CN101101461A - Toner for electrostatic image development, electrostatic image developer and image forming method using the same - Google Patents

Abstract

The invention provides a toner for electrostatic charge image development and developer for electrostatic charge image development using the said toner and imaging method. The toner for electrostatic charge image development can fix at low temperature and the antisticking agent in bonding resin has excellent dispersibility-concealment, and the toner has higer intensity. The toner for electrostatic charge image development contains bonding resin, colorant and antisticking agent, wherein the ratio G'(70)/G'(90) of storage modulus G'(70) at 70 degree and storage modulus G'(90) at 90 degree is 1*10<SUP>2</SUP>~1*10<SUP>5</SUP>, and the storage modulus is obtained by dynamic viscosity at 1 radian/second. The said toner contains a compound which has an anionic ionicity dissociable group and a cationic ionicity dissociable group in the same molecule.

Description

Electrostatic image developing toner and use the developer for static charge image development and the formation method of this toner

Technical field

The present invention relates to be used to utilize xerography to form the electrostatic image developing toner of image, also relate to developer for static charge image development and the formation method of using this toner.

Background technology

In the xerography, on photoreceptor, form electrostatic image by charged, step of exposure, utilize the developer contain toner develop for electrostatic latent image forming toner image, with this toner image transfer printing and photographic fixing in recording medium, thereby form image.Here comprise the tow-component developer that contains toner and carrier in the employed developer and use single component developer of magnetic color tuner or nonmagnetic toner separately.Usually can use so-called mixing pulverizing method for making when making toner, in the method, with detackifier melting mixings such as pigment, charged controlling agent, waxes, cooling back micro mist is broken, further classification then with thermoplastic resin.

In the toner made from common mixing pulverizing method for making, being shaped as of toner-particle is unsetting, and the surface structure of toner-particle can change knifeedge owing to comminuted and the different of pulverising step condition of material therefor, therefore, shape and the surface structure of controlling toner-particle wittingly is difficult.

Relative therewith, as controlling the shape of toner and the method for surface structure wittingly, people have proposed to utilize the wet type method for making to make the method for toner in recent years.As the wet type method for making, by the wet type spheroidization method that can control shape, the suspension comminution granulation of can control surface forming, can control the inner suspension polymerization of forming, emulsion polymerization agglutination etc.

On the other hand, along with people are more and more higher to requirements of saving energy, for province's electrification and the expansion of photographic fixing scope, the further fixing temperature of reduction toner that is implemented in the photographic fixing step that takies certain electrification in the duplicating machine.Reduce the fixing temperature of toner, not only can realize economizing the expansion of electrification and photographic fixing scope, and the fixing roller surface temperature rises to the stand-by period that can carry out the temperature of photographic fixing, so-called preheating time can shorten the power supply of opening duplicating machine etc. the time, thereby prolong the life-span of fixing roller.

The low temperature meeting of the fixing temperature of toner causes the reduction of the glass transition temperature of toner simultaneously, has the problem of the keeping quality variation and so on of toner.Therefore, low temperatureization and the keeping quality of taking into account fixing temperature is difficult.In order to take into account the keeping quality of low-temperature fixingization and toner, need remain at peeling off transition temperature under the situation of higher temperature toner, the viscosity of toner is sharply descended in high temperature range, promptly will have so-called rapid fusion (sharp melting) property.

Yet the resin that is used for toner has amplitude of fluctuation at aspects such as glass transition temperature and molecular weight usually, obtain rapid meltbility and will make the composition of resin or molecular weight consistent terrifically.And to obtain this resin, just need to use special method for making or utilize process resin such as chromatography to adjust the molecular weight of resin.Therefore, it is very high that the manufacturing cost of resin becomes, and produce the secondary product of unwanted resin simultaneously.From the viewpoint of environmental protection, this is not preferred.

As the method for the fixing temperature that reduces toner, people have proposed to use in binder resin the method for crystalline resin (for example to open clear 62-129867 communique referring to the spy, the spy opens clear 62-170971 communique, the spy opens clear 62-170972 communique, the spy opens clear 62-205365 communique, the spy opens clear 62-276565 communique, the spy opens clear 62-276566 communique, the spy opens clear 63-038949 communique, the spy opens clear 63-038950 communique, the spy opens clear 63-038951 communique, the spy opens clear 63-038952 communique, the spy opens clear 63-038953 communique, the spy opens clear 63-038954 communique, the spy opens clear 63-038955 communique, the spy opens clear 63-038956 communique, Te Kaiping 05-001217 communique, Te Kaiping 06-148936 communique, Te Kaiping 06-194874 communique, Te Kaiping 05-005056 communique, Te Kaiping 05-112715 communique etc.).

Though these methods can reduce fixing temperature, resin viscosity is bigger with respect to the variation of temperature variation.Therefore, when making toner, for example following situation can occur: can't obtain sufficient viscosity when mixing, colorant, detackifier etc. are dispersed unstable to resin, generate the uneven toner of color emissivity or fixation performance easily.And when utilizing mixing comminuting method to make toner, the pulverizing of mixing thing is difficulty also.Therefore be difficult to obtain the little toner of particle diameter.In order to address these problems, the method for auxiliary agents such as adding thickening agent, grinding aid is for example arranged.Yet these auxiliary agents are distributed in the resin, have destroyed the crystallinity of binder resin, so not preferred.

For above-mentioned viewpoint, people have carried out positive ardent research to not needing the manufacturing technology excessive temperature and the mixing energy, that make toner-particle according to above-mentioned wet type method for making.

Yet, molecular weight, molecular weight distribution, the melt viscosity by regulating binder resin and contain method such as crystalline resin and realize rapid meltbility, the result can reduce mechanical strength of resin.Thus, cause the reduction of toner intensity and the reduction of image intensity sometimes.As mentioned above, it is very difficult taking into account two or more characteristics.

And, when adding crystalline resin, particularly the property contained in binder resin such as detackifier etc. reduces sometimes, and damages particles such as particle size and particle shape control sometimes and make stability, and is also influential to the factor beyond the quality of toner.

On the other hand, for the viewpoint of no used toner (waste tonerless), people have proposed to use the formation method of no detersive mode or toner circulation mode in recent years.Especially the granule strength of employed toner in based on the formation method of toner circulation mode, particle size, shape homogeneity etc. there is requirement.Yet under a lot of situations, these characteristics can hamper the realization of above-mentioned rapid meltbility.

And then, considering environmental pressure in recent years, people expect the xeroprinting that the life-span is long.Particularly in photoreceptor, use the photoreceptor etc. that has adopted the photoreceptor of high rigidity materials such as a-Si or had protective seam (this protective seam has three-dimensional crosslinking structure) in outmost surface, thereby realized the photoreceptor life-time dilatation.

Usually the surface of these photoreceptors of cleaning is difficult.Therefore, when as mechanical cleaning unit such as cleaning unit use cleaning doctors, need apply bigger pressure in the contact portion of cleaning unit and photoreceptor.In this case, be attached to the trend that increase is also arranged by the pressure on the toner-particle of this contact portion.Therefore, especially in the recycle design of toner, need the big toner of granule strength.

But when using crystalline resin as binder resin, because the toner-particle deliquescing, toner is dealt with the insufficient strength of big pressure.Therefore, the utilization under the toner circulation mode is difficult, or is embedded in the toner surface at the long-term back additive that uses, and causes the flowability of toner to descend.

In order to remedy the reduction of this toner permanance (intensity), there be a kind of non-crystalline resin and crystalline resin of making up to come toner as binder resin.Yet for this toner, the dispersed relatively poor and non-crystalline resin of crystalline resin in the toner-particle and detackifier and the compatibility of detackifier and crystalline resin are relatively poor.Thus, crystalline resin and detackifier are exposed to the surface of toner, cause keeping stability and charged stability to reduce.

In addition, in order to take into account low-temperature fixing and toner permanance, as the trial of the dispersiveness of detackifier and crystalline resin in the control toner, people have proposed a kind ofly to control the toner of the dispersed texture of detackifier-surperficial exposed state by containing crystalline polyester resin and detackifier.

Specifically, can enumerate following toner etc.: the toner (for example opening the 2002-49180 communique) that contains detackifier by the part multi-stage polymeric manufacturing, outside outermost layer referring to the spy; A kind of toner that uses block polyester, contain crystallinity polyester and amorphism polyester in this toner as binder resin, and the crystallinity polyester is (for example opening the 2005-62510 communique referring to the spy) that the copolymerization of amorphism block by constituting the amorphism polyester and crystallinity block obtains; The toner (for example opening the 2004-264331 communique) that utilizes masterbatch to make referring to the spy.

Yet the manufacture method of these toners is defined in specific method for making.And the method for making complexity, not too practical.In addition, if increase the crystalline resin that contains in the toner and the amount of detackifier in order to improve low-temperature fixing and antistick characteristic, will be difficult to control the dispersiveness of detackifier.

And, in the toner of particularly in damp process, making, when using the amorphism polyester, owing to it is easy to mix the amalgamation variation that causes toner mutually with hydrophilic solvent as binder resin.So the permanance of toner becomes problem.

As mentioned above, in the existing technology, it is difficult taking into account the crystalline resin and containing property-dispersiveness-compatibility and the permanance (intensity) of detackifier in binder resin that contain in low-temperature fixing, the toner simultaneously.

Summary of the invention

The present invention proposes for addressing the above problem.Promptly, the object of the present invention is to provide a kind of electrostatic image developing toner, use developer for static charge image development, and the formation method of this toner, the photographic fixing at low temperatures of described electrostatic image developing toner, dispersiveness-the containing property excellence of detackifier wherein in binder resin, and this toner has higher intensity.

Can realize above-mentioned purpose by following the present invention.

1. electrostatic image developing toner, this toner contains binder resin, colorant and detackifier, and ratio G ' (70)/G ' (90) of the storage modulus G ' (90) of its storage modulus G ' (70) in the time of 70 ℃ during with 90 ℃ is 1 * 10 ²～1 * 10 ⁵, this storage modulus is to obtain by Measurement of Dynamic Viscoelasticity under the condition determination of 1 radian per second; Described toner is characterised in that, it contains the compound of the ionic leaving group of the ionic leaving group that has anionic property in a part and cationic.

2. as above-mentioned 1 described electrostatic image developing toner, wherein, described binder resin synthesizes by addition polymerization or polycondensation reaction.

3. as above-mentioned 1 described toner, wherein, the compound of the ionic leaving group of described ionic leaving group that has anionic property in a part and cationic is expressed from the next;

In the above-mentioned formula, x, y and z represent the integer more than 1, are 2～5 integers, and y＞x.

4. as above-mentioned 1 described toner, wherein, the content of compound in toner of the ionic leaving group of described ionic leaving group that has anionic property in a part and cationic is 0.5 quality %～5 quality %.

5. as above-mentioned 1 described toner, wherein, described binder resin contains crystalline resin.

6. as above-mentioned 5 described toners, wherein, the fusing point of described binder resin is 45 ℃～110 ℃.

7. as above-mentioned 1 described toner, wherein, the addition of described detackifier is 0.5 quality %～50 quality % with respect to toner.

8. as above-mentioned 1 described toner, wherein, mean grain size exists ratio less than 10 number % more than or equal to the big particle of 0.8 μ m in the described colorant.

9. as above-mentioned 1 described toner, wherein, the volume average particle size D50v of described toner is 3 μ m～7 μ m.

10. as above-mentioned 1 described toner, wherein, the volume average particle sizes profile exponent GSDv of described toner is smaller or equal to 1.28.

11. as above-mentioned 1 described toner, wherein, the number average particle size distribution index GSDp of described toner is smaller or equal to 1.30.

12. as above-mentioned 1 described toner, wherein, the average circularity of described toner is 0.94～0.98.

13. a manufacture method of making above-mentioned 1 described toner, described manufacture method comprises the steps:

Granulation step, in this step, in the mixed solvent of water, organic solvent or water and organic solvent, produce the pigmentary resin particle of compound, described binder resin, described colorant and the described detackifier of the ionic leaving group that contains described ionic leaving group that in a part, has an anionic property and cationic; And

Washing-drying steps in this step, washs-drying above-mentioned pigmentary resin particle.

14. as the manufacture method of above-mentioned 13 described toners, wherein, described granulation step has following step:

The dispersion liquid preparation process, in this step, preparation binder resin particle dispersion, coloring agent particle dispersion liquid and anti-sticking agent particle dispersion liquid;

The aggegation step in this step, mixes above-mentioned various dispersion liquids and the described compound that has the ionic leaving group of anionic property and cationic in a part, is prepared into the agglutinating particle dispersion liquid; And

Integrated step in this step, is heated to the temperature of the glass transition temperature that is not less than described binder resin with described agglutinating particle dispersion liquid, makes described agglutinating particle integrated.

15. a developer for static charge image development, it contains above-mentioned 1 described electrostatic image developing toner.

16. as above-mentioned 15 described developer for static charge image development, this developer for static charge image development is characterised in that it further contains carrier, described carrier has core and coats the resin bed of this core.

17. a formation method, described formation method comprises the steps:

Electrostatic latent image forms step, in this step, forms electrostatic latent image on sub-image supporting body surface;

Development step in this step, uses the developer that contains toner to make described latent electrostatic image developing, to form toner image;

Transfer step in this step, is transferred to described toner image on the recording medium; And

The photographic fixing step, in this step, with described toner image on described recording medium,

Described formation method is characterised in that described toner is above-mentioned 1 described electrostatic image-developing toner.

18., it is characterized in that the layer that constitutes described sub-image supporting body outmost surface contains siloxane resin or the phenolics with cross-linked structure as above-mentioned 17 described formation methods.

19., it is characterized in that this formation method contains following step as above-mentioned 18 described formation methods:

Cleaning in this step, is removed and is reclaimed remaining in the lip-deep remaining toner of described sub-image supporting body after the described transfer step; And

The toner circulation step, in this step, the remaining toner that will in above-mentioned cleaning, reclaim as described developer to utilize again.

According to aforesaid the present invention, a kind of electrostatic image developing toner can be provided, use developer for static charge image development, and the formation method of this toner, the photographic fixing at low temperatures of described electrostatic image developing toner, the excellent dispersion of detackifier wherein in binder resin, and this toner has higher intensity.

Embodiment

Electrostatic image developing toner of the present invention (hereinafter sometimes economize slightly " toner of the present invention ") contains binder resin, colorant and detackifier, and ratio G ' (70)/G ' (90) of the storage modulus G ' (90) of its storage modulus G ' (70) in the time of 70 ℃ during with 90 ℃ is 1 * 10 ²～1 * 10 ⁵, this storage modulus is to obtain by Measurement of Dynamic Viscoelasticity under the condition determination of 1 radian per second; Described toner is characterised in that, it contains the compound of the ionic leaving group of the ionic leaving group that has anionic property in a part and cationic.The ionic leaving group by in a part, containing anionic property and the ionic leaving group of cationic, particularly in the granulation step in damp process, this toner can show cationic under acid condition, produce cohesive force, can also under alkali condition, show anionic property, obtain the narrower size-grade distribution of width.By in same molecular structure, having the different functional group of polarity simultaneously, can make also height aggegation between the particulate of the different material of the electric charge that constitutes toner-particle, or it is stopped.Thus, can in toner-particle, stably add the different crystalline resin of structure, colorant and detackifier and can not destroy granulation.Therefore, toner of the present invention photographic fixing at low temperatures, the excellent dispersion of the detackifier that is contained in the toner in binder resin can obtain higher intensity.Therefore, particularly using superficial layer to have under the situation of Electrophtography photosensor of silicone cross-linked structure, or utilizing under the situation based on the formation method of toner circulation mode, long-term use also can obtain high image quality.

Toner of the present invention is preferably binder resin through addition polymerization and polycondensation reaction and the synthetic product that obtains.Specifically, can enumerate vibrin, urethane resin, epoxy resin, polyol resin etc.Wherein, consider adjust melt viscosity relatively easy, with the compatibility of the crystalline resin that is used in combination and the aspects such as the property contained excellence of detackifier, preferably use vibrin.

Toner preferred volume mean grain size D50v of the present invention is 3 μ m～7 μ m.If D50v is less than 3 μ m, then charging property is insufficient, disperse sometimes to around, cause the image blushing.On the other hand, greater than 7 μ m, then the resolution of image reduces, and is difficult to realize high image quality sometimes as if D50v.D50v is 4 μ m～7 μ m more preferably, more preferably 5 μ m～6.5 μ m.

Toner preferred volume average particle size distribution index GSDv of the present invention is smaller or equal to 1.28.GSDv can pass through calculating formula GSDv=(D84v/D16v) ^1/2Obtain.In this calculating formula, D84v is accumulated to 84% o'clock particle size values by the little side of particle diameter in the volume distributed median of particle diameter, and D16v is accumulated to 16% o'clock particle size values by the little side of particle diameter in the volume distributed median of particle diameter.If GSDv greater than 1.28, then reduces the vividness and the resolution of image sometimes.GSDv more preferably 1.15～1.27, and more preferably 1.17～1.25.

The preferred number average particle size distribution of toner of the present invention index GSDp is smaller or equal to 1.30.GSDp can pass through calculating formula GSDp=(D84p/D16p) ^1/2Obtain.In this calculating formula, D16p is accumulated to 16% o'clock particle size values by the little side of particle diameter during the number of particle diameter distributes, and D84p is the particle size values that particle diameter was accumulated to 84% o'clock.If GSDp is greater than 1.30, then the ratio of small particle size toner uprises, and except initial performance, reliability is also had great influence.That is, as in the past, because the adhesion of the toner of small particle diameter is big, it is difficult that the control of static becomes easily, remains on the carrier easily sometimes when using tow-component developer.At this moment,, then cause carrier contamination sometimes, impel the carrier deterioration if give mechanical force repeatedly.

And, because the adhesion of small particle size toner is bigger, the reduction of the efficient that also can occur sometimes developing, the result causes the image quality defective.Particularly in transfer step, be developed in the toner on the photoreceptor, it is difficult that the transfer printing of small particle diameter composition becomes easily.Therefore, the transfer efficiency variation, the discharge that occurs toner sometimes increase or image quality bad etc.Its result is not increased by the toner of Electrostatic Control or reversed polarity toner and around polluting.Especially, because these uncontrolled toners are accumulated charging roller by photoreceptor etc., cause charged bad sometimes.

Among the present invention, volume average particle size D50v and various particle size distribution index for example can use that coal tar counter device TA II (Beckman Coulter Inc.'s manufacturing), Multisizer II analyzers such as (Beckman Coulter Inc.'s manufacturings) and electrolytic solution ISOTON-II (Beckman Coulter Inc.'s manufacturing) measure.

During mensuration, add the mensuration sample of 0.5mg～50mg in as the surfactant (being preferably 5% alkyl benzene sulphonate sodium water solution) of spreading agent to 2ml.It is added in the electrolytic solution of 100ml～150ml then.

Use ultrasonic disperser that the electrolytic solution that is suspended with sample is carried out 1 minute dispersion treatment, utilizing above-mentioned coal tar counter device TA-II type to use slit aperture is that the hole seam of 100 μ m is that the size-grade distribution of the particle of 2 μ m～50 mu m ranges is measured to particle diameter.The population of sampling is 50000.

Based on the size-grade distribution of as above measuring, with respect to the particle size range after cutting apart (cut section) respectively from the small-bore one side retouch out the cumulative distribution of volume, number, the particle diameter that is accumulated at 16% o'clock is defined as cumulative volume mean grain size D16v, cumulative number mean grain size D16p, the particle diameter that is accumulated at 50% o'clock is defined as cumulative volume mean grain size D50v, cumulative number mean grain size D50p, the particle diameter that is accumulated at 84% o'clock is defined as cumulative volume mean grain size D84v, cumulative number mean grain size D84p.

