CN100555089C - Toner and developer and the formation method and the device that use this developer - Google Patents

Abstract

The present invention discloses a kind of toner, and it comprises that average circularity is female toner of 0.93-0.99, and the vibrin and the colorant that comprise modification; And primary particle size is that 5-20nm and secondary granule diameter are the external additive of 50-200nm, its amount is the female toner of 0.3-5.0 weight portion external additive/100 weight portions, wherein the melt viscosity of toner is 70-140Pas down at 160 ℃, weight median particle diameter is 3-7 μ m, weight median particle diameter is 1.91-1.25 with the ratio of number average particle diameter, diameter is the amount of 4 μ m or littler particle, pressing number calculates, less than 10%, perhaps diameter is the amount of 8 μ m or bigger particle, by volume calculate, less than 2%.

Description

Toner and developer and the formation method and the device that use this developer

Technical field

The present invention relates to a kind of toner that is used in the developer, and the electrophotographic image forming method and the imaging device that use this toner, this developer is used at developing electrostatic latent images such as electrofax, electrostatic recording and xeroprinting.

Background technology

In developing process, the developer that uses in the electrostatic latent image in electrofax, electrostatic recording and the xeroprinting etc. adheres to image carrier, in the time of for example on the photoreceptor, forms electrostatic latent image thereon; In transfer process, electrostatic latent image is transferred on the offset medium from it, for example on the transfer paper; And in fixing, with its photographic fixing on offset medium.The developer that is formed on the electrostatic latent image on the image carrier that develops comprises two-component developing agent and monocomponent toner, and wherein two-component developing agent is made by carrier and toner; Monocomponent toner does not have carrier, that is, and and magnetic and nonmagnetic toner.

By convention, the dry toner that is used for wherein is by under heating, mediates toner binder and colorant as styrene resin and vibrin etc., forms and mediates potpourri, cool off this potpourri solidifying this potpourri, and the potpourri of pulverizing this curing forms.

Reduce the particle diameter of toner, have high definition and high-quality image with generation.Yet, has unbodied shape and can not classification by the toner that routine is mediated and breaking method forms, this is because the ultra-fine grain (ultrafine Particle) of strong adhesive force even after classification, remains adhered on the toner of required particle diameter.In imaging device, owing in the image developing device, stir and because the contact pressure of regulating blade and frictional electrification blade with developer roll, toner supplying roller, bed thickness with carrier, so this ultra-fine grain is attached on carrier and the device feature, and it is fixed thereon, simultaneously fluidizing agent is buried in the surface of toner, and this causes the deterioration of image quality that generates.In addition, (fluidity) is low for the flowability of unbodied toner, and as powder, it needs a large amount of fluidizing agents, and its filling rate that is packed into toner bottle is so low, so that unbodied toner is one of obstacle that reduces plant bulk.Therefore, can't fully use the toner of small particle diameters.And kneading and breaking method have the limitation of particle diameter, and can not further reduce particle diameter.

And for stablizing the various character of toner, for example the chargeability of toner uses a kind of method to come the distribution of peaking (sharpen) toner-particle diameter.Yet when the average particulate diameter of toner did not match mutually with concrete particle diameter distribution, this method can not be brought into play good effect.That is to say that the average particulate diameter of toner is mean value after all, and can not show the content of the toner of less and larger particles diameter.In addition, insufficient in their summary and concrete relations therebetween, and toner preferably has concrete particle diameter distribution and the shape consistent with average particulate diameter, and further suitable correlativity is arranged with external additive.

And, for producing full-colour image, to just become complicated from the transfer process that photoreceptor is transferred on offset medium and the paper by the image that multiple color toner forms, and because the transfer printing (transferability) of its difference, the toner that consumes a large amount of amorphous pulverizing remedies image impairment (imageomission).

Yet, remove the clearer of remaining toner from photoreceptor and offset medium, can not be used for removing spherical toner as cleaning blade and cleaning brush, and produce bad cleaning.In addition, the whole surface of spherical toner is exposed to the outside, and spherical toner easily with carrier with contact such as live parts such as charged blades.Therefore, the external additive and the charge control agent (charge controlling agent) that are present on the toner surface are buried in the toner easily, thereby worsen the flowability of toner.

Therefore, require to reduce the consumption of toner by the transfer printing that improves toner, thereby reach the image that reduces operating cost and produce high definition, and do not have image impairment, this requirement increases just gradually.This is because better transfer performance can be save the cleaning element (cleaning unit) that the toner of not transfer printing is removed from photoreceptor and offset medium, thereby can further reduce device size, reduces its cost, and does not have waste of toner simultaneously.For improving unfavorable factor, invented the method for producing the toner of different shape owing to shape.The method that produces toner by suspension polymerization only can produce the toner of sphere or subglobular, and because irregular shearing force acts in the water on the toner materials in the suspended dispersed body, so be easy to generate superfines.Therefore the toner that generates still has relatively poor cleanablity (cleanability), and on the parts attached to carrier and device.On the other hand, the method by emulsion polymerization generation toner can produce amorphous and spherical toner.Yet when heating, the further shape of toner after the control polymerization, and the superfines of condensing in water is tended to keep, and therefore the toner of generation still has relatively poor cleanablity, and on the parts attached to carrier and device.And, the toner that produces by these two kinds of methods as former method, do not considered separately toner and with the suitability of external additive.

A kind of polymer dissolution suspension process that volume is reduced is disclosed among the Japanese Patent Application Publication text 7-152202.

This method comprises: toner materials is dispersed or dissolved in the volatile solvent, for example in the low melting point organic solvent, to form dispersion or solution; In comprising the aqueous medium of spreading agent, this dispersion or emulsifying soln are become drop; And therefrom remove volatile solvent.Then, the volume-diminished of drop when the solid particle spreading agent that uses water insoluble medium during as spreading agent, only forms amorphous granular.

When increasing solid content when boosting productivity, the viscosity of disperse phase increases and the particle that generates has bulky grain diameter and wide particle diameter distribution.When the viscosity of disperse phase reduces by using low-molecular-weight resin, but the heat resistanceheat resistant offset behavior of fixation performance (fixability), particularly gained toner (hot offset resistance) worsens.

A kind of method is disclosed among the Japanese Patent Application Publication text 11-149179, this method uses low-molecular-weight resin to reduce the viscosity of disperse phase in the polymer dissolution suspension process, and make emulsification easier, and carry out intergranular polymerization (inter-particle polymerization) but improve the fixation performance of gained toner.Yet this does not improve transfer printing, cleanablity and the control shape ability of toner.

In addition, because irregular shearing force acts on the toner materials in the suspended dispersed body in the water, so be easy to generate superfines.Therefore the toner that generates still has relatively poor cleanablity, and on the parts attached to carrier and device.

After shifting, heat these dry toner photographic fixing at offset medium, for example on the paper by warm-up mill.When the temperature of warm-up mill is too high, toner excess molten and melt bonded (thermal migration) thereon.When temperature was too low, toner is fully fusing not, and photographic fixing fully thereon.

With regard to energy savings with reduce with regard to the device size, but require toner to have heat resistanceheat resistant offset behavior and low temperature fixation performance.And, but require toner to have heat-resisting keeping quality (thermostablepreservability), so that it does not at room temperature lump in device (block).Particularly, the toner that requires to be used for panchromatic duplicating machine and printer has gloss and color miscibility, thereby requires this toner to have lower melt viscosity, and the polyester toner bonding agent that uses clear and definite fusion (sharp melting) within it.Yet this toner has relatively poor heat resistanceheat resistant offset behavior, thereby generally silicone oil (silicone oil) is coated on the warm-up mill of panchromatic device.

Yet the method that silicone oil is coated on the warm-up mill needs fuel tank and baster, thereby makes that the complicated also change of volume of device is big.In addition, warm-up mill worsens and needs periodic maintenance.And silicone oil is attached on copy paper and OHP (the top formula projector) film inevitably, and particularly, silicone oil has damaged the tone of ohp film.

For above-mentioned reasons, need toner to have smaller particles diameter and good flowability, development property (developability) and transfer printing, and can produce high-quality image for a long time, and do not have film forming, and have long serviceable life.

Summary of the invention

Therefore, the purpose of this invention is to provide a kind of toner, it has smaller particles diameter and good flowability, development property and transfer printing, and can produce high-quality image for a long time, and does not have film forming, and has long serviceable life.

Another object of the present invention provides a kind of toner container (tonercontainer) of toner, the developer that comprises this toner, the formation method that uses this developer and imaging device of being filled with.

Briefly, these purposes of the present invention and other purpose will become more apparent hereinafter, these purposes can obtain by a kind of toner, this toner comprises average circularity (circularity) and is the particle toner materials of 0.93-0.99, and comprises the polyester binder resin and the colorant of modification; And primary particle size is that 5-20nm and secondary granule diameter are the external additive of 50-200nm, wherein the melt viscosity of toner under 160 ℃ is 70-140Pas, the weight median particle diameter of toner (D4) is 3-7 μ m, the ratio (D4/Dn) of the weight median particle diameter of toner and number average particle diameter (Dn) is 1.91-1.25, by number, particle diameter is no more than the amount of particle of 4 μ m less than 10%, perhaps by volume, particle diameter is not less than the amount of 8 μ m particles less than 2%, and the particle toner materials that whenever comprises 100 weight portions, comprise the external additive of 0.3-5.0 weight portion in the toner.

Consider the description of the following preferred embodiment of the invention and in conjunction with the accompanying drawings, these and other purposes of the present invention, characteristics and benefit will be apparent.

Description of drawings

When considering various other purposes of the present invention, characteristics and subsidiary benefit in conjunction with the accompanying drawings, will more fully understand and understand various other purposes of the present invention, characteristics and subsidiary benefit, similar Reference numeral is represented corresponding parts in whole accompanying drawing, wherein:

Figure 1A-1D is illustrative embodiment that the photographic layer of amorphous silicon photoreceptor used in this invention is constituted respectively;

An embodiment of Fig. 2 illustrative imaging device of the present invention;

Another embodiment of Fig. 3 illustrative imaging device of the present invention;

The embodiment of Fig. 4 illustrative handle box of the present invention (process cartridge);

Fig. 5 illustrative is used the 3rd embodiment of the imaging device of the present invention of turbulent waves fuser (surf fixer);

Fig. 6 shows the figure with the charged character of the photoreceptor of the present invention after the charging of contact charging device;

Fig. 7 illustrates the part explanation to use four embodiment of charging roller as the imaging device of the present invention of contact charging device; And

Fig. 8 illustrates part explanation to use hairbrush (fur brush) or magnetic force brush the 5th embodiment as the imaging device of the present invention of contact charging device.

Embodiment

Usually, the invention provides a kind of toner, it has smaller particles diameter and good flowability, development property and transfer printing, and can produce high-quality image for a long time, and does not have film forming, and has long serviceable life.

Typically, when the method for producing toner and toner dissolving that will comprise prepolymer or be dispersed in the organic solvent, with preparation solution or dispersion; And when disperseing this solution or dispersion with the polyester of production modification in the process that forms toner, this toner has core-shell structure.When by warm-up mill in the fuser and the heating of the shearing force between the backing roll (back-up roller), mediate this toner.Therefore, the resin that forms core and have a low softening point is exposed to the outside, the inside of the toner contamination fuser of fusion causes polluting transfer paper.This toner preferably has the melt viscosity of 160 ℃ of following 70-140Pas.When viscosity during less than 70Pas, the inside of the toner contamination fuser of fusion causes polluting transfer paper.When viscosity during greater than 140Pas, cold skew (cold offset) problem takes place.If just control the thermal behavior of toner simply, then be difficult to address these problems, and be necessary in fuser, to repeat the fusion and the kneading state of toner.

Typically, when the toner-particle diameter more little, favourable more generation high definition and high-quality image.Yet the transfer printing of toner and cleanablity are poor more, and this makes the image that produces owing to relatively poor cleanablity has not enough image density and striped.Behind the toner of long-time stirring weight median particle diameter less than the scope of the invention in the image developing device, the carrier surface in this toner and the two-component developing agent is melt bonded, and worsens the chargeability of this carrier.When being used for monocomponent toner, be easy on charging roller to form the toner film, toner is easy to and the melt bonded formation toner thin layer of parts such as blade.Especially, when losing the quantity balance of superfines, toner is easier to carrier surface melt bonded, is easier on charging roller to form the toner film, and toner is easier to and the melt bonded formation toner thin layer of parts such as blade.According to open, the toner that comprises the vibrin of modification can prevent that these phenomenons from taking place.

Particle diameter is difficult to produce high definition and high-quality image greater than the toner of the scope of the invention, and simultaneously when consuming toner, and when it was added developer, it is big that the variation of the particle diameter of toner will become.This is equally applicable to the weight median particle diameter (D4) of toner and the ratio (D4/Dn) of number average particle diameter.

Only the toner that has a narrow particle diameter distribution by formation is to be difficult to address these problems, the concrete content of attritive powder and/or the concrete content of corase meal, and the concrete form range of following toner also is absolutely necessary.

