CN101351747A - Electrostatic charge image developing toner, carrier, developer, image forming method, and image forming device - Google Patents

Abstract

A toner comprising a colorant and a binder resin as the essentials, wherein the binder resin contains at least one polyester resin obtained by polycondensation in the presence of at least one titanium-containing catalyst represented by the general formula (I) or (II) and the toner has a volume-mean particle diameter (Dv) of 2.0 to 10.0[mu]m and a ratio of Dv/Dn (number-mean particle diameter) of 1.00 to 1.40: Ti(-X)m(-OH)n (I) O=Ti(-X)p(-OR)q (II) wherein X is a residue derived from a monoalkanolamine or polyalkanolamine having 2 to 12 carbon atoms by the removal of one hydroxylic hydrogen; the other OH groups of the polyalkanolamine bonded to a Ti atom may be each intramolecularly polycondensed with an OH group bonded directly to the Ti atom to form a ring structure or the other OH groups thereof may be each intermolecularly polycondensed with an OH group bonded directly to another Ti atom to form a repeating structure; R is hydrogen or C1-8 alkyl which may contain one to three ether linkages; m is an integer of 1 to 4 and n is an integer of 0 to 3, the sum of m and n being 4; and p is an integer of 1 to 2 and q is an integer of 0 to 1, the sum of p and q being 2.

Description

Toner for developing electrostatic latent image, toner Cartridge and image processing system

Technical field

The present invention relates to a kind of toner for developing electrostatic latent image, toner Cartridge and image processing system, as adhesive resin, the dry toner purposes that the conduct in xerography, electrostatic recording or videograph etc. of this adhesive resin is used for the development of electrostatic image or magnetic sub-image is useful to described toner for developing electrostatic latent image with vibrin.

Background technology

Up to now, in order to improve the low-temperature fixing performance of toner, known use vibrin is as bonding agent (with reference to patent documentation 1 and 2).In order further to improve the low-temperature fixing of toner, be necessary to reduce molecular weight or glass transition temperature (Tg), but have the problem of the anti-adhesive difference of the toner under the hot and humid degree this moment.In addition, if use such resin, then exist toner components to be bonded on carrier or the development sleeve and cause the problems such as charged ability reduction of developer.Further, this charged ability be reduced under the hot and humid environment or the low temperature and low humidity environment under and under hi-vision area output, As time goes on begin to become remarkable.Therefore, expectation is provided under the environment for use of the no problem but wider model of user of common environment for use, can be with stable toner and the image processing system of exporting high quality images of any one using method.

In addition,, prevent background stained (backgroundsmear), the known technology (with reference to patent documentation 3) that contains charging control agent (charged controlling agent) in the bonding agent that makes for the charging property that improves toner, charged stability.But charging control agent is compared with vibrin, and the low-temperature fixing performance is low, owing to be present in the toner, has the ill-effect that hinders the low-temperature fixing performance that vibrin had.Therefore, in order further to improve the low-temperature fixing of toner, be necessary charging control agent is dispersed in the toner equably, thereby can bring into play sufficient chargeding performance with amount still less.

The developer that in electrofax, electrostatic recording, xeroprinting etc., uses, in this development step, for example in case attached on the photoreceptor that is formed with electrostatic image, then in transfer step, be transferred on the recording medium such as paper from photoreceptor after, photographic fixing is on paper in the photographic fixing step.At this moment, the developer of the electrostatic image development on the sub-image maintenance face will be formed at, the known single component class developer (magnetic color tuner, nonmagnetic toner) that contains the bi-component class developer of carrier and toner and do not need carrier as being used for.In the bi-component visualization way, because toner particle is attached on the carrier surface, developer degradation, in addition, because the toner concentration that only consumes in toner, the developer reduces, thus must keep mixing ratio with carrier with certain ratio, so developing apparatus is than relatively large.On the other hand, in the single component development mode,, install more miniaturization by the multifunction of developer roll etc.

In recent years, the OAization of office or colorize further develop, be not only the duplicating of the original copy that only contains literal in the past, and printer output such as the chart made from personal computer, the image of taking with digital camera, the diagram original copy that reads by scanner etc., increase as the chance of many duplicating such as data of displaying usefulness.For the image of printer output, image, line image, half tone image etc. mix in an original copy on the spot complicated structure, has also improved for the requirement and the multiduty requirement of the high reliability of image.

The electronic camera technology of use single component class developer in the past is categorized as the magnetic single component development mode of using magnetic color tuner and the non-magnetic mono-component visualization way of using nonmagnetic toner.The magnetic single component development mode, owing to use the inner developer carrier that is provided with magnetic field generation device such as magnet, keep containing the magnetic color tuner of magnetics such as magnetic iron ore, carry out thin layerization and develop, so a large amount of practicability in miniprinter etc. in recent years by the layer thickness control parts.But, what magnetic mostly was greatly coloured (black system), there is the shortcoming that is difficult to colorize.

On the other hand, the non-magnetic mono-component visualization way is crimped on toner replenishing roller etc. on the developer carrier because toner does not have magnetic force, supplies with toner on developer carrier, and static keeps, and by layer thickness control parts thin layerization, develops.Owing to wherein do not contain coloured magnetic, have the advantage that can realize colorize, in addition because developer carrier does not use magnet, can further lightweight of implement device and cost degradation, in small-sized panchromatic printer etc., be practical in recent years.

In addition, in the bi-component visualization way, since use carrier as toner charged, transmit material with toner and carrier after the inner fully stirring of developer, mixing, be sent on the developer carrier and develop, even also can keep stable charging property and transmission property, in addition also easily corresponding to developing apparatus at a high speed so the long time uses.

In contrast to this, present situation is: in the single component development mode, the problem that should improve is still a lot.In the single component development mode owing to do not have such stable charged of carrier or transmit material, therefore long-time use or be easy to generate during high speed charged bad, transmit bad.Promptly, in the single component development mode, after transmitting toner on the developer carrier, with the layer thickness control parts toner thin layerization is developed, but because the contacting of toner and frictional electrification parts such as developer carrier, layer thickness control parts, frictional electrification time are very short, compare with the bi-component visualization way of using carrier, easily form low charged, contrary charged toner mostly.

Particularly in the non-magnetic mono-component developing method, usually adopt by at least one toner transfer member and transmit toner (developer) and make the method that is formed on the latent electrostatic image developing on the latent image carrier, but the toner bed thickness on toner transfer member surface must be extremely thin at this moment by the toner that transmits.This also is suitable under the situation of the very little bi-component class developer of carrier use diameter, in addition, when particularly using single component class developer and using the high toner of resistance, owing to be necessary to make this toner charged according to developing apparatus, so the bed thickness of toner must be extremely thin.This is that it is charged that toner layer integral body is difficult to homogeneous because if toner layer is very thick, then only the near surface of toner layer is charged.Therefore, require toner is kept charged more rapidly speed and suitable carried charge.

Therefore, added charged controlling agent and adjuvant for the charged stabilization that makes toner in the past.Above-mentioned charged controlling agent plays the frictional electrification amount of control toner, the effect that keeps its frictional electrification amount.As the representational charged controlling agent of negative charging, coordination compound that can enumerate the metal complex, two azo-compounds of slaine, the dicarboxylic acid of for example monoazo dyes, salicylic acid, naphthoic acid, dicarboxylic acid, obtains by boron etc.In addition, as the representational charged controlling agent of Positively chargeable, can enumerate for example quarternary ammonium salt compound, imidazolium compounds, nigrosine, azines etc.

But, in these charged controlling agents, existing to have coloured charged controlling agent, the charged controlling agent that can not be used for color toner is many.In addition, in these charged controlling agents, since poor to the compatibility of adhesive resin, easily break away from the charged big relevant charged controlling agent that is present on the toner surface, and the charged generation of toner is uneven.In addition, shortcomings such as the pollution of the easy generation of existence development sleeve or photoreceptor film forming.

Therefore, though existed the initial stage to obtain excellent image in the past, image quality changes, produces the phenomenon of background stained or unclear (Pot そ つ I) lentamente.Particularly if be applied in the color photocopying, if use continuously on supply toner limit, limit, then the carried charge of toner reduces, form tone and the remarkable different image of the copy image at initial stage, not anti-long use is only carried out about thousands of duplicating and just must be changed the image-forming block that is called as handle box in advance.Therefore, big to the load of environment, the user feels trouble.Further,, consider from the security aspect in recent years, becoming problem because these boxes contain heavy metals such as chromium mostly.

Therefore, as the material that improves the problems referred to above, known improvement is to the compatibility of adhesive resin, the transparency of toner fixing image, the resin strip controling agent of security.These resin strip controling agents since with the compatibility excellence of adhesive resin, therefore in stable charging property, also excellent aspect transparent.But if compare with the toner of the slaine/metal complex that uses monoazo dyes, salicylic acid, naphthoic acid, dicarboxylic acid, then there is the shortcoming of carried charge and charged velocity contrast in these resin strip controling agents.In addition, by increasing the addition of resin strip controling agent, charging property improves, but toner fixation performance (low-temperature fixing, anti-hectograph print through (offset) property) is had harmful effect.Further, the environmental stability of the carried charge of these compounds (moisture resistance) is big, therefore has the problem (with reference to patent documentation 4～7) that easily produces background stained (photographic fog).

Therefore, the monomer and multipolymer of acylate such as sulfonate groups have been proposed to contain with aromatic monomer of electron withdraw group.Yet, though owing to be considered to guarantee sufficient carried charge because of the hydroscopicity or the cohesive of the monomer that contains acylate such as above-mentioned sulfonate groups, but the dispersion in adhesive resin is insufficient, suppress for a long time toner charged inequality, prevent the effect insufficient (with reference to patent documentation 8～11) of film forming etc. to development sleeve or photoreceptor.

In addition, in order to improve to compatibility as the styrene resin and the polyester resin of adhesive resin, proposed respectively to contain monomer, aromatic monomer and the styrene monomer of acylates such as sulfonate groups or the multipolymer of polyesters monomer, but the maintenance of the long charged amount of these materials, prevented that development sleeve or photoreceptor film-formation result are insufficient with electron withdraw group.Particularly as the full-color toner adhesive resin, for considering that from colour rendering, image intensity aspect preferred polyester resin or polyol resin are inadequate.

In addition, in recent years printer needs to enlarge, the miniaturization of device, high speed or cost degradation development, device is begun higher reliability of requirement and long lifetime, toner is required to keep various characteristics for a long time, but these resin strip controling agents can not keep its charged control effect, exist to pollute development sleeve or layer thickness control parts (scraper plate or roller) and make the chargeding performance of toner reduce or produce the problem of photoreceptor film forming.

In addition,, form the technology of using a spot of developer to develop at short notice, require electrically (band Electricity founds Ga り on the Chi) more excellent developer of initial strip owing to miniaturization, high speed.For development, when proposing two-component developing agent, monocomponent toner, various visualization way have been proposed, but can miniaturization and lightweight aspect etc. excellence, do not use carrier and the non-magnetic mono-component finished to be developed in the printer use be suitable.In this visualization way and since toner to developer roll the supply or the toner retentivity of developer roll poor, force toner coated or by the toning dosage on the scraper plate control developer roll to developer roll.Toner film forming on developer roll easily produces the lost of life of developer roll or the carried charge problem of unstable of toner as a result.In addition, can not carry out good development thus.Therefore, in the color toner of non-magnetic mono-component development usefulness, except the necessary characteristic of common color toner, the situation of the poor heat resistance of the binder resin that uses in the toner is many, is easy to generate toner to film forming of developer roll etc.

But in the example of above-mentioned patent documentation 1～4 record, there is the shortcoming of carried charge, charged velocity contrast.If prevent these shortcomings and increase the addition of resin strip controling agent that though then charging property is improved, (low-temperature fixing, anti-print through) has harmful effect to the toner fixation performance.Further, the environmental stability of the carried charge of these compounds (moisture resistance) is big, therefore has the shortcoming that easily produces background stained (photographic fog).

In addition, in the above-mentioned patent documentation 8～11, guarantee sufficient carried charge, but the dispersion in adhesive resin is insufficient, exists and suppress charged inequality, prevent the inadequate problem of effect the film forming of sleeve and photoreceptor by hydroscopicity or cohesive.

In addition, in the image that is undertaken by the electrofax mode forms, on image-carriers such as photoconductivity material, form sub-image by static charge, for this electrostatic latent image, after adhering to charged toner particle formation visual image, this toner image is transferred on the recording medium such as paper, carries out photographic fixing, form output image.In recent years, use the duplicating machine of electrofax mode or the technology of printer, develop rapidly to panchromatic from monochrome, there is the trend of expansion in panchromatic market.

Form in the coloured image by panchromatic xerography, generally with the color toner of trichromatic yellow, magenta, these three kinds of colors of cyan or add the color toner lamination of four kinds of colors that black arranged and obtain therein and carry out the reproduction of all colours.Therefore, in order to obtain the full-colour image of colorrendering quality excellence, distinctness, except being necessary to make the toner image surface of photographic fixing for to a certain degree level and smooth, and reduce outside the light scattering etc., in order to ensure colorrendering quality, pigment is dispersed in the toner equably and disperse after the not obvious cohesion of pigment and keep differential to loose.

Particularly in order to reproduce people's colors such as the colour of skin, be necessary to use the substractive color mixing of being undertaken to come apparent color, study as problem to yellow uitramarine, magenta pigment and as the best of breed of the resin that disperses parent by the coincidence of Yellow toner and pinkish red toner.

For example, the pinkish red toner of electrostatic image development is disclosed in the patent documentation 12, it is the method for producing toner and toner that dissolving contains the polyester resin of the modification that can carry out the urea bonding in organic solvent, make it in water-medium, carry out addition polymerization, the toner that contains colorant at least that the solvent of this dispersion liquid is removed and washed and obtains again, wherein, described colorant is the compound of regulation.

In addition, the pinkish red toner of a kind of electrophotography is disclosed in the patent documentation 13, it is in the pinkish red toner of the electrophotography that contains binder resin and colorant at least, at least contain have the regulation structure aphthols pigment as above-mentioned colorant, and the shape coefficient SF1 of toner is 110～140, volume average particle size is 2～9 μ m.

But actual conditions are: when only utilizing said method, can not prevent because the problem of the colorrendering quality difference that the cohesion again of the pigment in the toner is caused can not realize the colorrendering quality of image, particularly can not verily reproduce people's the colour of skin.

Patent documentation 1: Japanese kokai publication sho 62-178278 communique

Patent documentation 2: Japanese kokai publication hei 4-313760 communique

Patent documentation 3: Japanese kokai publication hei 7-062766 communique

Patent documentation 4: Japanese kokai publication sho 63-88564 communique

Patent documentation 5: Japanese kokai publication sho 63-184762 communique

Patent documentation 6: Japanese kokai publication hei 3-56974 communique

Patent documentation 7: Japanese kokai publication hei 6-230609 communique

Patent documentation 8: Japanese kokai publication hei 8-30017 communique

Patent documentation 9: Japanese kokai publication hei 9-171271 communique

Patent documentation 10: Japanese kokai publication hei 9-211896 communique

Patent documentation 11: Japanese kokai publication hei 11-218965 communique

Patent documentation 12: TOHKEMY 2004-77664 communique

Patent documentation 13: TOHKEMY 2003-215847 communique

Summary of the invention

The objective of the invention is to, a kind of toner for developing electrostatic latent image is provided, the anti-adhesive of the toner of this developer under hot and humid degree environment and low-temperature fixing be all excellent, it is stained not produce background, even and under hot and humid environment or under the low temperature and low humidity environment and then under high quality image area output As time goes on, toner components can not be bonded on carrier or the development sleeve yet and cause the charged ability of developer to reduce, and can stablize the output high quality image.

In addition, the objective of the invention is to, a kind of dry type toner for developing electrostatic latent image is provided, this toner can stably control, keep the frictional electrification amount and the environmental turbulence of toner little, can keep stable frictional electrification, in addition, the transmission of toner, development, transfer printing, keeping quality excellence can not produce the abnormal image that causes owing to adhering to of photoreceptor.

In addition, the objective of the invention is to, monocomponent toner, two-component developing agent that uses above-mentioned toner for developing electrostatic latent image and the image processing system that uses these developers are provided.

In addition, the objective of the invention is to, a kind of toner for developing electrostatic latent image box is provided, wherein, when the preparation toner,, can not hinder the colorrendering quality of toner in case the pigment that is dispersed in the resin condenses once more, have good toner colorrendering quality, particularly can reproduce colorrendering quality excellently by the redness yellow, pinkish red, that substractive color mixing is carried out.

In order to address the above problem, the inventor etc. further investigate, the result finds first, by using toner binder that contains the polycondensation vibrin that in the presence of specific catalyst, forms and particle diameter, the size-grade distribution that the particle diameter of toner is controlled to be regulation, perhaps, can address the above problem by using specific charged controlling agent.

The above-mentioned discovery that the present invention is based on the inventor makes, and is as being used for solution of the above problems, as described below.