Use above-mentioned numerical value, can be according to calculating formula (D84v/D16v) ^1/2Obtain volume average particle sizes profile exponent (GSDv), according to calculating formula (D84p/D16p) ^1/2Obtain volume average particle sizes profile exponent (GSDp).

The preferred average circularity of toner of the present invention is 0.94～0.98.If it is unsetting that average circularity less than 0.94, then is shaped as, cause reductions such as transfer printing, permanance and flowability sometimes.And if on average circularity is greater than 0.98, then the ratio of spheric grain becomes big, and spatter property becomes difficult sometimes.Average circularity more preferably 0.955～0.975, more preferably 0.960～0.970.

The average circularity of toner can use flow-type particle image analytical equipment FPIA-2000 (East Asia Medical Electronics Co., Ltd's manufacturing) to measure.As concrete assay method, in advance to removing of 100ml～150ml add the surfactant (preferred alkyl benzene sulfonate) of 0.1ml～0.5ml in the water of impure solid content as spreading agent, further add the mensuration sample about 0.1g～0.5g.To being dispersed with the dispersion treatment that the suspending liquid of measuring sample carried out 1 minute～3 minutes, making dispersion liquid concentration is 3000/μ l～10000/μ l with ultrasonic disperser, utilizes said apparatus to measure the average circularity of toner.

Toner preferred volume mean grain size D50v of the present invention is 3 μ m～7 μ m, and volume average particle sizes profile exponent GSDv is smaller or equal to 1.28, and number average particle size distribution index GSDp is smaller or equal to 1.30, and average circularity is 0.940～0.980.

Ratio G ' (70)/G ' (90) of the storage modulus G ' (90) of storage modulus G ' (70) during toner of the present invention obtain by Measurement of Dynamic Viscoelasticity under the condition determination of 1 radian per second 70 ℃ during with 90 ℃ is preferably 10 ²～10 ⁵By G ' (70)/G ' (90) is controlled in the above-mentioned scope, can under fixing temperature, obtain necessary viscosity, can guarantee low-temperature fixing.And if G ' (70)/G ' (90) outside above-mentioned scope, then has to improve fixing temperature owing to obtaining the needed viscosity of photographic fixing, thereby can't obtain low-temperature fixing.The preferred value of G ' (70)/G ' (90) is 10 ³～10 ⁴, preferred value is 2 * 10 ³～8 * 10 ³

G ' (70) is preferably 1 * 10 ⁴Pa～1 * 10 ⁷Pa, more preferably 5 * 10 ⁴Pa～5 * 10 ⁶Pa.G ' (90) is preferably 1 * 10 ²Pa～5 * 10 ³Pa, more preferably 5 * 10 ²Pa～1 * 10 ³Pa.

Toner of the present invention contains the compound (hereinafter being sometimes referred to as " compound that the present invention relates to ") of the ionic leaving group of the ionic leaving group that has anionic property in a part and cationic.Compound as the present invention relates to is not particularly limited, and gets final product so long as have the two the compound of ionic leaving group of the ionic leaving group of cationic and anionic property in the molecular structure simultaneously.

As the ionic leaving group (gegenion shows the group of cationic) of cationic, can enumerate carboxyl, sulfonic group, oxo sulfonic group, phosphate, sulfoethyl, phosphonic acids methyl, ethyloic.Wherein preferred carboxyl and sulfonic group.

As the ionic leaving group (gegenion shows the group of anionic property) of anionic property, can enumerate ammonium, amino, methylamino, dimethylamino and diethylamino.Wherein preferred ammonium and amino.

Concrete example as the compound that the present invention relates to, preferably use for example N-alkyl nitrilotriacetic acid(NTA), N-alkyl dimethyl betaine, α-trimethyl ammonium fatty acid, N-alkyl-Beta-alanine salt, N-alkyl-β-iminopropinate, N-alkyl oxo methyl-N, N-diethyl betaines, N-alkyl-N, amphoteric surfactant classes such as N-diamino ethyl glycine hydrochloride, 2-alkyl imidazoline derivatives, amino ethyl imidazoline acylate, N-alkyl sulfobetaines, N-alkyltaurate; Or following general formula has Amphiphatic high polymer agglutinant of cationic monomer unit and anionic property monomeric unit etc. when representing.

Have when above-mentioned general formula is represented in the Amphiphatic high polymer agglutinant of cationic monomer unit and anionic property monomeric unit, x, y and z represent the integer more than 1, are preferably 2～5 integer, and preferably satisfy the relation of y＞x.

Owing in a part, have the different functional group of polarity, thus a spot of compound that the present invention relates to can have simultaneously two aspects effect.Specifically, the cohesive force of ionic leaving group in acid field of anionic property (gegenion shows the group of cationic) is higher, thereby makes the particles of material aggegation that constitutes toner-particle.And, by share known inorganic agglutinant, further aggegation to heavens.On the other hand, in alkaline field, the cationic leaving group plays a role the ability of particle stabilizedization.So can be while keeping its structure to merge through the agglutinating particle of overstabilization.Particularly with the vibrin particulate in water-based system during aggegation, be difficult for aggegation, fusion owing to the compatibility of itself and water is higher, has the tendency that is difficult for bag in colorant, detackifier and the crystalline resin etc. beyond the resin particle, and the compound that the present invention relates to of the ionic leaving group by containing the ionic leaving group that has cationic simultaneously and anionic property, just can take in equably and merge, thereby obtain having low-temperature fixing and the high toner of intensity.

The content of the compound that the present invention relates in toner of the present invention is preferably 0.5 quality %～5 quality %, more preferably 1 quality %～3 quality %, more preferably 1.5 quality %～2.5 quality %.If the content of the compound that the present invention relates to then is difficult for keeping the charged characteristic of toner greater than 5 quality %, it is bad to occur image quality such as blushing, striped sometimes.If this content is less than 0.5 quality %, then cohesive force in acid field and the stability in alkaline field are not enough, are difficult to control size distribution sometimes.

The situation of known so far following use amphoteric surfactant: the situation of the stabilizing agent when as described in the spy opens the 2005-140952 communique, making as polymerization; The situation of as described in the spy opens the 2005-091813 communique, when dispersed color, adding; The situation of as described in the spy opens the 2005-296839 communique, adding in order to ensure emulsification-dispersion footpath.But the example that is used to control the aggegation of toner constituent material-merge, the property contained, dispersiveness and compatibility as the present invention does not have report as yet.And the addition when making an addition in each material also seldom can not be obtained the such effect of the present invention.

Toner of the present invention contains detackifier.The average scope of disperseing the footpath to be preferably 0.3 μ m～0.8 μ m of detackifier, the more preferably scope of 0.4 μ m～0.8 μ m.If the average dispersion footpath of detackifier is less than 0.3 μ m, then antistick characteristic becomes insufficient sometimes, and particularly this tendency is obvious all the more under the fast situation of operating speed.And, if average dispersions of detackifier footpath is greater than 0.8 μ m, then transparency decline when using OHP (overhead projector) sheet sometimes, the exposure of detackifier composition on toner surface becomes obvious.

The standard deviation in the dispersion footpath of detackifier is preferably smaller or equal to 0.05, more preferably smaller or equal to 0.04.If the standard deviation in the dispersion of detackifier footpath is greater than 0.05, the transparency during then sometimes to antistick characteristic, use OHP sheet and the exposure of detackifier on toner surface etc. produce harmful effect.

In addition, disperseing to contain the average dispersion footpath of the detackifier in toner can obtain as follows: (Nireco makes to utilize image analysis apparatus, the Luzex image analysis apparatus) resolves TEM (transmission electron microscope) photo, calculate the mean value in the dispersion footpath (disperseing footpath=(major diameter+minor axis)/2) of the detackifier in 100 toner-particles, standard deviation disperses the footpath to obtain according to each of gained.

And then, detackifier in the exposure on the toner surface preferably in the scope of 5 atom %～12 atom %, more preferably in the scope of 6 atom %～11 atom %.If this exposure is less than 5 atom %, the fixation performance variation of high temperature one side sometimes in the system of particularly using at a high speed then, and if this exposure greater than 12 atom %, when then using for a long time, occurs because the skewness of additive or the phenomenon that causes development property, transfer printing reduction such as imbed sometimes.

Herein, exposure is measured by XPS (x-ray photoelectron beam split) and is obtained.When measuring, use JPS-9000MX (NEC society system), use MgK α line during mensuration, will speed up voltage and be set at 10kV, transmitter current is set at 30mA as the X line source as the XPS determinator.Herein, the peak partition method of utilizing C1S spectrum is carried out quantitatively the antiseized dosage of toner surface.In the peak partition method, use curve fitting method that the C1S spectrum of measuring is separated into each composition based on least square method.Become in the one-tenth open score of benchmark of separation, the detackifier, binder resin and the crystalline resin that use when making toner use measures the C1S spectrum that obtains separately.

In more detail below the manufacture method of toner of the present invention and constituent material etc. are described.

Toner of the present invention can utilize known method for preparing toner to make, but preferably in so-called wet type method for making (promptly in water or organic solvent, or in their mixed solvent), make through granulation step and washing-drying steps, produce the pigmentary resin particle that contains the compound that binder resin, colorant, detackifier and the invention described above relate in the described granulation step, in described washing-drying steps this pigmentary resin particle is washed-drying.

As above-mentioned wet type method for making, can enumerate: suspension polymerization, in the method, other compositions that make compound that the invention described above relates to, colorant, detackifier, use as required suspend with the polymerizable monomer that is used to form binder resin such as non-crystalline resin, make polymerizable monomer generation polymerization; The dissolving suspension method, in the method, the constituent material of toners such as the compound that the invention described above is related to, non-crystalline resin, colorant, detackifier is dissolved in the organic solvent, be distributed in the aqueous solvent with suspended state after, remove organic solvent again; The emulsion polymerization agglutination in the method, is made the binder resin composition of compound that the invention described above relates to, non-crystalline resin etc. by emulsion polymerization, carries out heteroagglutination with dispersion liquids such as pigment, detackifiers, afterwards fusion-combination again; Or the like, but be not limited to these methods.

In these methods, consider excellent aspects such as distribution of shapes that the particle diameter of the toner that obtains controlled, narrow size-grade distribution, shape are controlled, narrow and inner decentralised control, most preferably the emulsion polymerization agglutination.

Utilize under the situation of above-mentioned emulsion polymerization agglutination, through the dispersion liquid preparation process, aggegation step and integrated step are carried out the granulation of pigmentary resin particle, further make toner of the present invention afterwards through washing-drying process, in described dispersion liquid preparation process, prepare the binder resin particle dispersion respectively, coloring agent particle dispersion liquid and anti-sticking agent particle dispersion liquid, the compound that in described aggegation step above-mentioned various dispersion liquids and the invention described above is related to mixes back preparation agglutinating particle dispersion liquid, described agglutinating particle dispersion liquid is heated to temperature more than the glass transition temperature of above-mentioned binder resin in described integrated step so that above-mentioned agglutinating particle is integrated.In addition, can be as required in various dispersion liquids, add the inorganic particles dispersion liquid, be dispersed with other the dispersion liquid such as crystalline resin particle dispersion of crystalline resin.

In addition, among the present invention, " crystalline resin " is meant the resin that does not have stepped caloric receptivity variation and have clear and definite endothermic peak in differential scanning calorimetry (DSC).And if polymer phase has other compositions for the main chain copolymerization of above-mentioned crystalline resin, then when other compositions during smaller or equal to 50 quality %, this polymkeric substance is also referred to as crystalline resin.Crystalline resin normally weight-average molecular weight more than or equal to 10000 crystalline resin.

-crystalline resin-

Because crystalline resin has fusing point, the reduction amplitude of viscosity is big under specified temp, when photographic fixing during the heating toner, the crystalline resin molecule can be dwindled from beginning the movable temperature difference to can the field of photographic fixing of heat.Therefore, can give toner with excellent more low-temperature fixing by containing crystalline resin.The preferred content of the crystalline resin in the toner is 1 quality %～10 quality %, the more preferably scope of 2 quality %～8 quality %.

In order to ensure the storage stability of low-temperature fixing and toner, the suitable fusing point that has in 45 ℃～110 ℃ scopes of the crystalline resin that uses among the present invention.If fusing point is lower than 45 ℃, then the preservation of toner becomes difficult, and if fusing point is higher than 110 ℃, then can't enjoy the effect of low-temperature fixing sometimes.The preferred melting range of crystalline resin is 50 ℃～100 ℃, and preferred scope is 55 ℃～90 ℃.The fusing point of described crystalline resin is obtained according to method shown in the JIS K-7121:87.

And the number-average molecular weight of crystalline resin (Mn) is preferably more than 2000, more preferably more than 4000.If number-average molecular weight (Mn) is less than 2000, then sometimes when photographic fixing toner infiltrate in the surface of recording mediums such as paper and the photographic fixing spot occurs, or the photographic fixing image is for the intensity reduction of crooked patience.

As the crystalline resin that uses among the present invention, preferable weight-average molecular weight surpasses 5000 and have a crystalline resin, specifically, can enumerate crystalline polyester resin, crystallinity vinyl resins, when considering photographic fixing and the fusing point adjustment in the adaptation of paper, charging property and the preferable range, preferred crystalline polyester resin.And, more preferably have the aliphatic category crystalline polyester resin of suitable fusing point.

As above-mentioned crystallinity vinyl resins, can enumerate (methyl) acrylic acid long-chain alkyl groups, alkenyl esters such as (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecane ester, (methyl) acrylic acid tridecane ester, (methyl) acrylic acid tetradecane ester, (methyl) acrylic acid hexadecane ester, (methyl) stearyl acrylate ester, (methyl) acrylic acid oleyl alcohol ester, (methyl) acrylic acid docosane ester.In addition, in this instructions, " (methyl) acrylic acid " expression comprises any one of " acrylic acid " and " methacrylic acid ".

On the other hand, described crystalline polyester resin is by carboxylic acid (dicarboxylic acid) composition and the synthetic product of alcohol (glycol) composition.Below carboxylic acid composition and pure composition are further described.In addition, among the present invention, with respect to the main chain of crystalline polyester resin, the multipolymer that obtains with other compositions of ratio copolymerization below the 50 quality % also belongs to crystalline polyester resin.

-carboxylic acid composition-

The carboxylic acid composition is preferably aliphatic dicarboxylic acid, preferred especially straight chain type carboxylic acid.For example can enumerate oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic acid, 1,11-heneicosane dicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-astrotone, 1,14-tetradecane dicarboxylic acid, 1,16-hexadecane dicarboxylic acid, 1,18-octadecane dicarboxylic acid etc., or its lower alkyl esters or acid anhydrides, but be not limited to these examples.

As above-mentioned carboxylic acid composition, except above-mentioned aliphatic dicarboxylic acid composition, also preferably include dicarboxylic acid composition and have the constituent that sulfonic dicarboxylic acid becomes to grade with two keys.In the described dicarboxylic acid composition with two keys, except constituent, also comprise constituent derived from the lower alkyl esters of dicarboxylic acid or acid anhydrides etc. with two keys derived from dicarboxylic acid with two keys.In addition, described have in the sulfonic dicarboxylic acid composition, except derived from the constituent with sulfonic dicarboxylic acid, also comprises the constituent derived from lower alkyl esters with sulfonic dicarboxylic acid or acid anhydrides etc.

Because above-mentioned dicarboxylic acid with two keys can utilize its pair key to make all resin crosslinks, the above-mentioned dicarboxylic acid with two keys of therefore preferred use prevents the hot sticky dirt (hot offset) in the photographic fixing.As this dicarboxylic acid, can enumerate for example fumaric acid, maleic acid, 3-hexene diacid, 3-octendioic acid etc., but be not limited to these examples.But also can enumerate the lower alkyl esters of these dicarboxylic acid and acid anhydrides etc.Wherein, consider cost, preferred fumaric acid and maleic acid etc.

It is above-mentioned that to have sulfonic dicarboxylic acid be effective aspect dispersed color isochrome material well.And as described below, when by with the emulsification or suspend when preparing particulate in water of all resins, sulfonic existence can help emulsification or suspension and need not to use surfactant.Have a sulfonic dicarboxylic acid as this, can enumerate for example 2 sulfotere phthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, sulfosuccinic acid sodium salt etc., but be not limited to these examples.But also can enumerate these lower alkyl esters and acid anhydrides etc. with sulfonic dicarboxylic acid.Wherein, consider cost, preferred 5-sulfoisophthalic acid sodium salt etc.

The content of carboxylic acid composition's (have the dicarboxylic acid composition of two keys and/or have sulfonic dicarboxylic acid composition) in the carboxylic acid composition beyond these aliphatic dicarboxylic acid compositions is preferably 1 and constitutes a mole %～20 formation mole %, is more preferably 2 and constitutes mole %～10 formation mole %.

When the content of the carboxylic acid composition beyond the above-mentioned aliphatic dicarboxylic acid composition constituted mole % less than 1, then the pigment-dispersing in the toner became bad sometimes.And when utilizing the emulsion polymerization agglutination to make toner, the emulsified particles particle diameter in the dispersion liquid increases sometimes, is difficult to utilize aggegation to adjust the particle diameter of toner.

On the other hand, when above-mentioned content surpassed 20 formation mole %, then the crystallinity of crystalline polyester resin reduced sometimes, and fusing point descends, the keeping quality variation of image.

And when utilizing the emulsion polymerization agglutination to make toner, the emulsified particles particle diameter in the dispersion liquid is too small sometimes, and emulsified particles is dissolved in the water and does not generate emulsion (latex).In addition, " constitute mole a % " among the present invention is meant, each constituent in the vibrin (carboxylic acid composition, pure composition) add up to 1 unit (mole) time percent.

-pure composition-

As pure constituent preferred aliphat glycol, can enumerate for example ethylene glycol, 1, ammediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane glycol, 1,12-dodecanediol, 1,13-tridecane glycol, 1,14-tetradecane glycol, 1,18-octacosanol and 1,20-eicosane glycol etc., but be not limited to these examples.

In the above-mentioned pure composition, the content of aliphatic diol composition is preferably greater than and equals 80 formation mole %, and can contain other compositions as required.In the above-mentioned pure composition, the content of more preferably above-mentioned aliphatic diol composition constitutes mole % more than or equal to 90.

Constitute mole % if above-mentioned content is lower than 80, then because the crystallinity of vibrin descends and fusing point reduces, deterioration can take place in anti-sometimes toner adhesive, image keeping quality and low-temperature fixing.As other compositions that contain as required, can enumerate the diol component with two keys, constituent with sulfonic diol component etc.

As above-mentioned glycol, can enumerate the 2-butene-1,4-glycol, 3-butene-1,6-two pure and mild 4-butene-1s, 8-glycol etc. with two keys.On the other hand, have a sulfonic glycol, can enumerate 1,4-dihydroxy-2-benzene sulfonic acid sodium salt, 1,3-dihydroxymethyl-5-benzene sulfonic acid sodium salt and 2-sulfo group-1,4-butylene glycol sodium salt etc. as above-mentioned.

When adding the pure composition (have the diol component of two keys and/or have sulfonic diol component) beyond these straight chain type aliphatic diol compositions, the content of pure composition in pure composition beyond the straight chain type aliphatic diol composition is preferably 1 and constitutes a mole %～20 formation mole %, and more preferably 2 constitute mole %～10 formation mole %.When above-mentioned content is lower than 1 when constituting mole %, then dispersing of pigments becomes insufficient sometimes, and the particle diameter of emulsified particles increases, or by the particle diameter that toner is adjusted in the aggegation difficulty that becomes.On the other hand, when this content constituted mole % greater than 20, then because the crystallinity of vibrin descends and the fusing point reduction causes the keeping quality variation of image, or the emulsified particles particle diameter was too small, was dissolved in the water and did not generate emulsion.