Typically, when the shape of toner approaches sphere, can improve its transfer printing, but remain in the cleanablity variation of the toner on the photoreceptor after the transfer printing.In the present invention, add that the average spherical degree (sphericity) of toner behind the particle diameter is preferably between 0.93-0.99.When the average spherical degree less than 0.93 the time, the development property of toner is low, and the image that produces has low image density.When the average spherical degree greater than 0.99 the time, initial toner has height development property, and produces the image with high image density, but development property deterioration after long-time the use, and image density worsens significantly.When spherical toner satisfied particle diameter of the present invention, the external additive and the charge control agent that are present on the toner surface were difficult to be buried in wherein.This is because the danger that hypothesis machinery is applied on the toner has disperseed, even and when the shape subglobular of toner, the dangerous sharply reduction on each toner-particle; Under the condition of particle diameter distribution in toner has the scope of the invention and single-size diameter, the toner with larger particles diameter is easy to take place the phenomenon in the surface that external additive and charge control agent be buried in toner.

Similarly, the form factor of toner (SF-1) is preferably between 105-170.When its greater than 170 the time, in the image developing device, stir long-time after, toner atomizing, thereby its development property deterioration, and this toner produces blurred picture, and its transfer printing deterioration further, and this toner produces the image of low image density.When its less than 105 the time, to work the external additive that improves its mobile effect such as silicon dioxide etc. on the toner surface within it buried owing to be coated in, so the flowability of toner and chargeability change, thereby its development property deterioration and this toner produce blurred picture, and the cleanablity variation that remains in the toner on the photoreceptor further after the transfer printing.

The form factor of toner (SF-1) is represented its circularity (degree of roundness), is expressed from the next:

SF-1＝MXLNG/AREA×π/4×100

In the formula, MXLNG represents the absolute maximum length of particle, and AREA represents its projected area.

It is that 5-20nm and secondary granule diameter are the external additive of 50-200nm that toner of the present invention comprises primary particle size, and its amount is the female toner (mother toner) of 0.3-5.0 weight portion external additive/100 weight portions.When its during less than 0.3 weight portion, the illiquidity of gained toner, and its transfer printing deterioration.When its during greater than 5.0 weight portions, external additive can not be fully attached on the surface of toner and some of them dissociate.Therefore, external additive adheres to separately and the surface of the photoreceptor that weares and teares, and this generation has the image of white point and background stain, but and the fixation performance of gained toner worsen.

Primary particle size is that 5-20nm and secondary granule diameter are flowability and the chargeability that the external additive of 50-200nm is preferred for improving the gained toner.Although its reason is not clarification as yet, can followingly suppose: when toner being filled in the image developing device, toner presents intensive state and has the particle diameter of 50-200nm, and stably fills within it; When the carrier in the image developing device stirred, toner disperseed and reaches gradually the state of primary granule, and it has development property suitable when developing.In addition, the energy that produces when the carrier in the image developing device stirs together is used for disperseing the gathering of external additive, and can prevent the change of the various character of toner, as the mobile change that worsens etc. of toner.This external additive comprises inorganic particulate material and particulate polymers material.

The concrete enforcement of inorganic particle comprises silicon dioxide, titania, aluminium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, zinc paste, tin oxide, silica sand, clay, mica, grey matter sand, zeyssatite, chromium oxide, cerium oxide, iron oxide red, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit, silicon nitride etc.

The instantiation of polymer beads material comprises the particle that polystyrene, methacrylate or the acrylate copolymer, silicone resin, benzoguanamine (benzoguanamine) resin, the polycondensation that are formed by emulsifier-free emulsion polymerization (soap-free emulsifyingpolymerization), suspension polymerization or dispersin polymerization form, as the polymer beads of nylon and thermoset resin.

Even surface conditioning agent can increase the hydrophobicity of these fluidizing agents and can prevent that when high humility the flowability of gained toner and chargeability from worsening.The instantiation of surface conditioning agent comprises the silicone oil of silane coupling agent, silanizing agent (sililating agent), the silane coupling agent with fluorinated alkyl, organotitanate coupling agent, aluminum coupling agent silicone oil (aluminium coupling agents silicone oils) and modification.

Preferably use silicon dioxide, titania and aluminium oxide as external additive in the present invention; Especially, more preferably use hydrophobized silica as external additive.

The vibrin of modification of the present invention comprises: have by the mode except that ester bond the vibrin of the group of the functional group's bonding that contains with acid and pure monomeric unit in it; Vibrin of the resin Composition of a plurality of different structures by covalent bond or the mutual bonding of ionic link etc.

For example, also use following vibrin, described vibrin has functional group with acidic group and hydroxyl reaction at its end, and as isocyanate group, wherein said end is further by comprising the compound modified of active hydrogen atom or stretching.And, also can use the vibrin that has with the terminal bonding of the compound that contains a plurality of hydrogen atoms, for example vibrin of urea modification (urea-modified polyesterresin) and urethane-modified vibrin (urethane-modified polyester resin).

In addition, also can use the following vibrin that in its main chain, has as two key isoreactivity groups, thereby it has graft component by free radical polymerization, promptly carbon and carbon combine or wherein two key crosslinked between mutually, for example phenylethene modified vibrin and acrylic acid modified vibrin.

Also can use vibrin with different resins of forming, has the copolymerization or at its terminal and carboxyl and hydroxyl reaction on its main chain of the different resins of forming, for example with the vibrin of terminal-modified silicone resin copolymerization, wherein said end is by having by carboxyl, hydroxyl, epoxy radicals and sulfhydryl modified for example silicone modified vibrin.

Below, will the vibrin of modification be described more specifically.

The synthetic embodiment of the vibrin of polystyrene modification

In the reactor that is equipped with cooling tube, stirrer and nitrogen conduit, mix the addition product of 724 parts of bisphenol-As and 2 moles of ethylene oxide, 200 parts of m-phthalic acids, 70 parts of fumaric acid and 2 parts of dibutyl tin oxides, and with it in normal pressure and 230 ℃ reaction 8 hours down.Then potpourri was reacted 5 hours under the decompression of 10-15mm Hg, and in it, add 32 parts of phthalic anhydrides, and reacted 2 hours down at 160 ℃.Then, with this potpourri be dissolved in 200 parts of styrene in the ethyl acetate, 1 part of benzoyl peroxide, 0.5 part of xylidin in 80 ℃ of reactions 2 hours down, distill then and remove ethyl acetate, obtain weight-average molecular weight and be the vibrin (i) of polystyrene graft-modification of 92000.

The vibrin of urea modification (i)

The instantiation of the vibrin of urea modification (i) comprises the reaction product of polyester prepolyer (A) with isocyanate group and amine (B).Polyester prepolyer (A) is reacted by polyester with active hydrogen atom and polyisocyanate (3) and forms, and wherein the polyester of local active hydrogen atom is to form by the polycondensation reaction between polyvalent alcohol (1) and the polycarboxylic acid (2).The instantiation that contains the group of reactive hydrogen comprises hydroxyl (alcoholic extract hydroxyl group and phenolic hydroxyl group), amino, carboxyl, sulfydryl etc.Especially, preferably use alcoholic extract hydroxyl group.

As polyvalent alcohol (1), can use glycol (1-1) and have trivalent or higher polyvalent alcohol (1-2), preferred use separately (1-1) or (1-1) and the potpourri of a small amount of (1-2).

The instantiation of glycol (1-1) comprises aklylene glycol, ethylene glycol, 1 for example, 2-propylene glycol, 1, ammediol, 1,4-butylene glycol and 1,6-hexanediol; Alkylidene two ether alcohols, for example diglycol, triethylene glycol, dipropyl glycol, polyglycol, polypropylene glycol and polytetramethylene glycol; Alicyclic diol, for example 1,4 cyclohexane dimethanol and hydrogenated bisphenol A; Bis-phenol, for example bisphenol-A, Bisphenol F and bisphenol S; The addition product of above-mentioned alicyclic diol and alkylene oxide (for example oxirane, epoxypropane and epoxy butane); The addition product of above-mentioned bis-phenol and alkylene oxide (for example oxirane, epoxypropane and epoxy butane) etc.Especially, the preferred use has the aklylene glycol of 2-12 carbon atom and the addition product of bis-phenol and alkylene oxide, and the potpourri that more preferably uses them.

Instantiation with trivalent or higher polyvalent alcohol (1-2) comprises having 3-8 valency or higher multivalence aliphatic alcohol, for example glycerine, trimethylolethane, trimethylolpropane, pentaerythrite and sorbierite; Has trivalent or higher phenol, for example trisphenol PA, phenol novolaks and cresols novolaks; And above-mentionedly have trivalent or the higher polyhydric phenol and an addition product of alkylene oxide.

As polycarboxylic acid (2), can use dicarboxylic acid (2-1) and have trivalent or higher polycarboxylic acid (2-2).Preferred use separately (2-1) or (2-1) and the potpourri of a small amount of (2-2).

The instantiation of dicarboxylic acid (2-1) comprises alkylene dicarboxylic acids, for example succinic acid, hexane diacid and decanedioic acid; Alkenylene dicarboxylic acid, for example maleic acid and fumaric acid; Aromatic dicarboxylic acid, for example phthalic acid, m-phthalic acid, terephthalic acid (TPA) and naphthalenedicarboxylic acid etc.Especially, preferred alkenylene dicarboxylic acid with 4-20 carbon atom and the aromatic dicarboxylic acid of using with 8-20 carbon atom.

Instantiation with trivalent or higher polycarboxylic acid (2-2) comprises the aromatic multi-carboxy acid with 9-20 carbon atom, for example trimellitic acid and pyromellitic acid.

Polybasic carboxylic acid (2) can be reacted with polyvalent alcohol (1) and formed by the acid anhydrides of above-mentioned acid or lower alkyl esters (for example methyl esters, ethyl ester or isopropyl ester).

Polyols blend (1) and polycarboxylic acid (2) are so that the equivalent proportion between hydroxyl [OH] and the carboxyl [COOH] ([OH]/[COOH]) is generally between 2/1 to 1/1, preferably between 1.5/1 to 1/1, more preferably between 1.3/1 to 1.02/1.

The instantiation of polyisocyanate (3) comprises aliphatic polymeric isocyanate, for example tetramethylene diisocyanate, two isocyanic acids, six methylene esters and 2,6-diisocyanate methyl caproate; Alicyclic polymeric isocyanate, for example isophorone diisocyanate and cyclohexyl-methane diisocyanate; Aromatic diisocyanates, for example toluene diisocyanate and '-diphenylmethane diisocyanate; The aryl aliphatic vulcabond, α for example, α, α `, α `-tetramethylxylylene diisocyanate; Isocyanuric acid ester; The block polyisocyanate that forms by phenol derivatives, oxime or the above-mentioned polyisocyanate of caprolactam block; And they combination.

Mix polyisocyanate (3) and polyester, so that isocyanate group [NCO] and have equivalent proportion ([NCO]/[OH]) between the polyester of hydroxyl [OH] generally between 5/1 to 1/1, preferably between 4/1 to 1.2/1, more preferably between 2.5/1 to 1.5/1.When [NCO]/[OH] greater than 5 the time, but the low temperature fixation performance of gained toner worsens.When the mol ratio of [NCO] less than 1 the time, urea groups content reduces in the ester of the polyester of modification, and the heat resistanceheat resistant offset behavior of gained toner worsens.

In its end had polyisocyanate-based polyester prepolyer (A), polyisocyanate component content was 0.5-40% weight, was preferably 1-30% weight, and 2-20% weight more preferably.When this content during less than 0.5% weight, the heat resistanceheat resistant offset behavior of gained toner worsens, and in addition, but the heat resistance of toner and low temperature fixation performance also worsen.On the contrary, when this content during greater than 40% weight, but the low temperature fixation performance of gained toner worsens.

The isocyanate group number that comprises in each polyester prepolyer (A) molecule is at least 1, preferred average out to 1.5-3, and more preferably average out to 1.8-2.5.When the isocyanate group number in the per molecule less than 1 the time, the polyester of modification (i) molecular weight reduces and the heat resistanceheat resistant offset behavior of gained toner worsens.

The instantiation of amine (B) comprises diamines (B1), has the block amine (B6) that the polyamines (B2) of three or more amino, amino alcohol (B3), amineothiot (B4), amino acid (B5) and above-mentioned amine (B1-B5) are formed by block.

The instantiation of diamines (B1) comprises aromatic diamine, for example phenylenediamine, diethyl toluene diamine and 4,4`-diaminodiphenyl-methane; Alicyclic diamine, for example 4,4`-diamido-3,3`-dimethyl dicyclohexyl methyl hydride, diamino-cyclohexane and isophorone diamine; Aliphatic diamine, for example ethylenediamine, tetra-methylenedimine and hexamethylene diamine) etc.

Instantiation with polyamines (B2) of three or more amino comprises diethylene triamine, trien.

The instantiation of amino alcohol (B3) comprises monoethanolamine and ethoxylaniline.

The instantiation of amineothiot (B4) comprises aminoethyl mercaptan and aminopropyl mercaptan.

The instantiation of amino acid (B5) comprises alanine and aminocaproic acid.