＜1〉a kind of toner, it contains colorant and adhesive resin at least, wherein,

Above-mentioned adhesive resin contains at least a vibrin, described vibrin be at following general formula (I) and the titanium-containing catalyst (II) at least a in the presence of polycondensation form;

The volume average particle size of above-mentioned toner is 2.0～10.0 μ m, and the ratio (Dv/Dn) of this volume average particle size (Dv) and number average particle diameter (Dn) is 1.00～1.40.

[Chemical formula 1]

Ti(-X)m(-OH)n (I)

O＝Ti(-X)p(-OR)q (II)

Above-mentioned general formula (I) and (II) in, X removes the residue that the H of an OH base obtains from carbon number is any one of 2～12 monoalkanolamine and many alkanolamines, other OH base of these many alkanolamines can carry out polycondensation with the OH base of Direct Bonding on same Ti atom and form ring structure in molecule, also can carry out polycondensation and form repetitive structure intermolecular with the OH base of Direct Bonding on other Ti atom.The degree of polymerization when in addition, forming repetitive structure is 2～5.

R represents any one of alkyl of hydrogen atom and the optional carbon number 1～8 that contains 1～3 ehter bond.

M is that 1～4 integer, n are that 0～3 integer, m and n sum are 4.P is that 1～2 integer, q are that 0～1 integer, p and q sum are 2.M and p are 2 when above, and X separately can be identical or different.

＜2〉above-mentioned＜1〉described toner, wherein, vibrin contains at least a in the following vibrin, described vibrin be at general formula (I) and the titanium-containing catalyst of the residue that obtains for the H that from any one of two (three alkanolamines) and three alkanolamines, removes an OH base of the X (II) in the presence of polycondensation form.

＜3〉above-mentioned＜1 〉～＜2 in each described toner, wherein, vibrin contains at least a in the following vibrin, described vibrin be at general formula (I) and the m (II) or p be more than 2 and all X be same group titanium-containing catalyst in the presence of polycondensation form.

＜4〉above-mentioned＜1 〉～＜3 in each described toner, wherein, contain at least a polyepoxide modified resin to the small part vibrin.

＜5〉above-mentioned＜1 〉～＜4 in each described toner, wherein, vibrin does not contain the insoluble composition of THF and in the molecular weight distribution of gel permeation chromatography, molecular weight is 5 * 10 ²The content of following composition is below the 4 quality %, and in mass molecular weight 3 * 10 ³～9 * 10 ³The zone in have main peak.

＜6〉above-mentioned＜1 〉～＜5 in each described toner, wherein, the endothermic peak that adhesive resin obtains by differential scanning calorimeter (DSC) is 60～70 ℃.

＜7〉above-mentioned＜1 〉～＜6 in each described toner, wherein, the ratio (Mw/Mn) of the weight-average molecular weight of adhesive resin (Mw) and number-average molecular weight (Mn) is 2≤Mw/Mn≤10.

＜8〉above-mentioned＜1 〉～＜7 in each described toner, wherein, the acid number of adhesive resin is below the 10mgKOH/g.

＜9〉above-mentioned＜1 〉～＜8 in each described toner, wherein, adhesive resin reaches 10 by the apparent viscosity that flow tester obtains ³Temperature during Pas is 95～120 ℃.

＜10〉a kind of toner Cartridge, it comprises above-mentioned＜1 〉～＜9 in each described toner, and contain Yellow toner, pinkish red toner and cyan toner at least, wherein,

Above-mentioned pinkish red toner contains the organic pigment of following structural formula (1) expression,

Above-mentioned Yellow toner contains the organic pigment that has two following structural frameworks (A) in the molecule and do not have halogen atom,

[Chemical formula 2]

Above-mentioned formula (1) and (A) in ,=C=N-NH-comprises=situation of CH-N=N-.

＜11〉above-mentioned＜10〉described toner Cartridge, wherein, the organic pigment that has two said structure skeletons (A) and do not have a halogen atom is the organic pigment shown in any one at least of following structural formula (2) and (3).

[chemical formula 3]

[chemical formula 4]

＜12〉a kind of image processing system, it comprises at least: electrostatic latent image carrier; The electrostatic latent image that forms electrostatic latent image on this electrostatic latent image carrier forms parts; Use above-mentioned＜10 〉～＜11 in each described toner Cartridge above-mentioned latent electrostatic image developing is formed at least three developing parts of visual image; Above-mentioned visual image is transferred to transfer member on the recording medium; With fixing member with the transferred image photographic fixing of transfer printing on aforementioned recording medium.

Description of drawings

Fig. 1 is the structural representation of the developing apparatus of image processing system of the present invention.

Fig. 2 A is the synoptic diagram that is used to illustrate the toner shape of shape coefficient SF-1.

Fig. 2 B is the synoptic diagram that is used to illustrate the toner shape of shape coefficient SF-2.

Fig. 3 A is the synoptic diagram that is used to illustrate the toner shape of shape coefficient SF-1, shape coefficient SF-2.

Fig. 3 B is the synoptic diagram that is used to illustrate the toner shape of shape coefficient SF-1, shape coefficient SF-2.

Fig. 3 C is the synoptic diagram that is used to illustrate the toner shape of shape coefficient SF-1, shape coefficient SF-2.

Fig. 4 is the figure of another example of the apparatus structure of expression image processing system of the present invention.

Fig. 5 is the figure of another example of the apparatus structure of expression image processing system of the present invention.

Fig. 6 is the synoptic diagram of a part of structure of the image processing system of expression use contact Charging system of the present invention.

Fig. 7 is the synoptic diagram that expression tandem type coloured image of the present invention forms the structure of device.

Fig. 8 is the synoptic diagram of the structure of the expression tandem type coloured image of the present invention image processing system with intermediate transfer body that forms device.

Fig. 9 is the synoptic diagram of entire infrastructure of the image processing system of expression tandem type indirect transfer printing mode of the present invention.

Figure 10 is the synoptic diagram of structure of the image processing system of the expression tandem type indirect transfer printing mode with handle box of the present invention.

Figure 11 draws L for the toner of embodiment 75～78 and comparative example 26～29 ^*a ^*b ^*A in the color specification system aberration ^*And b ^*The figure of measured value.

Figure 12 draws L for the toner of embodiment 75,78 and comparative example 26,27 ^*a ^*b ^*A in the color specification system aberration ^*And b ^*The figure of measured value.

Figure 13 is the part enlarged drawing of Figure 12.

Figure 14 draws L for the toner of embodiment 76,77 and comparative example 28,29 ^*a ^*b ^*A in the color specification system aberration ^*And b ^*The figure of measured value.

Figure 15 is the enlarged drawing of Figure 14.

Embodiment

(toner)

Toner of the present invention contains colorant and adhesive resin at least, also contains other composition as required.

Above-mentioned adhesive resin contain at least a at following general formula (I) and at least a titanium-containing catalyst (II) in the presence of the vibrin that forms of polycondensation.

Above-mentioned titanium-containing catalyst be following general formula (I) and (II) shown in compound, also can make up two or more uses.

[chemical formula 5]

Ti(-X)m(-OH)n (I)

O＝Ti(-X)p(-OR)q (II)

Above-mentioned general formula (I) and (II) in, X removes the H of an OH base and the residue that obtains from any one of the monoalkanolamine of carbon number 2～12 and many alkanolamines, other OH base of these many alkanolamines can carry out polycondensation with the OH base of Direct Bonding on same Ti atom and form ring structure in molecule, also can carry out polycondensation and form repetitive structure intermolecular with the OH base of Direct Bonding on other Ti atom, the degree of polymerization when in addition, forming repetitive structure is 2～5.

R represents any one in the alkyl of hydrogen atom and the optional carbon number 1～8 that contains 1～3 ehter bond.

M is that 1～4 integer, n are that 0～3 integer, m and n sum are 4.P is that 1～2 integer, q are that 0～1 integer, p and q sum are 2.M and p are 2 when above, and X separately can be the same or different.

Above-mentioned general formula (I) and (II) in, X removes the H of an OH base and the residue that obtains from any one of the monoalkanolamine of carbon number 2～12 and many alkanolamines, the number of nitrogen-atoms, promptly primary, the sum of the second month in a season and uncle's amino is preferably 1～2, more preferably 1.

As above-mentioned monoalkanolamine, be not particularly limited, can suitably select according to purpose, can enumerate for example monoethanolamine, Propanolamine etc.

As above-mentioned many alkanolamines, be not particularly limited, can suitably select according to purpose, can enumerate for example dioxane hydramine (diethanolamine, N methyldiethanol amine, N butyl diethanol amine etc.), three alkanolamines (triethanolamine, tripropanol amine etc.), four alkanolamines (N, N, N ', N '-tetrahydroxyethyl-ethylene diamine etc.) etc.

Under the situation of above-mentioned many alkanolamines, the OH base of the residue that obtains except being used for forming the removing H of Ti-O-C key with the Ti atom, also there is an above OH base, it can carry out polycondensation with the OH base of Direct Bonding on same Ti atom and form ring structure in molecule, also can carry out polycondensation and form repetitive structure intermolecular with the OH base of Direct Bonding on other Ti atom.The degree of polymerization when forming repetitive structure is 2～5.If this degree of polymerization surpasses 5, then the oligomer composition is increased owing to catalyst activity reduces, become the reason of the adhesive deterioration of toner sometimes.

As X, can enumerate the residue of dioxane hydramine (particularly diethanolamine), the residue of three alkanolamines (particularly triethanolamine), the residue of preferred especially triethanolamine.

R is hydrogen atom (H) or the optional alkyl that contains the carbon number 1～8 of 1～3 ehter bond.As this carbon number is 1～8 alkyl, can enumerate for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, n-hexyl, n-octyl, 'beta '-methoxy ethyl, β-ethoxyethyl group etc.Among this R, preferred hydrogen atom, the not alkyl of the carbon number 1～4 of ether-containing key, more preferably hydrogen atom, ethyl, isopropyl.

In the above-mentioned general formula (I), m is 1～4 integer, is preferably 1～3 integer.N is 0～3 integer, is preferably 1～3 integer.M and n sum are 4.

In the above-mentioned general formula (II), p is that 1～2 integer, q are that 0～1 integer, p and q sum are 2.M or p are 2 when above, and a plurality of X of existence can be the same or different, but preferably all identical.

In the above-mentioned titanium-containing catalyst, as the compound shown in the above-mentioned general formula (I), for example can enumerating, dihydroxy two (triethanolamine) closes titanium (titanium dihydroxy (triethanol aluminate)), the trihydroxy triethanolamine closes titanium, dihydroxy two (diethanolamine) closes titanium, dihydroxy two (monoethanolamine) closes titanium, dihydroxy two (single Propanolamine) closes titanium, dihydroxy two (N methyldiethanol amine) closes titanium, dihydroxy two (N butyl diethanol amine) closes titanium, the tetrahydroxy titanium, they and N, N, N ', the reaction product of N '-tetrahydroxyethyl-ethylene diamine, or in their molecule or intermolecular condensed polymer etc.

In the above-mentioned titanium-containing catalyst, as the compound shown in the above-mentioned general formula (II), for example can enumerate in two (triethanolamine) network oxygen titanium (titanylbis (triethanol aluminate)), two (diethanolamine) network oxygen titanium, two (monoethanolamine) network oxygen titanium, hydroxyl ethanol amine network oxygen titanium, hydroxyl triethanolamine network oxygen titanium, ethoxy triethanolamine network oxygen titanium, isopropoxy triethanolamine network oxygen titanium or their molecule or intermolecular condensed polymer etc.

Wherein, preferred dihydroxy two (triethanolamine) closes titanium, dihydroxy two (diethanolamine) closes titanium, two (triethanolamine) network oxygen titanium or their condensed polymer or their combination, more preferably dihydroxy two (triethanolamine) closes titanium or its condensed polymer, is preferably dihydroxy two (triethanolamine) especially and closes titanium.

These titanium-containing catalysts for example can stably obtain by making commercially available dialkoxy two (alkanolamine) close titanium (manufacturing of Dupont company) reaction in the presence of water, under 70～90 ℃.

As the addition of above-mentioned titanium-containing catalyst, consider from aspects such as polymerization activities, with respect to the condensed polymer that obtains, be preferably 0.0001～0.8 quality %, more preferably 0.0002～0.6 quality %, 0.0015～0.55 quality % more preferably.

And, in the scope of the catalyst effect of not damaging above-mentioned titanium-containing catalyst, can be used in combination other esterification catalyst.As this other esterification catalyst, titanium-containing catalyst (for example, titanium alkoxide, titanium oxalate acyl potassium, terephthalic acid (TPA) titanium etc.) beyond tin-containing catalyst (for example Dibutyltin oxide etc.), antimony trioxide, this titanium-containing catalyst, zirconium-containing catalyst (for example zirconium acetate etc.) be can enumerate, germanium catalyst, alkali (soil) metallic catalyst (for example carboxylate of alkaline metal or earth alkali metal, lithium acetate, sodium acetate, potassium acetate, calcium acetate, Sodium Benzoate, Potassium Benzoate etc.), zinc acetate etc. contained.The addition of these other catalyzer with respect to the polymkeric substance that obtains, is preferably 0～0.6 quality %.By making above-mentioned adjuvant is below the 0.6 quality %, and the painted minimizing of vibrin is suitable for the toner of colored purposes.And the content of the above-mentioned titanium-containing catalyst in whole catalyzer of interpolation is preferably 50～100 quality %.

＜adhesive resin 〉

As the polycondensation vibrin that constitutes above-mentioned adhesive resin, can enumerate the vibrin (AX) as polyvalent alcohol and polybasic carboxylic acid condensed polymer, the modified polyester resin (AY) that this (AX) further obtains with polyepoxide reactions such as (C) etc.These (AX), (AY) may be used singly or in combination of two or more and make the potpourri use.

As above-mentioned polyvalent alcohol, can enumerate dibasic alcohol (g), the above polyvalent alcohol (h) of ternary.As above-mentioned polybasic carboxylic acid, can enumerate dicarboxylic acids (i), the above polybasic carboxylic acid (j) of ternary.They can make up two or more uses respectively.

As above-mentioned vibrin (AX) and (AY), can enumerate following vibrin, also these vibrin can be used in combination.

(AX1): the linear polyesters resin that uses (g) and (i) obtain

(AX2): use (g) and (i) in use (h) and/or the non-linear polyesters resin that (j) obtains

(AY1): (AX2) modified polyester resin that obtains with (c) reacting

As above-mentioned dibasic alcohol (g), preferred hydroxyl value is the dibasic alcohol of 180～1900mgKOH/g.Specifically, can enumerate the aklylene glycol (ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol etc.) of carbon number 2～36; The alkylene ether glycol of carbon number 4～36 (diglycol, triethylene-glycol, dipropylene glycol, polyglycol, polypropylene glycol, polytetramethylene glycol etc.); The ester ring type glycol of carbon number 6～36 (1,4 cyclohexane dimethanol, hydrogenated bisphenol A etc.); The oxyalkylene of the carbon number 2～4 of above-mentioned ester ring type glycol [oxirane (below abbreviate " EO " as), epoxypropane (below abbreviate " PO " as), epoxy butane (below abbreviate " BO " as) etc.] addition product (addition molal quantity 1～30); Oxyalkylene (EO, PO and the BO etc.) addition product (addition molal quantity 2～30) of the carbon number 2～4 of bisphenols (bisphenol-A, Bisphenol F, bisphenol S etc.) etc.

Wherein, aklylene glycol, the oxyalkylene addition product of bisphenols or their combination of preferred carbon number 2～12, oxyalkylene addition product, the aklylene glycol of carbon number 2～4 or their the two or more combination of preferred especially bisphenols.

Above-mentioned hydroxyl value for example can be measured by the method for stipulating among the JIS K0070.

As the polyvalent alcohol (h) of (3～8 yuan or more polynary) more than the above-mentioned ternary, preferred hydroxyl value is the polyvalent alcohol of 150～1900mgKOH/g.Specifically, can enumerate 3～8 yuan or more polynary aliphatic polyol (alkane polyol and molecule thereof interior or intermolecular dehydrate, for example glycerine, trihydroxyethyl ethane, trimethylolpropane, pentaerythrite, D-sorbite, sorbitan, polyglycereol, dipentaerythritol of carbon number 3～36; Carbohydrate and derivant thereof, for example sucrose and methyl glucoside etc.); The oxyalkylene of the carbon number 2～4 of above-mentioned aliphatic polyol (EO, PO, BO etc.) addition product (addition molal quantity 1～30); The carbon number of triphen phenols (trisphenol PA etc.) is 2～4 oxyalkylene (EO, PO, BO etc.) addition product (addition molal quantity 2～30); Novolac resin (phenol novolaks and cresols novolaks etc.: the oxyalkylene of carbon number 2～4 average degree of polymerization 3～60) (EO, PO, BO etc.) addition product (addition molal quantity 2～30) etc.

Wherein, preferred 3～8 yuan or more polynary aliphatic polyol, the oxyalkylene addition product (addition molal quantity 2～30) of novolac resin are preferably the oxyalkylene addition product of novolac resin especially.