Manufacture method to described crystalline polyester resin is not particularly limited, can adopt and utilize the general polyester method of carboxylic acid composition and the reaction of pure composition to make, for example can enumerate direct polycondensation and ester-interchange method etc., can select proper method manufacturing flexibly according to the kind of used monomer.Because the mol ratio (sour composition/pure composition) of described sour composition and pure composition changes with reaction conditions etc. when reacting, thereby cannot treat different things as the same, but is about 1/1 usually.

Above-mentioned crystalline polyester resin can be made in 180 ℃～230 ℃ polymerization temperature, and will reduce pressure in the reaction system as required, reacts when removing water that condensation reaction generates and alcohol.If monomer does not dissolve or be incompatible, then can make its dissolving by the high boiling solvent that adds as solubilizer under temperature of reaction.In polycondensation reaction, the solvent that adds as solubilizer is steamed, react simultaneously.In copolyreaction, exist in the situation of the relatively poor monomer of compatibility, can make the relatively poor monomer of compatibility in advance and will carry out condensation with the carboxylic acid composition or the pure composition of this monomer polycondensation, and then with the major component polycondensation.

As the catalyzer that can when making described crystalline polyester resin, use, can enumerate alkali-metal compounds such as sodium, lithium; Alkaline earth metal compounds such as magnesium, calcium; The compound of metals such as zinc, manganese, antimony, titanium, tin, zirconium or germanium; Phosphorons acid compound; Phosphate cpd and amines etc. specifically, can be enumerated following compound.

Can enumerate for example sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, four titanium propanolates, titanium tetraisopropylate, four butanols titaniums, antimony trioxide, antimony triphenyl, tributyl antimony, formic acid tin, tin oxalate, tetraphenyltin, dibutyl tin dichloride, Dibutyltin oxide, diphenyl tin oxide, tetrabutyl zirconate (zirconium tetrabutoxide), zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octoate, germanium oxide, triphenyl phosphite, three (2, the 4-di-tert-butyl-phenyl) phosphite ester, bromination ethyl triphenyl phosphine, compound such as triethylamine and triphenylamine.

In addition, for the fusing point of adjusting crystalline resin and molecular weight etc., except above-mentioned polymerizable monomer, can also use compound with the shorter alkyl of chain, thiazolinyl, aromatic rings etc.

As concrete example, can enumerate alkyl dicarboxylic aid's classes such as succinic acid, malonic acid, oxalic acid in the situation of dicarboxylic acid; Phthalic acid, m-phthalic acid, terephthalic acid (TPA), high phthalic acid, 4,4 '-two benzoic acid, 2,6-naphthalene dicarboxylic acids, 1, aromatic dicarboxylic acids such as 4-naphthalene dicarboxylic acids; Two picolinic acids, two nicotinic acid, quinolinic acid, 2, nitrogenous aromatic dicarboxylic acids such as 3-pyrazine dicarboxylic acid; Can enumerate the glycols of short-chain alkyls such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid in the situation of glycol; Can enumerate (methyl) esters of acrylic acid of short-chain alkyls such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, thiazolinyl in the situation of the ethylenic polymer monomer of short-chain alkyl; Ethene such as vinyl cyanide, methacrylonitrile nitrile; Vinyl ethers such as methoxy ethylene, VINYL ISOBUTYL ETHER; Vinyl ketone, vinyl ethyl ketone, the different propylene ketone of vinyl; Olefines such as ethene, propylene, butadiene, isoprene etc.These polymerizable monomers both can be used alone, and also can share two or more.

-non-crystalline resin-

In the toner of the present invention, preferred binder resin is a non-crystalline resin.As being used for non-crystalline resin of the present invention, can utilize the known amorphism binder resin that is used for toner, for example, can utilize styrene-propene acid resin etc., but preferably use non-crystalline polyester resin.

The glass transition temperature of preferred employed non-crystalline polyester resin is 50 ℃～80 ℃ a scope, more preferably 55 ℃～65 ℃ scope.And preferable weight-average molecular weight is 8000～30000 scope, but considers low-temperature fixing and physical strength, and more preferably weight-average molecular weight is 8000～16000 scope.And, consider low-temperature fixing and Combination, also can the third composition of copolymerization.

In addition,, crystalline polyester resin then can improve Combination if not having with pure composition or the carboxylic acid composition identical with its crystallinity ester compounds that is used in combination, thus preferred.

Identical with the manufacture method of above-mentioned crystalline polyester resin, the manufacture method of non-crystalline polyester resin there is not particular restriction yet, can use common polyester method as described above to make.

As the carboxylic acid composition who is used for synthetic non-crystalline polyester resin, can similarly use the various dicarboxylic acid of when the explanation crystalline polyester resin, being enumerated.

As above-mentioned pure composition, can use the various glycol that are used for synthetic non-crystalline polyester resin, except those aliphatic diols of when crystalline polyester resin is described, being enumerated, can also use bisphenol-A, bisphenol-A ethylene oxide adduct, bisphenol-A propylene oxide adduct or hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct etc.

Further, consider manufacturing, thermotolerance and the transparency of toner, especially preferably use the derivant of bisphenol Ss such as bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct.And carboxylic acid composition and pure composition can contain two or more compositions, and especially, bisphenol S has the stable on heating effect of raising.

The crosslinking Treatment of-binder resin etc.-

Below to as the crosslinking Treatment of the non-crystalline resin of binder resin, the crystalline resin that uses as required and can use when the synthetic resin adhesive be copolymerized into to grade and describe.

During synthetic resin adhesive, can other compositions of copolymerization, can use the compound of possess hydrophilic property polar group.

As concrete example, binder resin is can enumerate sulfonyls such as sulphonyl-terephthalic acid (TPA) sodium salt, 3-sulphonyl phthalic acid sodium salt in the situation of vibrin directly to be substituted in dicarboxylic acid compound on the aromatic rings.

In addition, binder resin is can enumerate unsaturated aliphatic carboxylic acidss such as (methyl) acrylic acid, itaconic acid in the situation of vinyl resins; (methyl) acrylic acid monoglyceride; The ester class of (methyl) acrylic acid such as fatty acid modified (methyl) glycidyl acrylate, list (methyl) zinc acrylate resin, two (methyl) zinc acrylate resin, (methyl) 2-Hydroxy ethyl acrylate, polyglycol (methyl) acrylate, polypropylene glycol (methyl) acrylate and alcohols etc.; Cinnamic derivant with any sulfonyl in ortho position, a position, the contraposition; The aromatic vinyl resin that is substituted with sulfonyl etc. that contains the vinyl naphthalene etc. of sulfonyl.

In order to prevent in the high temperature field luster mottlings, color development spot, hot sticky dirt etc. to occur when the photographic fixing, can in binder resin, add crosslinking chemical as required.

As the concrete example of crosslinking chemical, can enumerate the many vinyl compounds of aromatic series such as divinylbenzene and divinyl naphthalene; Many vinyl esters of aromatic series polybasic carboxylic acids such as phthalic acid divinyl ester, m-phthalic acid divinyl ester, terephthalic acid (TPA) divinyl ester, high phthalic acid divinyl ester, trimesic acid divinyl/trivinyl ester, naphthalene dicarboxylic acids divinyl ester and biphenyl carboxylic acids divinyl ester; The divinyl ester of nitrogen-containing aromatic compounds such as pyridinedicarboxylic acid divinyl ester; Unsaturated heterocyclic compound such as pyrroles, thiophene class; The vinyl ester of unsaturated heterocyclic compound carboxylic acids such as pyromucyl acid vinyl esters, furancarboxylic acid vinyl esters, pyrroles-2-vinyl esters of carboxylic acids and thiophene carboxylic acid's vinyl esters; (methyl) esters of acrylic acid of straight chain polyvalent alcohols such as methacrylic acid butanediol ester, acrylic acid hexanediol ester, methacrylic acid ethohexadiol ester, acrylic acid decanediol ester and methacrylic acid dodecanediol ester; Dimethacrylate DOPCP and 2-hydroxyl-1, (methyl) acrylate of side chains such as 3-two propylene Ethylene Oxides, replacement polyvalent alcohol; Polyglycol two (methyl) acrylate, polypropylene polyglycol two (methyl) esters of acrylic acid; Succinic acid divinyl ester, fumaric acid divinyl ester, maleic acid vinyl/divinyl ester, diglycolic acid divinyl ester, vinyl itaconate base/divinyl ester, acetone dicarboxylic acid divinyl ester, glutaric acid divinyl ester, 3,3 '-thio-2 acid divinyl ester, trans-aconitic acid divinyl/trivinyl ester, hexane diacid divinyl ester, heptandioic acid divinyl ester, suberic acid divinyl ester, azelaic acid divinyl ester, decanedioic acid divinyl ester, many vinyl esters of polybasic carboxylic acids such as dodecanedioic acid divinyl ester and brazilic acid divinyl ester etc.

In addition, particularly in crystalline polyester resin, can also following method carry out crosslinked: in polyester, make unsaturated polybasic carboxylic acid class copolymerization such as fumaric acid, maleic acid, itaconic acid and trans-aconitic acid, utilize the multiple bonding in the resin partly to be cross-linked to each other afterwards, or carry out crosslinked with other ethylene compounds.Among the present invention, these crosslinking chemicals both can be used alone, and also can share two or more.

As utilizing these crosslinking chemicals to carry out crosslinked method, both can adopt when the polymerization of polymerizable monomer (monomer) crosslinked method with the crosslinking chemical polymerization, also can adopt following method: unsaturated part is remained in the binder resin, treat binder resin generation polymerization or or after making toner, pass through the crosslinked unsaturated part of cross-linking reaction again.

Binder resin is under the situation of vibrin, and polymerizable monomer can come polymerization by polycondensation.The catalyzer that can use known catalyzer to use as polycondensation can be enumerated four butanols titaniums, Dibutyltin oxide, germanium dioxide, antimony trioxide, tin acetate, zinc acetate, stannic disulfide etc. as concrete example.Binder resin is under the situation of vinyl resins, and polymerizable monomer can pass through the incompatible polymerization of radical polymerization.

Share initiating agent for radical polymerization and be not particularly limited, as long as can cause emulsion polymerization.Specifically, can enumerate hydrogen peroxide, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, the peroxidating propionyl, benzoyl peroxide, the chlorine peroxide benzoyl, dichlorobenzoyl peroxide, peroxidating bromomethyl benzoyl, lauroyl peroxide, ammonium persulfate, sodium peroxydisulfate, potassium persulfate, peroxidating carbonic acid diisopropyl ester, the hydrogen peroxide tetralin, 1-phenyl-2-methyl-propyl-1-hydroperoxides, triphenyl t-butyl peroxy-acetate hydroperoxides, the performic acid tert-butyl ester, t-butyl peroxy-acetate, t-butyl perbenzoate, the phenyl t-butyl peroxy-acetate, the methoxyl t-butyl peroxy-acetate, cross peroxides such as N-(3-toluyl) t-butyl carbamate; 2,2 '-azo, two propane, 2,2 '-two chloro-2,2 '-azo, two propane, 1,1 '-azo (Methylethyl) diacetate esters, 2,2 '-azo two (2-amidine propane) hydrochloride, 2,2 '-azo two (2-amidine propane) nitrate, 2,2 '-azo diisobutane, 2,2 '-azo, two isobutyramides, 2,2 '-azoisobutyronitrile, 2,2 '-azo, two-2 Methylpropionic acid methyl esters, 2,2 '-two chloro-2,2 '-azo, two butane, 2,2 '-azo, two-2-methylbutyronitrile, 2,2 '-azo-bis-iso-dimethyl, 1,1 '-azo two (1-methylbutyronitrile-3-sodium sulfonate), 2-(4-aminomethyl phenyl azo)-2-methyl-prop dintrile, 4,4 '-azo, two-4-cyanopentanoic acid, 3,5-dihydroxymethyl phenyl azo-2-methyl-prop dintrile, 2-(4-bromophenyl azo)-2-allyl malononitrile, 2,2 '-azo, two-2-methyl valeronitrile, 4,4 '-azo, two-4-cyanopentanoic acid dimethyl ester, 2,2 '-azo two-2, the 4-methyl pentane nitrile, 1,1 '-azo, two cyclohexanenitriles, 2,2 '-azo, two-2-propyl group butyronitrile, 1,1 '-azo, two-1-chlorphenyl ethane, 1,1 '-azo, two-1-cyclohexanenitrile, 1,1 '-azo, two-1-encircles heptonitrile, 1,1 '-azo, two-1-vinylbenzene, 1,1 '-azo, two cumenes, 4-nitrobenzophenone azo benzyl cyan-acetic ester, the phenylazo diphenyl methane, the phenylazo triphenyl methane, 4-nitrobenzophenone azo triphenyl methane, 1,1 '-azo two-1,2-diphenylethane, poly-(bisphenol-A-4,4 '-azo, two-4-cyanopentanoic acid ester) and poly-azo-compound classes such as (TEG-2,2 '-azo-bis-isobutyrates); 1,4-two (five the ethylidene)-2-tetrazene and 1,4-dimethoxy carbonyl-1,4-diphenyl-2-tetrazene etc.Initiating agent when these polymerization initiators also can be used as cross-linking reaction.

In addition, as binder resin, above main be illustrated around crystalline polyester resin and non-crystalline polyester resin, but can also use homopolymer, the combination multipolymer of two or more following monomers or their potpourri of following monomer as required, these monomers have: styrene, to phenylethylenes such as chlorostyrene, α-Jia Jibenyixi; Acrylic monomers such as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, butyl acrylate, lauryl acrylate, acrylic acid-2-ethyl caproite; Methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, lauryl methacrylate, methacrylic acid-methacrylic monomers such as 2-Octyl Nitrite; Also have vinyl unsaturated acid monomers such as acrylic acid, methacrylic acid, Sodium styrene sulfonate; Also have vinyl nitriles such as vinyl cyanide, methacrylonitrile; Vinyl ethers such as methoxy ethylene, VINYL ISOBUTYL ETHER; Vinyl ketones such as vinyl ketone, vinyl ethyl ketone, the different propenone of vinyl; Olefines such as ethene, propylene, butadiene, can use non-ethene such as epoxy resin, vibrin, urethane resin, polyamide, celluosic resin, polyether resin to contract and resinoid in addition, or the potpourri of they and above-mentioned vinyl resins, or under their coexistence resulting graft polymer of polymerising ethylene class monomer etc.

-particulate resin dispersion-

The preparation method of the particulate resin dispersion that uses when utilizing the emulsion polymerization agglutination to make toner of the present invention describes below.

Can easily obtain particulate resin dispersion by emulsion polymerization and the polymerization in heterogeneity dispersed system similar with it.And can wait arbitrary method to obtain particulate resin dispersion by the following method: with in advance with solution polymerization process or mass polymerization etc. equably the polymkeric substance that obtains of polymerization add in the solvent that does not dissolve this polymkeric substance with stabilizing agent, carry out mechanical mixture then and disperse.

For example, use under the situation of vinyl monomer, can use (preferably share ionic surfactant and non-ionics) such as ionic surfactants, utilize emulsion polymerization and seeding polymerization method to make particulate resin dispersion.

The surfactant of Shi Yonging can be enumerated anionic surface active agent such as sulfuric ester salt, Sulfonates, phosphoric acid ester, soap class herein; Cationic surfactants such as amine salt type, quaternary; Non-ionics such as polyethylene glycols, alkylphenol ethylene oxide adduct class, alkylol ethylene oxide adduct class, polyalcohols; And various graft polymer etc., but be not subject to these examples.

When utilizing emulsion polymerization to make particulate resin dispersion; can add a spot of such as unsaturated acid such as acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acids as the part of monomer component to form the protecting colloid layer at microparticle surfaces; can realize emulsifier-free emulsion polymerization (soap-freepolymerization) thus, so preferably do so especially.

The mean grain size of described resin particle is preferably below the 1 μ m, more preferably 0.01 μ m～1 μ m.If the mean grain size of resin particle is greater than 1 μ m, it is big that the size-grade distribution of the electrostatic image developing toner that then finally obtains becomes, and produces free particles, causes the reduction of Performance And Reliability sometimes.On the other hand, if the mean grain size of resin particle is in above-mentioned scope, then not only do not have above-mentioned shortcoming, also have advantage aspect following: reduce resin particle in the uneven distribution between toner, make resin particle in toner, fully disperse, dwindle deviation on the Performance And Reliability.In addition, the mean grain size of resin particle for example can be utilized MICROTRAC (laser particle analyzer) to wait to measure.

In addition, for the dispersion liquid of dispersed crystalline ester compounds, also can prepare according to the method identical with above-mentioned particulate resin dispersion.

-detackifier-

As being used for detackifier of the present invention, can enumerate low-molecular-weight polyolefins such as tygon, polypropylene, polybutylene; Silicone; Fatty acid amides such as oleamide, mustard acid amides, castor oil acid amides and stearmide; Brazil wax, rice wax, candelila wax, haze tallow and Jojoba Oil vegetable waxs such as (jojoba oil); Animal waxs such as beeswax; Mineral substance wax, petroleum-type waxes such as montan wax, ceresine, ceresin, paraffin, microcrystalline wax and Fischer-Tropsch wax; And their modifier etc.

In addition, when utilizing the emulsion polymerization agglutination to make toner, these detackifiers can be distributed in the water with macromolecule dielectrics such as ionic surfactant, polymer acid, polymeric alkalis, be heated to more than the fusing point, use homogenizer or the pressure spray type dispersion machine that to give stronger shear strength to carry out corpusculed simultaneously, make and contain the detackifier dispersion liquid of mean grain size, use detackifier with the form of this detackifier dispersion liquid then smaller or equal to the anti-sticking agent particle of 1 μ m.

These anti-sticking agent particles both can add in the mixed solvent with other resin particle compositions when making toner simultaneously, also can add on portioning multistage ground.

With respect to toner, the addition of these detackifiers is preferably the scope of 0.5 quality %～50 quality %.The scope of 1 quality %～30 quality % more preferably, the further scope of preferred 5 quality %～15 quality %.If addition is less than 0.5 quality %, then do not reach the effect of adding detackifier, and, detackifier is stayed in the image easily if addition greater than 50 quality %, then is difficult for being exuded to fully the surface of image during photographic fixing, cause transparent variation, so not preferred.

-colorant-

As the colorant that uses among the present invention, can use a kind of in various pigment as described below and the various dyestuff or share two or morely, described pigment for example is: carbon black, chrome yellow, hansa yellow, benzidine yellow, intellectual circle's Huang, quinoline yellow, solid forever orange GTR, pyrazolone orange, Wu Erkan orange (vulcanorange), C lake red CAN'T, permanent bordeaux, bright fuchsin 3B, bright fuchsin 6B, Du Pont's oil red, pyrazolone red, lithol red, rhodamine B lake, lake red C, Rose Bengal, aniline blue, ultramarine blue, bayonet socket indigo plant (Calco oil blue), methylene chloride indigo plant, phthalocyanine blue, phthalocyanine green and peacock green oxalates etc.; Described dyestuff is: acridine, xanthene class, azo class, benzoquinones class, azines, anthraquinone class, thioindigo (thioindico) class, dioxazines, thiazide, azomethine class, indigo class, phthalocyanines, nigrosine class, polymethine class, triphenylmethane, diphenylmethanes, thiazoles etc.