The instantiation of block amine (B6) comprise by one of among the above-mentioned amine B1-B5 with reactive ketones such as for example acetone, methyl ethyl ketone and methyl isobutyl ketones and the ketimine compound for preparing; Oxazoline compound etc.In these amine (B), preferably use diamines (B1), perhaps the potpourri that mixes of diamines and a small amount of polyamines (B2).

If desired, can utilize elongation anticatalyst (elongation anticatalyst) randomly the molecular weight of the polyester of modification to be controlled.The instantiation of this elongation anticatalyst comprises monoamine (for example diethylamide, dibutylamine, butylamine and lauryl amine), and the block amine (being ketimine compound) that forms by the above-mentioned monoamine of block.

Mixing ratio (i.e. [NCO]/[NH with prepolymer (A) Yu amine (B) of isocyanate group _X]) between 1/2 to 2/1, preferably between 1.5/1 to 1/1.5, more preferably between 1.2/1 to 1/1.2.When this ratio greater than 2 or less than 1/2 the time, the molecular weight of the polyester of gained urea modification reduces, thereby causes the deterioration of the heat resistanceheat resistant offset behavior of gained toner.The polyester of modification (i) not only can comprise amino-formate bond (urethane bonding) but also comprise urea key (urea bonding).The mol ratio of urea key and amino-formate bond (urea/carbamate) is between 100/0 to 10/90, preferably between 80/20 to 20/80, more preferably between 60/40 to 30/70.When the content of urea key less than 10% the time, the heat resistanceheat resistant offset behavior of gained toner worsens.

The vibrin of modification of the present invention (i) can be made by single stage method methods such as (one-shot method).The weight-average molecular weight of the vibrin of modification (i) is not less than 10000, is preferably 20000-10000000, and 30000-1000000 more preferably.When this weight-average molecular weight less than 10000 the time, the heat resistanceheat resistant offset behavior of gained toner worsens.When with following unmodified vibrin (LL) when being used in combination, the number-average molecular weight of the vibrin (i) of this modification is not particularly limited.That is to say that the weight-average molecular weight of the vibrin of this modification (i) is better than its number-average molecular weight.Yet when the vibrin (i) of independent use modification, this number-average molecular weight is 2000-15000, is preferably 2000-10000, and 2000-8000 more preferably.When this number-average molecular weight greater than 20000 the time, but the low temperature fixation performance of gained toner worsen, and the glossiness of full-colour image worsens.

Unmodified vibrin (LL)

In the present invention, can be used in combination the vibrin (i) of unmodified vibrin (LL) and modification as the toner binder resin.The vibrin that is used in combination unmodified vibrin (LL) and modification is preferable over the vibrin of independent use modification, this be because unmodified vibrin (LL) but and the vibrin of modification be used in combination the low temperature fixation performance that improved the gained toner and the glossiness of full-colour image.The instantiation of unmodified vibrin (LL) comprises the polyvalent alcohol (1) of the vibrin (i) that is similar to modification and the condensed polymer of polycarboxylic acid (2), and those of the vibrin (i) of the preferred product that uses and modification are identical.But with regard to the low temperature fixation performance and heat resistanceheat resistant offset behavior of gained toner, the preferred part of vibrin of modification (i) and unmodified vibrin (LL) is solvable mutually.Therefore, the vibrin of modification (i) preferably has similar composition with unmodified vibrin (LL).When being used in combination the vibrin (i) of unmodified vibrin (LL) and modification, weight ratio ((i)/(LL)) between vibrin of modification (i) and the unmodified vibrin (LL) is between 5/95 to 80/20, preferably between 5/95 to 30/70, more preferably between 5/95 to 25/75, and most preferably between 7/93 to 20/80.When the weight ratio of the vibrin (i) of modification less than 5%, the gained toner has relatively poor heat resistanceheat resistant offset behavior, but but and is difficult to have heat-resisting keeping quality and low temperature fixation performance.

Unmodified vibrin (LL) preferably has 1000-20000, more preferably 1500-10000, and the peak molecular weight of 2000-8000 (peak molecular weight) most preferably.When its less than 1000 the time, but the heat-resisting keeping quality of gained toner worsens.When its greater than 10000 the time, but its low temperature fixation performance worsens.Unmodified vibrin (LL) preferably has the 5mg of being not less than KOH/g, more preferably 10-120mg KOH/g, and the hydroxyl value of 20-80mg KOH/g most preferably.When its less than 5 the time, but but the gained toner is difficult to have heat-resisting keeping quality and low temperature fixation performance.Unmodified vibrin (LL) preferably has the acid number of 10-30mg KOH/g, but so that the gained toner tend to have negative electricity and have fixation performance preferably.When its during greater than 30mg KOH/g, particularly when using in the environment of high humility and high temperature, the chargeability of gained toner worsens, and produces the image with background stain.

In the present invention, unmodified vibrin (LL) preferably has 35-55 ℃, and more preferably 40-55 ℃ glass transition temperature (Tg).But but the gained toner can have heat-resisting keeping quality and low temperature fixation performance.When even this glass transition temperature hangs down, comprise unmodified vibrin (LL) and modification vibrin (i) but dry toner of the present invention have better heat-resisting keeping quality than known polyester toner.

In the present invention, the toner binder resin preferably has the temperature that is not less than 100 ℃ (TG '), and more preferably 110-200 ℃ temperature (TG '), be 10000 dyne/cm in the storage modulus (storage modulus) of toner binder resin under this temperature and under the survey frequency at 20Hz ²When its during less than 100 ℃, the heat resistanceheat resistant offset behavior of gained toner worsens.The toner binder resin preferably has the temperature (T η) that is no more than 180 ℃, and more preferably 90-160 ℃ temperature (T η), and viscosity is 1000 pools (poise) under this temperature.When its during greater than 180 ℃, but the low temperature fixation performance of gained toner worsens.That is to say, but with regard to the low temperature fixation performance and heat resistanceheat resistant offset behavior of gained toner, TG ' preferably is higher than T η.In other words the difference between TG ' and the T η (TG '-T η) is preferably and is not less than 0 ℃, more preferably is not less than 10 ℃, and further preferably is not less than 20 ℃.Maximal value to this difference is not particularly limited.But but with regard to the heat-resisting keeping quality and low temperature fixation performance of gained toner, the difference between TG ' and the T η (TG '-T η) be preferably 0-20 ℃, more preferably 10-90 ℃, and most preferably be 20-80 ℃.

The instantiation that is used for colorant of the present invention comprises any known dyestuff and pigment, carbon black for example, aniline black byestuffs, iron oxide black, naphthol yellow S, hansa yellow (10G, 5G and G), cadmium yellow, yellow iron oxide, loess, chrome yellow, titan yellow, poly-azophosphine, oil yellow, hansa yellow (GR, A, RN and R), pigment yellow L, benzidine yellow (G and GR), permanent yellow NCG, sulfuration fast yellow (5G and R), tartrazine lake, quinoline yellow lake, the yellow BGL of anthracene (anthrazane), isoindolinone (isoindolinone) Huang, iron oxide red, the red lead, orange lead, cadmium red, cadmium mercury is red, antimony orange, permanent bordeaux 4R, para red, red as fire, to the chloro-ortho-nitraniline, lithol that fast scarlet G, strong brilliant scarlet G, bright fuchsin BS, permanent bordeaux (F2R, F4R, FRL, FRLL and F4RH), fast scarlet VD, vulcanize strong rubine B, brilliant scarlet G G, lithol that rubine GX, permanent bordeaux F5R, bright fuchsin 6B, pigment scarlet 3B, the red 5B of wine, toluidine chestnut palm fibre, consolidate the red F2K of wine forever, the red BL of sun wine, the red 10B of wine, shallow bone purplish red (Bon Maroon Light), middle bone purplish red (Bon Maroon Medium), eosine lake, rhodamine color lake B, rhodamine color lake Y, alizarine lake, thioindigo red B, thioindigoid maroons, oil red, quinoline a word used for translation ketone is red, pyrazolone red, poly-azophloxine, chrome vermilion, benzidine orange perylene ketone (perynone) orange, the oil orange, cobalt blue, cerulean blue, alkali blue lake, peacock blue lake, the Victoria blue color lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS and BC), indigo-blue, ultramarine, Prussian blue, anthraquinone blue, Fast violet, the methyl violet color lake, cobalt violet, manganese violet diox purple, the anthraquinone purple, chrome green, zinc green, chromium oxide, emerald green, emerald green, pigment green B, naphthol green B, green gold, the acid green color lake, the peacock green color lake, the phthalein mountain valley with clumps of trees and bamboo is green, anthraquinone green, titanium dioxide, zinc paste, lithopone etc.These raw materials can be used alone or as a mixture.

Based on the general assembly (TW) of toner, the percentage by weight of colorant is preferably 1-15% in the toner, more preferably 3-10%.

When using with resin-bonded, colorant used in this invention can be used as masterbatch pigment (masterbatch pigment).

The instantiation that is used in resin in the masterbatch pigment or that be used in combination with masterbatch pigment comprises above-mentioned modification or unmodified vibrin; The styrene polymer of styrene polymer and replacement, for example polystyrene, poly-to chlorostyrene and polyvinyl toluene; Styrol copolymer, for example styrene is to chloro-styrene copolymer, the styrene-propene multipolymer, styrene-ethylene base toluene multipolymer, styrene-ethylene base naphthalenedicarboxylate copolymer, styrene-propene acid methyl terpolymer, styrene-propene acetoacetic ester multipolymer, the styrene-propene butyl acrylate copolymer, the misery ester copolymer of styrene-propene, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl propylene acid methyl terpolymer, styrene-acrylonitrile copolymer, styrene-ethylene ylmethyl ketone copolymers, Styrene-Butadiene, the styrene-isoprene multipolymer, styrene-acrylonitrile-indene copolymer, phenylethylene-maleic diacid copolymer and phenylethylene-maleic two acid ester copolymers; And other resin, for example polymethylmethacrylate, poly-n-butyl methacrylate, Polyvinylchloride, polyvinyl acetate, tygon, polypropylene, polyester, epoxy resin, epoxy polyol resin, urethane resin, polyamide, polyvinyl butyral resin, acrylic resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin etc.These resins can be used alone or as a mixture.

Be used in masterbatch in the toner of the present invention generally by hybrid resin and colorant, and it is applied high shear force mediate and prepare.In this case, can add organic solvent to improve the interaction between colorant and the resin.In addition, because can not carrying out drying, just can use the wet cake of gained, so preferably use water squeezing method (flushing method).In this water squeezing method, the water-based thickener that will contain colorant mixes with the resin solution of organic solvent, so that colorant transfers in the resin solution, separates then and removes waterborne liquid and organic solvent.The dry powder that certainly, also can use the dry wet filter cake and obtain is as colorant.In this case, preferably use the three-roll rolling machine to apply high shear force and mediate this potpourri.

Toner of the present invention can comprise wax, and wax and adhesive resin and colorant triplicity are used.But the release property (releasability) the when existence of wax influences its photographic fixing to a great extent in the toner, and all carefully be dispersed in the toner when wax, and a large amount of wax is during near toner surperficial, but toner has good release property.Especially, preferably to be no more than the major axis dispersing wax of 1 μ m.When a large amount of wax is positioned at toner surperficial, after long-time stirring the in the image developing device, these waxes break away from from the surface of toner easily, and on the surface attached to the parts of carrier and image developing device, thereby the developer chargeability that causes comprising this toner worsens.

The disperse state of wax can be by observing in the captured amplification photo of transmission electron microscope.

The instantiation of wax comprises known wax, for example polyolefin-wax, for example Tissuemat E and polypropylene wax; Hydrocarbon with long-chain, for example paraffin and SASOL wax; And the wax that comprises carbonyl.In these waxes, the preferred wax that comprises carbonyl that uses.The instantiation that comprises the wax of carbonyl (for example comprises the polyalkane acid esters, Brazil wax, montan wax, trimethylolpropane tris behenate, pentaerythrite four behenates, pentaerythrite diacetate two behenates, glycerine three behenates and 1,8-octadecyl glycol distearate); Polyalkane alcohol ester (for example three stearoyl trimellitates and distearyl maleate); Polyalkane acid acid amides (for example ethylenediamine two mountain Yu acid amides); Poly-alkylamide (for example triphen pregnancy acid three stearmides); And dialkyl ketone (for example distearyl ketone).Comprise at these and preferably to use the polyalkane acid esters in wax of carbonyl.

The wax that is used for toner of the present invention has 40-160 ℃ usually, and preferred 50-120 ℃, more preferably 60-90 ℃ fusing point.But fusing point has adverse effect less than 40 ℃ wax to its high temperature keeping quality, tends to cause the cold skew of gained toner and fusing point is higher than 160 ℃ wax when low-temperature fixing.In addition, wax preferably has the 5-1000 centipoise, more preferably the melt viscosity of 10-100 centipoise (when measuring under the temperature under high 20 ℃ than fusing point).But melt viscosity is greater than feasible heat resistanceheat resistant offset behavior and the low temperature fixation performance that is difficult to improve the gained toner of the wax of 1000 centipoises.The content of wax is preferably 0-40% weight in the toner, more preferably 3-30% weight.