As above-mentioned dicarboxylic acids (i), preferred acid number is the dicarboxylic acids of 180～1250mgKOH/g.Specifically, can enumerate the alkane dicarboxylic acid's (succinic acid, hexane diacid, decanedioic acid etc.) and the alkenyl succinic (dodecenyl succinic succinic acid etc.) of carbon number 4～36; The ester ring type dicarboxylic acid of carbon number 4～36 [dimer acid (dimerized linoleic acid) etc.]; The alkene dicarboxylic acid of carbon number 4～36 (maleic acid, fumaric acid, citraconic acid, mesaconic acid etc.); The aromatic dicarboxylic acid of carbon number 8～36 (phthalic acid, m-phthalic acid, terephthalic acid (TPA), naphthalene dicarboxylic acids etc.) etc.Wherein, the alkene dicarboxylic acid of preferred especially carbon number 4～20, the aromatic dicarboxylic acid of carbon number 8～20.In addition, as (i), can also use the acid anhydrides or low alkyl group (carbon number is 1～4) ester (methyl esters, ethyl ester, isopropyl ester etc.) of above-mentioned dicarboxylic acids.

As the polybasic carboxylic acid (j) of (3～6 yuan or more polynary) more than the ternary, preferred acid number is the polybasic carboxylic acid of 150～1250mgKOH/g.Specifically, can enumerate the aromatic series polybasic carboxylic acid (trimellitic acid, pyromellitic acid etc.) of carbon number 9～20; The polyvinyl of unsaturated carboxylic acid [number-average molecular weight ((GPC) obtains by gel permeation chromatography): 450～10000] (styrene/maleic acid, styrene/acrylic acid co-polymer, alpha-olefin/maleic acid, styrene/fumaric acid multipolymer etc.) etc.Wherein, the aromatic series polybasic carboxylic acid of preferred carbon number 9～20, preferred especially trimellitic acid, pyromellitic acid.In addition, as the polybasic carboxylic acid more than the ternary (j), can also use the acid anhydrides or low alkyl group (carbon number is 1～4) ester (methyl esters, ethyl ester, isopropyl ester etc.) of above-mentioned polybasic carboxylic acid.

In addition, can be simultaneously with lactone (l) copolymerization of the aliphatics of (g), (h), (i), (j) and carbon number 4～20 or aromatic hydroxy-carboxylic (k), carbon number 6～12.

As hydroxycarboxylic acid (k), can enumerate for example hydroxy stearic acid, hydrogenated castor oil fatty etc.As lactone (l), can enumerate caprolactone etc.

As polyepoxide (c), for example can enumerate polyglycidyl ether [ethylene glycol diglycidylether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, T 55, pentaerythrite four glycidol ethers, phenol novolaks (average degree of polymerization 3～60) glycidyl ether thing etc.]; Oxidation diene (titanium dioxide pentadiene, titanium dioxide hexadiene etc.) etc.Wherein, preferred polyglycidyl ether is preferably ethylene glycol diglycidylether, bisphenol A diglycidyl ether especially.

Per 1 molecule (c) the epoxy radix be preferably 2～8, more preferably 2～6, more preferably 2～4.The epoxide equivalent of above-mentioned (c) is preferably 50～500.The lower limit of epoxide equivalent is preferably 70, more preferably 80, and higher limit is preferably 300, more preferably 200.If the above-mentioned epoxide equivalent of above-mentioned epoxy cardinal sum is in above-mentioned scope, then development property and fixation performance are all excellent.Further preferably satisfy the scope of the epoxy cardinal sum epoxide equivalent of above-mentioned per 1 molecule simultaneously.

The reactive ratio of above-mentioned polyvalent alcohol and above-mentioned polybasic carboxylic acid as equivalent proportion [OH]/[COOH] of hydroxyl [OH] with carboxyl [COOH], is preferably 2/1～1/2, more preferably 1.5/1～1/1.3, more preferably 1.3/1～1/1.2.In addition, the kind of the polyvalent alcohol of use and polybasic carboxylic acid is preferably considered and is adjusted molecular weight so that the glass transition temperature (Tg) of the final polyesters toner binder resin of adjusting is 40～90 ℃ selects.

Above-mentioned adhesive resin panchromatic usefulness, monochromatic with in require various rerum natura, the design of vibrin is difference also.That is, in panchromatic usefulness,, therefore be necessary to form low-viscosity adhesive resin owing to require the high glaze image, and necessary especially owing to gloss in monochrome is used, but pay attention to heat penetration seal property, so be necessary to form elastomeric adhesive resin.

When obtaining high glaze image useful in panchromatic duplicating machine etc., be preferably (AX1), (AX2), (AY1) or their potpourri.At this moment, owing to be preferably low viscosity, as follows for (h) and/or the ratio (j) that constitute these vibrin: as, (h) to be preferably 0～20 mole of %, more preferably 0～15 mole of %, 0～10 mole of % more preferably with (j) molal quantity sum with respect to the total of the molal quantity of (g)～(j).

When obtaining in one-color copier etc. useful high heat-resisting print through, preferred (AX2), (AY1) and their potpourri.At this moment, because preferred high resiliency, as this vibrin, especially preferably use (h) and (j) both vibrin.(h) and ratio (j) as follows: with respect to the total of the molal quantity of (g)～(j), (h) be preferably 0.1～40 mole of %, more preferably 0.5～25 mole of %, 1～20 mole of % more preferably with (j) molal quantity sum.

Use under the situation of vibrin complex viscosity coefficient (η panchromatic ^*) temperature (TE) when reaching 100Pas is preferably 90～170 ℃, more preferably 100～165 ℃, more preferably 105～150 ℃.Said temperature (TE) is can obtain sufficient gloss below 170 ℃ the time, is heat-resisting excellent storage stability more than 90 ℃ the time.

Following the trying to achieve of said temperature (TE): use commercially available Measurement of Dynamic Viscoelasticity device, for service test with plasticator under 130 ℃, 70rpm with the piece of resin melting mixing after 30 minutes, measure complex viscosity coefficient (η when changing resin temperature ^*), try to achieve temperature (TE) thus.

In addition, consider that the insoluble composition of panchromatic tetrahydrofuran with vibrin (THF) is preferably below the 10 quality %, more preferably below the 5 quality % from the glossiness aspect.

Wherein, insoluble composition of above-mentioned THF and the solvable composition of THF obtain by following method.

Precision weighing 0.5g sample in the band Sai Maier of 200mL flask, the THF of adding 50mL, stirring and refluxing 3 hours after the cooling, is filtered insoluble composition with glass filter.The value of the insoluble composition of THF (quality %) by the resinous principle on the glass filter 80 ℃ of following drying under reduced pressure after 3 hours quality and the mass ratio of sample calculate.

In addition, in the mensuration of molecular weight described later, use this filtrate as the solvable composition of THF.

With under the situation of vibrin, consider that in monochrome the temperature (TG) of the storage modulus of vibrin (G ') when reaching 6000Pa is preferably 130～230 ℃, more preferably 140～230 ℃, more preferably 150～230 ℃ from heat-resisting print through aspect.

Following the trying to achieve of temperature (TG): use commercially available Measurement of Dynamic Viscoelasticity device, for service test with plasticator under 130 ℃, 70rpm with the piece of resin melting mixing after 30 minutes, mensuration storage modulus when changing resin temperature (G '), try to achieve temperature (TG) thus.

Consider monochromatic complex viscosity coefficient (η with vibrin from low-temperature fixing and heat-resisting storage stability aspect ^*) temperature (TE) when reaching 1000Pas is preferably 80～140 ℃, more preferably 90～135 ℃, more preferably 105～130 ℃.

Monochromatic preferably contain the insoluble composition of THF of 2～70 quality %, more preferably 5～60 quality %, 10～50 quality % more preferably with vibrin.The insoluble composition of THF is 2 quality % when above, and heat-resisting print through excellence is 70 quality % when following, obtains excellent low-temperature fixing.

The peak molecular weight of above-mentioned vibrin (Mp) all is preferably 1000～30000, more preferably 1500～25000, more preferably 1800～20000 under any one situation of monochrome usefulness, panchromatic usefulness.Peak molecular weight (Mp) is 1000 heat-resisting storage stability when above and powder flowbility excellences, is the comminuted raising of 30000 toners when following, the productivity excellence.

Molecular weight in the toner when in addition, using the toner binder resins toner that contains vibrin of the present invention be the ratio of the composition 1500 below be preferably 1.8 quality % following, more preferably below the 1.3 quality %, more preferably below the 1.1 quality %.By making above-mentioned molecular weight is that the ratio of the composition below 1500 is that storage stability is more excellent below the 1.8 quality %.

Above and hereinafter, the peak molecular weight of vibrin or toner (Mp), number-average molecular weight (Mn) and molecular weight are that the ratio of the composition below 1500 uses GPC to measure under the following conditions to the solvable composition of THF.

Device: the HCL-8120 that Tosoh Co. makes

Post: TSKgelGMHXL (two)

TSKgelmultiporeHXL-M (one)

Measure temperature: 40 ℃

Sample solution: 0.25% THF solution

Solution injection rate IR: 100 μ l

Pick-up unit: RI-detector

Standard substance: polystyrene

The molecular weight of the peak heights that expression on the chromatogram that obtains is maximum is called peak molecular weight (Mp).In addition, the ratio of the peak area when cutting apart with molecular weight 1500 thinks poorly of the ratio that exists of Middle Molecular Substance.

The acid number of this vibrin all is preferably 0.1～60mgKOH/g, more preferably 0.2～50mgKOH/g, 0.5～40mgKOH/g more preferably under monochrome any one situation with, panchromatic usefulness.When above-mentioned acid number is the scope of 0.1～60mgKOH/g, the charging property excellence.

The hydroxyl value of above-mentioned vibrin all is preferably 1～70mgKOH/g, more preferably 3～60mgKOH/g, 5～55mgKOH/g more preferably under monochrome any one situation with, panchromatic usefulness.When above-mentioned hydroxyl value is the scope of 1～70mgKOH/g, the environmental stability excellence.

The glass transition temperature of above-mentioned vibrin (Tg) all is preferably 40～90 ℃, more preferably 50～80 ℃, more preferably 55～75 ℃ under any one situation of monochrome usefulness or panchromatic usefulness.When above-mentioned glass transition temperature (Tg) is 40～90 ℃ a scope, heat-resisting storage stability and low-temperature fixing excellence.

And DSC20, SSC/580 that the glass transition temperature of above-mentioned vibrin (Tg) for example can use Seiko Instruments Inc to make measure with the method for stipulating among the ASTM D3418-82 (DSC method).

The above-mentioned vibrin that uses as above-mentioned adhesive resin (A) can similarly prepare with the preparation method of common polyester.For example, under non-active gas (nitrogen etc.) atmosphere, in the presence of titanium-containing catalyst, temperature of reaction is preferably 150～280 ℃, more preferably 160～250 ℃, more preferably 170～240 ℃.In addition, consider that the reaction time is preferably more than 30 minutes, more preferably 2～40 hours from positively carrying out the polycondensation reaction aspect.In order to improve the reaction velocity of last stage reaction, reducing pressure, (for example 1～50mmHg) is effective.

Preparation method as linear polyesters resin (AX1), for example can enumerate following method: the quality with respect to the polymkeric substance that obtains be the titanium-containing catalyst of 0.0001～0.8 quality % and other catalyzer as required in the presence of, dibasic alcohol (g) and dicarboxylic acids (i) are heated to 180～260 ℃, under normal pressure and/or reduced pressure, carry out dehydrating condensation, thereby obtain (AX1).

Preparation method as non-linear polyesters resin (AX2), for example can enumerate following method: the quality with respect to the polymkeric substance that obtains be the catalyzer (a) of 0.0001～0.8 quality % and other catalyzer as required in the presence of, the polyvalent alcohol (h) that dibasic alcohol (g), dicarboxylic acids (i) and ternary is above is heated to 180～260 ℃, after carrying out dehydrating condensation under normal pressure and/or the reduced pressure, further with the reaction of polybasic carboxylic acid (j) more than the ternary, thereby obtain (AX2).Can also make (j) with (g), (i) and (h) react simultaneously.

Preparation method as modified polyester resin (AY1), can enumerate by add polyepoxide (c) in vibrin (AX2), the molecule lengthening reaction (molecule-extending reaction) of carrying out polyester under 180～260 ℃ obtains the method for (AY1).

Be preferably 1～60mgKOH/g, 5～50mgKOH/g more preferably with the acid number of (AX2) of (c) reaction.If above-mentioned acid number be more than the 1mgKOH/g, then do not have (c) unreacted residues and to the performance of resin bring dysgenic may, if be below the 60mgKOH/g, the excellent heat stability of resin then.

In addition, consider that the amount that is used to obtain (c) of (AY1) is 0.01～10 quality %, 0.05～5 quality % more preferably with respect to (AX2) preferably from low-temperature fixing and heat-resisting print through aspect.

Among the present invention,, consider, preferably use above-mentioned polycondensation vibrin from colour rendering, image intensity aspect as the full-color toner adhesive resin.Coloured image is because several plies of several toner layers, and the toner layer thickening produces because crackle, the defective of the insufficient image that causes of intensity of toner or lose suitable gloss.Therefore, use above-mentioned vibrin in order to keep suitable gloss or excellent intensity.

The above-mentioned vibrin of such adhesive resin does not especially preferably have the insoluble composition of THF, and in the molecular weight distribution of gel permeation chromatography, mass molecular weight is 5 * 10 ²The content of following composition is below the 4 quality %, and in mass molecular weight 3 * 10 ³～9 * 10 ³The zone in have the vibrin at a peak.If there is the insoluble composition of THF, then glossiness reduces, and the transparency reduces simultaneously, can not obtain high quality images when using the OHP sheet.Toner of the present invention for the molecular weight distribution of adhesive resin, is 5 * 10 with mass molecular weight preferably ²Following quality % is defined in below 4%, and in addition, preferably the ratio with weight-average molecular weight (Mw) and number-average molecular weight (Mn) is defined in 2≤Mw/Mn≤10, thus, is difficult for producing the film forming to scraper plate, sleeve etc.In addition, if mass molecular weight is 5 * 10 ²Following composition is more than the 4 quality %, then owing to long-time the use polluted scraper plate or sleeve, easily produces film forming.

In addition, the molecular weight distribution of the adhesive resin that uses in the toner of the present invention is by the following mensuration of gel permeation chromatography.In 40 ℃ hot cells (heat chamber), make post stable, in the post under this temperature, flow through THF, inject the THF sample solution 200 μ l that sample solution concentration is adjusted into the parent toner of 0.05～0.6 quality % and measure with the flow velocity of per minute 1ml.The THF sample solution is removed the insoluble composition of THF with the phase chromatography-use filtrator of 0.45 μ m before injection.

In the molecular weight determination of the sample of toner, the molecular weight distribution that sample has is calculated by the logarithm value of the typical curve of making by several monodisperse polystyrene standard samples and the relation of calculation times.As the polystyrene standard sample that standard curve making is used, the molecular weight that for example uses PressureChemical Co. or Tosoh Co. to make is 6 * 10 ², 2.1 * 10 ³, 4 * 10 ³, 1.75 * 10 ⁴, 5.1 * 10 ⁴, 1.1 * 10 ⁵, 3.9 * 10 ⁵, 8.6 * 10 ⁵, 2 * 10 ⁶, 4.48 * 10 ⁶The polystyrene standard sample, preferably use the polystyrene standard sample about 10 at least.In addition, detecting device uses RI (refractive index) detecting device.And adhesive resin has or not the insoluble composition of THF to judge when the THF of molecular weight distribution determination sample solution prepares.That is, the filter element of 0.45 μ m is installed in the top of syringe, when in syringe, extruding liquid, then judges the insoluble composition of no THF if filtrator does not block.

In addition, the adhesive resin that uses among the present invention endothermic peak that preferably adopts differential scanning calorimeter (DSC) to measure is 60～70 ℃.If above-mentioned endothermic peak is lower than 60 ℃, then influential to the toner keeping quality, might produce problems such as toner solidifies in box or in the hopper.On the other hand,, then influence the toner productivity, might produce the problems such as feed reduction when pulverizing if surpass 70 ℃.The endothermic peak that adopts differential scanning calorimeter (DSC) to measure, for example, the RigakuTHRMOFLEX TG8110 that makes by Rigaku Denki Co., Ltd measures under the condition of 10 ℃/min of programming rate, reads the very big peak of main body of endothermic curve.

In addition, as mentioned above, the weight-average molecular weight of above-mentioned vibrin (Mw) is preferably 2≤Mw/Mn≤10 with the ratio (Mw/Mn) of number-average molecular weight (Mn).If above-mentioned ratio (Mw/Mn) surpasses 10, can not get gloss when then making toner fixing, might can not obtain high quality images.On the other hand, less than 2, then productivity reduces in the pulverising step when toner prepares as if above-mentioned ratio (Mw/Mn), because long-time pollution scraper plate or the sleeve of using easily produces film forming.