In addition, when utilizing the emulsion polymerization agglutination to make toner, these colorants are dispersed in the solvent, use as colorant dispersion.The mean grain size of the coloring agent particle of this moment is preferably below the 0.8 μ m, more preferably 0.05 μ m～0.5 μ m.If the mean grain size of colorant is greater than 0.8 μ m, the size-grade distribution of the electrostatic image developing toner that then finally obtains broadens, and produces free particles, causes Performance And Reliability to reduce sometimes.And, if the mean grain size of coloring agent particle less than 0.05 μ m, then not only can reduce the coloring of colorant in toner, also can destroy as the shape of one of emulsion agglutination feature controlledly, can't obtain shape sometimes near positive spherical toner.

And mean grain size preferably is less than 10 number % more than or equal to the ratio that exists of the big particle of 0.8 μ m in the colorant dispersion, more preferably is essentially 0 number %.The existence of this big particle can destroy the stability of aggegation step, not only causes the free of thick colored particles, and size-grade distribution is widened.

In addition, mean grain size exists ratio preferably smaller or equal to 5 number % smaller or equal to the molecule of 0.05 μ m in the colorant dispersion.The shape that the existence of this molecule can destroy in the fusion steps is controlled, can't obtain average circularity sometimes smaller or equal to the slick and sly particle of 0.940 what is called.

Relative therewith, if the mean grain size of coloring agent particle, big particle, molecule are in above-mentioned scope, not only do not have above-mentioned shortcoming, also have advantage aspect following: reduce coloring agent particle in the uneven distribution between toner, in toner, fully disperse, the deviation on the Performance And Reliability is little.

In addition, the mean grain size of coloring agent particle for example can be utilized MICROTRAC to wait to measure.Need to prove that with respect to toner, the addition of colorant preferably sets the scope at 1 quality %～20 quality %.

As the process for dispersing of these colorants in solvent, can use arbitrary method and without any restriction, for example rotation is cut off the type homogenizer, is had the arbitrary method such as bowl mill, sand mill, ball mill of medium.

And, can use through rosin, polymkeric substance etc. and carry out the colorant that surfaction is handled.The colorant of handling through surfaction has advantage aspect following: its stabilization fully in colorant dispersion, colorant is separated into the mean grain size of appointment in colorant dispersion after, when mixing mutually, can in aggegation step etc., keep good disperse state and aggegation between the colorant can not occur with particulate resin dispersion.On the other hand, the colorant of handling through superfluous surfaction leave in aggegation step middle reaches sometimes and not with resin particle generation aggegation.Therefore, carry out above-mentioned surfaction under the top condition of suitably selecting handles.

In addition, as the surface-treated polymkeric substance that is used for colorant, can enumerate acrylonitrile polymer, methylmethacrylate polymer etc.

Condition as surfaction, generally can use the polymerization that in the presence of colorant (pigment), makes monomer generation polymerization, or use colorant (pigment) thus being distributed to solubleness that back in the polymer solution reduces this polymkeric substance makes polymkeric substance precipitate into the phase separation method etc. on colorant (pigment) surface.

-other adding ingredients-

Toner of the present invention as adding the magnetic powder under the situation of magnetic color tuner, as the magnetic powder that uses herein, can be enumerated metals such as ferrite, magnetic iron ore, reduced iron, cobalt, nickel, manganese, alloy or contained the compound etc. of these metals.In addition, can also add normally used various charged controlling agents such as quaternary ammonium salt, nigrosine compounds or triphenylmethane pigment as required.

In the toner of the present invention, can also contain inorganic particles as required.Consider permanance, with respect to the total amount of toner, more preferably medium particle diameter is that the content of the inorganic particles of 5nm～30nm and the inorganic particles that medium particle diameter is 30nm～100nm is 0.5 quality %～10 quality %.

The colloidal silica that above-mentioned inorganic particles can use monox, the monox through hydrophobic treatments, titanium dioxide, aluminium oxide, lime carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, handle through cationic surface, the colloidal silica handled through anionic surface etc.These inorganic particles can use ultrasonic dispersing machine etc. to carry out dispersion treatment in the presence of the ionic surfactant in advance, but more preferably use the colloidal silica that does not need this dispersion treatment.

The addition of above-mentioned inorganic particles is during less than 0.5 quality %, even then add this inorganic particles, when the toner fusion, also can't obtain enough intensity (toughness), not only can not in oilless fixing, improve fissility, and particulate disperses only can increase viscosity in toner simply when the toner fusion, and the result is sometimes owing to the stringiness variation has been destroyed the fissility in the oilless fixing.And the addition of above-mentioned inorganic particles is during greater than 10 quality %, though obtained enough intensity, the flowability during the toner fusion significantly reduces, and destroys the image glossiness sometimes.

And, can also add known additive at home and abroad to toner of the present invention.Can utilize inorganic particles such as monox, aluminium oxide, titanium dioxide, lime carbonate, magnesium carbonate, tricalcium phosphate as additive.For example, as flow aid and cleaning additive, can use inorganic particles such as monox, aluminium oxide, titanium dioxide, lime carbonate; Resin particles such as vinyl resins, polyester, silicone.Adding method for additive is not particularly limited, and can apply shear strength it is added to the toner-particle surface under drying regime.

The all rerum naturas of other of-toner-

Glass transition temperature (Tg) to toner of the present invention is not particularly limited, and preferably selects in 40 ℃～70 ℃ scope.If Tg is lower than this scope, then go wrong on the permanance in toner keeping quality, photographic fixing image keeping quality and physical machine sometimes.And Tg is when being higher than this scope, produces sometimes then that fixing temperature uprises, required temperature such as uprises at problem during granulation.

Tg can for example utilize DSC to measure machine (differential thermometric analysis device: DSC-7, PerkinElmer company makes) according to ASTMD3418-8 and measure.The temperature revisal of device test section utilizes the fusing point of indium and zinc, and the heat revisal utilizes the heat of fusion of indium.Use aluminum crucible working sample under 10 ℃/minute programming rate, blank crucible is set in contrast.

With absolute value representation, the carried charge of electrostatic image developing toner of the present invention is preferably the scope of 10 μ C/g～40 μ C/g, more preferably the scope of 15 μ C/g～35 μ C/g.If be lower than 10 μ C/g, then produce in background portion easily and pollute, if surpass 40 μ C/g, then image color reduces easily.

Electrostatic image developing toner is preferably 0.5～1.5 at the carried charge in summer (28 ℃, 85%RH) and ratio at the carried charge in winter (10 ℃, 30%RH), and more preferably 0.7～1.3.If this ratio breaks away from above-mentioned scope, then toner is to the dependence grow of environment, and the charging property deficient in stability is not preferred in practicality.

-utilize the emulsion polymerization agglutination make toner-

Be concrete example with the emulsion polymerization agglutination below, illustrate in greater detail the manufacture method of toner of the present invention.

When utilizing the emulsion polymerization agglutination to make toner of the present invention, as mentioned above, at least to make through aggegation step and fusion steps (integrated step), but attachment steps can also be set, in this attachment steps, on the surface of the agglutinating particle (nuclear particle) that forms through the aggegation step, adhere to resin particle, thereby form agglutinating particle with core/shell structure.

-aggegation step-

In the aggegation step,, form agglutinating particle being mixed with the compound that the present invention relates to, the binder resin particle dispersion that is dispersed with binder resin, the colorant dispersion that is dispersed with colorant, being dispersed with in the raw material dispersion liquid of detackifier dispersion liquid of detackifier.

Specifically, with the raw material dispersion liquid heating that mixes various dispersion liquids and obtain, make the microparticle agglutination in the raw material dispersion liquid form agglutinating particle.In addition, under the temperature of the glass transition temperature that is lower than non-crystalline resin slightly, heat.Preferred temperature range is the scope than low 5 ℃～25 ℃ of the glass transition temperature of non-crystalline resin.

Cut off in rotation under the stirring of type homogenizer, add agglutinant, the pH of raw material dispersion liquid is adjusted to acidity, form agglutinating particle thus in room temperature.

As the agglutinant that is used for above-mentioned aggegation step, the surfactant that can use and be used as the surfactant that makes an addition to the spreading agent in the raw material dispersion liquid to have opposite polarity is an inorganic metal salt, can suit to use the above metal complex of divalent in addition.Especially, can reduce the use amount of surfactant during owing to the use metal complex, improve charged characteristic, so preferred especially.

As above-mentioned inorganic metal salt, can enumerate for example slaines such as lime chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, aluminium sulphate; And inorganic metal salt polymkeric substance such as polyaluminium chloride, poly-aluminium hydroxide, calcium polysulfide etc.Wherein preferred especially aluminium salt and polymkeric substance thereof.The size-grade distribution of more concentrated in order to obtain (sharp), for the valence mumber of inorganic metal salt, divalent is better than 1 valency, and 3 valencys are better than divalent, and 4 valencys are better than 3 valencys, and valence mumber is when identical, more preferably the inorganic metal salt polymkeric substance of aggretion type.

-attachment steps-

After the aggegation step, also can carry out attachment steps if need.In the attachment steps, on the surface of the agglutinating particle that forms through above-mentioned aggegation step, adhere to resin particle, thereby form clad.Can obtain having the toner of the so-called stratum nucleare and the core/shell structure of the clad that coats this stratum nucleare thus.

Usually can in the dispersion liquid that in the aggegation step, forms agglutinating particle (nuclear particle), append the dispersion liquid that contains the non-crystalline resin particle and form clad.In addition, the non-crystalline resin that utilizes in the attachment steps both can be identical with the non-crystalline resin that utilizes in the aggegation step, also can be different with it.

In addition, attachment steps generally is used to make the situation of the toner with following core/shell structure, contains detackifier in the described stratum nucleare and contains crystalline resin as binder resin simultaneously as principal ingredient.The fundamental purpose of doing like this is that the detackifier and the crystalline resin that suppress to contain in the stratum nucleare expose on the surface of toner, and the intensity of inadequate toner-particle in the additional nuclear layer monomer.

Yet, in the toner of the present invention, dispersiveness-compatibility the excellence of detackifier in toner not only, and owing to used non-crystalline resin as binder resin, even do not implement attachment steps stratum nucleare is not set, also can suppress to bring dysgenic composition to be exposed to the surface of toner, can also obtain full intensity simultaneously the charging property or the keeping property of detackifier etc.Therefore, when using the emulsion polymerization agglutination, can not produce special influence even omit attachment steps, so can further simplify the manufacturing of toner yet.

-fusion steps (integrated step)-

Through after the aggegation step or through carrying out fusion steps after aggegation step and the attachment steps, in this fusion steps, the pH that will contain the suspending liquid of the agglutinating particle that forms through above-mentioned steps transfers to 6.0～8.0 scope, the carrying out of blocked lectin merges agglutinating particle by heating then thus.In addition, during fusion, merge agglutinating particle by under the temperature more than the glass transition temperature of non-crystalline resin, heating.

Can pine for adding when merging or merges end after carry out cross-linking reaction.And, also can when merging, carry out cross-linking reaction.Carry out in the situation of cross-linking reaction, use crosslinking chemical as described above and polymerization initiator when making toner.

Polymerization initiator both can be pre-mixed in dispersion liquid in the stage of making the raw material dispersion liquid, also can be directed in the agglutinating particle in the aggegation step.In addition, also can after fusion steps or fusion steps, import.Under situation about importing after aggegation step, attachment steps, fusion steps or the fusion steps, there is the liquid of polymerization initiator to be added into to dispersion liquid dissolving or emulsification.For the purpose of the control degree of polymerization, also can in these polymerization initiators, add known crosslinking chemical, chain-transferring agent, polymerization inhibitor etc.

-washing-drying steps etc.-

After the fusion steps of agglutinating particle finishes, the toner-particle that obtains to expect through washing step, solid-liquid separation step, drying steps at random.In the washing step, consider charging property, preferably carry out displacement washing fully with ion exchange water.In the solid-liquid separation step,, consider production efficiency, preferably carry out suction filtration and pressure filtration etc. though be not particularly limited.In the drying steps,, consider production efficiency though be not particularly limited, preferably carry out freeze-dried, dodge that spray is dry, dry, the oscillating mode of flowing flows drying etc.And, can in dried toner-particle, add above-mentioned various additives as required.

(developer for static charge image development)

Developer for static charge image development of the present invention (hereinafter economizing slightly " developer " sometimes) contains toner of the present invention, can mix other compositions according to application target.

Specifically, if the independent developer for static charge image development that uses toner of the present invention then to be prepared as single constituent class, and, if carrier and toner combination of the present invention are used, then be prepared as the developer for static charge image development of two constituent classes.

Carrier herein is not particularly limited, and can enumerate known carrier, and that for example can use that the spy opens that clear 62-39879 communique, spy open record in the clear 56-11461 communique etc. coats the carrier known carriers such as (resin-coated carriers) of core with resin bed.

As the core of resin-coated carrier, can enumerate the moulder of iron powder, ferrite, magnetic iron ore etc., its mean grain size is about 30 μ m～200 μ m.

As forming the resin-coated of clad, can enumerate the homopolymer of following monomer for example etc. or contain the multipolymer of two or more following monomers; Silicone such as methyl silicone, Methylphenylsilanone; The polyesters that contains bis-phenol, glycol etc.; Epoxy resin; Urethane resin; Polyamide; Celluosic resin; Polyether resin; Polycarbonate resin etc.These resins both can be used alone, and also can share two or more.Described monomer is: styrene, to phenylethylenes such as chlorostyrene, α-Jia Jibenyixi; Methyl acrylate, ethyl acrylate, acrylic acid n-propyl, lauryl acrylate, acrylic acid-2-ethyl caproite, methyl methacrylate, n propyl methacrylate, lauryl methacrylate, methacrylic acid-alpha-methylene fatty acid monocarboxylic acid classes such as 2-Octyl Nitrite; Nitrogenous acrylic compounds such as dimethylaminoethyl methacrylate; Vinyl such as vinyl cyanide, methacrylonitrile nitrile; Vinylpyridine classes such as 2-vinylpyridine, 4-vinylpridine; Vinyl ethers such as methoxy ethylene, VINYL ISOBUTYL ETHER; Vinyl ketones such as vinyl ketone, vinyl ethyl ketone, the different propenone of vinyl; Olefines such as ethene, propylene; Vinyl fluorochemical monomers such as vinylidene fluoride, tetrafluoroethene, hexafluoroethylene.

With respect to the core of 100 mass parts, resin-coated amount is the scope of 0.1 mass parts～10 mass parts, the scope of preferred 0.5 mass parts～3.0 mass parts.Can use hot type kneader, hot type Henschel stirring machine, UM stirring machine etc. in the manufacturing of carrier, can use hot type to flow according to resin-coated amount and rotate bed, hot type drying oven etc.Mixing ratio for toner in the developer for static charge image development and carrier is not particularly limited, and can suitably select according to purpose.

(formation method)

Below formation method of the present invention is described.Formation method of the present invention is not particularly limited, as long as use toner of the present invention (developer), specifically, formation method of the present invention be preferably included on the sub-image supporting body surface electrostatic latent image that forms electrostatic latent image form step, use the developer that contains toner of the present invention make above-mentioned latent electrostatic image developing with the development step that forms toner image, with above-mentioned toner image be transferred on the recording medium transfer step and with the photographic fixing step of above-mentioned toner image on the aforementioned recording medium.

In addition, except these steps, can also be combined in the known steps of using based on rope in the formation method of xerography, for example, can also comprise finish the toner circulation step that the cleaning that will remain in the lip-deep remaining toner of sub-image supporting body after the transfer step and remove and reclaim, the remaining toner that will reclaim utilize as developer again in cleaning.

Herein, electrostatic latent image forms step and is meant, makes the exposure of sub-image supporting body with laser optics system or led array etc. make the surperficial uniform charged of sub-image supporting body by charged elements after, thereby forms the step of electrostatic latent image.Be not particularly limited for above-mentioned charged elements, can enumerate for example charger of noncontact mode such as corona tube, grid type corona tube; And by applying the charger that voltage makes the way of contact of sub-image supporting body surface charging to the electroconductive component that contacts with sub-image supporting body surface.The charger of preferred contact electrification mode, because it can give play to following effect: the generation of ozone is few, is beneficial to environmental protection, and the printing durability excellence.In the charger of above-mentioned contact electrification mode, the shape of electroconductive component is not particularly limited, and can be arbitrary shapes such as brush shape, doctor-like, pin electrode shape, roller shape.And formation method of the present invention forms in the step at sub-image and is not subjected to any special restriction.

Above-mentioned development step is meant, make the surface be formed with the developer carrier contact of the developer layer that contains toner at least or near sub-image supporting body surface, make toner-particle be attached to the electrostatic latent image on above-mentioned sub-image supporting body surface, thereby form the step of toner image on sub-image supporting body surface.Visualization way in the formation method of the present invention is not particularly limited, and can make in a known manner to develop.When developer is tow-component developer, there be series connection (カ ス ケ one De) mode and magnetic brush mode as visualization way.

Above-mentioned transfer step is meant, the toner image that is formed at sub-image supporting body surface is transferred to the step of recording medium.Transfer printing mode in the formation method of the present invention is not particularly limited, and except toner image directly is needed on the mode of recording mediums such as paper, also can be to be needed on the mode that is needed on recording mediums such as paper behind drum type or the banded intermediate transfer body again.

For in formation method of the present invention, use toner image is not particularly limited by the transfer device that the sub-image supporting body is needed on paper etc., for example can utilize corona tube.Corona tube is as making that the unit with the paper uniform charged is effectively, for make as recording medium with paper tape the electric charge of appointment is arranged, must apply voltage, so need high-voltage power supply up to several kV.And, because corona discharge can produce ozone, thereby can cause the deterioration of rubber components or sub-image supporting body.Therefore, the electric conductivity transfer roll that preferably will contain resilient material is needed on toner image with the transfer printing mode that contacts on the paper with the crimping of sub-image supporting body.

Above-mentioned cleaning is meant, scraper, brush, roller etc. and sub-image supporting body surface is directly contacted, thus the step that will remove attached to the toner on sub-image supporting body surface, paper powder, dust etc.

As the mode of common employing, can enumerate the scraper that makes rubber systems such as polyurethane and be crimped on scraper cleaning mode on the sub-image supporting body.Relative therewith, also can use the cylindric non magnetic sleeve that can rotate, support magnetic carrier reclaiming the magnetic brush mode of toner in sleeve surface again, thereby or the hair of the resin fibre of semiconduction and animal is made the roller shape makes it can rotate, apply then the mode of removing toner with the opposite polarity bias voltage of toner on this roller at internal fixation configuration magnetite, in its periphery setting.In the former magnetic brush mode, cleaning pre-treatment corona tube can be set.In the formation method of the present invention, relevant cleaning is not particularly limited.

Above-mentioned photographic fixing step is meant in fixing device the step with the toner image of transfer printing on the recording medium surface.Be not particularly limited the preferred heat fixing device that utilizes hot-rolling that uses as the fixing device that is used for formation method of the present invention.Heat fixing device has the thermolamp of heating usefulness in metal-cored inside cylindraceous, this device is by fixing roller and backer roll or add pressure zone and constitute, described fixing roller forms so-called " adherent layer " by heat-resistant resin overlay film layer or thermotolerance rubber overlay film layer on its outer peripheral face, described backer roll or add pressure zone and fixing roller crimping configuration forms the heat-resistant elastomer layer respectively on the surface of the outer peripheral face of cylindrical metal core or banding substrate.In the photographic fixing operation of toner image, the recording medium that will be formed with toner image is inserted into fixing roller and backer roll or adds between the pressure zone, and the heat fusing by binder resin in the toner and adjuvant etc. carries out photographic fixing.