Toner of the present invention can be chosen wantonly and comprise charge control agent.Anchor at the chargeability that charge control agent on the toner surface can improve toner.

When charge control agent anchors on the surface of toner, can stablize the amount and the state of toner, thereby can stablize the chargeability of toner.Especially, when comprising charge control agent in the toner, toner of the present invention has better chargeability.

The instantiation of charge control agent comprises any known charge control agent, for example the compound of aniline black byestuffs, kiton colors, the metallized dye that contains chromium, molybdic acid chelate, rhodamine dyes, alkoxyamine, quaternary ammonium salt (quaternary ammonium salt that comprises the fluorine modification), alkyl amine, phosphorus and phosphorous compound, tungsten and tungstenic, fluorine-containing activator, salicylic slaine, salicyclic acid derivatives etc.

This charge control agent commercially available prod instantiation comprise Orient Chemical IndustriesCo., BONTRON 03 (aniline black byestuffs), BONTRON P-51 (quaternary ammonium salt), BONTRON S-34 (metallic azo dyes), BONTRON E-82 (metal complex of α naphthols acid), BONTRON E-84 (salicylic metal complex) and BONTRON E-89 (phenolic condensation compound) that Ltd. produces; Hodogaya Chemical Co., TP-302 and TP-415 (molybdenum match of quaternary ammonium salt) that Ltd. produces; COPY CHARGE PSY VP2038 (quaternary ammonium salt), COPY BLUEPR (triphenylmethane derivative), COPY CHARGE NEG VP2036 and COPY CHARGE NXVP434 (quaternary ammonium salt) that Hoechst AG produces; Japan Carlit Co., LRA-901 and LR-147 (boron complexes) that Ltd. produces; Copper phthalocyanine, perylene (perylene), quinoline a word used for translation ketone, AZO pigments and have polymkeric substance of functional groups such as sulfonic group, carboxyl, quaternary ammonium group for example etc.

The content of charge control agent depends on used adhesive resin kind, to whether adding adjuvant and used method for preparing toner (for example, dispersion method) is not particularly limited.Yet, whenever comprising the adhesive resin of 100 weight portions in the toner, the content of charge control agent is generally the 0.1-10 weight portion, is preferably the 0.2-5 weight portion.When this content was too high, the quantity of electric charge of toner was too big, thereby attracted the electrostatic force of the developer roll of toner to increase, and caused the flowability of toner and the image density of toner image to worsen.

Can be these charge control agents and release agent is kneaded together with masterbatch pigment and resin by heating, perhaps add dissolving or be dispersed in the interior toner component of organic solvent.

Toner of the present invention can comprise spatter property improver (cleanability improver), and this spatter property improver is used to remove the developer that remains in after the transfer printing on the photoreceptor and first offset medium.The instantiation of spatter property improver comprises fatty acid metal salts, for example zinc stearate, calcium stearate and stearic acid; And the polymer beads that passes through the preparation of emulsifier-free emulsion polymerization method, for example poly methyl methacrylate particle and granules of polystyrene.Comparatively speaking, the equal particle diameter that polymer beads has narrow particle diameter distribution and preferably has body 0.01-1 μ m.

Toner of the present invention prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

Toner binder of the present invention can pass through, and for example following method prepares.At known catalyzer, exist down as four titanium butoxide acid esters and dibutyl tin oxide, at 150-280 ℃ stable heating polyvalent alcohol (1) and polycarboxylic acid (2) down.Then, under reduced pressure remove the water of generation in case of necessity, have the vibrin of hydroxyl with preparation.Vibrin and polyisocyanate (3) are reacted, the prepolymer (A) that preparation has isocyanate group under 40-140 ℃ temperature.Further, make prepolymer (A) and the stable down reaction of amine (B) at 0-140 ℃, the vibrin (i) of preparation modification.When making polyisocyanate and A and B reaction, can use solvent in case of necessity.Suitable solvent comprises the solvent of refusing polyisocyanate (3) reaction.The instantiation of this solvent comprises arsol, for example toluene and dimethylbenzene; Ketone, for example acetone, methyl ethyl ketone and methyl isobutyl ketone; Ester class, for example ethyl acetate; Amide-type, for example dimethyl formamide and dimethyl acetyl amide (dimethylacetoaminde); Ethers, for example tetrahydrofuran.

When the polyester that does not contain the urea key (LL) is used in combination with the polyester of urea modification, use is similar to the vibrin (LL) that the method preparation for preparing the vibrin with hydroxyl does not contain the urea key, and after the reaction of the polyester (i) of modification is finished, the polyester (LL) that does not contain the urea key is dissolved and be blended in the solution.

Available following method prepares dry toner, but the preparation method is not limited thereto.

Will be as toner component, charge control agent and the pigment mechanical mixture of the toner binder resin of the vibrin (i) that comprises modification.Can under normal condition, carry out this hybrid technique, this mixed process is not particularly limited with conventional mixer.

After finishing this hybrid technique, mediate this potpourri by the kneader heating.Kneader comprises single shaft and twin shaft continuous kneader and rolls the batch-type kneader.From in essence, heat and mediate the strand that does not cut off the toner binder resin.Particularly, mediate the softening point that temperature depends on the toner binder resin.When mediating temperature far below softening point, the strand of toner binder resin cuts off to be increased.When mediating temperature, can not disperse the toner binder resin equably far above softening point.

After finishing kneading technology, pulverize the potpourri of mediating.This potpourri of preferably at first crushing is pulverized then.Preferred use following method, be about to potpourri crush to shock plate (collision board) and in the rotor of mechanical rotation and the slit between the stator crushed mixture.

After finishing disintegrating process, by the centrifugal force potpourri that classification is pulverized in air-flow, to prepare the toner of predetermined particle diameter, for example toner of 5-20 μ m average particulate diameter.

In addition, but for improving flowability keeping quality, development property and the transfer printing of toner, with inorganic subparticle, for example above-mentioned hydrophobic silica attritive powder is added into toner from the outside.Can use conventional powder blenders mixing external additive, and this mixer preferably has chuck, and can control its internal temperature.For a change the load history of external additive can be added external additive or adding gradually near mixed process.Certainly, can change rotation number, velocity of rotation, time and the temperature of mixer.Can apply big load earlier to toner, then little load is perhaps opposite.

The instantiation of mixer comprises vee-blender, closed mixer (locking mixer), Loedge mixer, Nauta mixer (Nauter Mixer), Henschel mixer (Henschel Mixer) etc.

For making toner spheroidization (ensphere), can use following method: melt the method that (Mechanofusion) makes toner machinery spheroidization by blending together device (hybridizer) or machinery behind the disintegrating process; With after the toner materials dissolving and being dispersed in the solvent that can dissolve toner binder, make the spray drying process of toner spheroidization except that desolvating by spray dryer (spray dryer); And the method that makes the toner spheroidization by toner in the heating aqueous medium.Yet, be not limited to these methods.

Prepare toner of the present invention by following method.

At first, preparation oil dispersion (oil dispersion) in this oil dispersion, comprises the polyester prepolyer A dissolving of isocyanate group, and colorant dispersion and release agent dissolve or be dispersed in the organic solvent.

(wet pulverizer) pulverized this oil dispersion 30-120 minute by wet crushing mill, so that colorant is pulverized and is dispersed in the oil dispersion.

Then, in the presence of machine particulate material and/or particulate polymers material, this oil dispersion of emulsification to be forming the vibrin C of oil-in-water (oil-in-water) emulsion and urea modification, and the vibrin C of urea modification is by the polyester prepolyer A that comprises isocyanate group and amine B reaction and preparation.

The instantiation of organic solvent comprises the organic solvent of dissolved polyester resin, and it is insoluble to, is insoluble in or is slightly soluble in the water.Organic solvent preferably has 60-150 ℃, and more preferably 70-120 ℃ boiling point.The instantiation of this organic solvent comprises ethyl acetate, methyl ethyl ketone etc.

The solid particle spreading agent of aqueous phase disperses the oil droplet (oilspot) in it equably.This solid particle spreading agent is positioned on the surface of oil droplet, and dispersed oil droplets and can prevent assimilation between the oil droplet (assimilation) equably.Therefore, the gained toner has narrow particle diameter distribution.

The solid particle spreading agent is preferably the inorganic particulate material that average particulate diameter is 0.01-1 μ m, and it is difficult to be dissolved in the water and solid in aqueous medium.

The instantiation of inorganic particulate material comprises silicon dioxide, aluminium oxide, titania, barium titanate, magnesium titanate, calcium titanate, strontium titanates, zinc paste, tin oxide, silica sand, clay, mica, grey matter sand, zeyssatite, chromium oxide, cerium oxide, iron oxide red, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit, silicon nitride etc.

And, preferably use tricalcium phosphate, lime carbonate, colloidal titanium dioxide, colloidal silica and hydroxylapatite.Especially, more preferably use the hydroxylapatite of the alkaline reaction prod of sodium phosphate and lime chloride.

Process for dispersing is not particularly limited, can uses low velocity shear method, high speed shear method, rubbing method, high-pressure injection method and ultrasonic method etc.In these methods, preferably use the high speed shear method, this is because this method can prepare the particle that particle diameter is 2-20 μ m easily.At that point, particle diameter (2-20 μ m) is meant the particle diameter of the particle that comprises liquid.When using high speed shear type dispersion machine, rotational speed is not particularly limited, but rotational speed is generally 1000-30000rpm, be preferably 5000-20000rpm.Jitter time also is not particularly limited, but was generally 0.1-5 minute.Temperature in the dispersing technology is generally 0-150 ℃ (under the pressure), and is preferably 40-98 ℃.When this temperature is high relatively, can disperse the polyester (i) or the prepolymer (A) of modification easily, this is because the dispersion that is formed by them has low viscosity.

Whenever contain the polyester (i) that 100 weight portions comprise modification or the toner component of prepolymer (A), generally contain the 50-2000 weight portion, preferably contain the aqueous medium of 100-1000 weight portion.When the amount of this aqueous medium during less than 50 weight portions, the dispersion of toner component in aqueous medium is insufficient, thereby the female toner-particle of gained does not have required particle diameter.On the contrary, when this aqueous medium during greater than 2000 weight portions, production cost increases.The preferred dispersion of using spreading agent to prepare stable dispersion, this dispersion comprises the particle of narrow particle diameter distribution.

Be used for emulsification and disperse the instantiation of oil phase (moisture liquid wherein is dispersed with the toner component) spreading agent to comprise anionic surfactant, for example alkyl benzene sulfonate, alpha-alkene sulfonate and phosphate; Cationic surfactant, for example amine salt (for example alkylamine salt, amino alcohol fatty acid derivatives, polyamines derivative of fatty acid and imidazoline) and quaternary ammonium salt (for example alkyl trimethyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt, alkyl dimethyl benzyl quaternary ammonium salt, pyridiniujm, alkyl isoquinolinium salt and iso-octyl benzene two polyglycol ether dimethyl benzyl ammonium chlorides (benzethonium chloride)); Nonionic surfactant, for example fatty acid amide derivant, polyol derivative; And amphoteric surfactant, for example alanine, dodecyl (nitrilo acetic acid) glycocoll, two (octyl group nitrilo acetic acid) glycocoll and N-alkyl-N, N-Dimethyl Ammonium betaine (N-alkyl-N, N-dimethylammonium betaine).

Use on a small quantity even have the surfactant of fluoroalkyl, also can prepare dispersion with good dispersion.Instantiation with anionic surfactant of fluoroalkyl comprises fluoroalkyl carboxylic acid and the slaine thereof with 2-10 carbon atom; PFO sulphonyl disodium glutamate salt; 3-{ Ω-fluoroalkyl (C6-C11) oxo }-1-alkyl (C3-C4) sodium sulfonate; 3-{ Ω-fluothane acyl group (C6-C8)-N-ethylamino-}-1-propane sulfonic acid sodium; fluoroalkyl (C11-C20) carboxylic acid and slaine thereof; perfluoro carboxylic acid and slaine thereof; perfluoroalkyl (C4-C12) sulphonic acid ester and slaine thereof; the Perfluorooctane sulfonates diglycollic amide; N-propyl group-N-(2-hydroxyethyl) PFO sulfo group acid amides; perfluoroalkyl (C6-C10) sulfo group amido propyl leptodactyline; perfluoroalkyl (C6-C10)-N-ethyl sulfonyl glycine salt; single perfluoroalkyl (C6-C16) ethyl phosphonic acid (ester) salt etc.

Instantiation with surfactant commercially available prod of fluoroalkyl comprises the Co. by Asahi Glass, SARFRON S-111, S-112 and S-113 that Ltd. produces; FLUORAD FC-93, FC-95, FC-98 and FC-129 by Sumitomo 3M Ltd. production; By Daikin Industries, UNIDYNE DS-101 and DS-102 that Ltd. produces; By Dainippon Ink and Chemicals, MEGAFACE F-110, F-120, F-113, F-191, F-812 and F-833 that Inc produces; By Tohchem ProductsCo., ECTOP EF-102,103,104,105,112,123A, 306A, 501,201 and 204 that Ltd. produces; FUTARGENT F-100 that produces by Neos and F-150 etc.