In addition, when the above-mentioned vibrin that uses among the present invention particularly used aftermentioned resin strip controling agent, in the interaction of this resin strip controling agent and adjuvant, acid number was preferably below the 10mgKOH/g.The charging property of known vibrin and the pass of acid number are roughly proportional relation, and the negative charging of the high more then resin of acid number is big more, and be also influential to charged environmental characteristics simultaneously.That is, if the acid number height then under the low temperature and low humidity carried charge increase, hot and humid carried charge down reduces.Because because of the variation of the carried charge that environment caused, background is stained, the variation of image color, colorrendering quality increases, and is difficult to keep high quality image.In general, if acid number surpasses 20mgKOH/g, then might produce the increase of carried charge, the deterioration of environmental turbulence etc.

In the above-mentioned vibrin that uses among the present invention, controls such as the charging property that is had by aftermentioned resin strip controling agent, hydrophobicity monox, hydrophobic titanium oxide, resistance are as the resistance of toner particle.Therefore, if the acid number of vibrin surpasses 10mgKOH/g, then hinder the charged control effect of resin strip controling agent, hydrophobicity monox, hydrophobic titanium oxide.The acid number of the above-mentioned vibrin that uses among the present invention is preferably below the 10mgKOH/g, more preferably below the 5mgKOH/g.

The apparent viscosity that flow tester obtains of passing through of preferred above-mentioned vibrin reaches 10 ³Temperature during Pas is 95～120 ℃.If said temperature is lower than 95 ℃, then the abundant intensity forfeiture of the heat penetration seal during photographic fixing if surpass 120 ℃, then might can not get sufficient gloss.Apparent viscosity reaches 10 ³In the mensuration of the temperature of Pas, as flow tester, the CFT-500 type that for example uses Shimadzu Seisakusho Ltd. to make is at load 10kg/cm ², aperture 1mm * long 1mm, programming rate measure viscosity down for 5 ℃/minute, reading apparent viscosity is 10 ³The temperature of Pas.

-resin strip controling agent-

Contain the sulfonate groups monomer as the monomer that constitutes above-mentioned resin strip controling agent by interpolation, the negative charging of resin strip controling agent is given effect and is improved.On the other hand, because hydroscopicity, the environmental stability of toner (humiture stability) reduces, and uses so the general known aromatic monomer that will have electron withdraw group etc. are made multipolymer.Yet, though can use about thousands of, but if the long-term toner that uses more than tens thousand of, then produce the pollution or the photoreceptor film forming of development sleeve or layer thickness control parts (scraper plate or roller), exist the maintenance of the charged stability of toner or high quality image insufficient, the problem that productivity also reduces.

In order to remedy such shortcoming, in the toner of the present invention, for colour rendering or the image intensity aspect preferred polyester resin of using adhesive resin as full-color toner, use is contained the monomer of sulfonate groups by (1), (2) has the aromatic monomer of electron withdraw group, (3) three kinds of multipolymers that monomer is made of (methyl) acrylate monomer, or the multipolymer that the four kinds of monomers by (1)～(4) that further contain (4) aromatic vinyl monomer are made obtains charged stability and environmental stability excellence for a long time thus as the resin strip controling agent, the pollution of Nonvisualization sleeve or layer thickness control parts (scraper plate or roller), thin layer forms excellence, prevent the photoreceptor film forming, keep high quality image, the toner for developing electrostatic latent image that productivity is high.

For the molecular weight distribution of above-mentioned resin strip controling agent, definite quality molecular weight 1 * 10 ³Following quality %.Mass molecular weight 1 * 10 ³Following composition is low molecular weight compositions, multipolymer, ionomer, residual monomer etc., and they hinder charged generation, is subjected to the influence of humiture in addition and makes charged change.In addition, these compositions are influential to securities such as skin irritation or fish toxicities.If mass molecular weight 1 * 10 ³Following composition is more than the 10 quality %, then is subjected to the influence of humiture significantly, the charging property instability.

Infer that above-mentioned effect is owing to following reason realizes.That is, be used in combination by monomer that will contain sulfonate groups and the aromatic monomer with electron withdraw group, negative charging is given effect and is improved.In addition, except (methyl) acrylate monomer, also use aromatic vinyl monomer, further improve charged environmental stability thus, resin hardness uprises simultaneously, the comminuted excellence that becomes, and the pollution of Nonvisualization sleeve or layer thickness control parts (scraper plate or roller) prevents that the effect of photoreceptor film forming from improving.

And, except the low molecular weight compositions of these resin strip controling agents, by will by the resin strip controling agent that is combined to form of these monomers with make up as the colour rendering and the image intensity aspect preferred polyester resin of full-color toner with adhesive resin, obtain suitable dispersiveness, the toner for developing electrostatic latent image of carried charge narrowly distributing be can obtain, long-term charged stability and high image quality obtained.

As the monomer that contains sulfonate groups that constitutes above-mentioned resin strip controling agent, can enumerate for example fatty family sulfonate groups monomer, contain the monomer of aromatic sulphonate group etc., as the monomer of above-mentioned fatty family sulfonate groups, can enumerate for example alkali metal salt, alkali salt, amine salt or the quaternary ammonium salt etc. of vinyl sulfonic acid, allyl vinyl sulfonic acid, 2-acrylamide-2-methyl propane sulfonic acid, methacryloxy ethyl sulfonic acid, perfluorooctane sulfonate etc.As the above-mentioned aromatic sulphonic acid alkali monomer that contains, for example can enumerate alkali metal salt, alkali salt, amine salt or the quaternary ammonium salt etc. of styrene sulfonic acid, sulfo group Phenyl Acrylamide, sulfo group phenyl maleimide, sulfo group phenyl clothing health acid imide etc.In the above-mentioned slaine, the salt of heavy metal (nickel, copper, zinc, mercury, chromium etc.) is not preferred from the security aspect.

As the aromatic monomer that constitutes above-mentioned resin strip controling agent with electron withdraw group, for example can enumerate, chlorostyrene, dichlorostyrene, bromstyrol, fluorobenzene ethene, nitrostyrolene, styrene substituents such as cyano styrene, chlorphenyl (methyl) acrylate, bromophenyl (methyl) acrylate, nitrobenzophenone (methyl) acrylate, phenyl (methyl) acrylate substituents such as chlorphenyl oxygen ethyl (methyl) acrylate, chlorphenyl (methyl) acrylamide, bromophenyl (methyl) acrylamide, phenyl (methyl) acrylamide substituents such as nitrobenzophenone (methyl) acrylamide, the chlorphenyl maleimide, the dichlorophenyl maleimide, the nitrobenzophenone maleimide, phenyl maleimide substituents such as nitroxyl chloride phenyl maleimide, chlorphenyl clothing health acid imide, dichlorophenyl clothing health acid imide, nitrobenzophenone clothing health acid imide, phenyl clothing health acid imide substituents such as nitroxyl chloride phenyl clothing health acid imide, the chlorphenyl vinyl ether, Vinyl phenyl ether substituents such as nitrobenzophenone vinyl ether etc.Wherein, the phenyl maleimide substituent that is replaced by chlorine atom or nitro, phenyl clothing health acid imide substituent are preferred especially aspect charging property or the anti-film forming.

As (methyl) acrylate monomer that constitutes above-mentioned resin strip controling agent, for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) stearyl acrylate ester, (methyl) dodecylacrylate, (methyl) 2-EHA etc.

As the aromatic vinyl monomer that constitutes above-mentioned resin strip controling agent, can enumerate for example styrene, vinyltoluene, α-Jia Jibenyixi etc.

In the constituent ratio of each monomer in the above-mentioned resin strip controling agent, at first, the monomer that contains sulfonate groups is preferably 1～30 quality %, 2～20 quality % more preferably with respect to the gross mass of resin strip controling agent.If the above-mentioned monomer that contains sulfonate groups is less than 1 quality %, then initial strip electrical property or saturated zone electric weight are insufficient, easily image are brought influence sometimes.On the other hand, if surpass 30 quality %, then charged environmental stability worsens, and the carried charge when hot and humid is low, and in addition, the carried charge during low temperature and low humidity increases, and the charged stability of toner or the maintenance of high image quality are insufficient.Also there are the following problems: easily produce the pollution or the photoreceptor film forming of development sleeve or layer thickness control parts (scraper plate or roller), the productivity the when toner in mixing, the breaking method prepares also reduces.

Aromatic monomer with electron withdraw group is preferably 1～80 quality %, 20～70 quality % more preferably with respect to the gross mass of resin strip controling agent.If aromatic monomer with electron withdraw group is less than 1 quality %, then carried charge is insufficient, easily produces the stained or toner of background and disperses.In addition, if surpass 80 quality %, the poor dispersion in toner then, the carried charge of toner distributes and broadens, and easily produces the stained or toner of background and disperses, and the maintenance of high image quality is insufficient.

Acrylate monomer and/or methacrylate monomers are preferably 10～80 quality %, 20～70 quality % more preferably with respect to the resin strip controling agent.If acrylate monomer and/or methacrylate monomers are less than 10 quality %, then can not get charged environmental stability fully, in addition, comminuted insufficient when the toner in mixing, the breaking method prepares can not fully prevent the pollution or the photoreceptor film forming of development sleeve or layer thickness control parts (scraper plate or roller).If surpass 80 quality %, then initial charged or carried charge is insufficient, easily image is brought influence.

Above-mentioned aromatic vinyl monomer is preferably 0～30 quality %, 3～20 quality % more preferably with respect to the gross mass of resin strip controling agent.If above-mentioned aromatic vinyl monomer surpasses 30 quality %, then resin strip controling agent hardening, the dispersiveness in toner reduces, and charged distribution broadens, and easily produces the toner that background is stained or machine is interior and disperses.In addition, the colour rendering variation the during colour mixture of the fixation performance of toner, particularly color toner.

In the above-mentioned resin strip controling agent,, can use as mentioned above by the phenyl maleimide substituent or the phenyl clothing health acid imide substituent monomer of chlorine atom or nitro replacement as aromatic monomer.The inequality of the specific insulation that residue caused of the catalyzer when generation is considered to result from these monomers synthetic, polymerization inhibitor, solvent etc., influential to the toner carried charge of expectation sometimes.Therefore, might produce the problems such as increase of the initial charged or saturated zone electric weight of the toner that contains resin negative charging controlling agent.

Therefore, in the present invention, the specific insulation of resin strip controling agent is preferably 9.5～11.5Log Ω cm, 10.0～11.0Log Ω cm more preferably.If the specific insulation of above-mentioned resin strip controling agent is less than 9.5Log Ω cm, then the toner initial stage on the developer roll can not fully obtain desired carried charge, produces the stained or toner of background sometimes and disperses.On the other hand, if the specific insulation of resin strip controling agent surpasses 11.5Log Ω cm, though then the toner initial stage on the developer roll obtains desired carried charge, but increase through the certain hour carried charge, toner thin layer in the single component development mode on the developer roll heterogeneity that becomes produces color striped, inequality on image.In addition, image color reduces in the bi-component visualization way, produces the stained or toner of background sometimes and disperses.

The mensuration of the specific insulation of above-mentioned resin strip controling agent for example can be measured according to JIS K6911.The resin strip controling agent is carried out whole grain with sieve, damping under 23 ℃, 50%RH.With the automatic pressure forming machine of this sample, at sample size 3g, pressurization 500kg/cm ²Compacted under, the discoideus test film of manufacturing thickness 2mm, diameter 4cm.On the correct basis of measuring, be installed on the dielectric loss analyzer (Ando Electric Co., Ltd's manufacturing, TR-10C) with vernier caliper at thickness, apply the alternating voltage of frequency 1kHz, measure specific insulation.

Above-mentioned resin strip controling agent preferably reaches 10 by the apparent viscosity that flow tester obtains ⁴Temperature during Pas is 85～110 ℃.If said temperature is lower than 85 ℃, then can not get the suitable dispersiveness in toner, not only charged reduction but also storage-stable be variation also, and easily cohesion is solidified.In addition, in the method that the production stage by mixing, pulverizing, classification obtains, easily generation is bonding in the pulverising step, and productivity reduces sometimes.On the other hand, if said temperature surpasses 110 ℃, then the dispersiveness in toner reduces, and carried charge distributes and broadens, and easily produces background toner stained or that machine is interior and disperses.In addition, the colour rendering variation the during colour superimposition of the fixation performance of toner, particularly color toner.Above-mentioned apparent viscosity is 10 ⁴In the mensuration of the temperature of Pas, the CFT-500 type that for example uses Shimadzu Seisakusho Ltd. to make as flow tester is at load 10kg/cm ², aperture 1mm * long 1mm, programming rate measure viscosity down for 5 ℃/minute, reading apparent viscosity is 10 ⁴Temperature during Pas.

The quality mean molecular weight of above-mentioned resin strip controling agent is preferably 5 * 10 ³～1 * 10 ⁵If above-mentioned quality mean molecular weight is less than 5 * 10 ³, then can not get the suitable dispersiveness in toner, not only charged reduction but also obtain in the method for toner at the production stage of, pulverizing mixing by containing, classification easily produces bondingly in pulverising step, and productivity reduces sometimes.On the other hand, if above-mentioned quality mean molecular weight surpasses 1 * 10 ⁵, then the dispersiveness in toner reduces, and carried charge distributes and broadens, and easily produces background toner stained or that machine is interior and disperses, and in addition, the fixation performance of toner, colour rendering be variation sometimes.

In addition, the mass molecular weight 1 * 10 of above-mentioned resin strip controling agent ³Following composition is preferably below the 10 quality %, more preferably below the 6 quality %.Mass molecular weight 1 * 10 ³Following composition is low molecular weight compositions, multipolymer, ionomer, residual monomer etc., and they hinder charged generation, also is subjected to the influence of humiture in addition and makes charged change.In addition, these compositions are influential to securities such as skin irritation or fish toxicities.

In addition, with above-mentioned adhesive resin of the present invention to pass through the apparent viscosity that flow tester obtains be 10 ³The temperature of Pas be set at T1, with above-mentioned resin strip controling agent to pass through the apparent viscosity that flow tester obtains be 10 ⁴When the temperature of Pas is set at T2, preferably satisfy the relation of following formula 0.9＜T1/T2＜1.4.

The dispersion of above-mentioned charged controlling agent in adhesive resin becomes the key factor of the chargeding performance of decision toner.Among the present invention,, can obtain the electrically excellent toner of charging property excellence, initial strip by the combination of specific adhesive resin and specific resin strip controling agent.But as shown in the above description, the dispersiveness (compatibility) of adhesive resin and resin strip controling agent is influential to chargeding performance.The inventor be conceived to adhesive resin and resin strip controling agent separately pass through the apparent viscosity that flow tester obtains, simultaneously their dispersion degree is studied, obtain optimum range.The T1/T2 ratio was less than 0.9 o'clock, and the apparent viscosity of adhesive resin and resin strip controling agent is approaching, and adhesive resin and resin strip controling agent form compatible state, and deficiency, the initial strip of generation saturated zone electric weight is electrically poor etc.If T1/T2 is than surpassing 1.4, then the apparent viscosity of adhesive resin and resin strip controling agent has big difference, resin strip controling agent poor dispersion, and generation initial stage background is stained, the charged reduction of process certain hour.For specific resin strip controling agent, constitute monomer, regulation apparent viscosity, stipulate and the apparent viscosity ratio of the adhesive resin that disperses by regulation, show excellent charging property, also be difficult for the generation film forming simultaneously.

The addition of above-mentioned resin strip controling agent is preferably 0.1～20 quality %, 0.5～10 quality % more preferably with respect to toner particle.If above-mentioned addition is less than 0.1 quality %, then initial charged or carried charge is insufficient, background is stained, dust etc. easily influences image sometimes.On the other hand, if surpass 20 quality %, then disperse variation, carried charge distributes and broadens, and easily produces background toner stained or that machine is interior sometimes and disperses.

As the adjuvant that uses in the toner of the present invention, be illustrated below, when using the resin strip controling agent, monox, primary particle size 0.01～0.03 μ m and the specific surface area handled through hydrophobization that can enumerate primary particle size 0.01～0.03 μ m are 60～140m ²The titanium dioxide of/g with particular characteristic through the hydrophobization processing.By these adjuvants are used with above-mentioned vibrin, resin strip controling agent, obtain the stable toner of charging property.

The monox of handling through hydrophobization by making primary particle size 0.01～0.03 μ m is given necessary flowability of toner and charging property attached on the parent toner surface, becomes excellent to the development of photoreceptor on the developer roll and from developer roll.The addition of such monox is preferably more than 2.1 mass parts with respect to 100 mass parts parent toners.Thus, the thin layer of toner on the developer roll homogeneous that becomes, the inequality of thin layer is significantly improved, by the stirring of long-term developer roll, prevent since toner to the generation of the molten sticking informal voucher line that is caused that stirs developer coating scraper plate.When the addition of monox was less than this scope, existence can not fully obtain the flowability of toner and not supply with the toner of the necessary amount of developer roll or can not get the situation of the carried charge of necessary toner.In addition, the thin layer of toner on the developer roll heterogeneity that becomes, have the situation of the development of the homogeneous that can not get toner and image or produce since toner to the situation of the molten sticking informal voucher line that is caused that stirs developer coating scraper plate.