In addition, in the formation method of the present invention, the following formation method of preferred employing under the situation of making full-colour image: two or more sub-image supporting bodies have developer carrier of all kinds respectively, form the series of steps of step, development step, transfer step and cleaning by the sub-image that utilizes sub-image supporting body of all kinds and developer carrier, on same recording medium surface, stack gradually the toner image of all kinds that forms above-mentioned each step, in the photographic fixing step, this stacked full-color toner image is carried out hot photographic fixing then.So, by in above-mentioned formation method, using developer of the present invention, can in for example being suitable for series connection (the Application デ system) mode of small-sized, color high speed, obtain stable development, transfer printing, fixing performance.

Be not particularly limited as the mode of carrying out the toner circulation step, for example can enumerate following method etc.: utilizing travelling belt or transmit screw rod will be at toner supply that cleaning section reclaims in supply usefulness toner Cartridge, in medial compartment with supply to method in the developer etc. after developer or supply mix with toner.Can preferably enumerate the mode that directly turns back in the developer, or in medial compartment, supply be mixed the mode that the back is supplied with toner with the circulation toner.

Recycle in the situation of toner, need toner-particle to have high strength, and need detackifier to be exposed to the surface with exceeding in inner fully dispersion of toner.At this on the one hand, because toner of the present invention has enough intensity, the long-term use can not cause the image quality deterioration yet.

As the imaging device that utilizes formation method of the present invention, can be with inscapes such as photoreceptor (sub-image supporting body), developer, clearers as handle box in conjunction with constituting one, this unit can freely be loaded and unloaded with respect to device body.And, also can be with charger, integrated to form handle box as at least a device in exposer, developer, transfer or separation vessel and the clearer and photoreceptor, this handle box is the single unit that freely loads and unloads on device body, and the guidance units such as track of use device body freely load and unload.

As the recording medium of transfer printing toner image, can enumerate the common paper used in the duplicating machine, printer etc. of electrofax mode, OHP sheet etc.For the flatness of imaging surface after the further raising photographic fixing, the surface of preferred above-mentioned transfer printing body is level and smooth as far as possible, for example can preferably use the surface coated in common paper that the coated paper of resin or the drawing paper of printing usefulness etc. are arranged.

-electrophotographic photoconductor (sub-image supporting body)-

Optimal way to the electrophotographic photoconductor (the sub-image supporting body hereinafter is sometimes referred to as " photoreceptor ") that is used for formation method of the present invention describes below.

Employed photoreceptor can utilize the known photoreceptor that is provided with photographic layer on the electric conductivity support at least in the formation method of the present invention, preferably uses Organophotoreceptor.At this moment, the layer of formation photoreceptor outmost surface preferably contains the resin with cross-linked structure.As resin with cross-linked structure, can utilize phenolics, urethane resin, siloxane resin, but preferred phenolics, siloxane resin, most preferably siloxane resin.

The layer that constitutes outmost surface contains the photoreceptor of the resin with cross-linked structure, because its intensity height to the permanance height of abrasion and scraping, can make the life-span of photoreceptor prolong.But,, when using cleaning doctor, need cleaning doctor be contacted with photoreceptor as the cleaning unit of photoreceptor in order to ensure spatter property.At this moment, at the contact site of cleaning doctor and photoreceptor, owing to residue in the toner container cracky of photosensitive surface, cause the constituent material of toner to be easy on the surface attached to photoreceptor, or consequent charged variation occurs.Because toner of the present invention has excellent intensity, so can suppress this problem.In addition, with recycling toner utilize mode combined again, also can keep image quality deterioration not for a long time.

Be not particularly limited for the layer structure that is used for photoreceptor of the present invention; as long as contain electric conductivity support and the photographic layer that is arranged on this electric conductivity support; but preferred photographic layer is the function divergence type photoreceptor that contains charge generating layer and charge transport layer; specifically, preferably on the surface of conductive base, stack gradually prime coat, charge generating layer, charge transport layer and protective seam.Below each layer described in detail.

As the electric conductivity support, can enumerate the sheet metal, metal drum, the metal tape that have for example used metal or alloy such as aluminium, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, platinum; Or coating, evaporation or lamination have paper, plastic foil, band of metal or alloy such as conductive compound such as electric conductive polymer, indium oxide, aluminium, palladium, gold etc.When photoreceptor is used for laser printer, be preferably 350nm～850nm as the oscillation wavelength of laser, wavelength is short more, and resolution is excellent more just preferred more.

In addition, the interference fringe that produces when preventing irradiating laser, preferably with the average rugosity Ra of center line of 0.04 μ m～0.5 μ m with the support surface roughening.Method as roughening is preferably as follows method: carry out the wet type honing on the support by being suspended in lapping compound in the water and spraying to; Support is crimped on the centerless grinding of carrying out attrition process on the grinding stone of rotation continuously; Utilize anodic oxidation to make to contain the method for layer of the semiconduction particulate of organic or inorganic; Or the like.If Ra is less than 0.04 μ m, then owing to can't obtain to prevent effects of jamming near minute surface, greater than 0.5 μ m, even then form overlay film, it is coarse and inapplicable that image quality also becomes as if Ra.When utilizing non-stray light to make light source, be used to prevent that the roughening of interference fringe from not being necessary especially, can prevent the concavo-convex defective that produces owing to substrate surface, thereby can further aptly life-saving.

In the anodized, make anode and in dielectric solution, carry out anodic oxidation, on the aluminium surface, form oxide film thus with aluminium.Can enumerate sulfuric acid solution, oxalic acid solution etc. as dielectric solution.But the porous anodic oxide film under this state is a chemical activity, pollutes easily, and is bigger based on the resistance variations of environmental change.So, in pressure (hydraulic) water steam or boiling water (also can add nickel etc. slaine) by blocking the micropore of anode oxide film based on the volumetric expansion of hydration reaction, thereby the sealing of hole that is changed to more stable hydrous oxid is handled.About the thickness of anode oxide film, be preferably 0.3 μ m～15 μ m.Thickness lacks for the barrier that injects during less than 0.3 μ m, and effect is insufficient.And thickness is during greater than 15 μ m, because use can cause the rising of rest potential repeatedly.

The acidic treatment liquid that following use contains phosphoric acid, chromic acid and fluoric acid is handled.Blending ratio for phosphoric acid, chromic acid and fluoric acid in the acidic treatment liquid, preferably phosphoric acid is the scope of 10 quality %～11 quality %, chromic acid is the scope of 3 quality %～5 quality %, fluoric acid is the scope of 0.5 quality %～2 quality %, and all concentration of these acid is the scope of 13.5 quality %～18 quality %.Treatment temperature is 42 ℃～48 ℃, keeps the high processing temperature can form thicker overlay film quickly.For the thickness of overlay film, be preferably 0.3 μ m～15 μ m.Thickness lacks for the shielding of injecting during less than 0.3 μ m, and effect is insufficient.And thickness is during greater than 15 μ m, because use can cause the rising of rest potential repeatedly.

Can pass through in 90 ℃～100 ℃ pure water, to flood 5 minutes～60 minutes, or contact 5 minutes among the hot steam～carry out boehmite (Boehmite) and handle in 60 minutes with 90 ℃～120 ℃ add.The thickness of overlay film is preferably 0.1 μ m～5 μ m.Can also use the low electrolyte solutions of Film Fractionation such as hexane diacid, boric acid, borate, phosphate, phthalate, maleate, benzoate, tartrate, citrate that it is carried out anodized.As the semiconduction particulate of organic or inorganic, can enumerate the spy and open perylene pigment, the bisbenzimidazole perylene pigment put down in writing in the clear 47-30330 communique, encircle organic pigments such as quinone pigments, indigo pigment, quinacridone pigment more; Or have organic pigments such as the disazo pigment of electron-withdrawing substituents such as cyano group, nitro, nitroso-, halogen atom or phthalocyanine color; Inorganic pigments such as zinc paste, titanium dioxide, aluminium oxide.In these pigment, preferred zinc paste, titanium dioxide, because it is its charge transport can be higher, effective to thick filmization.

In order to improve dispersiveness or to adjust energy level, can carry out surface treatment to the surface of these pigment with organic titanic compounds such as titanate coupling agent, aluminium chelate compound compound, aluminum coupling agent etc.Especially preferably use vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three-2-methoxy ethoxy silane, vinyltriacetoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-metacryloxy propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-r-chloropropyl trimethoxyl silane, γ-2-aminoethyl aminopropyl trimethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-urea groups propyl-triethoxysilicane, β-3, silane coupling agents such as 4-epoxycyclohexyl trimethoxy silane are handled.

If the semiconduction particulate of organic or inorganic is too much, then the intensity of prime coat reduces, and paint film defect occurs.Therefore, the semiconduction particulate of this organic or inorganic preferably uses below the 95 quality %, more preferably uses below the 90 quality %.In the atomic mixing/process for dispersing of the semiconduction of organic or inorganic, use the method for bowl mill, roller mill, sand mill, masher, ultrasound wave etc. comparatively suitable.Mix/be dispersed in the organic solvent and carry out, can use organic solvent arbitrarily as organic solvent, as long as can dissolve organometallics or resin or mix/do not cause when disperseing gelation or aggegation at semiconduction particulate to organic or inorganic.For example can use organic solvent commonly used such as methyl alcohol, ethanol, n-propanol, normal butyl alcohol, phenmethylol, methyl cellosolve, ethyl cellosolve, acetone, MEK, cyclohexanone, methyl acetate, n-butyl acetate, diox, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene separately, or two or more above-mentioned solvents be mixed use.

Can between electric conductivity support and photographic layer, form prime coat as required.

As the material that is used to form prime coat, except organic zirconates such as zirconium chelate compound, zirconium alkoxide cpd, zirconium coupling agents; Organic titanic compounds such as titanium chelate compound, titanium alkoxide cpd, titanate coupling agent; Beyond the organo-aluminum compounds such as aluminium chelate compound, aluminum coupling agent, can also enumerate organometallicss such as antimony alkoxide cpd, germanium alkoxide cpd, indium alkoxide cpd, indium chelate compound, manganese alkoxide cpd, manganese chelate compound, tin alkoxide compound, tin chelate compound, aluminium silicon alkoxide compound, aluminium titanium alkoxide cpd, aluminium zirconium alkoxide cpd.Preferred especially organic zirconate, organic titanium oxygen compound and organo-aluminum compound because their rest potential is low, can show the good electron photographic property.

And, can also add vinyl trichlorosilane, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three-2-methoxy ethoxy silane, vinyltriacetoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-metacryloxy propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-r-chloropropyl trimethoxyl silane, γ-2-aminoethyl aminopropyl trimethoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-urea groups propyl-triethoxysilicane, β-3, silane coupling agents such as 4-epoxycyclohexyl trimethoxy silane use.

In addition, can also use so far known binder resins such as the polyvinyl alcohol (PVA) that uses as prime coat, polyvinyl methyl ether, poly-N-vinyl imidazoles, polyoxyethylene, ethyl cellulose, methylcellulose, ethylene-acrylic acid copolymer, polyamide, polyimide, casein, gelatin, tygon, polyester, phenolics, vinyl chloride vinyl acetate copolymer, epoxy resin, polyvinyl pyrrolidone, polyvinylpyridine, polyurethane, polyglutamic acid, polyacrylic acid.Can suitably set the blending ratio of these binder resins as required.

Can mix/disperse electron transport pigment in prime coat uses.As electron transport pigment, can enumerate the spy and open perylene pigment, the bisbenzimidazole perylene pigment put down in writing in the clear 47-30330 communique, encircle organic pigments such as quinone pigments, indigo pigment, quinacridone pigment more; Or have organic pigments such as the disazo pigment of electron-withdrawing substituents such as cyano group, nitro, nitroso-, halogen atom or phthalocyanine color; Inorganic pigment such as zinc paste, titanium dioxide.

Preferred perylene pigment, bisbenzimidazole perylene pigment in these pigment, encircle quinone pigments, zinc paste and titanium dioxide, because their electron mobility height more.And, in order to control dispersiveness and charge-transporting, also can carry out surface treatment to the surface of these pigment with above-mentioned coupling agent, bonding agent etc.Because electron transport pigment too much can cause the intensity of prime coat to reduce, and paint film defect occurs, thus the use amount of this pigment be preferably below the 95 quality %, more preferably below the 90 quality %.

In the mixing/process for dispersing, use the method for bowl mill, roller mill, sand mill, masher, ultrasound wave etc. comparatively suitable.Mix/be dispersed in the organic solvent and carry out, can use organic solvent arbitrarily, as long as can dissolve organometallics or resin or when mixing/dispersion electron transport pigment, not cause gelation or aggegation as organic solvent.For example can use organic solvent commonly used such as methyl alcohol, ethanol, n-propanol, normal butyl alcohol, phenmethylol, methyl cellosolve, ethyl cellosolve, acetone, MEK, cyclohexanone, methyl acetate, n-butyl acetate, diox, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene separately, or two or more above-mentioned solvent is used.

The thickness of prime coat is generally 0.1 μ m～30 μ m, is preferably 0.2 μ m～25 μ m.As the coating process that prime coat is set, can use knife coating, line rod (Meyer bar) rubbing method, spraying process, dip coating, pearl to be coated with method commonly used such as method, airblade coating method, curtain coating method.Carry out drying after the coating, obtain prime coat.Dry under the temperature of can evaporating solvent carrying out film forming, carry out usually.Especially, because become insufficient easily, so be preferably formed the middle layer through its ability of covering the base material defective of base material that acid solution is handled and boehmite is handled.

Below charge generating layer is described.

Electric charge generating material as being used to form charge generating layer can use AZO pigments such as bisdiazo, trisazo-; Condensed nucleus aromatic pigment such as dibromo anthanthrone; Organic pigments such as perylene pigment, pyrrolo-pyrrole pigments, phthalocyanine color; All known materials such as inorganic pigment such as three prismatic crystal selenium, zinc paste especially, when using the exposure wavelength of 380nm～500nm, preferably use inorganic pigment; When using the exposure wavelength of 700nm～800nm, preferable alloy and metal-free phthalocyanine.Wherein, preferred especially spy opens flat 5-263007 and spy and opens among the flat 5-279591 disclosed hydroxyl phthalocyanine gallium, spy and open among the flat 5-98181 disclosed gallium chloride phthalocyanine, spy and open flat 5-140472 and spy and open among the flat 5-140473 that disclosed dichloro tin phthalocyanine, spy open flat 4-189873 and the spy opens disclosed titanyl phthalocyanine among the flat 5-43813.

As the binder resin that is used to form charge generating layer, can be from selecting the insulative resin widely, and can from the electrical polymkeric substance of organic light-guide such as poly-N-vinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, polysilane, select.As preferred binder resin, can enumerate insulative resins such as polyvinyl butyral resin, polyacrylate resin (condensed polymer of bisphenol-A and phthalic acid etc.), polycarbonate resin, vibrin, phenoxy resin, vinyl chloride vinyl acetate copolymer, polyamide, acryl resin, polyacrylamide resin, polyvinylpyridine resin, celluosic resin, urethane resin, epoxy resin, casein, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, but be not limited to these.These binder resins can use separately, also can mix two or more uses.

The mixing ratio of electric charge generating material and binder resin (weight ratio) is preferably 10: 1～1: 10 scope.As the method for disperseing these materials, can use usual ways such as bowl mill dispersion method, masher dispersion method, sand mill dispersion method.The condition that need this moment is: the crystal type of this electric charge generating material does not change because of dispersion.Incidentally, for above-mentioned any one the dispersion method of implementing among the present invention, not not changing before all confirming its crystal type and disperseing.In addition, during dispersion, it is effectively that the size of particle is set at below the 0.5 μ m, is preferably below the 0.3 μ m, more preferably below the 0.15 μ m.

As the solvent that is used to disperse, can use organic solvent commonly used such as methyl alcohol, ethanol, n-propanol, normal butyl alcohol, phenmethylol, methyl cellosolve, ethyl cellosolve, acetone, MEK, cyclohexanone, methyl acetate, n-butyl acetate, diox, tetrahydrofuran, methylene chloride, chloroform, chlorobenzene, toluene separately, or two or more above-mentioned solvent is used.

The thickness of charge generating layer is generally 0.1 μ m～5 μ m, is preferably 0.2 μ m～2.0 μ m.Coating process when being used to charge generating layer is set can use knife coating, line rod rubbing method, spraying process, dip coating, pearl to be coated with method commonly used such as method, airblade coating method, curtain coating method.

Below charge transport layer is described.

As charge transport layer, can use the charge transport layer that utilizes technique known to form.Charge transport layer perhaps carries material to form by containing polymer charge by containing charge transport material and binder resin forms.

As above-mentioned charge transport material, can enumerate quinones, the four cyano quinone bismethane compounds, 2 of 1,4-benzoquinone, chloranil, bromine quinone, anthraquinone etc., 4, electron transport compounds such as Fluorenone compounds such as 7-trinitro-fluorenone, xanthone compounds, benzophenone compound, cyano group vinylic chemical compound, ethylene compounds; Cavity conveying compounds such as triarylamine compounds, diphenyl amine compound, aryl paraffinic compound, aryl substituted ethylene compounds, talan (stilbene) compounds, anthracene compounds, hydrazone compounds.These charge transport materials can use separately or mix two or more uses, but are not limited to these materials.And these charge transport materials can use separately or mix two or more uses, but consider mobility, are preferably as follows the compound of structure.

In the following formula, R ¹⁴Expression hydrogen atom or methyl.And n represents 1 or 2.Ar ₆And Ar ₇Expression replaces or the aryl of non-replacement, represents with following radicals as substituting group: alkyl in 1～5 scope of halogen atom, carbon number, carbon number in 1～5 scope alkoxy or be the substituted-amino that 1～3 alkyl replaces with carbon number.

In the following formula, R ¹⁵, R ¹⁵' can be identical or different, expression hydrogen atom, halogen atom, carbon number are that 1～5 alkyl, carbon number are 1～5 alkoxy.R ¹⁶, R ¹⁶', R ¹⁷, R ¹⁷' can be identical or different, expression hydrogen atom, halogen atom, carbon number be 1～5 alkyl, carbon number be 1～5 alkoxy, with carbon number be 1～2 the alkyl amino, replacement or the non-replacement that replace aryl ,-C (R ¹⁸)=C (R ¹⁹) (R ²⁰) or-CH=CH-CH=C (Ar) ₂R ¹⁸, R ¹⁹, R ²⁰The aryl of alkyl, replacement or the non-replacement of expression hydrogen atom, replacement or non-replacement.M and n represent 0～2 integer.

In the following formula, R ₂₁Expression hydrogen atom, carbon number be 1～5 alkyl, carbon number be 1～5 alkoxy, replacement or non-replacement aryl or-CH=CH-CH=C (Ar) ₂Ar represents to replace or the aryl of non-replacement.R ₂₂, R ₂₃Can be identical or different, expression hydrogen atom, halogen atom, carbon number are that 1～5 alkyl, carbon number are 1～5 alkoxy, are the aryl of 1～2 the alkyl amino, replacement or the non-replacement that replace with carbon number.

