chemical formula 2)

In the formula, R ¹, R ²Be respectively that hydrogen atom, halogen atom, hydroxyl, methoxyl, carbon number are 1～4 alkyl or phenyl; R ³, R ⁴, R ⁵And R ⁶The expression carbon number is 1～4 alkyl or phenyl, and n represents average degree of polymerization and is positive integer.

52. image processing system, it possesses magnetic field and produces mechanism and heating and pressurizing mechanism, this heating and pressurizing mechanism comprises heater block with turning effort and the pressure-producing part with turning effort at least, wherein said heater block has heating layer and the release layer by the electromagnetic induction heating at least, and described pressure-producing part and described heater block are formed with predetermined gap;

Described device have between described heater block and described pressure-producing part, make transfer printing the offset medium of toner by carrying out the photographic fixing technology of photographic fixing, the toner in the toner that wherein said toner is the toner of any one record of claim 1-16, made by the method for any one record of claim 17-41 or the two-component developing agent of any one record of claim 42-51.

53. an image processing system, it has a plurality of toner images and forms station and transferring system, and described toner image forms charged mechanism and the toner carrier that the station comprises image-carrier at least, forms electrostatic latent image on described image-carrier;

Described transferring system is constituted as implements primary transfer technology and secondary transfer printing technology;

Wherein in described primary transfer technology, toner development in the toner that the electrostatic latent image that forms on described image-carrier is made with the toner of any one record of claim 1-16, by the method for any one record of claim 17-41 or the two-component developing agent of any one record of claim 42-51, thereby and make described image-carrier and annular transfer article contact the described toner image that above-mentioned latent electrostatic image developingization is formed to be transferred on the described transfer article;

Described primary transfer technology is implemented successively continuously, thereby on described transfer article, form the multilayer transfer toner image, implement secondary transfer printing technology then, this secondary transfer printing technology is that the multilayer toner image that will form on described transfer article is transferred on the offset medium together;

Wherein said transfer printing process is the formation that satisfies following condition: will be d1 (mm) from the distance between 2 primary transfer positions, the 1st primary transfer position to the or from the distance between 3 primary transfer positions, the 2nd primary transfer position to the or from the distance setting between 4 primary transfer positions, the 3rd primary transfer position to the, the peripheral speed of photoreceptor is set at v when (mm/ second), d1/v≤0.65 (second).

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