In addition, be 60～140m by making primary particle size 0.01～0.03 μ m and specific surface area ²On the surface of titanium dioxide attached to the parent toner through the hydrophobization processing of/g, the stabilization of the charging property of toner particularly prevents the electrical and carried charge increase of initial strip.The addition of the titanium dioxide of the type is preferably 0.4～1.0 mass parts with respect to 100 mass parts parent toners.If above-mentioned addition is less than 0.4 mass parts, then the charging property of toner is too high, does not carry out the development of sufficient toner sometimes, and addition is during more than 1.0 mass parts, exist the charging property of toner low excessively, toner disperses or becomes the situation of the stained reason of background from developer roll.

And above-mentioned parent toner is meant the material beyond the adjuvant, is the particle that contains at least in the preparation process of adhesive resin, colorant and resin strip controling agent.

In addition, in toner binder resin of the present invention (A), except above-mentioned polycondensation vibrin, can also contain other resin etc. as required.

As above-mentioned other resin, can enumerate styrene resin for example [multipolymer of styrene and multipolymer, styrene and the dienes monomer of (methyl) alkyl acrylate etc.], epoxy resin (bisphenol-A diglycidyl ether ring-opening polymerization polymer etc.), urethane resin (polyvalent alcohol more than dibasic alcohol and/or the ternary and the addition polymer of diisocyanate etc.) etc.

The quality mean molecular weight of above-mentioned other resin is preferably 1000～2,000,000.

The content of above-mentioned other resin in toner binder resin (A) is preferably 0～40 quality %, more preferably 0～30 quality %, 0～20 quality % more preferably.

During when being used in combination two or more vibrin and with at least a vibrin and other mixed with resin, can carry out powder or melting mixing in advance, also can when the preparation toner, mix.

Temperature during melting mixing is preferably 80～180 ℃, more preferably 100～170 ℃, more preferably 120～160 ℃.If mixing temperature is low excessively, then can not fully mix, heterogeneity sometimes becomes.When mixing two or more vibrin, if mixing temperature is too high, then because ester exchange reaction causes equalization etc., so can not keep sometimes as the necessary resin rerum natura of toner binder.

Incorporation time during melting mixing is preferably 10 seconds～and 30 minutes, more preferably 20 seconds～10 minutes, more preferably 30 seconds～5 minutes.When mixing two or more vibrin, if incorporation time is long, then because ester exchange reaction causes equalization etc., so can not keep sometimes as the necessary resin rerum natura of toner binder.

Mixing arrangement during as melting mixing can be enumerated batch-mixed device and continous way mixing arrangements such as reactive tank.For homogeneous in the suitable following short time of temperature mixes, preferred continous way mixing arrangement.As the continous way mixing arrangement, can enumerate extruder, continuous kneader, three rollers etc.Wherein, be preferably extruder and continuous kneader.

During mixed-powder, can in common mixing condition and mixing arrangement, mix.

Mixing condition during as mixed-powder, mixing temperature are preferably 0～80 ℃, more preferably 10～60 ℃.Incorporation time is preferably more than 3 minutes, more preferably 5～60 minutes.As mixing arrangement, can enumerate for example Henschel mixer, nauta mixer, banbury mixers etc.Wherein, be preferably Henschel mixer especially.

Toner for developing electrostatic latent image of the present invention is made of adhesive resin (A) and colorant (B) at least, also contains release agent (C), charged controlling agent (D) and flowing agent various adjuvants such as (E) as required.

-colorant-

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

When using dyestuff or pigment, the content of above-mentioned colorant is preferably 1～15 quality %, 3～10 quality % more preferably with respect to toner.

In addition, when using Magnaglo as colorant, with respect to toner be preferably 1～70 quality %, more preferably 15～70 quality %, more preferably 30～60 quality %, be preferably 2～30 quality % especially.

Above-mentioned colorant also can be made the rubber master batch material with resin compoundedization and use.Preparation as the rubber master batch material, perhaps with the mixing adhesive resin of rubber master batch material, can enumerate polystyrene, poly-to chlorostyrene, the polymkeric substance of styrene such as polyvinyl toluene or its substituent, or the multipolymer of they and vinyl compound, polymethylmethacrylate, poly-n-butyl methacrylate, Polyvinylchloride, polyvinyl acetate (PVA), tygon, polypropylene, polyester, epoxy resin, the many alcohol resins of epoxy, polyurethane, polyamide, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, aliphatics or alicyclic hydrocarbon resin, fragrance same clan petroleum resin, chlorinated paraffin, paraffin etc.They can be used alone, and also can make up two or more uses.

-release agent-

As above-mentioned release agent (C), fusing point be 50～120 ℃ low-melting wax and the dispersion of adhesive resin in more effectively between fixing roller and toner interface, work as release agent, thus to fixing roller coating wet goods release agent and print through shows effect for high temperature.

As such wax composition,, can enumerate vegetable waxs such as Brazil wax, cotton wax, haze tallow, rice wax as the wax class; Animal wax such as beeswax, sheep oil; Ceresine, purification ceresine mineral waxs such as (cerasin); Pertroleum waxes such as paraffin, microcrystalline wax, vaseline etc.

In addition, except these natural waxs, can enumerate synthetic chloroflos such as fischer-tropsch wax, Tissuemat E; The synthetic wax of ester, ketone, ether etc. etc.In addition, can also use fatty acid amides such as 12-hydroxyl stearmide, stearmide, anhydride phthalic acid acid imide, chlorinated hydrocabon; On side chain, has crystalline polymer of long alkyl etc. as the homopolymer of polyacrylate such as the positive stearyl ester of the polymethylacrylic acid of low-molecular-weight crystalline polymer resin, polymethylacrylic acid dodecyl ester or multipolymer (for example, multipolymer of the positive stearyl ester-Jia Jibingxisuanyizhi of acrylic acid etc.) etc.

As above-mentioned release agent (C), can enumerate Brazil wax (C1), fischer-tropsch wax (C2), paraffin (C3), polyolefin-wax (C4) etc.

As (C1), can enumerate natural Brazil wax, take off free-fat acid type Brazil wax.

As (C2), the wax that can enumerate petroleum-type fischer-tropsch wax (ParaflintH1, Paraflint H1N4 that Schumann Sasol Co. makes and Raflint C105 etc.), natural-gas class fischer-tropsch wax (FT100 that Shell MDS Co. makes etc.) or these fischer-tropsch wax are obtained with method purifying such as crystallization respectively [MDP-7000, MDP-7010 etc. that Japanese smart wax Co., Ltd. makes] etc.

As (C3), can enumerate the paraffin [paraffinwax HNP-5, the HNP-9 that Japanese smart wax Co., Ltd. makes, HNP-11 etc.] of pertroleum wax class etc.

As (C4), can enumerate Tissuemat E [Sunwax171P, Sunwax LEL400P etc. that Sanyo Chemical Industries, Ltd. makes], polypropylene wax [Biscol550P, Biscol 660P etc. that Sanyo Chemical Industries, Ltd. makes] etc.

In these waxes, preferred Brazil wax, fischer-tropsch wax, more preferably Brazil wax and petroleum-type fischer-tropsch wax.

By using these waxes as release agent, the low-temperature fixing excellence when making toner.

The content of above-mentioned release agent (C) in toner is preferably 0～15 quality %, 1～10 quality % more preferably.

-charged controlling agent-

As charged controlling agent (D), be not particularly limited, can use known charged controlling agent, for example nigrosine class dyestuff, triphenylmethane dye, contain chromium metal complex dyestuff, molybdic acid chelate pigment, contain golden azo dyes, rhodamine class dyestuff, alcoxyl base class amine, quaternary ammonium salt (containing the fluorine modified quaternary ammonium salt), alkylamide, the simple substance of phosphorus or compound, the simple substance of tungsten or compound, fluorine class activating agent, contain QAS polymer, contain the sulfonic group polymkeric substance, the fluorinated polymkeric substance, Halogen substituted aroma cyclopolymer, the slaine of salicylic acid metal salt and salicyclic acid derivatives etc.Specifically, can enumerate the Bontron 03 of nigrosine class dyestuff, the Bontron P-51 of quaternary ammonium salt, the Bontron S-34 of containing metal azo dyes, the E-82 of hydroxynaphthoic acid metalloid coordination compound, the E-84 of salicylic acid metal complex, the E-89 of phenolic condensate (above by Orient Chemical Industries, Ltd. makes); TP-302, TP-415 (being Baotugu Chemical Industrial Co., Ltd makes) as the quaternary ammonium salt molybdenum complex; As the Copy Charge PSY VP 2038 of quaternary ammonium salt, as the Copy BluePR of triphenylmethane derivative, Copy Charge NEG VP 2036, Copy Charge NX VP 434 (being Hoechst Ltd. makes) as quaternary ammonium salt; LRA-901, as the LR-147 of boron coordination compound (be JapanCarlit Co., make); Copper phthalocyanine, perylene, quinacridone, azo class pigment, other the compound of high score subclass with functional groups such as sulfonic group, carboxyl, quaternary ammonium salts.Wherein, the preferred especially material that toner is controlled to be negative polarity that uses.

The content of above-mentioned charged controlling agent is because the toner preparation processes decision that has or not, comprises process for dispersing of the adjuvant that uses according to the kind of adhesive resin, as required, be not limited to unique content, but, be preferably 0.1～10 mass parts, 0.2～5 mass parts more preferably with respect to 100 mass parts adhesive resins.If above-mentioned content surpasses 10 mass parts, then the charging property of toner effect excessive, charged controlling agent reduces, and with the electrostatic attraction increase of developer roll, causes the flowability reduction of developer or the reduction of image color sometimes.

As the charged controlling agent that uses among the present invention, be preferably above-mentioned resin strip controling agent, two [1-(5-chloro-2-hydroxy phenyl azo)-beta naphthal] chromium (III) acid, the charged controlling agent of nigrosine, perfluoroalkyl trimethyl ammonium iodide, polyhydroxy-alkanoates or following general formula (III), (IV), (V) expression.

[chemical formula 6]

[chemical formula 7]

[chemical formula 8]

In addition, above-mentioned charged controlling agent preferably contains the monomer and the multipolymer that contain quaternary ammonium salt group of quality mean molecular weight in 2000～10000 scopes of following general formula (VII) expression of the monomer of following general formula (VI) expression of 65～97 quality % and 3～35 quality %.

[chemical formula 9]

[Chemical formula 1 0]

Above-mentioned general formula (VI) and (VII) in, R ₁Be hydrogen atom or methyl, R ₂Be hydrogen atom or methyl, R ₃Be alkylidene, R ₄, R ₅And R ₆Be respectively alkyl.

In addition, the preferred following general formula of above-mentioned charged controlling agent (VIII) or (IX) the charged controlling agent of expression.

[Chemical formula 1 1]

[Chemical formula 1 2]

Above-mentioned general formula (VIII) and (IX) in, a ₁Be 0.8～0.98, b ₁Be 0.01～0.19, c ₁Be 0.01～0.19, a ₁+ b ₁+ c ₁Be 1.

Above-mentioned charged controlling agent shows the charging property of remarkable excellence, and its content in toner is preferably 0.01～20 quality %, 0.1～15 quality % more preferably.

-flowing agent and toner external additive-

Inorganic particles as the external additive that adds the flowing agent (E) in the toner of the present invention to, for example can enumerate silicon dioxide, aluminium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, iron oxide, cupric oxide, zinc paste, tin oxide, silica sand, clay, mica, wollastonite, zeyssatite, chromium oxide, cerium oxide, iron oxide red, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit, silicon nitride etc.Wherein, preferable alloy oxide, metal nitride, metal carbide, and preferred number average particle diameter is the external additive of 8～80nm scope and the external additive of 120～300nm scope.In the above-mentioned inorganic particles, preferred silicon dioxide, aluminium oxide, titanium dioxide are preferably silicon dioxide, titanium dioxide especially.In addition, consider that the number average particle diameter that more preferably contains primary particle at least is that the titanium dioxide of 5～40nm is as external additive from toner charging property, mobile aspect.

It is 0.01～5 quality % that the external additive of this inorganic particles etc. more preferably uses with respect to the toner parent.

As the method for the flowability of highly controlling toner, not only control the preparation condition of external additive, and the pulverizing of external additive after generating, to sieve etc. also be effectively, in addition, also be important attached to the attachment state of toner surface.

As above-mentioned external additive; can be used in combination inorganic particles or hydrophobization and handle inorganic particles; but more preferably on toner surface, have at least two kinds of small particle diameter inorganic particles and big particle diameter inorganic particles, the mean grain size of the primary particle of described small particle diameter inorganic particles after hydrophobization is handled be preferably 1～20nm, more preferably 6～15nm (specific surface area of measuring by the BET method is 100～400m ²/ g), the mean grain size of the primary particle of described small particle diameter inorganic particles after hydrophobization is handled be preferably 30～150nm, more preferably 90～130nm (specific surface area of measuring by the BET method is 20～100m ²/ g).In addition, further preferred small particle diameter inorganic particles be silicon dioxide or titanium dioxide, if exist these both then more preferably.In addition, big particle diameter inorganic particles silicon dioxide more preferably.The more preferably silicon dioxide by damp process such as sol-gal process preparations.In addition, (specific surface area of measuring by the BET method is 40～100m if further there is 20～50nm on toner surface ²/ g) inorganic particles as in the particle diameter inorganic particles, then be more preferably, this inorganic particles is silicon dioxide more preferably.

As above-mentioned inorganic particles, then can use known all inorganic particles as long as satisfy condition.For example, can contain silicon dioxide microparticle, hydrophobic silica, fatty acid metal salts (zinc stearate, aluminium stearate etc.), metal oxide (titania, aluminium oxide, tin oxide, antimony oxide etc.), fluoropolymer etc.

As particularly preferred adjuvant, can enumerate silicon dioxide, titania, titanium dioxide, the alumina particulate of hydrophobization.As silicon dioxide microparticle, there are HDK H2000, HDK H2000/4, HDKH2050EP, HVK21, HDK H1303 (to be

Co. make); R972, R974, RX200, RY200, R202, R805, R812 (being Nippon Aerosil Co. makes).In addition, as titanium dioxide fine particles, P-25 (Nippon Aerosil Co. manufacturing) is arranged; STT-30, STT-65C-S (being TitaniumIndustries Ltd. makes); TAF-140 (Fuji Titanium Industry, Co. makes); MT-150W, MT-500B, MT-600B, MT-150A (being Tayca Co. makes) etc.Titanium oxide microparticle after particularly handling as hydrophobization has T-805 (Nippon Aerosil Co. manufacturing); STT-30A, STT-65S-S (being Titanium Industries Ltd. makes); TAF-500T, TAF-1500T (be Fuji TitaniumIndustry, Co. makes); MT-100S, MT-100T (being Tayca Co. makes); IT-S (Ishihara Sangyo Kaisha, Ltd.'s manufacturing) etc.

In order to obtain oxide fine particle, silicon dioxide microparticle, titanium dioxide fine particles and the alumina particulate that hydrophobization is handled, can handle hydrophilic particulate and obtain with silane coupling agents such as methyltrimethoxy silane, methyl triethoxysilane, octyl group trimethoxy silanes.In addition, if necessary, be preferably the silicone oil of inorganic particles being handled with the silicone oil heating and handle oxide fine particle, inorganic particles.

As silicone oil, for example, can use dimethyl silicon oil, methyl phenyl silicone oil, chlorphenyl silicone oil, hydrogenated methyl silicone oil, alkyl modified silicon oil, fluorine modified silicon oil, polyether modified silicon oil, the alcohol modified silicon oil, amino-modified silicone oil, epoxide modified silicone oil, epoxy/polyether modified silicon oil, phenol modified silicon oil, carboxy-modified silicone oil, sulfhydryl modified silicone oil, acrylic acid, methacrylic acid modified silicon oil, α-Jia Jibenyixi modified silicon oil etc.As inorganic particles, can enumerate for example silicon dioxide, aluminium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, iron oxide, cupric oxide, zinc paste, tin oxide, silica sand, clay, mica, wollastonite, zeyssatite, chromium oxide, cerium oxide, iron oxide red, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit, silicon nitride etc.Wherein preferred especially silicon dioxide and titania.Addition is preferably 0.1～5 quality %, 0.3～3 quality % more preferably with respect to toner.

The mean grain size of the primary particle of above-mentioned inorganic particles is preferably following, the 3nm～70nm more preferably of 100nm.If less than this scope, then inorganic particles buries in toner, is difficult to bring into play effectively its function.In addition, if greater than this scope, then damage photosensitive surface unevenly, so not preferred.