Instantiation oil phase, cationic surfactant that can in water, disperse to contain the toner component comprise have fluoroalkyl primary, the second month in a season and tert-aliphatic amine; Aliphatic quaternary ammonium salt, for example perfluoroalkyl (C6-C10) sulfo group amido propyl leptodactyline, phenylmethane ammonium salt (benzalkonium salts), iso-octyl benzene two polyglycol ether dimethyl benzyl ammonium chlorides (benzetonium chloride), pyridiniujm, imidazoline salt etc.The instantiation of product comprises SARFRON S-121 (Asahi Glass Co., Ltd. produces) on its market; FLUORAD FC-135 (Sumitomo 3M Ltd. production); UNIDYNEDS-202 (Daikin Industries, Ltd. produces); MEGAFACE F-150 and F824 (DainipponInk and Chemicals, Inc produces); ECTOP EF-132 (Tohchem Products Co., Ltd. produces); FUTARGENT F-300 (Neos production) etc.

In addition, can use and be difficult to mineral compound spreading agent soluble in water, for example tricalcium phosphate, lime carbonate, titania, colloidal silica and hydroxylapatite.

And, use polymkeric substance protecting colloid (polymeric protection colloid), can in water, stably disperse the toner component.The instantiation of this protecting colloid comprises the polymkeric substance and the multipolymer that become in order to the system that places an order: for example, and acid (acrylic acid for example; methacrylic acid; alpha-cyanoacrylate; the alpha-cyano methacrylic acid; itaconic acid; butenoic acid; fumaric acid; maleic acid and maleic anhydride); acrylic monomers (beta-hydroxyethyl acrylate for example with hydroxyl; the beta-hydroxyethyl methacrylate; β-hydroxypropyl acrylate; β-hydroxypropyl methyl acrylate; γ-hydroxypropyl acrylate; γ-hydroxypropyl methyl acrylate; 3-chloro-2-hydroxypropyl acrylate; 3-chloro-2-hydroxypropyl methyl acrylate; diethylene glycol monoacrylate; the diethylene glycol monomethacrylates; the glycerine mono acrylic ester; N hydroxymethyl acrylamide and N-methylol methacrylamide); vinyl alcohol and ether thereof (vinyl methyl ether for example; EVE and vinyl propyl ether); vinyl alcohol (is a vinyl acetate with the ester class of closing carboxyl compound; propionate and vinyl butyrate); acrylamide (acrylamide for example; Methacrylamide; the diacetone acrylamide) and methylol compound; acid chloride (for example acrylic acid acid chloride and methacrylic acid acid chloride); and contain the monomer of nitrogen-atoms or have the alicyclic ring (vinylpyridine for example of nitrogen-atoms; vinyl pyrrolidone; vinyl imidazole; aziridine).In addition, for example polyoxyethylene ene compound polymkeric substance such as (for example polyoxyethylene, PPOX, polyoxyethylene alkyl amine, PPOX alkyl amine, polyoxyethylene alkylamide, PPOX alkylamide, polyoxyethylene nonylplenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene octadecyl phenylester and polyoxyethylene nonyl phenylesters) and for example cellulosic cpds such as methylcellulose, hydroxyethyl cellulose and hydroxypropyl cellulose also can be used as the polymkeric substance protecting colloid.

When using such as the acid of calcium phosphate etc. or being dissolved in that material is as spreading agent in the alkali, calcium phosphate mixes with acid (for example, hydrochloric acid), and the water flushing is to remove calcium phosphate from toner-particle then.Except that this method, can also remove by enzyme hydrolysis.

When using spreading agent, spreading agent can be retained on the particle.Yet, preferably after the elongation and/or cross-linking reaction of prepolymer and amine, wash and remove spreading agent.

And, for reduction comprises the viscosity of the dispersion medium of toner component, can use can be soluble modified polyester (i) or the solvent of prepolymer (A), this is because the gained particle has narrow particle diameter distribution.This solvent preferably has volatility and has the fusing point that is not less than 100 ℃, and this is because after particle forms, and removes this solvent easily from dispersion.The instantiation of this solvent comprises toluene, dimethylbenzene, benzene, phenixin, methylene chloride, 1,2-ethylene dichloride, 1,1,2-trichloroethanes, triclene, methenyl choloride, monochloro-benzene, 1,1-ethylene dichloride (dichloroethylidene), methyl acetate, ethyl acetate, methyl ethyl ketone and methyl isopropyl ketone.These solvents can be used alone or as a mixture.In these solvents, preferably use for example arsol such as toluene and dimethylbenzene, for example methylene chloride, 1, halogenated hydrocarbons such as 2-ethylene dichloride, methenyl choloride and phenixin etc.

Every use 100 weight portion prepolymers (A) add the 0-300 weight portion, preferred 0-100 weight portion, the more preferably solvent of 25-70 weight portion.When this solvent is used to prepare particle dispersion, stand the elongation and/or the cross-linking reaction of prepolymer and amine at particle, under normal pressure or decompression, therefrom remove and desolvate.

Elongation and/or cross-linking reaction time depend on the reactivity of the isocyanates structure of prepolymer (A) and amine (B), but are generally 10 minutes to 40 hours, are preferably 2-24 hour.Temperature of reaction is generally 0-150 ℃, is preferably 40-98 ℃.In addition, can use known catalyzer, for example dibutyltin dilaurate and dioctyl tin dilaurate.

For from the dispersion of emulsification, removing organic solvent, can use the temperature of the whole dispersion that raises gradually, remove the method for organic solvent in the drop fully by evaporation.In addition, also can make with the following method, promptly the dispersion of spraying emulsification in dry air is removed water-fast organic solvent in the drop fully, with the formation toner-particle, and by the evaporative removal water dispersant.Generally use air, nitrogen, carbon dioxide, the gaseous matter of heating flame gas is arranged in it, particularly be heated to the various air-flows of the temperature that is not less than the solvent for use boiling point as dry air.Spray dryer, belt dryer and rotary furnace can fully be removed organic solvent at short notice.

When the dispersion of flushing and dry emulsification also keeps its wide particle diameter distribution simultaneously, dispersion can be classified into required particle diameter distribution.

Cyclone separator, settler, centrifugal separator etc. can be removed the particle in the dispersion liquid.Powder after the gradable dry dispersion liquid, but with regard to efficient, preferred this liquid of classification.Unnecessary subparticle and coarse particle can be recycled to mediate in the technology and form particle.During recycle, these subparticles and coarse particle may wet.

Preferably from dispersion liquid, remove spreading agent, and more preferably remove spreading agent simultaneously carrying out above-mentioned classification.

Dried toner powder can be mixed with different types of particle, particle not of the same race comprises that for example, release agent particle, electric charge are controlled particle, fluidized particles and coloring agent particle.By mixed-powder being applied mechanical stress, can prevent that different types of particle breaks away from from composite particles with their sets and be melted on the surface of composite particles.

Concrete method comprises: the blade of use high speed rotating applies the method for impulsive force to potpourri; Potpourri is placed high-velocity fluid, and quicken this potpourri so that each particle runs foul of each other or makes the method etc. of its composite particles and shock plate collision.The instantiation of device comprises ONG comminutor (Hosokawa Micron Co., Ltd. improvement I type comminutor (the Nippon Pneumatic Mfg.Co. that manufacturing), has less pulverizing air pressure, Ltd. manufacturing), blend together (the Nara Machine Co. of system (HYBRIDIZATIONSYSTEM), Ltd. manufacturing), KRYPTRON SYSTEM (KawasakiHeavy Industries, Co., Ltd. makes), mortar etc. automatically.

Toner of the present invention can be used for two-component developing agent, and in two-component developing agent, toner and magnetic carrier are mixed together.Whenever contain 100 weight portion carriers, preferably contain the toner of 1-10 weight portion.

The suitable carrier that is used in the two-component developing agent comprises known carrier material, for example iron powder, ferrite dust, magnetic iron powder, magnetic resin carrier, and its particle diameter is between about 20 to about 200 μ m.

The surface of carrier can scribble resin.This instantiation that is coated in the resin on the carrier comprises amino resin, for example urea-formaldehyde resins, melamine resin, benzoguanamine resin, urea resin and polyamide, and epoxy resin.In addition, vinyl or ethenylidene resin, for example acrylic acid (ester) resinoid, plexiglass, polyacrylonitrile resin, polyvinyl acetate base resin, polyvinyl alcohol resin, polyvinyl butyral resin, polystyrene resin, styrene-propene acid based copolymer; The halogenated alkenes resin, for example polyvinyl chloride-based resin; Vibrin, for example pet resin and polybutylene terephthalate resin; Polycarbonate resin; Polyvinyl resin; Polyvinyl fluoride base resin; The polyvinylidene fluoride resin; Poly-trifluoro vinyl resin; The polyhexafluoropropylene resin; Vinylidene fluoride-acrylate copolymer; Vinylidene fluoride-ethylene fluoride multipolymer; Tetrafluoroethene, vinylidene fluoride and other do not comprise the multipolymer of the monomer of fluorine atom; And silicone resin.

Can choose wantonly in the toner and comprise conductive powder.This conductive powder instantiation comprise metal powder, carbon black, titania, tin oxide and zinc paste.The average particulate diameter of this conductive powder preferably is no more than 1 μ m.When this particle diameter is too big, be difficult to control the resistance of gained toner.

Toner of the present invention also can be used as single component magnetic or non magnetic developer, and does not have carrier.

Can use amorphous silicon photoreceptor (being designated hereinafter simply as the a-Si photoreceptor) in the present invention, the a-Si photoreceptor is by 50-400 ℃ of following electric conduction of heating substrate, and by vacuum deposition method, sputtering method, ion implantation, add hot CVD method, optical cvd method and plasma CVD method etc. and form in substrate that the a-Si photographic layer forms.Especially, preferably use plasma CVD method, this method forms the a-Si layer by using DC, high frequency or microwave glow discharge decomposition gas raw material in substrate.

Figure 1A-1D is illustrative embodiment that the photographic layer of amorphous silicon photoreceptor used in this invention is constituted respectively.Electrophtography photosensor 500 among Figure 1A comprises substrate 501 and the photographic layer 502 on it, and this photographic layer is photoconductive and is made by a-Si.Electrophtography photosensor 500 among Figure 1B comprises the a-Si superficial layer 503 on substrate 501, the photographic layer on it 502 and the photographic layer 502.Electrophtography photosensor 500 among Fig. 1 C comprises that substrate 501, the electric charge on it inject trapping layer (chargeinjection prevention layer) 504, electric charge and inject photographic layer 502 on the trapping layer 504 and the a-Si superficial layer 503 on the photographic layer 502.Electrophtography photosensor 500 among Fig. 1 D comprises the a-Si superficial layer 503 on substrate 501, the photographic layer on it 502 and the photographic layer 502, and wherein photographic layer 502 comprises charge generation layer 505 and the charge transfer layer of being made by a-Si 506 (charge transport layer).

The substrate of photoreceptor both can be conducted electricity, and also can insulate.The instantiation of substrate comprises metal, as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Ot, Od and Fe and their alloys, as stainless steel.In addition, can use such as synthetic resin and the film of pottery or the dielectric base of sheet, condition is to be formed with at least one surface of substrate of photographic layer on it through conductive processing, described synthetic resin comprises, for example polyester, tygon, polycarbonate, cellulose ethanoate, polypropylene, Polyvinylchloride, polystyrene, polyamide, glass.

The shape of substrate can be cylindrical, tabular or has the endless belt-shaped of smooth or convex-concave surface.Substrate can have required thickness, and when the Electrophtography photosensor that requires to comprise substrate has when flexible, the thickness of substrate is thin as far as possible.Yet with regard to the manufacturing and easy to operate and physical strength of Electrophtography photosensor, this thickness generally is not less than 10 μ m.

Shown in Fig. 1 C, a-Si photoreceptor of the present invention can be chosen the electric charge that comprises between conductive substrates and photographic layer wantonly and inject trapping layer.When the charge charging that will have certain polarity was given photographic layer, electric charge injected trapping layer and stops electric charge to inject photographic layer from substrate.Yet when the photographic layer charging had the electric charge of opposite polarity, it is inoperative that electric charge injects trapping layer, also just says, can electric charge inject trapping layer and work, and depends on polarity.The atom control that electric charge injects trapping layer comprises the height of conductivity than photographic layer.

With regard to required electrofax performance and economic benefit, electric charge injects trapping layer and preferably has 0.1-5 μ m, more preferably 0.3-4 μ m, the most preferably thickness of 0.5-3 μ m.

Photographic layer 502 is formed on the undercoat (undercoat layer), and undercoat randomly is formed on the substrate 501.Photographic layer 502 has required thickness, and with regard to required electrofax performance and economic benefit, the thickness of photographic layer 502 is preferably 1-100 μ m, and more preferably 20-50 μ m most preferably is 23-45 μ m.