In addition, for the binder resin that is used for charge transport layer, can use following polymer charge to carry material: polycarbonate resin, vibrin, methacrylic resin, acryl resin, polyvinyl chloride resin, the polyvinylidene chloride resin, polystyrene resin, the polyvinyl acetate resin, Styrene-Butadiene, vinylidene chloride-acrylonitrile copolymer, vinyl chloride vinyl acetate copolymer, vinyl chloride-vinyl acetate-copolymer-maleic anhydride, silicone resin, silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, the poly-N-vinyl carbazole, polysilane, and the spy opens flat 8-176293 communique, disclosed polyesters polymer charge is carried material etc. in the Te Kaiping 8-208820 communique.These binder resins can use or mix two or more uses separately.The mixing ratio of charge transport material and binder resin (weight ratio) is preferably charge transport material: binder resin=10: 1～1: 5.

And, also can use polymer charge to carry material separately.Carry material as polymer charge, can use poly-N-vinyl carbazole, polysilane etc. to have the well known materials of charge-transporting.Especially, the spy opens flat 8-176293 communique, the spy opens polyesters polymer charge disclosed in the flat 8-208820 communique and carries material to have higher charge-transporting, so preferred especially.Can only use polymer charge to carry material, can also mix the back film forming with above-mentioned binder resin as charge transport layer.

The thickness of the charge transport layer that uses among the present invention is generally 5 μ m～50 μ m, is preferably 10 μ m～30 μ m.As coating process, can use knife coating, line rod rubbing method, spraying process, dip coating, pearl to be coated with method commonly used such as method, airblade coating method, curtain coating method.As the solvent that is used to be provided with charge transport layer, can use following conventional solvent: benzene,toluene,xylene, chlorobenzene etc. are aromatic hydrocarbon based; Ketones such as acetone, 2-butanone; Halogenation aliphatic hydrocarbons such as methylene chloride, chloroform, vinyl chloride; The ethers of ring-type such as tetrahydrofuran, ether or straight chain shape etc., these solvents can use or mix two or more uses separately.In addition, in order to prevent that photoreceptor from because of the ozone that produces in the duplicating machine or oxidizing gas deterioration or because of the light and heat deterioration, can add adjuvants such as antioxidant, light stabilizer, thermal stabilizer in photographic layer.For example, can enumerate sterically hindered phenol, bulky amine, p-phenylenediamine (PPD), aromatic yl paraffin, quinhydrones, spiral shell benzodihydropyran, spiral shell indone and their derivant as antioxidant; Organosulfur compound, organic phosphorus compound etc.As the example of light stabilizer, can enumerate the derivant of benzophenone, benzotriazole, dithiocarbamate, tetramethyl piperidine etc.And,, can add at least a electronics material that is subjected in order to improve sensitivity, reduce rest potential, to reduce fatigue when using repeatedly etc.Be subjected to the electronics material as what can be used for photoreceptor of the present invention, can enumerate for example succinic anhydride, maleic anhydride, dibromomaleic acid acid anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetracyanoethylene, four cyanogen quinone bismethanes, o-dinitrobenzene, meta-dinitro-benzent, chloranil, dinitroanthraquinone, trinitro-fluorenes, picric acid, o-nitrobenzoic acid, paranitrobenzoic acid, phthalic acid etc., and the compound shown in the general formula described later (I).Wherein, preferred especially fluorenes class, quinones and have Cl, CN, NO ₂Benzene derivative Deng electron-attracting substituent.

Following opposed face protective seam describes.

For making superficial layer have abrasion performance and scratch resistance, the high strength superficial layer can be set.As this high strength superficial layer, can use and in adhesive resin, be dispersed with the layer that electrically conductive microparticle forms; The layer that in common charge transport layer material, is dispersed with lubricity particulate such as fluororesin, acryl resin and constitutes; The layer that hard paint such as silicon, acrylic acid forms.Consider aspects such as intensity, electrical specification, image quality maintenance, the material that preferably has cross-linked structure more preferably contains the material of charge-transporting material.Can use various materials as the material that forms cross-linked structure, preferred phenolics, urethane resin, silicone resin etc. aspect characteristic especially preferably contain the protective seam of siloxane resin.Wherein, consider intensity and excellent in stability, the protective seam that has derived from the structure of compound shown in following general formula (I) or the general formula (II) is particularly preferred.

F-[D-Si(R ²) _(3-a)Q _a] _b (I)

In the general formula (I), F represents the organic group derived from the compound with cavity conveying ability, and D represents flexible subunit, R ²The aryl of expression hydrogen, alkyl, replacement or non-replacement, Q represents hydrolization group, and a represents 1～3 integer, and b represents 1～4 integer.

F-((X) _nR ₁-ZH) _m (II)

In the general formula (II), F represents the organic group derived from the compound with cavity conveying ability, R ₁The expression alkylidene, Z represents oxygen atom, sulphur atom or NH, CO ₂, COOH, m represents 1～4 integer.X represents oxygen or sulphur, and n represents 0 or 1.

And,, can enumerate the compound that organic group F has adopted structure shown in the following general formula (III) as the preferred example of compound shown in general formula (I), (II).

In the formula (III), Ar ₁～Ar ₄The aryl of expression replacement independently of one another or non-replacement, Ar ₅The aryl or the arlydene of expression replacement or non-replacement, and Ar ₁～Ar ₅In 2～4 groups have with-D-Si (R ²) _(3-a)Q _aThe associative key of expression.D, R ², D, R in a, Q and the above-mentioned general formula (I) ², a, Q be identical.And k represents 0～1 integer.

Ar in the compound (III) ₁～Ar ₄The aryl of expression replacement independently of one another or non-replacement, specifically, the group shown in the structure group 1 that is preferably as follows.

-Ar-(Z’)s-Ar-Xm

Ar preferably selects from following structure group 2

Structure group 2

Z ' preferably selects from following structure group 3.

-(CH ₂)q--(CH ₂CH ₂O) _r-

Structure group 3

Above-mentioned various in, R ⁶Be selected from hydrogen, carbon number and be 1～4 alkyl, be that 1～4 alkyl or carbon number are that phenyl, non-substituted-phenyl or carbon number that 1～4 alkoxy replaces are 7～10 aralkyl with carbon number.R ⁷～R ¹³Be selected from hydrogen, carbon number and be 1～4 alkyl, carbon number and be 1～4 alkoxy, be that phenyl, non-substituted-phenyl, carbon number that 1～4 alkoxy replaces are 7～10 aralkyl or halogen with carbon number.M and s represent 0 or 1, and q and r represent 1～10 integer, the integer of t and t ' expression 1～3.Herein, X represent to have illustrated in the definition of general formula (I) with-D-Si (R ²) _(3-a)Q _aThe substituting group of expression.W is preferably the group shown in the following structure group 4.

-CH ₂- -C(CH ₃) ₂--O- -S- -C(CF ₃) ₂-

Structure group 4

-Si(CH ₃) ₂-

Herein, the integer of s ' expression 0～3.

As Ar in the general formula (III) ₅Concrete structure, when k=0, can enumerate above-mentioned Ar ₁～Ar ₄In the structure of m=1, when k=1, can enumerate above-mentioned Ar ₁～Ar ₄In the structure of m=0.

As the concrete example of the compound of general formula (I) expression, can enumerate compound shown in following table 1～table 7 (No.III-1～III-61), but the present invention is not subjected to any restriction of these compounds.In addition, the details when table 1～table 7 has been represented with " F " part in general formula (III) the expression general formula (I) is incorporated into the " [D-Si (R in the general formula (I) shown in " S " hurdle in " S " expression table on the phenyl ring in the table ²) _(3-a)Q _a] _b" part.

[table 1]

[table 2]

[table 3]

[table 4]

[table 5]

[table 6]

[table 7]

As the concrete example of general formula (II), can enumerate compound as follows, but the present invention is not subjected to any restriction of these compounds.

And,, also can in protective seam, add the compound shown in the following general formula (VI) in order to control various rerum naturas such as intensity and film resistance.

Si(R ²) _(4-c)Q _c (VI)

In the general formula (VI), R ²The aryl of expression hydrogen, alkyl, replacement or non-replacement, Q represents hydrolization group, c represents 1～4 integer.

Concrete example as compound shown in the general formula (VI) can be enumerated following silane coupling agent.Can enumerate four functionality alkoxy silanes (c=4) such as tetramethoxy-silicane, tetraethoxysilane; Methyltrimethoxy silane, methyl triethoxysilane, ethyl trimethoxy silane, methyl trimethoxy oxygen base oxethyl silane, vinyltrimethoxy silane, vinyltriethoxysilane, phenyltrimethoxysila,e, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-An Jibingjisanyiyangjiguiwan, the gamma-amino propyl trimethoxy silicane, gamma-amino propyl group methyl dimethoxysilane, N-β (amino-ethyl) γ-An Jibingjisanyiyangjiguiwan, (13 fluoro-1,1,2,2-tetrahydrochysene octyl group) triethoxysilane, (3,3, the 3-trifluoro propyl) trimethoxy silane, 3-(seven fluorine isopropoxies) propyl-triethoxysilicane, 1H, 1H, 2H, 2H-perfluoroalkyl triethoxysilane, 1H, 1H, 2H, 2H-perfluor decyl triethoxysilane, 1H, 1H, 2H, trifunctional alkoxy silanes (c=3) such as 2H-perfluoro capryl triethoxysilane; Two functionality alkoxy silanes (c=2) such as dimethyldimethoxysil,ne, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxy silane; One functionality alkoxy silane (c=1) such as trimethyl methoxy silane etc.In order to improve film strength, the alkoxy silane of preferred trifunctional and four functionalities is in order to improve flexibility and film forming, the alkoxy silane of preferred two functionalities and a functionality.

And, can use the hard paint of mainly making of silicon class by these coupling agents.As commercially available hard paint, can use KP-85, X-40-9740, the X-40-2239 of Silicone society of SHIN-ETSU HANTOTAI system, and Toray Dow Corning society makes AY42-440, AY42-441, AY49-208 etc.

And,, preferably use the compound shown in the general formula (IV) with the silicon atom more than 2 in order to improve intensity.

B-(Si(R ²) _(3-a)Q _a) ₂ (IV)

In the general formula (IV), B represents the organic group of divalent, R ²The aryl of expression hydrogen, alkyl, replacement or non-replacement, Q represents hydrolization group, a represents 1～3 integer.

Specifically, can enumerate material as shown in table 8 below, but the invention is not restricted to this.

[table 8]

Further, for controlling diaphragm characteristic, prolongation liquid life-span, can also add the resin that dissolves in alcohols, the ketones solvent.As this resin, the part that can enumerate polyvinyl butyral resin, vinyl-formal resin, butyral is by the polyvinyl acetal resins such as polyvinyl acetal resin of the part acetalation of modifications such as formal or acetyl acetal (for example S-LEC B, the S-LEC K etc. of the manufacturing of ponding chemistry society); Polyamide; Celluosic resin; Phenolics etc.Especially, consider electrical specification, preferably polyethylene alcohol acetate resin.And,, can add various resins in order to improve discharge gas patience, physical strength, scratch resistance, particle dispersion, control viscosity, reduce moment of torsion, control abrasion value, to prolong useful life etc.Especially, when using siloxane resin, the preferred resin that is dissolved in the alcohol that adds.As the resin that dissolves in the alcohols solvent, the part that can enumerate polyvinyl butyral resin, vinyl-formal resin, butyral is by the polyvinyl acetal resins such as polyvinyl acetal resin of the part acetalation of modifications such as formal or acetyl acetal (for example S-LEC B, the S-LEC K etc. of the manufacturing of ponding chemistry society); Polyamide; Celluosic resin; Phenolics etc.Especially, consider electrical specification, preferably polyethylene alcohol acetate resin.The molecular weight of above-mentioned resin is preferably 2000～100000, and more preferably 5000～50000.If molecular weight is less than 2000, the effect that can't obtain to expect then.If molecular weight is greater than 100000, then solubleness reduces, and causes addition limited, occurs the bad reason of film forming when becoming coating.Addition is preferably 1%～40%, and more preferably 1%～30%, most preferably be 5%～20%.Addition is less than at 1% o'clock, is difficult to the effect that obtains to expect, and if addition greater than 40%, then may occur image blurring under hot and humid condition easily.And these resins both can be used alone, but also also mix together.

In order to prolong useful life, controlling diaphragm characteristic, can add the ring compound with constitutional repeating unit shown in the following general formula (V) or the derivant of this ring compound.

In the general formula (V), A ¹, A ²The organic group of representing monovalence independently of one another.

As ring compound, can enumerate commercially available annular siloxane with constitutional repeating unit shown in the general formula (V).Specifically, can enumerate following annular siloxane etc.: ring-type dimethyl cyclosiloxane classes such as hexamethyl cyclotrisiloxane, octamethylcy-clotetrasiloxane, decamethylcyclopentaandoxane, ten diformazan basic rings, six siloxane; 1,3,5-trimethyl-1,3,5-triphenyl cyclotrisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl cyclotetrasiloxane, 1,3,5,7,9-pentamethyl-1,3,5,7, ring-type methyl phenyl ring siloxane classes such as 9-pentaphene basic ring five siloxane; Ring-type phenyl ring siloxane classes such as hexaphenyl cyclotrisiloxane; Fluorine-containing cyclosiloxane classes such as 3-(3,3, the 3-trifluoro propyl) methyl cyclotrisiloxane; Methyl hydrogen siloxane potpourri, pentamethyl D5, phenyl hydrogen cyclosiloxane etc. contain the cyclosiloxane of hydrogen silicyl; Five vinyl pentamethyl D5s etc. contain the cyclosiloxane class of vinyl etc.These cyclic siloxane compounds both can use separately, also can mix the back and use.

Further, in order to improve the anti-pollution thing tack and the lubricity on Electrophtography photosensor surface, can add various particulates.These particulates both can use separately, also can share.As an example of particulate, can enumerate the particulate that contains silicon.The particulate that contains silicon is meant the particulate that contains silicon in constituting element, can enumerate colloidal silica and silicone particulate etc. particularly.The mean grain size that can be used as the colloidal silica of the particulate that contains silicon is 1nm～100nm, be preferably 10nm～30nm, can select to be scattered in the colloidal silica in the organic solvents such as the aqueous dispersions of acidity or alkalescence or alcohol, ketone, ester, generally use commercially available product.Solid content for colloidal silica in the outmost surface layer is not particularly limited, consider the aspect of film forming, electrical specification and intensity, can use colloidal silica so that the scope that its content in whole solid contents of outmost surface layer is 0.1 quality %～50 quality %, this content is preferably 0.1 quality %～30 quality %.

The silicone particulate that uses as the particulate that contains silicon generally can use commercially available product, and this silicone particulate can be by selecting in the following material: being shaped as spherical, mean grain size is 1nm～500nm (preferred 10nm～silicone resin particle 100nm), silicone rubber particle, crystal silicon ketone surface-treated silicon oxide particle.The silicone particulate is the chemical inertness particle, is the small size particle of the excellent dispersion in resin, and it is lower to be used to obtain the required content of abundant characteristic, can improve the surface configuration of Electrophtography photosensor and can not hinder cross-linking reaction.That is, the silicone particulate can improve the lubricity and the water proofing property on Electrophtography photosensor surface under the state in being distributed in firm cross-linked structure equably, and long-term use also can keep good abrasion performance and anti-pollution thing tack.In the Electrophtography photosensor of the present invention, the content of silicone particulate accounts for the 0.1 quality %～30 quality % in all solid contents of outmost surface layer in the outmost surface layer, preferably accounts for the scope of 0.5 quality %～10 quality %.

And,, can enumerate fluorine based fine particles such as tetrafluoroethene, trifluoro-ethylene, hexafluoropropylene, fluorothene, vinylidene fluoride as other particulate; Containing above-mentioned fluororesin and have the particulate of the resin that the monomer copolymerization of hydroxyl obtains shown in " the 8th polymeric material forum lecture give original text collection (publication source: macromolecule association, imp d: 1999) " 89 pages; ZnO-Al ₂O ₃, SnO ₂-Sb ₂O ₃, In ₂O ₃-SnO ₂, ZnO-TiO ₂, ZnO-TiO ₂, MgO-Al ₂O ₃, FeO-TiO ₂, TiO ₂, SnO ₂, In ₂O ₃, semiconduction metal oxides such as ZnO, MgO.And,, can add oils such as silicone oil for same purpose.As silicone oil, can enumerate for example silicone oil such as dimethyl polysiloxane, diphenyl polysiloxane, phenyl methyl siloxane; Amino modified polysiloxane, epoxy radicals modified polyorganosiloxane, carboxy-modified polysiloxane, methyl alcohol modified polyorganosiloxane, methacrylic acid modified polyorganosiloxane, sulfhydryl modified polysiloxane, phenol-modified polysiloxane isoreactivity silicone oil etc.

The superficial layer exposure of above-mentioned particulate is preferably below 40%.If surpass above-mentioned scope, then the influence of particle monomer becomes big, easily owing to image disappearance (drawing stream れ) takes place low resistanceization.The more preferably scope of superficial layer exposure is below 30%, thus, the particle parts that can more effectively be cleaned that are exposed to the surface refresh, and long-term use also can keep following effect: suppress toner components in the photosensitive surface film forming, remove discharge product, by reducing the abrasion that moment of torsion reduces cleaning member.

And, can also use adjuvants such as plastifier, surface modifier, antioxidant, light deterioration preventing agent.As plastifier, can enumerate for example biphenyl, chlorinated biphenyl, terphenyl, dibutyl phthalate, diglycol phthalate, dioctyl phthalate, triphenyl phosphate, methylnaphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, various fluorhydrocarbons etc.Can in resin bed of the present invention, add the antioxidant with sterically hindered phenol, bulky amine, thioether or phosphite ester part-structure, the potential stability-image quality in the time of can effectively improving environmental change thus.Can enumerate following compound as antioxidant, for example can enumerate " Sumilizer BHT-R " as hindered phenolic antioxidants, " Sumilizer MDP-S ", " Sumilizer BBM-S ", " SumilizerWX-R ", " Sumilizer NW ", " Sumilizer BP-76 ", " Sumilizer BP-101 ", " Sumilizer GA-80 ", " Sumilizer GM ", " Sumilizer GS " (above make for Sumitomo Chemical Co), " IRGANOX1010 ", " IRGANOX1035 ", " IRGANOX1076 ", " IRGANOX1098 ", " IRGANOX1135 ", " IRGANOX1141 ", " IRGANOX1222 ", " IRGANOX1330 ", " IRGANOX1425WL ", " IRGANOX1520L ", " IRGANOX245 ", " IRGANOX259 ", " IRGANOX3114 ", " IRGANOX3790 ", " IRGANOX5057 ", " IRGANOX565 " (above is that Ciba Specialty Chemicals Co., Ltd. makes), " ADEKASTAB AO-20 ", " ADEKASTAB AO-30 ", " ADEKASTABAO-40 ", " ADEKASTAB AO-50 ", " ADEKASTAB AO-60 ", " ADEKASTABAO-70 ", " ADEKASTAB AO-80 ", " ADEKASTAB AO-330 " (above make for Asahi Denka Co., Ltd.).Can enumerate " SANOL LS2626 " as the steric hindrance amine antioxidants, " SANOL LS765 ", " SANOL LS770 ", " SANOL LS744 ", " TINUBIN 144 ", " TINUBIN 622LD ", " MARK LA57 ", " MARK LA67 ", " MARK LA62 ", " MARK LA68 ", " MARK LA63 ", " SUMILIZER TPS ", can enumerate " SUMILIZER TP-D " as thioether class antioxidant, can enumerate " MARK 2112 " as phosphorous acid lipid antioxidant, " MARK PEP8 ", " MARK PEP24G ", " MARKPEP36 ", " MARK 329K ", " MARK HP10 ".Wherein preferred especially sterically hindered phenol and steric hindrance amine antioxidants.These antioxidants can also be further can carry out modification with the substituting group that the material that forms cross linking membrane carry out cross-linking reaction with for example alkoxysilyl etc.