As other external additive, flowing agent, can enumerate the macromolecule based fine particles, the polystyrene that obtains by emulsifier-free emulsion polymerization or suspension polymerization, dispersin polymerization for example, methacrylate or acrylate copolymer, polycondensation classes such as silicone, benzoguanamine, nylon, the polymer particle that obtains by thermoset resin.

Such flowing agent can carry out surface treatment and improve hydrophobicity, even also can prevent the variation of flow characteristics or charged characteristic under high humility.Can enumerate for example preferred surface conditioning agent of conducts such as silane coupling agent, silylating agent, silane coupling agent, organic titanate class coupling agent, aluminium class coupling agent, silicone oil, modified silicon oil with fluorinated alkyl.

As the spatter property improving agent that is used to remove the developer after transfer printing residual on photoreceptor or the primary transfer body, can enumerate for example fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid; The polymer particles by preparation such as emulsifier-free emulsion polymerization such as polymethylmethacrylate particulate, ps particle etc. for example.The polymer particles preferred size distributes narrow and volume average particle size is the particulate of 0.01～1 μ m.

In the toner of the present invention, as other additive, for example can be used in combination fluoropolymer, low-molecular-weight polyolefin, metal oxide (aluminium oxide, tin oxide, antimony oxide etc.), electric conductivity imparting agent (carbon black, tin oxide etc.), magnetic and these additives are carried out surface treatment and additive of obtaining etc.These adjuvants can use a kind of, also can make up two or more uses, and its content is preferably 0.1～10 mass parts usually with respect to 100 mass parts toners.

Charged controlling agent, release agent can certainly dissolve, add when being scattered in the organic solvent with rubber master batch material, adhesive resin melting mixing.

As the method for in toner, adding, be not only the dry type of being undertaken and add processing outward, and to add adhering to that processing (solvent, water (contain and be used to activating agent that improves wetting state etc. as required)) carries out outward by wet type also be effective by Henschel mixer, Q mixer etc.

Though be the hybrid mode of external additive, but external additive can mix parent toner and external additive by using the mixer class to mix to the outer interpolation of parent toner, and stir, the dry type that covers toner surface when external additive is pulverized is mixed.At this moment, external additive such as inorganic particles or resin particle is evenly and securely attached to being important aspect the permanance on the parent toner.As the adding conditional of these external additives, the superficiality of the wing shape of mixer class, rotating speed, incorporation time, mixing number of times, external additive amount, parent toning dosage, parent toner (concavo-convex, hardness, viscoelasticity, other) is important.

In addition, as wet mixed, can in liquid, implement inorganic particles and adhere to processing.Can in water, form toner particle, carry out this step remove the surfactant etc. of use by washing after.Filter, the operation of Separation of Solid and Liquid such as centrifuging removes the remaining surfactant that is present in the water, filter cake, the slurry that obtains is scattered in the water-medium again.Further in this slurry, add and disperse inorganic particles.Inorganic particles is dispersed in the water system dispersion.At this moment, if use the surfactant of reversed polarity to disperse in advance, then can more effectively carry out adhering to surfaces of toner particles.In addition, inorganic particles is handled when being difficult to be dispersed in the water system dispersion through hydrophobization, can by with a spot of alcohol etc. be used in combination reduce interfacial tension become easily wetting after, inorganic particles is disperseed.Then, under agitation slowly add the water phase surfactant mixture of reversed polarity.The surfactant of reversed polarity preferably uses 0.01～1 quality % with respect to the toner particle solid constituent.By adding the surfactant of reversed polarity, the electric charge of inorganic particles dispersion in water is neutralized, and can make the inorganic particles cohesion attached on the surfaces of toner particles.This inorganic particles preferably uses 0.01～5 quality % with respect to the toner particle solid constituent.

Thereby these, after this by heating is fixed on the toner surface to slurry can prevent to break away from attached to the inorganic particles on the toner surface.At this moment, preferably under than the high temperature of the Tg of the resin that constitutes toner, heat.Can also carry out drying back heat treated when in addition, preventing to condense.

In addition, friction factor, raising spatter property in order to reduce photosensitive surface in toner of the present invention, can mix Metallic stearates as lubricant.Be preferably zinc stearate.

The preparation method of＜toner 〉

Electrostatic image developing toner of the present invention can prepare with hitherto known comminuting method or polymerization, for example can enumerate, air-flowing type comminuting method, mechanical type comminuting method, emulsion coagulation method, suspension polymerization etc. can not damage the effect of invention by this preparation method.

As the preparation method of toner, when for example carrying out, above-mentioned toner constituent is carried out after dry type mixes with known mixing comminuting method etc., melting mixing, then, it is broken that use jet mill etc. carries out micro mist, carry out air classification again, obtain the particle that volume average particle size is 2～10 μ m.

And above-mentioned volume average particle size uses Coulter-counter [trade name: Multitizer III (Beckman Coulter, Inc. makes)] to measure.

The preparation method of toner of the present invention can be known in the past any one method, if specifically describe, for example can use the preparation method of the toner that has following steps at least, described step is: with the step of the toner components mechanical mixture of adhesive resin, charged controlling agent and colorant, the step of melting mixing, the step of pulverizing and the step of classification.In addition, be also contained in the step of the step of mechanical mixture or melting mixing, will pulverize or classification step in powder beyond the particle that becomes goods that obtain return the preparation method who utilizes again.

Here the said particle powder (secondary product) in addition that becomes goods; particulate or corase particles after being meant the melting mixing step, beyond the composition of the goods that become the expectation particle diameter that obtain in the dispersion steps, particulate or corase particles beyond the composition of the goods that become the expectation particle diameter that perhaps in the classification step of carrying out subsequently, produce.Such secondary product preferably in blend step or melting mixing step with respect to raw material, preferably with respect to main raw material(s) 100 mass parts, mix 1～20 mass parts secondary product.

Carry out the blend step of mechanical mixture to major general's adhesive resin, colorant, resin strip controling agent or other toner components such as charged controlling agent, and the blend step that carries out mechanical mixture with adhesive resin, colorant, in charged controlling agent and the toner components that contains by-product, can use the common mixer etc. of the wing one-tenth by rotation under common condition, to carry out, be not particularly limited.

After above blend step finishes, potpourri added carry out melting mixing in the mixing roll.As the melting mixing machine, can use the continuous mixer of single shaft or twin shaft, the batch-type mixer that adopts roller to grind.For example, preferably use the KTK type biaxial extruder of Kobe Steel Ltd.'s manufacturing, the TEM type extruder that Toshiba Machinery Co., Ltd. makes, the biaxial extruder that KCK Co. makes, the PCM type biaxial extruder that Co., Ltd. of pond shellfish ironworker institute makes, the common kneader that Buss Co. makes etc.This melting mixing is important under the felicity condition of the molecular chain rupture that does not cause adhesive resin.Specifically, the melting mixing temperature should be carried out with reference to the softening point of adhesive resin, if compare too low temperature with softening point, then fracture is violent, and too high temperature then disperses and can not carry out.

After above melting mixing step finishes, then mixing thing is pulverized.In this pulverising step, preferably at first carry out coarse crushing and then carry out micro mist broken.At this moment, preferably use in jet-stream wind and impingement plate collision and the mode of pulverizing, in jet-stream wind, make collision between the particle to pulverize or in the close clearance of the rotor of mechanical rotation and stator, pulverize.After this pulverising step finished, crushed material was by centrifugal force classification in air-flow, preparation have the regulation particle diameter for example mean grain size be the developer of 5～20 μ m.

When preparing toner of the present invention,, in the parent toner of as above preparation, add the inorganic particles of enumerating more than mixing such as hydrophobic silica micropowder in order to improve flowability, keeping quality, development or transfer printing as developer.The mixer of general powder is used in the mixing of external additive, but preferably is equipped with chuck etc., can regulate temperature inside.In order to change the resume of the load that external additive is given, can be halfway or add external additive gradually.In addition, also can change the rotation number, velocity of rotation, time, temperature etc. of mixer.Can give strong load earlier, give more weak load then, also can carry out on the contrary.As operable mixing apparatus, can enumerate for example V-Mixer, shaking mixer (rocking mixers), Loedige mixer, nauta mixer, Henschel mixer etc.

Use the toner of the present invention of toner binder resin of the present invention, mix with the carrier particles such as ferrite that obtain by magnetic powder (iron powder, nickel powder, ferrite, magnetic iron ore etc.), beaded glass and/or resin (acryl resin, silicones etc.) coating surface as required, make the two-component developing agent of electric sub-image.In addition, also can form electric sub-image and substitute carrier particle with the friction of parts such as charged scraper plate.

Then, by photographic fixing on supporter (for example paper, polyester film etc.) such as known heat roller fixation methods, make recording materials.

In recent years, in order to obtain high meticulous and images with high image quality, the littler trend of particle diameter that makes toner is arranged.Though can reduce particle diameter by utilizing common preparation method mixing, comminuting method, consider that from energy or the yield rate aspect used it is very high that cost becomes, and has the pulverizing limit of particle diameter simultaneously, can not be corresponding to further reducing particle diameter.

Therefore, as the method that addresses this problem, polymerization toner preparation methods such as suspension polymerization, emulsion polymerization coacervation, dispersion copolymerization method have been proposed.

The preferred toner that uses adopts following method to obtain in the image processing system of the present invention, for example, the polyester prepolyer, vibrin, colorant and the release agent that have the functional group of containing nitrogen-atoms to the major general are dispersed in the organic solvent, obtain toner materials liquid, make this toner materials liquid in water solvent, carry out crosslinked or chain extending reaction.In addition, use above-mentioned polycondensation vibrin of the present invention in the vibrin of raw material at least.

Below, enumerate the constituent material of such toner and preparation method's example and describe.

-modified poly ester-

Above-mentioned toner contains modified poly ester (i) as adhesive resin.As this modified poly ester (i), be meant in vibrin, to have the binding groups beyond the ester bond or structure is different in vibrin resinous principle state by bondings such as covalent bond, ionic links.Specifically, be meant, react with the compound that contains active hydrogen again, the polyester end is carried out modification and the modified poly ester that obtains in the functional groups such as isocyanate group of the terminal importing of polyester with hydroxy-acid group, hydroxyl reaction.

As above-mentioned modified poly ester (i), can enumerate urea modified poly ester that polyester prepolyer (A) and amine (B) reaction by having isocyanate groups obtain etc.As the polyester prepolyer with isocyanate groups (A), can enumerate the polyester prepolyer that the polyester with active hydrogen group of the condensed polymer of polyvalent alcohol (PO) and polybasic carboxylic acid (PC) further obtains with polyisocyanate compound (PIC) reaction.As the active hydrogen group that above-mentioned polyester had, can enumerate hydroxyl (alcoholic extract hydroxyl group and phenolic hydroxyl group), amino, carboxyl, sulfydryl etc., wherein the preferred alcohols hydroxyl.

The following generation of urea modified poly ester.

As polyol compound (PO), can enumerate the above polyvalent alcohol (TO) of dibasic alcohol (DIO) and ternary, preferred independent (DIO) or (DIO) and the potpourri of a spot of (TO).As dibasic alcohol (DIO), can enumerate aklylene glycol (ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,6-hexanediol etc.); Alkylene ether glycol (diglycol, triethylene-glycol, dipropylene glycol, polyglycol, polypropylene glycol, polytetramethylene ether diol etc.); Ester ring type glycol (1,4 cyclohexane dimethanol, hydrogenated bisphenol A etc.); Bisphenols (bisphenol-A, Bisphenol F, bisphenol S etc.); The oxyalkylene of above-mentioned ester ring type glycol (oxirane, epoxypropane, epoxy butane etc.) addition product; The oxyalkylene of above-mentioned bisphenols (oxirane, epoxypropane, epoxy butane etc.) addition product etc.The aklylene glycol of wherein preferred carbon number 2～12 and the oxyalkylene addition product of bisphenols, the oxyalkylene addition product of preferred especially bisphenols with and with the combination of the aklylene glycol of carbon number 2～12.As the polyvalent alcohol more than the ternary (TO), can enumerate 3～8 yuan or more polynary multi-alcohol (glycerine, trimethylolethane, trimethylolpropane, pentaerythrite, D-sorbite etc.); The phenols (trisphenol PA, phenol novolaks, cresols novolaks etc.) that ternary is above; The oxyalkylene addition product of the polyatomic phenol that above-mentioned ternary is above etc.

As polybasic carboxylic acid (PC), can enumerate the above polybasic carboxylic acid (TC) of dicarboxylic acids (DIC) and ternary, preferred independent (DIC) and (DIC) and the potpourri of a spot of (TC).As dicarboxylic acids (DIC), can enumerate alkylene dicarboxylic acids (succinic acid, hexane diacid, decanedioic acid etc.); Alkenylene dicarboxylic acid (maleic acid, fumaric acid etc.); Aromatic dicarboxylic acid (phthalic acid, m-phthalic acid, terephthalic acid (TPA), naphthalenedicarboxylic acid etc.) etc.Wherein the alkenylene dicarboxylic acid of preferred carbon number 4～20 and carbon number are 8～20 aromatic dicarboxylic acid.As the polybasic carboxylic acid more than the ternary (TC), can enumerate the aromatic series polybasic carboxylic acid (trimellitic acid, pyromellitic acid etc.) of carbon number 9～20 etc.In addition, can also use the acid anhydrides of above-mentioned polybasic carboxylic acid or lower alkyl esters (methyl esters, ethyl ester, isopropyl ester etc.) to react as polybasic carboxylic acid (PC) and polyvalent alcohol (PO).

In equivalent proportion [OH]/[COOH] of hydroxyl [OH] with carboxyl [COOH], polyvalent alcohol (PO) is generally 2/1～1/1, is preferably 1.5/1～1/1, more preferably 1.3/1～1.02/1 with the ratio of polybasic carboxylic acid (PC).

As polyisocyanate compound (PIC), can enumerate aliphatic polyisocyante (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-two isocyanate group methyl caproates etc.); Ester ring type polyisocyanates (isophorone diisocyanate, cyclohexyl-methane diisocyanate etc.); Aromatic diisocyanate (toluene diisocyanate, '-diphenylmethane diisocyanate etc.); Aromatic-aliphatic diisocyanate (α, α, α ', α '-tetramethylbenzene dimethyl diisocyanate etc.); Isocyanates; With phenol derivatives, oxime, caprolactam etc. with the above-mentioned polyisocyanate blocked and material that obtains; And their two or more combinations.

In isocyanate groups [NCO] and equivalent proportion [NCO]/[OH] with hydroxyl [OH] of the polyester of hydroxyl, the ratio of polyisocyanate compound (PIC) is preferably 5/1～1/1, more preferably 4/1～1.2/1, more preferably 2.5/1～1.5/1.If above-mentioned [NCO]/[OH] surpasses 5, then low-temperature fixing worsens sometimes.The mol ratio of [NCO] was used under the situation of urea modified poly ester less than 1 o'clock, and the urea content in this ester reduces, heat-resisting print through deterioration.

Content with polyisocyanate compound (PIC) constituent in the polyester prepolyer (A) of isocyanate group is preferably 0.5～40 quality %, more preferably 1～30 quality %, 2～20 quality % more preferably.If above-mentioned content is less than 0.5 quality %, then heat-resisting print through deterioration, simultaneously have concurrently heat-resisting keeping quality and low-temperature fixing aspect unfavorable sometimes, if surpass 40 quality %, then low-temperature fixing worsens sometimes.

Per 1 molecule has that the isocyanate groups that contains in the polyester prepolyer (A) of isocyanate groups is preferably more than 1, more preferably 1.5～3 of average out to, further 1.8～2.5 of preferred average out to.If during less than 1, the molecular weight of urea modified poly ester reduces in per 1 molecule, heat-resisting print through worsens sometimes.

Then, as with the amine (B) of polyester prepolyer (A) reaction, can enumerate the above polyamine compound (B2) of diamine compound (B1), ternary, amino alcohol (B3), amineothiot (B4), amino acid (B5) and with the amino-terminated of B1～B5 and the material (B6) that forms etc.

As diamine compound (B1), can enumerate aromatic diamine (phenylenediamine, diethyl toluene diamine, 4,4 '-diaminodiphenyl-methane etc.); Ester ring type diamines (4,4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride, cyclohexane diamine, isophorone diamine etc.); And aliphatic diamine (ethylenediamine, butanediamine, hexane diamine etc.) etc.As the above polyamine compound of ternary (B2), can enumerate diethylene triamine, trien etc.As amino alcohol (B3), can enumerate monoethanolamine, ethoxylaniline etc.As amineothiot (B4), can enumerate aminoethyl mercaptan, aminopropyl mercaptan etc.As amino acid (B5), can enumerate alanine, aminocaproic acid etc.As the above-mentioned amine (B6) that the amino-terminated of B1～B5 formed, can enumerate ketimine compound, oxazolidine compound that amine and ketone (acetone, MEK, hexone etc.) by above-mentioned B1～B5 obtain etc.In these amines (B), the potpourri of preferred B1 and B1 and a spot of B2.