When function was separated photographic layer, the layer of transfer charge was a charge transfer layer.Charge transfer layer comprises silicon atom, carbon atom and fluorine atom at least, and optional hydrogen atom and the oxygen atom of comprising.And charge transfer layer has required light sensitivity, electric charge retention, charge generation ability and charge transport capability.In the present invention, charge transfer layer preferably includes oxygen atom.

With regard to electrofax performance and economic benefit, charge transfer layer has required thickness, and it is preferably 5-50 μ m, 10-40 μ m more preferably, and most preferably be 20-30 μ m.

When function was separated photographic layer, the layer that produces electric charge was charge generation layer (charge generationlayer).Charge generation layer comprises silicon atom at least but does not comprise carbon atom in fact and the optional hydrogen atom that comprises.And charge generation layer has required light sensitivity, charge generation ability and charge transport capability.

With regard to electrofax performance and economic benefit, charge generation layer has required thickness, and it is preferably 0.5-15 μ m, 1-10 μ m more preferably, and 1-5 μ m more preferably.

The a-Si photoreceptor that uses among the present invention can randomly comprise the superficial layer that is formed on the photographic layer, and wherein photographic layer is formed in the substrate, and superficial layer is preferably the a-Si superficial layer.This superficial layer has Free Surface, can reach purpose of the present invention, makes photoreceptor have moisture resistance, prevents reusability, resists voltage, environmental resistance and endurance quality.

The thickness of this superficial layer is preferably 0.01-3 μ m, and more preferably 0.05-2 μ m most preferably is 0.1-1 μ m.When its during less than 0.01 μ m, the wearing and tearing that produce when using photoreceptor disappear superficial layer.When its during greater than 3 μ m, the deterioration of electrofax performance takes place, increase as the residual electromotive force of photoreceptor.

In the image developing device 2 in Fig. 2, to be applied to from the vibration bias voltage (vibrationbias voltage) of power supply 10 on the development sleeve (developing sleeve) 4, developing bias (developing bias) with as developed image the time, wherein said vibration bias voltage is formed by stacking by dc voltage and AC voltage.Background electromotive force and image electromotive force are between the maximal value and minimum value of vibration bias potential.The alternately electric field that alternately changes direction is formed on and develops part (developing portion) (D).In electric field alternately, toner and carrier high vibration break away under the effect of the static adhesion that produces between development sleeve 4 and the carrier, and toner transits on the photoconductor drum 1, and are transferred on the sub-image on the photoconductor drum 1.

The maximal value and the difference between the minimum value (voltage between peak value) of vibration bias voltage are preferably 0.5-5KV, and its frequency is preferably 1-10KHz.The waveform of vibration bias voltage is square wave, sine wave and triangular wave etc.The dc voltage of vibration biasing is the value between above-mentioned background electromotive force and the image electromotive force, preferably near the background electromotive force, rather than the image electromotive force, thereby prevent that toner is attached on the background.

When the waveform of vibration bias voltage was square wave, duty ratio (duty ratio) preferably was no more than 50%.Duty ratio is a kind of time ratio, promptly in vibration biasing circulation once toner towards the used time of photoreceptor.Peak value and make the difference of toner between the time average of the biasing of photoreceptor can be bigger, thus toner move more active, and more reliably attached on the sub-image, to reduce roughness and to improve the image definition of toner image.In addition, peak value and make the difference of toner between the time average of the biasing of photoreceptor can be less, thereby carrier becomes inactive, and the probability that carrier is attached on the background of sub-image will reduce widely.

The embodiment of Fig. 3 illustrative handle box of the present invention.

In Fig. 3, Reference numeral 31 is entire process boxes, the 32nd, and photoreceptor, the 33rd, charger, the 34th, image developing device and 35 is clearers.

In having the imaging device of the present invention of handle box (handle box comprises the toner of developing electrostatic latent image), photoreceptor is with predetermined peripheral speed rotation.Make the peripheral surface of photoreceptor have positive electricity or negative electricity equably with charger, rotate photoreceptor simultaneously so that it has predetermined electromotive force.Then, photoreceptor receives the light that becomes image that irradiators such as slit irradiator and laser beam flying instrument send, to form electrostatic latent image on its peripheral surface.Then,, use the toner development electrostatic latent image, to form toner image by the image developing device.Then, on toner image transfer printing transfer materials, from document feeder, transfer materials is imported between photoreceptor and the transfer printing device (transferer) at the synchronization that rotates photoreceptor.The transfer materials that to receive toner image then from the surface of photoreceptor separates, and is introduced into the image fixing device, with toner image on transfer materials, to form the duplicating image that can from this device, come out.With the surface of clearer cleaning photoreceptor, removing residual toner after the transfer printing, and to its discharge with reimaging.

Fuser is the turbulent waves fuser that makes photographic fixing film (fixing film) rotation, as shown in Figure 5.The photographic fixing film is to have endless belt-shaped heat-resistant film, and the photographic fixing film hangs and strains between live-roller, driven voller and the well heater under both.

Driven voller also is a jockey pulley, and the photographic fixing film is driven by the live-roller that turns clockwise among Fig. 5 and turns clockwise.The rotational speed of photographic fixing film is identical with the rotational speed of the transfer materials at fusing nip area L place, is in contact with one another at this areal pressure roller and photographic fixing film.

Pressure roll has rubber elastic layer, silicone rubber for example, but this layer has good release property.When the general pressure with 4-10kg contacted with the fusing nip area L, pressure roll was rotated counterclockwise.

But the photographic fixing film preferably has good heat-resistant release property and endurance quality, and its gross thickness is no more than 100 μ m, preferably is no more than 40 μ m.The instantiation of photographic fixing film comprises the single or multiple lift film that is formed by for example polyimide, polyetherimide, polyether sulfides (PES) and tetrafluoroethene perfluoro alkyl ethylene copolymer resin heat stable resins such as (PFA), what for example 20 μ m were thick comprises that fluorocarbon resin (for example, tetrafluoroethylene resin (PTFE) and PFA) contact with at least one surface of image with the release layer of conductive material, be coated with the thick elastic layer of 10 μ m that forms by rubber such as fluorocarbon rubber and silicone rubbers on the release layer.

In Fig. 5, well heater is made of planar substrates and fixing heater, and planar substrates is made by the material of high thermal conductivity and high resistivity, for example aluminium oxide.The fixing heater that is formed by thermostabile bodies is positioned on the surface of well heater, and wherein well heater and the well heater photographic fixing film on vertically contacts.By silk screen print method etc., with resistance material, for example Ag/Pd and Ta2N wire or banded being coated on the fixing heater.The two ends of fixing heater have the electrode (not shown) and when electric current passed through electrode, thermostabile bodies produced heat.And the fixing temperature sensor that is formed by thermistor is positioned at the opposite side of substrate, and to be positioned at that side relative with fixing heater.

The temperature signal of the substrate that the fixing temperature sensor is recorded is sent to the controller of the electric energy that the control fixing heater provides, so that well heater has predetermined temperature.

Fig. 7 illustrative is used the embodiment of the imaging device of the present invention of contact charging device.Photoreceptor to be charged and image carrier rotate along the direction shown in the arrow with predetermined speed (process speed).Roll-type (roller-shaped) charging roller is as the charger that contacts with photoreceptor, and it is formed by the conductive rubber layer of metal shaft (metallic shaft) and periphery and concentric covering metal shaft substantially.The two ends of metal shaft are supported by the rotation of supporting seat (not shown), charging roller are pressed on the photoreceptor with predetermined pressure by the pressurizer (not shown).In Fig. 6, charging roller is driven by photoreceptor and rotates.Because charging roller is the metal shaft of 9mm and to be coated in resistivity on the metal shaft be that the rubber layer of the middle resistivity of about 100000 Ω cm is made by diameter, so the diameter of charging roller is 16mm.

The axle and the power supply of charging roller are electrically connected mutually, and power supply applies predetermined bias voltage to charging roller.Therefore, the peripheral surface of photoreceptor is charged equably, thereby has predetermined polarity and electromotive force.

The charger of Shi Yonging can have Any shape except that rollers such as magnetic force brush and hairbrush in the present invention, and is selectable according to the form of specification and electrophotographic imaging forming apparatus.Magnetic force brush is by constituting as various ferrite particles such as Zn-Cu ferrite, the non magnetic conducting sleeve that supports charging unit and the magnetic roll that is included in the non magnetic conducting sleeve as charging unit.Hairbrush be by through the axle of conductive processing and twine or attached on the axle, carry out the charger that the fur of conductive processing constitutes via carbon, copper sulfide, metal and metal oxide.

Fig. 7 illustrative is used another embodiment of the imaging device of the present invention of contact charging device.Photoreceptor to be charged and image carrier rotate along the direction shown in the arrow with predetermined speed (process speed).The hair roller that hairbrush constitutes contacts with the photoreceptor that is positioned at the roll-gap width place with predetermined pressure, to resist the elasticity of this brush.

Brush roll in this embodiment (fur brush roller) is that external diameter is that 14mm and longitudinal length are the roller brush of 250mm, and it is the metal shaft (also as electrode) of 6mm by diameter and is spirally wound on conduction rayon fiber REC-B on this

The webbing of (available from Unitika Ltd.) and constituting.Per 50 ultimate fibres are 300 deniers (denier) in this brush, and its density is every square millimeter of 155 fibers.It is in the pipe of 12mm that this round brush is inserted internal diameter, rotation simultaneously, so that should brush and manage with one heart, and be placed in the environment of high humility and high temperature, with the bristle that obtains tilting.

When applying 100V voltage, the resistance of brush roll is 1 * 10 ⁵Ω.When to be positioned at roll-gap width 3mm place, diameter is brush roll that the metal drum of 30mm contacts when applying the voltage of 100V, resistance is converted into electric current.

Require resistance to be not less than 10 ⁴Ω and be no more than 10 ⁷Ω, preventing to generate defect image, this is because flow to fault location when a large amount of leakage currents, for example during the pin hole on the photoreceptor, the roll gap charging is insufficient, and also insufficient to the photoreceptor charging.

Remove the REC-B of Unitika Ltd.

Outside, the instantiation of hairbrush material comprises the REC-C of the said firm

, REC-M1 And REC-M10

Toray Industries, the SA-7 of Inc. NihonSanmo Dyeing Co., the Thunderon of Ltd.

Kanebo, the Belltron of Ltd.

KurarayCo., the Clacarbo of Ltd.

The rayon fiber that carbon disperses; With MITSUBISHI RAYON CO., the Roval of LTD.

Hairbrush preferably has every fiber 3-10 denier, every batch of 10-100 ultimate fibre, and every square millimeter of 80-600 root fiber.This fiber preferably has the length of 1-10mm.

Brush roll is with predetermined peripheral speed (face velocity) rotation, and its sense of rotation is opposite with the sense of rotation of photoreceptor.To impose on brush roll from the predetermined charge voltages that power supply produces, and to the surface charging of photoreceptor, make it have predetermined polarity and electromotive force with equably.In this embodiment, brush roll contacts with photoreceptor, and with to photoreceptor charging, this mainly is directly to inject charging, and such charging makes the electromotive force of photosensitive surface and electromotive force that charging voltage is applied to brush roll much at one.

The charger of Shi Yonging can have Any shape except that rollers such as magnetic force brush and hairbrush in the present invention, and is selectable according to the form of specification and electrophotographic imaging forming apparatus.Charging roller is generally made by the metal shaft of the rubber layer that is coated with middle resistivity, and wherein resistivity is about 100000 Ω cm.Magnetic force brush is by constituting as various ferrite particles such as Zn-Cu ferrite, the non magnetic conducting sleeve that supports charging unit and the magnetic roll that is included in the non magnetic conducting sleeve as charging unit.

Fig. 8 illustrative is used another embodiment of the imaging device of the present invention of contact charging device.Photoreceptor to be charged and image carrier rotate along the direction shown in the arrow with predetermined speed (process speed).The hair roller that magnetic force brush constitutes contacts with the photoreceptor that is positioned at the roll-gap width place with predetermined pressure, to resist the elasticity of this brush.

The magnetic-particle that comprises the resin that is coated with middle resistivity as the magnetic force brush that is used for the present invention of contact charging device, it comprises that average particulate diameter is the potpourri of the Zn-Cu ferrite particles of 25 and 10 μ m, and mixed weight is 1/0.05 than (25 μ m/10 μ m).This contact charging device is made of the magnetic-particle that applies, the non magnetic conducting sleeve that supports magnetic-particle and the magnetic roll that is included in the non magnetic sleeve.The magnetic-particle of this coating is coated on the sleeve with the thickness of 1mm, thereby forms the charging roll gap of width for about 5mm between sleeve and photoreceptor, and the slit that forms about 500 μ m between them.The sense of rotation of magnetic roll is opposite with the sense of rotation of photoreceptor, and its rotational speed is the twice of the rotational speed of photosensitive surface, thereby makes the surface of mantle friction photoreceptor of sleeve, and magnetic force brush contacts with photoreceptor equably.