Preferably in coating fluid, add catalyzer or when making coating fluid, use catalyzer.As employed catalyzer, can use mineral acids such as hydrochloric acid, acetate, phosphoric acid, sulfuric acid; Organic acids such as formic acid, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid; Base catalysts such as potassium hydroxide, NaOH, calcium hydroxide, ammonia, triethylamine; And the solid catalyst that is insoluble in starting compound, resultant of reaction and the solvent etc. as follows.Described solid catalyst can be enumerated AMBERLITE 15, AMBERLITE 200C, AMBERLIST15E (above is that Rohm and Haas society makes); DOW X MWC-1-H, DOW X 88, DOW X HCR-W2 (above is that Dow Chemical Co., Ltd. makes); Levatit SPC-108, Levatit SPC-118 (above make for Bayer Corporation); DIAION RCP-150H (Mitsubishi chemical Co., Ltd's manufacturing); SUMIKA ION KC-470, DUOLITE C26-C, DUOLITEC-433, DUOLITE-464 (above is that Sumitomo Chemical society makes); NAPHION-H Zeo-karbs such as (Dupont Kabushiki Kaisha's manufacturings); AMBERLITE IRA-400, AMBERLITEIRA-45 anion exchange resins such as (above are that Rohm and Haas Co., Ltd. makes); Zr (O ₃PCH ₂CH ₂SO ₃H) ₂, Th (O ₃PCH ₂CH ₂COOH) ₂Deng the inoganic solids that is combined with the group that contains the proton acidic group on the surface; Have sulfonic polysiloxane etc. and contain the polysiloxane of proton acidic group; Heteropoly acids such as cobalt wolframic acid, phosphomolybdic acid; Isopolyacids such as niobic acid, tantalic acid, molybdic acid; Single metal oxides such as silica gel, aluminium oxide, chromium oxide, zirconia, CaO, MgO; Composite metal oxides such as silica-alumina, monox-magnesium oxide, monox-zirconia, zeolites; Clay minerals such as acid sticking scholar, activated clay, smectite, porcelain earth; LiSO ₄, MgSO ₄Deng metal sulfate; Metal phosphate such as basic zirconium phosphate, lanthanum orthophosphate; LiNO ₃, Mn (NO ₃) ₂Deng metal nitrate; Make on the surface of the solid that obtains of aminopropyltriethoxywerene werene and silica gel reaction etc. and be combined with the inoganic solids that contains amino group; Amino modified silicone resins etc. contain amino polysiloxane etc.And when making coating fluid, the preferred use is insoluble to the solid catalyst of exhibiting optical function compound, resultant of reaction, water, solvent etc., because have the trend that improves coating fluid stability like this.Be not particularly limited for above-mentioned solid catalyst, as long as catalyst component is insoluble to the compound shown in general formula I, II, III, the IV, other adjuvants, water, solvent etc.Use amount for these solid catalysts is not particularly limited, and with respect to the total amount of the compound with hydrolization group of 100 mass parts, this use amount is preferably 0.1 mass parts～100 mass parts.

And, as mentioned above,, thereby can after reaction, these solid catalysts be removed simply according to conventional method because these solid catalysts are insoluble to starting compound, resultant of reaction, solvent etc.Temperature of reaction and reaction time can suitably be selected according to the kind and the use amount of starting compound and solid catalyst, but temperature of reaction is generally 0 ℃～100 ℃, preferred 10 ℃～70 ℃, more preferably 15 ℃～50 ℃, the reaction time is preferably 10 minutes～and 100 hours.If the reaction time surpasses above-mentioned higher limit, then there is the trend that causes gelation easily.

In the step of making coating fluid, use under the situation of above-mentioned catalyzer,, preferably further share the catalyzer that is dissolved in starting compound, resultant of reaction, the solvent etc. in order to improve intensity, fluid preservation stability.As this catalyzer, except above-mentioned catalyzer, can also use organo-aluminum compounds such as three aluminium ethylates, aluminum isopropylate, three aluminium secondary butylates, Mono-sec-butoxyaluminium diisopropylate, diisopropoxy (oacetic acid) aluminium, three (oacetic acid) aluminium, two (oacetic acid) single (diacetone) aluminium, aluminium tris(acetylacetonate), diisopropoxy (diacetone) aluminium, isopropoxy two (diacetone) aluminium, three (trifluoroacetylacetone (TFA)) aluminium, three (hexafluoroacetylacetone) aluminium.

Except organo-aluminum compound, can also use organo-tin compounds such as dibutyl tin dilaurate, two sad two fourth tin, oxalic acid two fourth tin; Organic titanic compounds such as four (diacetone) titanium, two (butoxy) two (diacetone) titanium, two (isopropoxies) two (diacetone) titanium; Zirconium compoundss such as four (diacetone) zirconium, two (butoxy) two (diacetone) zirconium, two (isopropoxies) two (diacetone) zirconium; Or the like.From the viewpoint of security, low cost, useful life length, preferably use organo-aluminum compound, preferred especially aluminium chelate compound.Use amount to these catalyzer is not particularly limited, and with respect to the total amount of the compound with hydrolization group of 100 mass parts, this use amount is preferably 0.1 mass parts～20 mass parts, preferred especially 0.3 mass parts～10 mass parts.

Use in the present invention under the situation of organometallics as catalyzer, consider useful life and curing efficiency, preferably add multidentate ligand simultaneously.As this multidentate ligand, can enumerate part as follows and derived ligand thereof, but the present invention is not limited to this.

The instantiation of multidentate ligand can be enumerated, beta-diketon classes such as diacetone, trifluoroacetylacetone (TFA), hexafluoroacetylacetone, two pivaloyl methyl acetones; Acetoacetic ester such as methyl acetoacetate, ethyl acetoacetate; The bidentate ligand of bipyridine and derivant thereof, glycocoll and derivant thereof, ethylenediamine and derivant thereof, oxine and derivant thereof, salicylide and derivant thereof, catechol and derivant thereof, 2-oxygen azo-compound etc.; Tridentate ligands such as diethyl triamine and derivant thereof, nitrilotriacetic acid(NTA) and derivant thereof; Sexadentate ligands such as ethylenediamine tetraacetic acid (EDTA) and derivant thereof; Or the like.In addition, except organic class part as described above, can also enumerate mineral-type parts such as pyrophosphoric acid, triphosphoric acid.As multidentate ligand, preferred especially bidentate ligand as concrete example, except above-mentioned bidentate ligand, can also be enumerated the bidentate ligand shown in the following general formula (7).Bidentate ligand shown in the wherein more preferably following general formula (7) is preferably as follows R in the general formula (7) especially ⁵And R ⁶Identical bidentate ligand.By making R ⁵And R ⁶Identical, can strengthen near the coordination ability of the part the room temperature, so that the smears is more stable.

In the general formula (7), R ⁵, R ⁶Represent that independently of one another carbon number is that 1～10 alkyl, fluorinated alkyl, carbon number are 1～10 alkoxy.

The combined amount of multidentate ligand can be set arbitrarily, and with respect to 1 mole of employed organometallics, preferred described combined amount is more than 0.01 mole, more preferably more than 0.1 mole, more preferably more than 1 mole.Though siliceous smears of the present invention also can be made under solvent-free condition, also can use all kinds of solvents manufacturing as required, described solvent for example is alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols; Ketone such as acetone, MEK; Tetrahydrofuran; Ethers such as diethyl ether, diox; And other all kinds of solvents.As this solvent, preferred boiling point can mix the back arbitrarily and use smaller or equal to 100 ℃ solvent.Though the amount of solvent can be set arbitrarily, if very few, then organo-silicon compound are separated out easily, so with respect to the organo-silicon compound of 1 mass parts, employed solvent is the solvent of 0.5 mass parts～30 mass parts, is preferably 1 mass parts～20 mass parts.

Temperature of reaction and reaction time when coating fluid is solidified are not particularly limited, consider the physical strength and the chemical stability of the silicones of gained, temperature of reaction is preferably more than 60 ℃, and more preferably 80 ℃～200 ℃, the reaction time is preferably 10 minutes～and 5 hours.To remain in the high humility state by the organic layer that the curing coating fluid obtains, can realize the stabilization of organic layer characteristic so effectively.Further, can use hexamethyldisilazane or trimethyl chlorosilane etc. that organic layer is carried out surface treatment according to purposes, so that its hydrophobization.

The resin bed that has charge-transporting and have cross-linked structure not only has excellent physical strength, and its optical characteristics is also very abundant.Therefore, this resin bed directly can be used as the charge transport layer of laminated-type photoreceptor.At this moment, can use usual way, for example knife coating, line rod rubbing method, spraying process, dip coating, pearl are coated with method, airblade coating method, curtain coating method etc.In the time of can not obtaining required thickness by 1 coating, can obtain required thickness by repeatedly being coated with repeatedly.When repeatedly repeating to be coated with, both can each time the coating in carry out heat treated, also can repeatedly repeat the coating after heat.

Photographic layer with single-layer type structure can form by comprising above-mentioned electric charge generation material and binder resin.As binder resin, can use and the binder resin identical materials that is used for above-mentioned charge generating layer and charge transport layer.The content of the electric charge generation material in the single-layer type photographic layer is about 10 quality %～85 quality %, is preferably 20 quality %～50 quality %.In order to improve photoelectric characteristic etc., can in the single-layer type photographic layer, add charge transport material or polymer charge transportation of substances.This addition is preferably 5 quality %～50 quality %.And, also can add the compound shown in the general formula (I).Solvent that is used to be coated with and coating process can use solvent same as described above and method.The thickness of filming is preferably about 5 μ m～50 μ m, more preferably 10 μ m～40 μ m.

Embodiment

Describe the present invention in detail below in conjunction with embodiment, but these embodiment to the present invention without any restriction.Unless stated otherwise, " part " and " % " among the following embodiment is represented " mass parts " and " quality % " respectively

The making of＜developer for static charge image development 〉

The preparation of-non-crystalline polyester resin (1)-non-crystalline resin particle dispersion (1a)-

With 35 molar part polyoxyethylene (2,0)-2, two (4-hydroxy phenyl) propane of 2-, 65 molar part polyoxypropylenes (2,2)-2, two (4-hydroxy phenyl) propane of 2-, 80 molar part terephthalic acid (TPA)s, the positive dodecenyl succinic succinic acid of 15 molar part, 10 molar part trihemellitic acids and be that the Dibutyltin oxide of 0.05 molar part is packed in the double-neck flask of heat drying with respect to these sour compositions (terephthalic acid (TPA), positive dodecenyl succinic succinic acid and trihemellitic acid), nitrogen is directed in this container keeping inert atmosphere gas, and temperature in the rising container.Then, in 150 ℃～230 ℃ carry out about 12 hours copolycondensation after, reduce pressure gradually in 210 ℃～250 ℃, thereby synthesized non-crystalline polyester resin (1).

Utilize GPC (gel permeation chromatography) determining molecular weight (polystyrene conversion), the weight-average molecular weight (Mw) of the non-crystalline polyester resin of gained (1) is 15000 as a result, and number-average molecular weight (Mn) is 6800.

In addition, with following condition determining molecular weight.Use " HLC-8120GPC, SC-8020 (TosohCo. manufacturings) " to carry out GPC, as chromatographic column, use THF (tetrahydrofuran) is as eluent to adopt two " TSK gel, Super HM-H (Tosoh Co. manufacturing, internal diameter 6.0mm * 15cm) ".As test condition, the concentration of sample is 0.5%, and flow velocity is 0.6ml/min, and the injection rate IR of sample is 10 μ l, and measuring temperature is 40 ℃, and uses the IR detecting device to test.In addition, typical curve is made by 10 samples of " the polystyrene standard sample TSK standard " of Tosoh Co. manufacturing: " A-500 ", " F-1 ", " F-10 ", " F-80 ", " F-380 ", " A-2500 ", " F-4 ", " F-40 ", " F-128 " and " F-700 ".

In addition, use differential scanning calorimeter (DSC) when non-crystalline polyester resin is measured, do not demonstrate clear and definite peak and observe the phasic Chang of caloric receptivity.The glass transition temperature that is obtained by the intermediate point of phasic Chang of caloric receptivity is 62 ℃.

3000 parts of above-mentioned non-crystalline polyester resin that obtain (1), 10000 parts of ion exchange waters and 90 parts of surfactant neopelexes are put into high temperature-high-pressure emulsification device (CAVITRON CD1010, slit 0.4mm) in the emulsion tank, is heated to 130 ℃ and makes its fusion.Then, the revolution with 10000 disperseed 30 minutes under 110 ℃ of flows at 3L/m.Make afterwards its by cooling tank reclaiming non-crystalline resin particle dispersion (high temperature-high-pressure emulsification device (CAVITRON CD1010, slit 0.4mm)), thereby obtain non-crystalline resin particle dispersion (1a).

(Shimadzu Scisakusho Ltd makes to use the laser diffraction granularity analyzer, SALD2000A) contained particle in the above-mentioned non-crystalline resin particle dispersion (1a) that obtains is measured, the volume average particle size D50v of this particle is 0.3 μ m as a result, and standard deviation is 1.2.

The preparation of-non-crystalline polyester resin (2)-non-crystalline resin particle dispersion (2a)-

In the process of making non-crystalline polyester resin (1), the addition of positive dodecenyl succinic succinic acid is changed into 30 molar part, in addition, make non-crystalline polyester resin (2) with the condition identical, and then make non-crystalline resin particle dispersion (2a) with the condition identical with non-crystalline resin particle dispersion (1a) with non-crystalline resin (1).

The weight-average molecular weight (Mw) of resulting non-crystalline polyester resin (2) is 12000, and number-average molecular weight (Mn) is 6000, and glass transition temperature is 56 ℃.The volume average particle size D50v of the particle that contains in the resulting particulate resin dispersion is 0.35 μ m, and standard deviation is 1.4.

The preparation of-crystalline polyester resin (3)-crystalline resin particle dispersion (3a)-

With 293 mass parts 1,4-butylene glycol (making with the pure medicine of light Co., Ltd.), 750 mass parts dodecanedicarboxylic acids (making with the pure medicine of light Co., Ltd.) and 0.3 mass parts are packed into as the Dibutyltin oxide of catalyzer in the three-neck flask of heat drying.Then, be inert atmosphere gas with nitrogen with the air displacement in the container by decompression operation, and stirred 2 hours in 180 ℃ by mechanical raking.Afterwards, under reduced pressure slowly be warming up to 230 ℃ and stirred 5 hours, carry out air cooling when becoming the thickness state, stop reaction, thus synthetic crystallization vibrin (3).

Utilize gel permeation chromatography (GPC) determining molecular weight (polystyrene conversion), the weight-average molecular weight of the non-crystalline polyester resin of gained (3) is 18000.

In addition, when using differential scanning calorimeter (DSC) to measure the fusing point (Tm) of crystalline polyester resin (3), demonstrate clear and definite peak, and summit temperature is 70 ℃ by the said determination method.

And then, except using crystallinity petchem (3), utilize the condition identical to make crystallinity petchem particle dispersion (3a) with particulate resin dispersion (1a).The volume average particle size D50v of the particle that contains in the resulting dispersion liquid is 0.25 μ m, and standard deviation is 1.3.

The preparation of-colorant dispersion (1)-

(Dainichiseika Color Chem makes phthalocyanine color, PVFASTBLUE): 25 parts

Anionic surfactant (Di-ichi Kogyo Seiyaku Co., Ltd. makes, Neogen RK): 2 parts

Ion exchange water: 125 parts

Behind mixing and the dissolving mentioned component, (IKA Co. makes, and ULTRATURRAX) carries out dispersion treatment, obtains colorant dispersion (1) to use homogenizer.

The preparation of-anti-sticking agent particle dispersion liquid (1)-

Pentaerythrite docosanoic acid four ester type waxes: 100 parts

Anionic surfactant (NOF Corp makes, NEWLEX R): 2 parts

Ion exchange water: 300 parts

Behind mixing and the dissolving mentioned component, (IKA Co. makes, and after ULTRATURRAX) disperseing, working pressure discharge type homogenizer carries out dispersion treatment, obtains anti-sticking agent particle dispersion liquid (1) to use homogenizer.

(manufacturing of developer (1))

The female particle (1) of-making toner-

Non-crystalline resin particle dispersion (1a): 145 parts

Crystalline polyester resin particle dispersion (3a): 30 parts

Colorant dispersion (1): 42 parts

Anti-sticking agent particle dispersion liquid (1): 36 parts

Amphoteric surfactant (Fine Chemicals Co., Ltd. system is ground in the river for dodecanamide propyl dimethyl oxidation amine, ソ Off ゾ リ Application LAO): 1 part

Aluminium sulphate (making): 0.5 part with the pure medicine of light Co., Ltd.

Ion exchange water: 300 parts

Mentioned component is added at the bottom of the into stainless steel rounding in the flask, and adjusts pH and be 2.7, use homogenizer (IKA Co. makes, ULTRA TURRAX T50) to disperse after, be heated to 45 ℃ while stirring in the oil bath that is used for heating.48 ℃ keep 120 minutes after, observe with optical microscope, confirm and formed the agglutinating particle that mean grain size is about 5.6 μ m.

Further in 48 ℃ keep carrying out heated and stirred in 30 minutes after, observe with optical microscope, confirm and formed the agglutinating particle that mean grain size is about 6.5 μ m.The pH of this agglutinating particle dispersion liquid is 3.2.

Then, slowly add the sodium hydrate aqueous solution of 1N, pH is adjusted to 8.0 after, be heated to 90 ℃ under continue stirring, kept this state 3 hours.Afterwards, the filtering reaction product after fully washing with ion exchange water, uses vacuum drier to carry out drying, thereby obtains the female particle (1) of toner.

Utilize the method stated, the equal average particle size distribution index of volume average particle size D50v, body GSDv, number average particle size distribution index GSDp, the average circularity of the toner-particle that obtains are measured.The result is in table 9 illustrate.Further, 70 of following mensuration ℃ storage modulus G ' (70) and ratio G ' (70)/G ' (90) of 90 ℃ storage modulus G ' (90) are also in (following toner too) table 9 illustrate.

Further, obtain the tangent loss (storage modulus G ') of toner, measure peak value and peak temperature by following Measurement of Dynamic Viscoelasticity.

The tangent loss is obtained by the dynamic viscoelastic that utilizes the sine wave oscillations method to measure.Use ARES determinator (manufacturing of Rheometric Scientific Co., Ltd.) when measuring dynamic viscoelastic.When measuring dynamic viscoelastic, be installed on the parallel discs of diameter 8mm after toner made tablet, make normal force (normal force) be 0 after, under the vibration frequency of 1 radian per second, apply sine wave oscillations.Mensuration lasts till 100 ℃ since 20 ℃, the tangent loss when measuring 70 ℃ and 90 ℃.

Minute is spaced apart 30 seconds, and intensification is 1 ℃/minute.Before measuring, in 20 ℃ to 100 ℃ scope, 10 ℃ of stress dependences of confirming dependent variable are obtained the dependent variable scope when the stress and strain amount is linear at each temperature at interval.In the mensuration, under each measures temperature, keep dependent variable, under all temperature, control, ask the calculation storage modulus by these measurement results so that the stress and strain amount is linear in 0.01%～0.5% scope.

Use Henschel mixer, the above-mentioned toner-particle with respect to 100 parts mixes and adds 1 part of fumed silica (Japanese AEROSIL Co., Ltd. makes, and R972), obtains electrostatic image developing toner (1).