In equivalent proportion [NCO]/[NHx] of the amino [NHx] in isocyanate groups [NCO] in the polyester prepolyer (A) with isocyanate groups and the amine (B), the ratio of amine (B) is preferably 1/2～2/1, more preferably 1.5/1～1/1.5, more preferably 1.2/1～1/1.2.If above-mentioned [NCO]/[NHx] is above 2 or less than 1/2, then the molecular weight of urea modified poly ester reduces, and heat-resisting print through worsens sometimes.

In addition, in the urea modified poly ester, can also contain urea key and amino-formate bond simultaneously.The mol ratio of urea linkage content and carbamate linkage content is preferably 100/0～10/90, more preferably 80/20～20/80, more preferably 60/40～30/70.If the mol ratio of above-mentioned urea key is less than 10%, then heat-resisting print through worsens sometimes.

The modified poly ester that uses among the present invention (i) is by single stage method, prepolymer method preparation.The quality mean molecular weight of above-mentioned modified poly ester (i) is preferably more than 10,000, more preferably 20,000～1,000 ten thousand, more preferably 30,000～1,000,000.The peak molecular weight of this moment is preferably 1000～10000.If above-mentioned peak molecular weight is difficult to carry out chain extending reaction less than 1000, the elasticity of toner is little, and the heat-resisting print through of result worsens sometimes; If surpass 10000, then aspect reduction, particlized or the pulverizing of fixation performance, it is serious that the problem in the preparation becomes sometimes.For the number-average molecular weight of above-mentioned modified poly ester (i), be not particularly limited when using unmodified polyester described later (ii), can be the number-average molecular weight that obtains above-mentioned quality mean molecular weight easily.During independent (i), number-average molecular weight is preferably below 20000, more preferably 1000～10000, more preferably 2000～8000.If above-mentioned number-average molecular weight surpasses 20000, then low-temperature fixing and the glossiness when being used for panchromatic device worsen sometimes.

At the crosslinked or chain extending reaction of the polyester prepolyer that is used for obtaining above-mentioned modified poly ester (i) (A) and amine (B), can use the molecular weight of the urea modified poly ester that reaction terminating agent adjustment obtains as required.As reaction terminating agent, can enumerate monoamine (diethylamine, dibutylamine, butylamine, dodecyl amine etc.), and the reaction terminating agent (ketimine compound) that their end-blockings are obtained etc.

And the molecular weight of the polymkeric substance of generation can be that solvent uses gel permeation chromatography (GPC) to measure with THF.

-unmodified polyester-

In the present invention, not only can use the polyester (i) of above-mentioned modification separately, can also contain unmodified polyester (ii) as the adhesive resin composition with this (i).By being used in combination (ii), the glossiness when improving low-temperature fixing and being used for panchromatic device is more preferably used separately.As (ii), can enumerate the condensed polymer of polyvalent alcohol (PO) identical and polybasic carboxylic acid (PC) etc. with the polyester composition of above-mentioned (i), preferred example is also identical with (i).In addition, (ii) not only can be unmodified polyester, also can be with the polyester of the chemical bond modification beyond the urea key, for example can carry out modification with amino-formate bond.(i) and (ii) at least a portion is compatible preferred aspect low-temperature fixing, heat-resisting print through.Therefore, polyester composition (i) and (ii) be preferably similar composition.(i) when containing (ii) is preferably 5/95～80/20, more preferably 5/95～30/70, more preferably 5/95～25/75, is preferably 7/93～20/80 especially with mass ratio (ii).If the mass ratio of above-mentioned (i) is less than 5%, then heat-resisting print through deterioration, simultaneously have concurrently aspect heat-resisting keeping quality and the low-temperature fixing unfavorable sometimes.

Peak molecular weight (ii) is preferably 1000～10000, more preferably 2000～8000, more preferably 2000～5000.If above-mentioned peak molecular weight is less than 1000, then heat-resisting keeping quality worsens sometimes, if surpass 10000, then low-temperature fixing worsens sometimes.Hydroxyl value (ii) is preferably 5mgKOH/g above, more preferably 10～120mgKOH/g, 20～80mgKOH/g more preferably.If above-mentioned hydroxyl value is less than 5mgKOH/g, then have concurrently aspect heat-resisting keeping quality and the low-temperature fixing unfavorable sometimes.Acid number (ii) is preferably 1～5mgKOH/g, 2～4mgKOH/g more preferably.Because wax uses the wax of high acid value, therefore bonding agent is complementary with the toner that is used for bi-component class developer easily because low acid value binder is relevant with charged or high specific insulation.

The glass transition temperature of above-mentioned adhesive resin (Tg) is preferably 35～70 ℃, more preferably 55～65 ℃.If above-mentioned glass transition temperature is lower than 35 ℃, then the heat-resisting keeping quality of toner worsens, if surpass 70 ℃, then low-temperature fixing becomes insufficient.Therefore the urea modified poly ester, in toner of the present invention, is compared with known polyesters toner owing to be present on the surface of the toner parent particle that obtains easily, even glass transition temperature is low, also shows the trend of heat-resisting keeping quality excellence.

In addition, above-mentioned glass transition temperature (Tg) can pass through differential scanning calorimeter (DSC) mensuration.

Above-mentioned toner, be not particularly limited for its shape, size etc., can suitably select as required, but preferably have following volume average particle size, volume average particle size and the ratio (volume average particle size/number average particle diameter) of number average particle diameter, average circularity, shape coefficient SF-1 and SF-2, glass transition temperature, condensation degree, specific insulation and apparent density etc.

The volume average particle size of toner of the present invention is 2.0～10.0 μ m, be preferably 3.0～7.0 μ m, 3.0～5.0 μ m more preferably.In addition, the ratio (Dv/Dn) of volume average particle size (Dv) and number average particle diameter (Dn) is 1.00～1.40 scope, is preferably 1.00～1.30, more preferably 1.00～1.20.

By using the toner of small particle diameter, can be to electrostatic image adhering toner densely.But volume average particle size is than scope of the present invention hour, and in two-component developing agent, toner is molten under the long-term stirring of developing apparatus is bonded on the surface of magnetic carrier, and the charged ability of magnetic carrier reduces.On the contrary, when the volume average particle size of toner is bigger than scope of the present invention, be difficult to obtain high resolving power, images with high image quality, simultaneously, during the revenue and expenditure of the toner in carrying out developer, the situation that the change of the particle diameter of toner increases is many.

In addition, narrow down by making size distribution, the carried charge of toner distributes and becomes evenly, can obtain the few high quality images of background fog, in addition, can improve transferring rate.But if Dv/Dn surpasses 1.40, then the expansion because carried charge distributes, resolution also reduce, so not preferred.

In addition, in above-mentioned toner, the following powder content of 4 μ m is preferably the above meal content of 0～20 number %, 12.7 μ m and is preferably 0～3 number %.

Wherein, the mean grain size of toner and size-grade distribution can use Coulter Counter TA-II, Coulter Multisizer II (being Coulter Co. makes) to measure.Among the present invention, use CoulterCounter TA-II type to be connected with PC (PC9801, NEC Co., Ltd. make), measure with the interface (day science and technology is ground Co., Ltd. and made) of the distribution of output number, volume distributed median.

In addition, the toner preferable shape coefficient S F-1 that the present invention relates to is 100～180 a scope, more preferably 100～150.In addition, shape coefficient SF-2 is preferably 100～180 scope, more preferably 100～160.

Fig. 2 A, Fig. 2 B and Fig. 3 A～Fig. 3 C are the synoptic diagram of representing the toner shape for shape coefficient SF-1, shape coefficient SF-2 are described.Shape coefficient SF-1 represents the ratio of the circularity of toner shape, with following formula (1) expression.Be toner is projected on the two dimensional surface and the maximum length MXLNG of the shape that obtains square divided by graphics area AREA, multiply by 100 π/4 again and the value that obtains.

[mathematical expression 1]

SF-1={ (MXLNG) ²/ AREA} * (100 π/4) ... formula (1)

The value of above-mentioned SF-1 is 100 o'clock, toner be shaped as proper sphere, the value of SF-1 is big more then become more amorphous.

In addition, shape coefficient SF-2 represents the concavo-convex ratio of the shape of toner, with following formula (2) expression.Be with toner project to the figure that obtains on the two dimensional surface girth PERI square divided by graphics area AREA, multiply by 100 π/4 again and the value that obtains.

SF-2={ (PERI) ²/ AREA} * (100 π/4) ... formula (2)

The value of SF-2 is 100 o'clock, on toner surface, do not exist concavo-convex, the big more then toner surface of the value of SF-2 concavo-convex remarkable more.

If the shape subglobular of toner, then because toner approaches a contact with toner or toner with contacting of photoreceptor 1, and the absorption affinity between the toner dies down, therefore flowability raises, in addition, the absorption affinity of toner and photoreceptor 1 also dies down, transferring rate raises.On the other hand, spherical toner is owing to easily enter in the gap of cleaning balde 7a and photoreceptor 1, and the shape coefficient SF-1 or the SF-2 of toner can reach to a certain degree.In addition, if SF-1 and SF-2 increase, then toner disperses on image, and image quality reduces.Therefore, SF-1 and SF-2 preferably are no more than 180.

And, particularly, the mensuration of shape coefficient is following carries out: use scanning electron microscope (FE-SEMS-4800, Hitachi make) to take the photo of toner, this photo is imported in the image analysis apparatus (Luzex AP, Nireco Co. make) carry out analytical calculation.

In addition, in the present invention, use spindle shape and above-mentioned spindle shape to stipulate (wherein with major axis r1, minor axis r2, thickness r3, during r1 〉=r2 〉=r3), the ratio (r2/r1) of minor axis r2 and major axis r1 is 0.5～1.0 scope, thickness r3 and the ratio (r3/r2) of minor axis r2 is the toner of 0.7～1.0 scope, is preferred aspect colorrendering quality stable.

Fig. 3 A～Fig. 3 C is the synoptic diagram of the shape of this toner.Among Fig. 3 A, with major axis r1, minor axis r2, thickness r3 (wherein, during the roughly spherical toner of the regulation of r1 〉=r2 〉=r3), the ratio (r2/r1) (with reference to Fig. 3 B) of the preferred minor axis of toner of the present invention and major axis is 0.5～1.0, the ratio (r3/r2) (with reference to Fig. 3 C) of thickness and minor axis is 0.7～1.0 scope.The ratio (r2/r1) of minor axis and major axis because it is poor to depart from proper sphere shape, some repeatability and transfer efficiency, can not obtain high-quality image quality less than 0.5 o'clock.In addition, the ratio (r3/r2) of thickness and minor axis is less than 0.7 o'clock, near flat pattern, can not obtain the high transferring rate of spherical toner.Particularly thickness is 1.0 o'clock with the ratio (r3/r2) of minor axis, and forming major axis is the rotary body of turning axle, can improve the flowability of toner.

And r1, r2, r3 change the angle shot photo in the visual field by scanning electron microscope (SEM), observe and measure.

The preferred average circularity of above-mentioned toner is more than 0.94 and less than 1.00, more preferably 0.96～0.99.Average circularity is 0.94 when above, puts the repeatability excellence, from the uneven aspect of the colorrendering quality of the thin thread part that can reduce image, is preferred particularly.In addition, because transfer printing is also excellent, consider it is preferred from obtaining the high image quality aspect.In addition, when average circularity was high, toner was developed equably, transfer printing, in shadow tone portion, portion's toner forms piece and the situation of adhering to is few on the spot, was evenly distributed.Thus, toner lamination and when making colour superimposition, the few the same Neutral colour of inequality that can reproducing color therewith.Average circularity was less than 0.94 o'clock, and toner is to depart under the situation of spherical shape, is difficult to obtain the high quality images of sufficient transfer printing or free from dust.Unbodied particle like this is many to the contact point of flatness media such as photoreceptor, and charge concentration is in protruding top ends, so Van der Waals force or image force are compared the adhesion height with relatively more spherical particle.Therefore, in the static printing step, in the toner that amorphous particle and spheroidal particle mix, move to spherical particle selection, produce literal portion or line portion image and come off.In addition, for following development step, residual toner must be removed, and produces the unfavorable condition that needs cleaning device or toner yield (ratio of the toner that uses when image forms) to reduce.

In addition, the average circularity of toner is preferably below 30% less than the ratio of 0.93 toner particle.Above-mentioned ratio surpasses in the big toner of the deviation of 30% circularity, because charged speed, charged level broaden, carried charge distributes and also broadens, so not preferred.

The value that the average circularity of above-mentioned toner obtains for the girth of the equivalent circular that detects particle optically, equate divided by projected area.Specifically, use flow-type particle picture analytical equipment (FPIA-2000, Sysmex Corp. make) to measure.In the container of regulation, add the water that 100～150mL has removed impure solid matter in advance, add 0.1～0.5mL surfactant, add again and measure sample about 0.1～9.5g as spreading agent.The suspending liquid that is dispersed with sample is carried out about 1～3 minute dispersion treatment with ultrasonic disperser, and making dispersion liquid concentration is 3000～10000/μ L, shape and the distribution of measuring toner.

The condensation degree of above-mentioned toner is preferably 1～25%, more preferably 3～15%.

The assay method of above-mentioned condensation degree is following to carry out.The powder test instrument that determinator uses Hosokawa Micron Co. to make is installed appurtenances by following order on shaking table.

(i) vibra shoot

(ii) filler

(iii) spacer ring

(iv) on the sieve (three kinds)＞in＞down

(V) depression bar (pressing bar)

Then, fix, make shaking table work with spherical bolt.Condition determination is as described below.

Mesh size (on) 75 μ m

" (in) 45 μ m

" (descending) 22 μ m

Wide scale 1mm shakes

Sampling amount 2g

Time of vibration 15 seconds

After the mensuration, try to achieve condensation degree by following calculating.

The quality % of residual powder * 1 in the sieve of epimere ... (a)

The quality % of residual powder * 0.6 in the sieve in stage casing ... (b)

The quality % of residual powder * 0.2 in the sieve of hypomere ... (c)

With the total of above-mentioned three calculated values as condensation degree (%).That is condensation number (%)=(a)+(b)+(c).

In the above-mentioned toner, preferred apparent bulk density (loose apparent density) is 0.2～0.7g/ml.

Above-mentioned apparent bulk density for example can be measured by the powder test instrument PT-S that Hosokawa Micron Co. makes.

Above-mentioned toner preferred volume resistivity is 8～15 (Log Ω cm), 9～13 (Log Ω cm) more preferably.

Above-mentioned specific insulation is following value: be arranged on the toner that pushes on the particle between the parallel pole in 2mm gap, interval, between two electrodes, apply DC 1000V, with high resistance meter (for example TR8601 of the AdvantestCo. manufacturing) resistance value of mensuration after 30 seconds, the value that obtains is converted by resistance value and grain thickness, is converted to the value (logarithm value) of specific insulation.

The softening point of above-mentioned toner is preferably 80～180 ℃, more preferably 90～130 ℃.

For the softening point of above-mentioned toner, use flow tester under the following conditions the constant heatingrate, its discharge is reached 1/2 o'clock temperature as softening point.

Device: Shimadzu Seisakusho Ltd. makes flow tester CTF-500D

Load: 20kgf/cm ²

Die head: 1mm φ-1mm

Programming rate: 6 ℃/min

Sample size: 1.0g

Above-mentioned toner preferred glass transition temperature T g is 35～90 ℃, more preferably 45～70 ℃.

The glass transition temperature of above-mentioned toner (Tg) for example can use following differential scanning type calorimeter, measure under the following conditions.

Differential scanning calorimeter: SEIKO1DSC100

SEIKO1SSC5040(Disk Station)

Condition determination:

Temperature range: 25～150 ℃

Programming rate: 10 ℃/min

Sample time: 0.5 second

Sample size: 10mg

(toner Cartridge)

Toner Cartridge of the present invention contains above-mentioned toner of the present invention, contains Yellow toner, pinkish red toner and cyan toner at least,

Above-mentioned pinkish red toner contains the organic pigment shown in the following structural formula (1).

Above-mentioned Yellow toner contains the organic pigment that has two following structural frameworks (A) and do not have halogen atom in molecule.

[Chemical formula 1 3]

Wherein, above-mentioned formula (1) and (A) in ,=C=N-NH-comprises=situation of CH-N=N-.

Toner Cartridge of the present invention, by in the vibrin that in the presence of specific novel above-mentioned titanium-containing catalyst, forms, disperseing specific yellow uitramarine, magenta pigment, improve the colorrendering quality of the redness of the colorrendering quality of image, particularly Neutral colour very effectively.

Though it is also indeterminate by the mechanism that above-mentioned specific raw materials formation toner improves colorrendering quality, but be presumed as follows:, realized being suitable for the strand state and/or the molecular weight distribution state of pigment dispersing along with novel above-mentioned titanium-containing catalyst has effective catalyst activity.Therefore, infer that the energy of the cohesion again of the pigment that temporarily is dispersed in when toner prepares in the resin reduces, can still keep the state that disperses, the raising that produces the toner colorrendering quality when thinking imaging.