The charger of Shi Yonging can have Any shape except that magnetic force brush and hairbrush isodynamic brush roll in the present invention, and is selectable according to the form of specification and electrophotographic imaging forming apparatus.Charging roller is generally made by the metal shaft of the rubber layer that is coated with middle resistivity, and wherein resistivity is about 100000 Ω cm.Hairbrush be by through the axle of conductive processing and twine or attached on the axle, carry out the charger that the fur of conductive processing constitutes via carbon, copper sulfide, metal and metal oxide.

After briefly having described the present invention, by with reference to following specific embodiment, can further understand the present invention, these embodiment purposes provided herein only are explanation, but not are intended to restriction.In the description of following embodiment, except as otherwise herein provided, umber is represented parts by weight.

Embodiment

Embodiment 1

Synthesizing of toner binder resin

In the reactor that is equipped with cooling tube, stirrer and nitrogen conduit, mix the addition product of 724 parts of bisphenol-As and 2 moles of ethylene oxide, 276 parts of m-phthalic acids and 2 parts of dibutyl tin oxides, and with it in normal pressure and 230 ℃ reaction 8 hours down.Then potpourri was reacted 5 hours under the decompression of 10-15mm Hg, and in it, add 32 parts of phthalic anhydrides, and reacted 2 hours down at 160 ℃.Then, 80 ℃ of reactions 2 hours down, preparation comprises the prepolymer of isocyanates (1) with the ethyl acetate solution of potpourri and 188 parts of isophorone diisocyanate.Then, mixed down 67 parts of prepolymers (1) and 14 parts of isophorone diamine 2 hours, to prepare the vibrin (1) that weight-average molecular weight is 64000 urea modification at 50 ℃.Similarly, under normal pressure and 230 ℃, the addition product of 724 parts of bisphenol-As of polycondensation and 2 moles of ethylene oxide and 276 parts of terephthalic acid (TPA)s 8 hours react potpourri 5 hours under the decompression of 10-15mm Hg then, are 5000 unmodified vibrin (a) with the preparation peak molecular weight.The polyester (1) of 200 parts of urea modifications and 800 parts of unmodified vibrin (a) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (1).Ethyl acetate/MEK solution to toner binder resin (1) partly reduces pressure and drying, to separate toner binder resin (1).The glass transition temperature (Tg) of toner binder resin (1) is that 62 ℃ and acid number are 10.

The preparation of toner

Under 60 ℃, by the speed of TK type uniform mixer with 12000rpm, with the ethyl acetate/MEK solution of 240 parts of toner binder resins (1), 20 parts of fusing points is that 81 ℃ and melt viscosity are that pentaerythrite four behenates (pentaelislitholtetrabehenate) and 10 parts of carbon blacks of 25cps are blended in the beaker, uniform dissolution and this potpourri of dispersion are with the preparation toner material solution.706 parts of ion exchange waters, 294 parts are comprised 10% hydroxylapatite suspending liquid 10, and (available from Nippon Chemical IndustrialCo., slurry Ltd.) and 0.2 part of neopelex are dissolved in the beaker equably.Then, under 60 ℃, stir this potpourri with the speed of 12000rpm, simultaneously above-mentioned toner material solution is joined wherein, stirred this potpourri 10 minutes by TK type uniform mixer.Then, this potpourri is transferred in the flask that is equipped with stirrer and stabilimeter, and 98 ℃ of heating down, to remove partial solvent.Further, at room temperature, stir this potpourri with the speed of 12000rpm by TK type uniform mixer, to remove whole solvents.Then, filtering mixt, flushing, drying is also used air classification, and obtaining weight median particle diameter (D4) is 6.35 μ m, and number average particle diameter (Dn) is that 5.57 μ m and D4/Dn are female toner of 1.14.At last, mix 100 parts of female toners and 0.5 part of hydrophobic silica, prepare toner of the present invention (1) by the Henschel mixer.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 2

Synthesizing of toner binder resin

Be similar to embodiment 1, after the addition product of the addition product of 334 parts of bisphenol-As of polycondensation and 2 moles of ethylene oxide, 334 parts of bisphenol-As and 2 moles of epoxypropane, 274 parts of m-phthalic acids and 20 parts of trimellitic anhydrides, make the product reaction of 154 parts of isophorone diisocyanate and polycondensation, with preparation prepolymer (2).Then, be similar to embodiment 1, make 213 parts of prepolymers (2), 9.5 parts of isophorone diamine and 0.5 part of butanediamine reaction, the preparation weight-average molecular weight is the vibrin (2) of 79000 urea modification.The polyester (2) of 200 parts of urea modifications and 800 parts of unmodified vibrin (a) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (2).Ethyl acetate/MEK solution to toner binder resin (2) partly reduces pressure and drying, to separate toner binder resin (2).The peak molecular weight of toner binder resin (2) is 5000, and it is 10 with acid number that glass transition temperature (Tg) is 62 ℃.

The preparation of toner

The preparation process that repeats toner among the embodiment 1 prepares female toner (2), and difference is toner binder resin (1) is replaced by toner binder resin (2), and is set to 50 ℃ dissolve with dispersion temperature.Further, in hot-air, will mix and stir as the zinc salt of 1.0 parts of salicyclic acid derivatives of charge control agent and 100 parts of female toners (2), with thereon with the charge control agent set.The weight median particle diameter (D4) of this mother's toner (2) is 5.64 μ m, and number average particle diameter (Dn) is that 4.98 μ m and D4/Dn are 1.13.At last, mix 100 parts of female toners and 1.0 parts of hydrophobic silicas and 0.5 part of hydrophobic silica, prepare toner of the present invention (2) by the Henschel mixer.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 3

Synthesizing of toner binder resin

The vibrin (1) of 30 parts of urea modifications and 970 parts of unmodified vibrin (a) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (3).Ethyl acetate/MEK solution to toner binder resin (3) partly reduces pressure and drying, to separate toner binder resin (3).The peak molecular weight of toner binder resin (3) is 5000, and it is 10 with acid number that glass transition temperature (Tg) is 62 ℃.

The preparation of toner

The preparation process that repeats toner among the embodiment 2 prepares female toner (3), and difference is toner binder resin (2) is replaced by toner binder resin (3), and colorant is replaced by 8 parts of carbon blacks.The weight median particle diameter of this mother's toner (D4) is 6.72 μ m, and number average particle diameter (Dn) is that 6.11 μ m and D4/Dn are 1.10.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 4

Synthesizing of toner binder resin

The vibrin (1) of 500 parts of urea modifications and 500 parts of unmodified vibrin (a) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (4).Ethyl acetate/MEK solution to toner binder resin (4) partly reduces pressure and drying, to separate toner binder resin (4).The peak molecular weight of toner binder resin (4) is 5000, and it is 10 with acid number that glass transition temperature (Tg) is 62 ℃.

The preparation of toner

The preparation process that repeats toner among the embodiment 1 prepares female toner (4), and difference is toner binder resin (1) is replaced by toner binder resin (4), and colorant is replaced by 8 parts of carbon blacks.The weight median particle diameter of this mother's toner (D4) is 4.98 μ m, and number average particle diameter (Dn) is that 4.35 μ m and D4/Dn are 1.14.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 5

Synthesizing of toner binder resin

The vibrin (1) of 750 parts of urea modifications and 250 parts of unmodified vibrin (a) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (5).Ethyl acetate/MEK solution to toner binder resin (5) partly reduces pressure and drying, to separate toner binder resin (5).The peak molecular weight of this toner binder resin (5) is 5000, and it is 10 with acid number that glass transition temperature (Tg) is 62 ℃.

The preparation of toner

The preparation process that repeats toner among the embodiment 1 prepares female toner (5), and difference is toner binder resin (1) is replaced by toner binder resin (5).The weight median particle diameter of this mother's toner (D4) is 5.93 μ m, and number average particle diameter (Dn) is that 5.25 μ m and D4/Dn are 1.14.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 6

Synthesizing of toner binder resin

The vibrin (1) of 850 parts of urea modifications and 150 parts of unmodified vibrin (a) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (6).Ethyl acetate/MEK solution to toner binder resin (6) partly reduces pressure and drying, to separate toner binder resin (6).The peak molecular weight of this toner binder resin (6) is 5000, and it is 10 with acid number that glass transition temperature (Tg) is 62 ℃.

The preparation of toner

The preparation process that repeats toner among the embodiment 1 prepares female toner (6), and difference is toner binder resin (1) is replaced by toner binder resin (6).The weight median particle diameter of this mother's toner (D4) is 3.90 μ m, and number average particle diameter (Dn) is that 3.38 μ m and D4/Dn are 1.15.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 7

Synthesizing of toner binder resin

With the addition product of 724 parts of bisphenol-As and 2 moles of ethylene oxide, 276 parts of terephthalic acid (TPA)s normal pressure and 230 ℃ of following polycondensations 2 hours.Then potpourri was reacted 5 hours under the decompression of 10-15mm Hg,, be 800 unmodified vibrin (b) with the preparation peak molecular weight.The vibrin (1) of 200 parts of urea modifications and 800 parts of unmodified vibrin (b) are dissolved and be blended in 2000 parts of mixed solvents that form by ethyl acetate and MEK (1/1), with the ethyl acetate/MEK solution of preparation toner binder resin (7).Ethyl acetate/MEK solution to toner binder resin (7) partly reduces pressure and drying, to separate toner binder resin (7).The glass transition temperature (Tg) of toner binder resin (7) is 45 ℃.

The preparation of toner

The preparation process that repeats toner among the embodiment 1 prepares female toner (7), and difference is toner binder resin (1) is replaced by toner binder resin (7).The weight median particle diameter of this mother's toner (D4) is 5.22 μ m, and number average particle diameter (Dn) is that 4.50 μ m and D4/Dn are 1.16.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 8

With 210 parts of toner binder solution of preparation among 210 parts of ethyl acetate dilution embodiment 1, with the method that is similar to embodiment 1 dispersion emulsification and granulation with 210 parts of dilutions.The preparation process that repeats toner among the embodiment 1 then prepares female toner (8).The weight median particle diameter of this mother's toner (D4) is 4.25 μ m, and number average particle diameter (Dn) is that 3.73 μ m and D4/Dn are 1.14.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 9

By evaporator the toner component of preparation among 350 parts of embodiment 1 (disperse and wait to remove solvent by uniform mixer) is concentrated into 175 parts, with the method that is similar to embodiment 1 with 210 parts of concentrated dispersion emulsification and granulations.Then, the preparation process of toner prepares female toner (9) among the repetition embodiment 1.The weight median particle diameter of this mother's toner (D4) is 6.95 μ m, and number average particle diameter (Dn) is that 5.65 μ m and D4/Dn are 1.23.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 10

With the toner component of preparation among 210 parts of embodiment 1 of 965 parts of ethyl acetate dilution (disperse and wait to remove solvent), with the method that is similar to embodiment 1 dispersion emulsification and granulation with 210 parts of dilutions by uniform mixer.Then, the preparation process of toner prepares female toner (10) among the repetition embodiment 1.The weight median particle diameter of this mother's toner (D4) is 3.95 μ m, and number average particle diameter (Dn) is that 3.43 μ m and D4/Dn are 1.15.Other detailed conditions and evaluation result are shown in table 1-3.

Embodiment 11

By evaporator the toner component of preparation among 350 parts of embodiment 1 (disperse and wait to remove solvent by uniform mixer) is concentrated into 125 parts, with the method that is similar to embodiment 1 with 210 parts of concentrated dispersion emulsification and granulations.Then, the preparation process of toner prepares female toner (11) among the repetition embodiment 1.The weight median particle diameter of this mother's toner (D4) is 6.84 μ m, and number average particle diameter (Dn) is that 5.61 μ m and D4/Dn are 1.22.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 1

Synthesizing of toner binder resin

Under 2 parts of dibutyl tin oxide catalyst actions, the addition product of 354 parts of bisphenol-As of polycondensation and 2 moles of ethylene oxide and 166 parts of m-phthalic acid polycondensations are 4000 comparison toner binder resin (1) with the preparation peak molecular weight.The glass transition temperature (Tg) of this comparison toner binder resin (1) is 57 ℃.

The preparation of toner

Under 50 ℃,, 100 parts of comparison toner binder resins (1), 200 parts of ethyl acetate solutions and 10 parts of carbon blacks are blended in the beaker, with uniform dissolution and dispersed mixture by the speed of TK type uniform mixer with 12000rpm.Then, the preparation process of toner prepares comparison toner (1) among the repetition embodiment 1.The weight median particle diameter of this mother's toner (D4) is 7.51 μ m, and number average particle diameter (Dn) is that 6.05 μ m and D4/Dn are 1.24.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 2

In the reactor that is equipped with cooling tube, stirrer and nitrogen conduit, mix the addition product of 343 parts of bisphenol-As and 2 moles of ethylene oxide, 166 parts of m-phthalic acids and 2 parts of dibutyl tin oxides, and with it in normal pressure and 230 ℃ reaction 8 hours down.Then potpourri was reacted 5 hours under the decompression of 10-15mm Hg, this potpourri is cooled to 80 ℃.Then, under 150 ℃, potpourri and 14 parts of toluene diisocyanates being reacted 5 hours, therefrom is 98000 urethane-modified vibrin then except that desolvating with the preparation weight-average molecular weight.Being similar to the method for embodiment 1, the addition product of 363 parts of bisphenol-As of polycondensation and 2 moles of ethylene oxide and 166 parts of m-phthalic acids, with the preparation peak molecular weight be 3800 and acid number be 7 unmodified vibrin.With the unmodified vibrin dissolving of 350 parts of urethane-modified polyester and 650 parts and be blended in the toluene, from potpourri, remove solvent, with preparation toner binder resin (2) relatively.The glass transition temperature (Tg) of this toner binder resin (2) is 58 ℃.