Further, (Powder tech Co., Ltd. makes with 100 parts of ferrite particles, mean grain size is 50 μ m), (Mitsubishi Rayon Co., Ltd makes for 2.5 parts of methacrylate resins, weight-average molecular weight is 95000) and 500 parts of toluene be added to together in the adding pressure type kneader, mixed 15 minutes in stirring at normal temperature.Then, on one side the decompression mixing, be warming up to 70 ℃ on one side, distill out toluene.Cool off afterwards, the use sieve aperture is that the sieve of 105 μ m carries out classification, makes ferrite carrier (resin-coated carrier) thus.This ferrite carrier is mixed mutually with above-mentioned electrostatic image developing toner (1), and producing toner concentration is two constituent class developers (1) of 7 quality %.

(manufacturing of developer (2))

With amphoteric surfactant (dodecanamide propyl dimethyl oxidation amine, ソ Off ゾ リ Application LAO, Fine Chemicals Co., Ltd. system is ground in the river) change alkyl betaine (ァ Application ヒ ト one Le 20BS into, Kao Corp makes), (1a) changes (2a) into the non-crystalline resin dispersion liquid, changes the amount of crystalline resin dispersion liquid (3a) into 20 parts, in addition, make with the condition identical, obtain the female particle (2) of toner with the female particle of toner (1).

The volume average particle size D50v of the female particle of resulting toner is 6.3 μ m.Then, with developer (1) similarly carry out with additive mix and with the mixing of carrier, make developer (2).

(manufacturing of developer (3))

With amphoteric surfactant (dodecanamide propyl dimethyl oxidation amine, ソ Off ゾ リ Application LAO, Fine Chemicals Co., Ltd. system is ground in the river) (DiaNitriX Co., Ltd. makes to change Amphiphatic high polymer agglutinant KA804E into, acrylamide and acrylic acid-acrylic acid dimethylamino ethyl ester is a major component), change the use amount of crystalline resin dispersion liquid (3a) into 10 mass parts, in addition, make, obtain the female particle (3) of toner with the condition identical with the female particle of toner (1).

The volume average particle size D50v of the female particle of resulting toner is 5.8 μ m.Then, with developer (1) similarly carry out with additive mix and with the mixing of carrier, make developer (3).

(manufacturing of developer (4))

The female particle (4) of-making toner-

Non-crystalline resin particle dispersion (1a): 145 parts

Colorant dispersion (1): 42 parts

Anti-sticking agent particle dispersion liquid (1): 36 parts

Aluminium sulphate (making): 0.5 part with the pure medicine of light Co., Ltd.

Ion exchange water: 300 parts

Except employed raw material dispersion liquid in the aggegation operation is adjusted into the above-mentioned composition, uses with the identical condition of developer (1) and make developer (4).The volume average particle size D50v of the female particle of resulting toner is 5.5 μ m.

(manufacturing of developer (5))

Vibrin (by the linear polyester that terephthalic acid (TPA)-bisphenol-A ethylene oxide adduct-cyclohexanedimethanol obtains, glass transition temperature Tg is 59 ℃, and weight-average molecular weight Mn is 3500, and number-average molecular weight Mw is 20000): 100 parts

(Dainichiseika Color Chem makes phthalocyanine color, PVFASTBLUE): 25 parts

Babassu cured (East Asia changes into Co., Ltd. and makes, 80 ℃ of fusing points): 5 parts

Use the mixing said mixture of extruder, after pulverizing with jet mill, carry out classification with air classifier, obtaining volume average particle size D50v is the female particle (5) of toner of 10.3 μ m.Then, with developer (1) similarly carry out with additive mix and with the mixing of carrier, make developer (5).

(manufacturing of developer (6))

Except (DiaNitriX Co., Ltd. makes with Amphiphatic high polymer agglutinant KA804E, acrylamide and acrylic acid-acrylic acid dimethylamino ethyl ester is a major component) addition change 2 into especially by 1 part, similarly operate with the female particle of toner (3), obtain the toner that D50v is 5.7 μ m.In addition, with developer (1) similarly carry out with additive mix and with the mixing of carrier, make developer (6).

In addition, in the developer of above-mentioned making (1)～(6) details of contained toner in illustrating as following table 9.

[table 9]

Developer No.	The shape of toner				G’(70)/G’(90)
						Volume average particle size D50v[μ m]	Volume average particle sizes profile exponent GSDv	Number average particle size distribution index GSDp	Average circularity
	Developer 1	6.5	1.21	1.25						0.962	8×10 4
Developer 2					6.3	1.24	1.24	0.970	8×10 3
	Developer 3	5.8	1.22	1.25						0.955	2×10 3
Developer 4					5.5	1.24	1.26	0.960	8×10 2
	Developer 5	10.3	1.30	1.32						0.938	7×10 2
Developer 6					5.7	1.18	1.22	0.960	5×10 3

The making of-photoreceptor-

(photoreceptor 1)

Utilize centreless grinding device grinding aluminum base plate cylindraceous (tube), making surface roughness Rz is 0.6 μ m.1 minute etch processes, neutralisation treatment and the pure water washing successively this aluminum barrel being carried out ungrease treatment, carries out with the sodium hydroxide solution of 2 quality % as washing step.Then, as the anodized step, the sulfuric acid solution that utilizes 10 quality % forms anode oxide film on the surface of tube, and (current density is 1.0A/dm ²).After the washing, dipping is 20 minutes in the nickel acetate solution of 80 ℃ 1 quality %, carries out sealing of hole and handles.Once more with carrying out dried after the pure water washing.So on the surface of aluminum barrel, form the anode oxide film of 7 μ m.

On this aluminum base material with 1 part of titanyl phthalocyanine and 1 part of polyvinyl butyral (S-LECBM-S, Sekisui Chemical Co., Ltd makes) and 100 parts of n-butyl acetates mix mutually, use beaded glass and coating vibrating machine to handle simultaneously and disperseed in 1 hour, the Bragg angle in the X ray diffracting spectrum of described titanyl phthalocyanine (2 θ ± 0.2 °) has stronger diffraction peak at 27.2 °.Afterwards, resulting coating fluid dip-coating to above-mentioned prime coat, in 100 ℃ of heat dryings 10 minutes, thereby is formed the charge generating layer that thickness is about 0.15 μ m.

Then, benzidine compound (following compound 1) and 2.5 parts of macromolecular compound (following compounds 2 with 2 parts of following structures, viscosity average molecular weigh is 39000, n is repeat number) be dissolved in 20 parts of chlorobenzenes, obtain coating fluid, utilize dip coating that this coating fluid is applied on the above-mentioned charge generating layer, in 110 ℃ of heating 40 minutes, forming thickness is the charge transport layer of 20 μ m, obtains photoreceptor 1 thus.

Compound 1 compound 2

(photoreceptor 2)

In constituent material as described below, add 5 parts of methyl alcohol, 0.5 part of ion exchange resin (AMBERLIST 15E), utilize the exchange reaction that stirs the following silane compound that carries out 24 hours under the room temperature.

-constituent material-

Following compound 3:2 part

Methyltrimethoxy silane: 2 parts

Tetraethoxysilane: 0.5 part

Colloidal silica: 0.4 part

Me (MeO) ₂Si-(CH ₂) ₄-SiMe (OMe) ₂: 0.5 part

(17 fluoro-1,1,2,2-tetrahydrochysene decyl) methyl dimethoxysilane: 0.1 part

Hexamethyl cyclotrisiloxane: 0.3 part

Compound 3

Then, add 10 parts of normal butyl alcohols, 0.3 part of distilled water, carry out 15 minutes hydrolysis.From hydrolyzed product isolated by filtration exchange of particles resin,, add 0.1 part of praseodynium aluminium (Al (aqaq) with respect to resulting solution ₃), 0.1 part of diacetone, 0.4 part 3,5-di-t-butyl-4-hydroxy-methylbenzene (BHT) and 0.5 part of S-LEC BX-L (Sekisui Chemical Co., Ltd's manufacturing) make coating fluid.Utilize annular dip coating that this coating fluid is applied on the charge transport layer of above-mentioned photoreceptor 1.Under room temperature air-dry 30 minutes afterwards, be cured in 1 hour in 170 ℃ of heat treated, form the superficial layer that thickness is about 3 μ m, obtain photoreceptor 2 thus.

＜embodiment 1～5, comparative example 1～3 〉

-estimate-

(this device has the cleaning means of cleaning doctor as photoreceptor to the transformation apparatus of the printer (DocuCentre color 400CP) that use Fuji-Xerox makes, has the circulating system that the toner in the recovery box is returned to developing machine inside), combination photoreceptor as shown in table 10 and developer carry out 5000 pages imaging test under the environment of hot and humid (28 ℃, 85%RH).Then, under the environment of low temperature and low humidity (10 ℃, 15%RH), carry out 5000 pages imaging test.Afterwards to low-temperature fixing, image glossiness, toner intensity, additive imbed, transfer printing, image durability, charging property estimate.The result is in table 10 illustrate.

In order to confirm circulating system, only under the situation of having used photoreceptor 2, start circulating system, further under the environment of hot and humid (28.5 ℃, humidity 85%), carry out 100000 pages imaging test, film forming whether on the photoreceptor after using 50 times magnifier visual inspection to test.The result is in table 10 illustrate.

In addition, the imaging that utilizes DocuCentre color 400CP transformation apparatus to carry out comprises that electrostatic latent image forms step, development step, transfer step, photographic fixing step.

[table 10]

	Developer No.	Photoreceptor No.	Low-temperature fixing	The image glossiness	Toner intensity	Additive is imbedded	Transfer printing	Image durability	Charging property	Film forming whether
											Embodiment 1	Developer 1	Photoreceptor 1	B	A	B	B	A	A	A	-
Embodiment 2	Developer 2	Photoreceptor 1	B	A	B	B	A	A	A	-
											Embodiment 3	Developer 3	Photoreceptor 1	B	A	B	B	A	A	A	-
Embodiment 4	Developer 3	Photoreceptor 2	B	A	B	B	A	A	A	A
											Embodiment 5	Developer 6	Photoreceptor 2	B	B	A	A	B	B	A	A
Comparative example 1	Developer 4	Photoreceptor 1	C	D	C	C	C	C	C	-
											Comparative example 2	Developer 5	Photoreceptor 1	D	B	D	D	D	D	D	-
Comparative example 3	Developer 4	Photoreceptor 2	C	D	C	C	C	C	C	C

The evaluation method and the evaluation criterion of the described assessment item of table 10 are as follows.

-low-temperature fixing-

Before the imaging test, use the temperature of external power source controller control photographic fixing machine, in 100 ℃～140 ℃ fixing temperature scope, photographic fixing is carried out for 5 ℃ in every interval, the mode that has certain reflection density according to the image that makes gained forms image, to the image that so obtains because the crooked image deflects that cause are carried out the sense evaluation, judge its low-temperature fixing.Used C2 paper (Fuji Xerox Co., Ltd makes, and the concentration of utilizing X-Rite404 densimeter (manufacturing of X-Rite Co., Ltd.) to measure is 1.5～1.8) with paper.

A: good (in photographic fixing below 110 ℃).

B: though there are image deflects in no problem in the practicality under low-temp. portion (110 ℃～135 ℃).

C: the image deflects under the low-temp. portion (110 ℃～135 ℃) are more, are in the practical level (under the temperature more than 135 ℃ can photographic fixing, do not have image deflects) of being unable to stand.

-portrait glossiness-

Before the imaging test, use the temperature of external power source controller control photographic fixing machine, fixing temperature is set at 140 ℃, the mode that has certain reflection density according to the image that makes gained forms image, utilize ミ ラ one ト リ グ ロ ス Grossmeters (manufacturing of Gardner society) to measure 60 degree glossiness and estimate, judge the image glossiness with following standard.Use MC256 paper (concentration of measuring with the X-Rite404 densimeter is 1.5～1.8) with paper.

A: very good (with identical with the paper grade or on it, or be not less than 95% with ratio) with the glossiness of paper.

B: good (with the ratio with the glossiness of paper be 60%～94%).

C: poor (with the ratio of the glossiness of paper smaller or equal to 59%).

-toner intensity-

Be extracted in the developer that carries out under the hot and humid and low temperature and low humidity environment behind the imaging test, whether shape and the observation of using scanning electron microscope (SEM) to observe toner-particle breakage occurs, compare with untapped toner-particle, toner intensity is carried out the sense evaluation.Evaluation criterion is as follows.

A: compare formless variation and breakage (1 number % is following) with untapped toner-particle.

B: compare the variation of shape and damaged less (greater than 1 number %, smaller or equal to 3 number %) with untapped toner-particle.

C: compare with untapped toner-particle, can confirm breaking or the distortion (greater than 3 number %, smaller or equal to 20 number %) of shape of toner.

D: compare with untapped toner-particle, can confirm breaking or the distortion (greater than 20 number %) of shape of toner.

-additive imbeds-

Be extracted in the developer that carries out under the hot and humid and low temperature and low humidity environment behind the imaging test, use scanning electron microscope (SEM), the additive particulate that adds is compared at lip-deep state of toner-particle and untapped toner-particle, additive is imbedded carried out the sense evaluation thus.Evaluation criterion is as follows.

A: do not confirm different with untapped toner.

B: compare with untapped toner-particle, almost not confirming on the surface of toner-particle has imbedding of additive particulate.

C: compare with untapped toner-particle, imbedding of additive particulate arranged on the surface of toner-particle to a certain extent.

D: compare with untapped toner-particle, imbedding of additive particulate obviously arranged on the surface of toner-particle.

-transfer printing-

Sample to not transfer printing is taken a sample, and for the first time gets the 500th page, then gets the 1000th page, gets one page every 1000 pages afterwards, measures the residual weight of toner on the photoreceptor, judges transfer printing thus.Evaluation criterion is as follows.

A: good

B: good basically

Significantly reduce after the C:1000 page or leaf.

D: sampling for the first time just reduces.

-image durability-

Before the test beginning, obtain image (fixing temperature is 135 ℃) so that it has certain reflection density (concentration of X-Rite404 densimeter mensuration is 1.5～1.8), in the scraping test of portrait (HEIDON Type:14DR (superficiality testing machine)), vertical the heavy burden for 200g, pin translational speed is under 1500mm/ minute the condition image deflects to be carried out the sense evaluation, thereby judges image durability.Evaluation criterion is as follows.

A: good (not having significant deficiency).

B: good (almost not having significant deficiency) basically.

C: though no problem in the practicality can confirm image deflects.

D: image deflects are many, are in the level of being unable to stand use.

-charging property-

When Δ TP=(carried charge * 5000 after printing 5000 pages page after toner concentration)/(initial stage carried charge * initial stage toner concentration), judge Δ TP value with following standard.

Toner concentration is meant the part by weight of the toner in the developer of having measured charged characteristic.And, the carried charge of following mensuration toner: on the sleeve pipe of developing machine, extract developer, measure the carried charge of toner with air blast (TB-200, Chemical society of Toshiba makes).

A：0.75≤ΔTP＜1.2。

B：0.65≤ΔTP＜0.75。

C：0.5≤ΔTP＜0.65。

D：ΔTP＜0.5。

Film forming evaluation during-startup circulating system-

Whether use on the photoreceptor after 50 times the magnifier visual inspection test film forming, with following standard evaluation.

A: confirm less than film forming.

B: can confirm film forming, but to not influence of image.

C: though influential to image, practical no problem.

D: problem is arranged in the practicality.

Claims (19)

1. electrostatic image developing toner, this toner contains binder resin, colorant and detackifier, and ratio G ' (70)/G ' (90) of the storage modulus G ' (90) of its storage modulus G ' (70) in the time of 70 ℃ during with 90 ℃ is 1 * 10 ²～1 * 10 ⁵, this storage modulus is to obtain by Measurement of Dynamic Viscoelasticity under the condition determination of 1 radian per second; Described toner is characterised in that, it contains the compound of the ionic leaving group of the ionic leaving group that has anionic property in a part and cationic.

2. electrostatic image developing toner as claimed in claim 1, wherein, described binder resin synthesizes by addition polymerization or polycondensation reaction.

3. toner as claimed in claim 1, wherein, the compound of the ionic leaving group of described ionic leaving group that has anionic property in a part and cationic is expressed from the next:

In the above-mentioned formula, x, y and z represent the integer more than 1, are 2～5 integers, and y＞x.

4. toner as claimed in claim 1, wherein, the content of compound in toner of the ionic leaving group of described ionic leaving group that has anionic property in a part and cationic is 0.5 quality %～5 quality %.

5. toner as claimed in claim 1, wherein, described binder resin contains crystalline resin.

6. toner as claimed in claim 5, wherein, the fusing point of described binder resin is 45 ℃～110 ℃.

7. toner as claimed in claim 1, wherein, the addition of described detackifier is 0.5 quality %～50 quality % with respect to toner.

8. toner as claimed in claim 1, wherein, mean grain size exists ratio less than 10 number % more than or equal to the big particle of 0.8 μ m in the described colorant.

9. toner as claimed in claim 1, wherein, the volume average particle size D50v of described toner is 3 μ m～7 μ m.

10. toner as claimed in claim 1, wherein, the volume average particle sizes profile exponent GSDv of described toner is smaller or equal to 1.28.

11. toner as claimed in claim 1, wherein, the number average particle size distribution index GSDp of described toner is smaller or equal to 1.30.

12. toner as claimed in claim 1, wherein, the average circularity of described toner is 0.94～0.98.

13. a manufacture method of making the described toner of claim 1, described manufacture method comprises the steps:

Granulation step, in this step, in the mixed solvent of water, organic solvent or water and organic solvent, produce the pigmentary resin particle of compound, described binder resin, described colorant and the described detackifier of the ionic leaving group that contains described ionic leaving group that in a part, has an anionic property and cationic; And

Washing-drying steps in this step, washs-drying above-mentioned pigmentary resin particle.

14. the manufacture method of toner as claimed in claim 13, wherein, described granulation step has following step:

The dispersion liquid preparation process, in this step, preparation binder resin particle dispersion, coloring agent particle dispersion liquid and anti-sticking agent particle dispersion liquid;

The aggegation step in this step, mixes above-mentioned various dispersion liquids and the described compound that has the ionic leaving group of anionic property and cationic in a part, is prepared into the agglutinating particle dispersion liquid; And

Integrated step in this step, is heated to the temperature of the glass transition temperature that is not less than described binder resin with described agglutinating particle dispersion liquid, makes described agglutinating particle integrated.

15. a developer for static charge image development, it contains the described electrostatic image developing toner of claim 1.

16. developer for static charge image development as claimed in claim 15, this developer for static charge image development are characterised in that it contains carrier, described carrier has core and coats the resin bed of this core.

17. a formation method, described formation method comprises the steps:

Electrostatic latent image forms step, in this step, forms electrostatic latent image on sub-image supporting body surface;

Development step in this step, uses the developer that contains toner to make described latent electrostatic image developing, to form toner image;

Transfer step in this step, is transferred to described toner image on the recording medium; And

The photographic fixing step, in this step, with described toner image on described recording medium,

Described formation method is characterised in that described toner is aforesaid right requirement 1 a described electrostatic image-developing toner.

18. formation method as claimed in claim 17 is characterized in that, the layer that constitutes described sub-image supporting body outmost surface contains siloxane resin or the phenolics with cross-linked structure.

19. formation method as claimed in claim 18 is characterized in that, this formation method contains following step:

Cleaning in this step, is removed and is reclaimed remaining in the lip-deep remaining toner of described sub-image supporting body after the described transfer step; And

The toner circulation step, in this step, the remaining toner that will in above-mentioned cleaning, reclaim as described developer to utilize again.