The preparation of toner

With 100 parts of Henschel mixer premixeds relatively toner binder resin (2) and 8 parts of carbon blacks, and mediate with continuous kneader.Then, pulverize the potpourri of mediating with jet mill, and by the air classifier classification, to prepare female toner.Mix 100 parts of female toners and 1.0 parts of hydrophobic silicas and 0.5 part of hydrophobic silica by the Henschel mixer, compare toner (2) with preparation.The weight median particle diameter of this mother's toner (D4) is 6.50 μ m, and number average particle diameter (Dn) is that 5.50 μ m and D4/Dn are 1.18.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 3

Synthesizing of toner binder resin

Under 2 parts of dibutyl tin oxide catalyst actions, the addition product of 354 parts of bisphenol-As of polycondensation and 2 moles of ethylene oxide and 166 parts of terephthalic acid (TPA)s are 12000 comparison toner binder resin (3) with the preparation peak molecular weight.It is 10 with acid number that the glass transition temperature (Tg) of this comparison toner binder resin (3) is 62 ℃.

The preparation of toner

Under 50 ℃,, 100 parts of comparison toner binder resins (3), 200 parts of ethyl acetate solutions and 4 parts of copper phthalocyanines are blended in the beaker, with uniform dissolution and dispersed mixture by the speed of TK type uniform mixer with 12000rpm.Then, the preparation process of toner prepares comparison toner (3) among the repetition embodiment 1.The weight median particle diameter of this mother's toner (D4) is 6.12 μ m, and number average particle diameter (Dn) is that 4.64 μ m and D4/Dn are 1.32.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 4

The preparation process that repeats toner among the embodiment 1 prepares comparison toner (4), and difference is to stir by the speed of uniform mixer with 18000rpm, to remove this solvent fully.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 5

The preparation process that repeats toner among the embodiment 1 prepares comparison toner (5), and difference is to mix 0.2 part of hydrophobic silica and 100 parts of female toner that primary particle size is 35 μ m by the Henschel mixer.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 6

The preparation process that repeats toner among the embodiment 1 prepares comparison toner (6), and difference is to mix 0.2 part of hydrophobic silica and 100 parts of female toners by the Henschel mixer.Other detailed conditions and evaluation result are shown in table 1-3.

Comparative example 7

The preparation process that repeats toner among the embodiment 1 prepares comparison toner (7), and difference is to mix 5.8 parts of hydrophobic silicas and 100 parts of female toners by the Henschel mixer.Other detailed conditions and evaluation result are shown in table 1-3.

By (Nikkaki Bios Co., Coulter counter (Coulter Counter) TA-II that Ltd.) links to each other with personal computer PC 9801 (NEC Corp.) measures the equal particle diameter of body (D4) and the number average particle diameter (Dn) of toner with the interface that produces number distribution and volume distributed median.The NaCl solution that use contains 1% one-level sodium is as following electrolytic solution:

With the 0.1-5ml washing agent, be preferably sodium alkyl benzene sulfonate and join in the electrolytic solution of 100-150ml as spreading agent;

2-20mg sample toner is joined in the electrolytic solution, disperseed about 1-3 minute, with preparation sample dispersion liquid by ultrasonic separating apparatus;

This sample dispersion liquid is joined in the 100-200ml electrolytic solution in another beaker, to have predetermined concentration;

Measure the particle diameter distribution of number average particle diameter by the Coulter counter TA-II that uses 100 μ m holes, and measure its volume distributed median and number distribution as the particle of 2-40 μ m;

Determine weight median particle diameter (D4) according to volume distributed median.

Pair cut apart with the perimeter of toner-particle, to determine the circularity of toner with the girth of the equal-sized circumference of its optical projection area.Particularly, determine the circularity of toner by flow model affected analyser FPIA-2000 (available from SYSMEX CORPORATION).Concrete measuring method comprises: will remove the wherein 0.1-0.5ml surfactant of impurity solid material in advance, and be preferably alkyl benzene sulphonate as spreading agent, and join in the 100-150ml water; The 0.1-0.5g toner is joined potpourri; Disperseing this potpourri 1-3 that comprises toner minute with ultrasonic separating apparatus, is the dispersion liquid of 3000-10000pieces/ μ l with preparation concentration; And the shape and the distribution of measuring toner with above-mentioned surveying instrument.

The assay method of SF-1 is as follows: random sampling (available from Hitachi, Ltd.) is amplified to 1000 times toner image of original image size, samples in 100 particles (or more) by scanning electron microscope S-800; By the interface image information is delivered to image Luzex III (available from NIRECOCorp.), to analyze this information.

By X-Rite 938 measurement image density, also measured background density, thereby be used for estimating the background stain.

Whether visual inspection the toner film forming takes place on developing roller surface.

Zero: do not take place

*: take place

Table 1

Table 2

Table 3

The application requires to be hereby incorporated by respectively on October 8th, 2003 and the Japanese patent application 2003-349060 of application on November 28th, 2003 and the right of priority of 2003-400263.

After intactly having described the present invention, it should be apparent to those skilled in the art that and under the situation of the spirit and scope above-mentioned, can make variations and modifications the present invention without prejudice to the present invention.

Claims (95)

1. toner, it comprises:

Average circularity is the particle toner materials of 0.93-0.99, and it comprises:

The polyester binder resin i of modification, and

Colorant; And

External additive, its amount is 0.3-5.0 weight portion external additive/100 weight portion particle toner materials,

The melt viscosity of wherein said toner is 70-140Pas down at 160 ℃,

Weight median particle diameter D4 is 3-7 μ m,

The weight median particle diameter of described toner is 1.10-1.25 with the ratio D4/Dn of number average particle diameter Dn,

By number, the amount of particle that particle diameter is no more than 4 μ m is less than 10% or by volume, particle diameter is not less than the particle of 8 μ m less than 2%.

2. the described toner of claim 1, wherein said toner has the shape factor S F-1 of 105-170.

3. the described toner of claim 1, the primary particle diameter of wherein said external additive is that 5-20nm and second particle diameter are 50-200nm.

4. the described toner of claim 1, the polyester binder resin i of wherein said modification is the modified polyester resin with urea groups.

5. the described toner of claim 2, the polyester binder resin i of wherein said modification is the modified polyester resin with urea groups.

6. the described toner of claim 1, wherein said external additive are at least a in inorganic particulate material and the particulate polymers material.

7. the described toner of claim 2, wherein said external additive are at least a in inorganic particulate material and the particulate polymers material.

8. the described toner of claim 3, wherein said external additive are at least a in inorganic particulate material and the particulate polymers material.

9. the described toner of claim 4, wherein said external additive are at least a in inorganic particulate material and the particulate polymers material.

10. the described toner of claim 5, wherein said external additive are at least a in inorganic particulate material and the particulate polymers material.

11. the described toner of claim 1, wherein said external additive is a hydrophobized silica.

12. the described toner of claim 2, wherein said external additive is a hydrophobized silica.

13. the described toner of claim 3, wherein said external additive is a hydrophobized silica.

14. the described toner of claim 4, wherein said external additive is a hydrophobized silica.

15. the described toner of claim 5, wherein said external additive is a hydrophobized silica.

16. the described toner of claim 6, wherein said external additive is a hydrophobized silica.

17. the described toner of claim 7, wherein said external additive is a hydrophobized silica.

18. the described toner of claim 8, wherein said external additive is a hydrophobized silica.

19. the described toner of claim 9, wherein said external additive is a hydrophobized silica.

20. the described toner of claim 10, wherein said external additive is a hydrophobized silica.

21. the described toner of claim 1, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

22. the described toner of claim 2, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

23. the described toner of claim 3, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

24. the described toner of claim 4, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

25. the described toner of claim 5, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

26. the described toner of claim 6, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

27. the described toner of claim 7, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

28. the described toner of claim 8, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

29. the described toner of claim 9, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

30. the described toner of claim 10, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

31. the described toner of claim 11, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

32. the described toner of claim 12, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

33. the described toner of claim 13, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

34. the described toner of claim 14, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

35. the described toner of claim 15, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

36. the described toner of claim 16, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

37. the described toner of claim 17, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

38. the described toner of claim 18, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

39. the described toner of claim 19, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

40. the described toner of claim 20, wherein said particle toner materials further comprises unmodified polyester binder resin LL, and the weight ratio i/LL of the polyester binder resin i of wherein said modification and unmodified polyester binder resin LL is between 5/95 to 80/20.

41. the described toner of claim 21, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

42. the described toner of claim 22, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

43. the described toner of claim 23, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

44. the described toner of claim 24, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

45. the described toner of claim 25, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

46. the described toner of claim 26, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

47. the described toner of claim 27, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

48. the described toner of claim 28, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

49. the described toner of claim 29, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

50. the described toner of claim 30, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

51. the described toner of claim 31, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

52. the described toner of claim 32, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

53. the described toner of claim 33, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

54. the described toner of claim 34, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

55. the described toner of claim 35, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

56. the described toner of claim 36, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

57. the described toner of claim 37, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

58. the described toner of claim 38, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

59. the described toner of claim 39, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

60. the described toner of claim 40, wherein unmodified polyester binder resin LL has the peak molecular weight of 1000-20000.

61. each described toner among the claim 21-60, wherein said unmodified polyester binder resin LL has the acid number of 10-30mg KOH/g.

62. each described toner among the claim 21-60, wherein said unmodified polyester binder resin LL has 35-55 ℃ glass transition temperature Tg.

63. the described toner of claim 61, wherein said unmodified polyester binder resin LL has 35-55 ℃ glass transition temperature Tg.

64. each described toner among the claim 1-60, further comprise wax, wherein said wax all is dispersed in the particle toner materials carefully, and wherein the concentration of the wax of particle toner materials surface is higher than the concentration of wax intracardiac in the particle toner materials.

65. the described toner of claim 61 further comprises wax, wherein said wax all is dispersed in the particle toner materials carefully, and wherein the concentration of the wax of particle toner materials surface is higher than the concentration of wax intracardiac in the particle toner materials.

66. the described toner of claim 62 further comprises wax, wherein said wax all is dispersed in the particle toner materials carefully, and wherein the concentration of the wax of particle toner materials surface is higher than the concentration of wax intracardiac in the particle toner materials.

67. the described toner of claim 63 further comprises wax, wherein said wax all is dispersed in the particle toner materials carefully, and wherein the concentration of the wax of particle toner materials surface is higher than the concentration of wax intracardiac in the particle toner materials.

68. each described toner further comprises charge control agent among the claim 1-60, wherein said charge control agent anchors on the surface of described particle toner materials.

69. the described toner of claim 61 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

70. the described toner of claim 62 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

71. the described toner of claim 63 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

72. the described toner of claim 64 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

73. the described toner of claim 65 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

74. the described toner of claim 66 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

75. the described toner of claim 67 further comprises charge control agent, wherein said charge control agent anchors on the surface of described particle toner materials.

76. each described toner among the claim 1-60, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

77. the described toner of claim 61, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

78. the described toner of claim 62, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

79. the described toner of claim 63, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

80. the described toner of claim 64, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

81. the described toner of claim 65, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

82. the described toner of claim 66, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

83. the described toner of claim 67, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

84. the described toner of claim 68, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

85. the described toner of claim 69, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

86. the described toner of claim 70, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

87. the described toner of claim 71, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

88. the described toner of claim 72, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

89. the described toner of claim 73, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

90. the described toner of claim 74, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

91. the described toner of claim 75, wherein said toner prepares volumetric contraction 10-90% by use solid dispersion in aqueous medium.

92. prepare the method for each described toner among the claim 1-91, this method comprises:

To comprise the toner components dissolved of prepolymer or be dispersed in the organic solvent, with preparation solution or dispersion; And

Described solution or dispersion are dispersed in the aqueous medium, with the polyester binder resin i of preparation modification.

93. prepare the method for each described toner among the claim 1-91, this method comprises:

At least the little drop particulate material that includes machine solvent, adhesive resin and colorant is dispersed in the aqueous medium that comprises particulate resin; And

Remove described organic solvent.

94. a developer, it comprises each described toner among the claim 1-91.

95. a formation method, it comprises:

To the Electrophtography photosensor charging, to form electrostatic latent image thereon;

With the described developer of the claim 94 described electrostatic latent image that develops, to form toner image thereon;

Described toner image is transferred on the transfer printing sheet; And

Toner image on the described transfer printing sheet of photographic fixing;

Clean described Electrophtography photosensor, to remove residual developer thereon.

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