Organic pigment shown in the structural formula of above-mentioned pinkish red toner (1) is an azo lake pigment.Up to now, as pinkish red toner pigment, use AZO pigments such as azo lake pigment, insoluble azo colour; Organic pigments such as many rings pigment of quinacridine ketone.Aphthols, hydroxynaphthoic acid class are arranged in the AZO pigments, wherein,, used C.I.PR49, C.I.PR68, C.I.PR184 etc. up to now as aphthols pigment.In addition, as the quinacridine ketone, C.I.PR122, C.I.PR209, C.I.PR206 etc. have been used.As above-mentioned pinkish red toner, it is characterized in that using organic pigment, the C.I.PR269 shown in the said structure formula (1) of hydroxynaphthoic acid class.This pigment has narrow absorption region in the wavelength region may of 500～600nm, therefore reproduce bright-coloured magenta.

Particularly after photographic fixing on the recording mediums such as transfer paper, diaphragm, use the X-RITE938 densimeter, the ID (image color: be-Log reflectivity), use L that the condition of spending by the observation visual angle under the observation light D50 (JIS Z-8720 (1983)) 2 obtains at 1.00 o'clock ^*a ^*b ^*Color specification system (CIE1976) expression, a ^*Be 55～75, b ^*It is 0～-8 scope.This makes the concentration that the people is given certain by measuring concentration with the complementary color filtrator, thereby can unify to measure.At this moment, a ^*Less than 55 or b ^*Less than 0 o'clock, if with other toner colour mixture, then the colorrendering quality of Neutral colour reduces, if a ^*Surpass 75 or b ^*Surpass-8, then must increase the content of pigment, the power of covering of toner increases, similarly if with the toner colour mixture of other color, then the colorrendering quality of Neutral colour reduces.

The content of the above-mentioned pinkish red toner of the organic pigment shown in the said structure formula (1) is preferably 2～15 quality %, 3～10 quality % more preferably.

Above-mentioned Yellow toner contains the organic pigment that has two following structural frameworks (A) and do not have halogen atom in molecule.

As having two said structure skeletons (A) and not having the organic pigment of halogen atom, be preferably the organic pigment shown in any at least of following structural formula (2) and (3).

[Chemical formula 1 4]

[Chemical formula 1 5]

Yellow toner contains the organic pigment shown in said structure formula (2) and/or (3), and this both is an insoluble azo colour.Up to now, as Yellow toner, used the AZO pigments of acetoacetate allylation bisdiazo class (acetoacetic acid allylid dis-azo), acetoacetate imidazolone, the organic pigment of many rings pigment of quinacridine ketone, indanthrone kinds.Particularly be extensive use of C.I.PY13, the C.I.PY17 of acetoacetate allylation diazonium class.But,, it is characterized in that using organic pigment (bisdiazo class) C.I.PY155 shown in (bisdiazo class) C.I.PY180 of the organic pigment shown in the said structure formula (2) and/or the said structure formula (3) as above-mentioned Yellow toner.These pigment are not halogen-containing, have narrow absorption region in the wavelength region may of 400～500nm, therefore reproduce bright-coloured yellow.

Particularly after photographic fixing on the recording mediums such as transfer paper, diaphragm, use the X-RITE938 densimeter, the ID that the condition of spending by the observation visual angle under the observation light D50 (JIS Z-8720 (1983)) 2 obtains is 1.00 o'clock, with L ^*a ^*b ^*During color specification system (CIE1976) expression, a ^*For-2～-12, b ^*It is 67～90 scope.This makes the concentration that the people is given certain by measuring concentration with the complementary color filtrator, thereby can unify to measure.At this moment, a ^*Less than-2 or b ^*Less than 67 o'clock, if with other toner colour mixture, then the colorrendering quality of Neutral colour reduces, if a ^*Surpass-12 or b ^*Surpass 90, then must increase the content of pigment, the power of covering of toner increases, similarly if with the toner colour mixture of other color, then the colorrendering quality of Neutral colour reduces.

In addition, reproduce red (R) look by the colour mixture of above-mentioned pinkish red toner and above-mentioned Yellow toner, but the L after photographic fixing ^*a ^*b ^*In the color specification system, use X-RITE938, the ID that the condition of spending by the observation visual angle under the observation light D50 (JISZ-8720 (1983)) 2 obtains is 1.00 o'clock, a ^*Be 60～68, b ^*Be 45～55.The L of this moment ^*a ^*b ^*Color reproduction scope in the color specification system can be passed through the content of the pigment of pinkish red toner, Yellow toner, and the adhesion amount of toner waits to be adjusted, but by in this scope, the reproduction regions from the colour of skin to vermeil redness is broadened.a ^*Less than 60 or b ^*Less than 45 o'clock, the color reproduction zone was narrow, can not reproduce the redness of various Neutral colour, if a ^*Surpass 68 or b ^*Surpass 55, then must increase the content of pigment, the power of covering of toner increases, and similarly can not reproduce the redness of various Neutral colour.

The red important color that is reproduced as performance people, other thing, but because the reproduction range of Neutral colour is narrow, compare with sensitized paper, subliming type such as photo, the transparency is low owing to use organic pigment, particularly under the big situation of the power of covering, red colorrendering quality step-down.Therefore, in the image processing system of the present invention, the color reproduction scope of the organic pigment by stipulating pinkish red toner and the organic pigment of Yellow toner can obtain red wide colorrendering quality.

The content of above-mentioned Yellow toner that has two said structure skeletons (A) in the molecule and do not have an organic pigment of halogen atom is preferably 3～20 quality %, 5～15 quality % more preferably.

Above-mentioned cyan toner preferably contains copper phthalocyanine.

In the present invention, the visual image on the recording medium preferably forms the layer of pinkish red toner under Yellow toner.The said structure formula (2) of the yellow uitramarine that uses in the toner of the present invention and the organic pigment shown in the said structure formula (3) can not cover the organic pigment that is in lower floor because the power of covering is low.Particularly the organic pigment shown in said structure formula (2) and the said structure formula (3) is because the absorption region of light is narrow, can not hinder magenta pigment by being in lower floor that carry out with red reproduction pinkish red toner.In addition, by under this Yellow toner, using the pinkish red toner that contains the magenta pigment shown in the said structure formula (1), can obtain red wide colorrendering quality.

By containing wax in the toner that makes toner Cartridge of the present invention, as seen imaging surface has pebbles, and the diffuse reflection composition increases as a result, and under the situation of Yellow toner, the spectral reflectance under wavelength 500～700nm improves; Under the situation of pinkish red toner, the spectral reflectance under wavelength 400～500nm improves; Under the situation of cyan toner, the spectral reflectance under wavelength 400～600nm improves.That is, when various toners passed through the substractive color mixing reproducing color therewith, by improving the reflectivity in the wavelength region may that should not absorb, colorrendering quality improved.

Toner Cartridge of the present invention be applicable to contain have Yellow toner, three kinds of developing apparatuss of cyan toner, pinkish red toner and further having in the image processing system of developing apparatus of black toner.

＜developer 〉

When toner of the present invention is used for bi-component class developer, can mix use with magnetic carrier, carrier in the developer and the content of toner ratio are 1～10 mass parts with respect to the preferred toner of 100 mass parts carriers.

As above-mentioned magnetic carrier, can use the known in the past carrier such as iron powder, ferrite powder, magnetite powder, magnetic resin coated carrier, beaded glass of particle diameter 20～200 μ m.

As the clad material of above-mentioned resin-coated carrier, can enumerate phenolics, amino resin, for example urea-formaldehyde resin, melamine resin, benzoguanamine resin, Lauxite, polyamide, epoxy resin etc.In addition, can enumerate tygon and Polyvinylidene resinoid, acryl resin for example, plexiglass, polyacrylonitrile resin, vinylite, polyvinyl alcohol resin, polyvinyl acetal resin, polyvinyl butyral resin, polystyrene resin, polystyrene resins such as styrene acrylic copolymer resins, Polyvinylchloride, halogenated olefins resins such as Vingon, polyester resins such as pet resin and polybutylene terephthalate resin, polycarbonate resin, polyvinyl resin, poly-fluorine carbon, polyfluoroethylene resin, polyvinylidene fluoride resin, poly-trifluoro-ethylene resin, the polyhexafluoropropylene resin, the multipolymer of vinylidene and acrylic monomers, the multipolymer of vinylidene and ethylene fluoride, the fluorine ter-polymers such as ter-polymers of tetrafluoroethene and vinylidene and non-fluorinated monomer, silicones etc.Wherein, the silicones coated carrier is in developer excellence aspect the life-span.In addition, also can in resin-coated, contain conducting powder etc. as required.As this conducting powder, can use metal powder, carbon black, titanium dioxide, tin oxide, zinc paste etc.The preferred mean grain size of these conducting powder is below the 1 μ m.If mean grain size greater than 1 μ m, then is difficult to controlling resistance.

The toner of above-mentioned two-component developing agent and the mixture ratio of carrier, with respect to 100 mass parts carriers, preferred toner is 0.5～20.0 mass parts.

In addition, toner of the present invention also can be used as the magnetic color tuner or the nonmagnetic toner use of the single component class of not using carrier.

-magnetic material-

Toner of the present invention can contain magnetic material, makes magnetic color tuner and uses.When making magnetic color tuner, in toner particle, can contain the particulate of magnetic.As above-mentioned magnetic material, can enumerate the compound that iron, nickel, cobalt of being representative with iron oxide (ferrite, magnetic iron ore, haematite) etc. show ferromagnetic metal, alloy or contains these elements, though and the alloy etc. that contains the kind that is called as the whistler alloy of manganese and copper such as copper-manganese aluminium, manganese-copper-Xi etc. does not contain the ferromagnetism element and reveals ferromagnetic alloy by implementing suitable heat treatment table, chromium dioxide etc.Magnetic preferably with mean grain size be 0.1～2 μ m, more preferably the form of the micropowder of 0.1～1 μ m disperses to exist equably.

Above-mentioned magnetic material contain ratio, with respect to the toner that 100 mass parts obtain, be preferably 5～150 mass parts, more preferably 10～70 mass parts, 20～50 mass parts more preferably.

＜image processing system and image forming method 〉

The image forming method that uses among the present invention contains electrostatic latent image at least and forms step, development step, transfer step and photographic fixing step, further contain other step of suitably selecting as required, for example remove electric step, cleaning, recirculation step, controlled step etc.

Image processing system of the present invention has electrostatic latent image carrier at least, electrostatic latent image forms parts, developing parts, transfer member and fixing member, further have as required other the parts of suitably selecting, for example remove electric parts, cleaning member, recirculation hardware, control assembly etc.

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

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

The formation of above-mentioned electrostatic latent image, for example, can make the surface charging of above-mentioned electrostatic latent image carrier identical after, expose into image and carry out, can form parts by above-mentioned electrostatic latent image and carry out.Above-mentioned electrostatic latent image forms parts and for example has the identical charged device of surface charging that makes above-mentioned electrostatic latent image carrier becomes image with the face exposure with above-mentioned electrostatic latent image carrier exposer at least.

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

As above-mentioned charged device, be not particularly limited, can suitably select according to purpose, for example can enumerate, the known contact zones electrical equipment of roller, brush, film, rubber slab etc. itself with electric conductivity or semiconduction, corona tube, corona are finished the charged device of noncontact etc. that electrical equipment (scorotron) etc. utilizes corona discharge.

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

As above-mentioned exposer, have no particular limits, as long as can expose to the image that will form on the surface supporting by the charged above-mentioned electrostatic latent image of above-mentioned charged device, can suitably select according to purpose, for example can enumerate various exposers such as duplicating optical system, rod type lens array system (rod-lens-eyesystems), laser optical system, liquid crystal optical shutter system.

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

-development step and developing parts-

Above-mentioned development step is to use above-mentioned toner of the present invention or above-mentioned developer that above-mentioned electrostatic latent image is developed and forms the step of visual image.

The formation of above-mentioned visual image, for example, above-mentioned toner that can the application of the invention or above-mentioned developer develop to above-mentioned electrostatic latent image and carry out, and can utilize above-mentioned developing parts to carry out.

Above-mentioned developing parts is not particularly limited, as long as for example can use above-mentioned toner of the present invention or above-mentioned developer to develop, can from known developing parts, suitably select, can for example preferably enumerate, at least have and take in above-mentioned toner of the present invention or developer, and may above-mentioned toner or above-mentioned developer be imparted to the developing parts of the developer on the above-mentioned electrostatic latent image by contact or noncontact mode, more preferably have the developer of the container that above-mentioned toner is housed etc.

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

In the above-mentioned developer, for example, above-mentioned toner and above-mentioned carrier mixed stir, the friction by this moment makes toner charged, and remains on the state that the wheat head is stood upright on the surface of magnetic roller of rotation, forms magnetic brush.This magnetic roller is owing to be arranged near the above-mentioned electrostatic latent image carrier (photoreceptor), and a part that is formed in the above-mentioned toner of the above-mentioned magnetic brush that forms on the surface of this magnetic roller is transferred on the surface of this electrostatic latent image carrier (photoreceptor) by electrical affinity.As a result, above-mentioned electrostatic latent image forms visual image by this toner by this toner development on the surface of this electrostatic latent image carrier (photoreceptor).

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

-transfer step and transfer member-

Above-mentioned transfer step is that above-mentioned visual image is transferred to step on the recording medium, the preferred intermediate transfer body that uses is with after the visual image primary transfer is to this intermediate transfer body, again with the mode of this visual image secondary transfer printing on the aforementioned recording medium, more preferably comprise the transfer step and the mode of transfer step for the first time for the second time, described first time, transfer step was to use more than two looks, the preferred full-color toner that uses is transferred to visual image the step that forms compound transferred image on the intermediate transfer body as above-mentioned toner; Described second time, transfer step was that this compound transferred image is transferred to step on the recording medium.

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

And, as above-mentioned intermediate transfer body, be not particularly limited, can be as required from known transfer article, suitably select, for example can preferably enumerate transfer belt etc.

Above-mentioned transfer member (above-mentioned first time transfer member, above-mentioned second time transfer member) preferably has at least and will be formed on above-mentioned visual image on the above-mentioned electrostatic latent image carrier (photoreceptor) to the transfer printing device of aforementioned recording medium side stripping charge.Above-mentioned transfer member can be one, also can be for more than two.

As above-mentioned transfer printing device, can enumerate the corona transfer device that utilizes corona discharge, transfer belt, transfer roll, pressure transfer roll, adhesive transfer device etc.

And, as aforementioned recording medium, be not particularly limited, can from known recording medium (recording chart), suitably select.

Above-mentioned photographic fixing step is to use the step of fixing device with the visual image photographic fixing of transfer printing on recording medium, can be transferred to respectively on the aforementioned recording medium toner of all kinds and carry out, also can be to toner of all kinds to carry out simultaneously the state of its lamination is disposable.

As above-mentioned fixing device, be not particularly limited, can suitably select preferred known heating and pressurizing parts according to purpose.As above-mentioned heating and pressurizing parts, the combination that can enumerate warm-up mill and backer roll, the combination of warm-up mill, backer roll and endless belt etc.

Heating in the above-mentioned heating and pressurizing parts is preferably 80～200 ℃ usually.

And, in the present invention, use for example known smooth fuser when can state photographic fixing step and fixing member in the use according to purpose, perhaps use known smooth fuser to replace above-mentioned photographic fixing step and fixing member.

Above-mentioned to remove electric step be that above-mentioned electrostatic latent image carrier is applied the step of removing electricity except that electrical bias, can preferably utilize except that electric parts and carry out.

Remove electric parts as above-mentioned, be not particularly limited,, can remove suitably selection the electrical equipment, for example can preferably enumerate except that electric light etc. from known as long as can apply except that electrical bias to above-mentioned electrostatic latent image carrier.

Above-mentioned cleaning is to remove the step that remains in the above-mentioned toner on the above-mentioned electrostatic latent image carrier, can preferably utilize cleaning member to carry out.

As above-mentioned cleaning member, be not particularly limited, as long as can remove the above-mentioned electrofax tinter that remains on the above-mentioned electrostatic latent image carrier, can from known clearer, suitably select, can preferably enumerate for example magnetic brush clearer, static bruss clearer, magnetic roller clearer, scraper plate clearer, brush clearer, net clearer etc.

Above-mentioned recirculation step is the step that makes above-mentioned toner recycle in above-mentioned developing parts of removing by above-mentioned cleaning, can preferably utilize recirculation hardware to carry out.

As above-mentioned recirculation hardware, be not particularly limited, can enumerate known transfer member etc.

Above-mentioned control assembly is the step of control above steps, can preferably utilize control assembly to carry out.

As above-mentioned control assembly, as long as can control the running of above-mentioned each parts, then be not particularly limited, can suitably select according to purpose, can enumerate for example equipment such as program control device, computing machine.

In the image processing system that present embodiment relates to, Charging system, exposure device, developing apparatus, transfer device, cleaning device etc. have been set gradually at the periphery of photoreceptor.In addition, have to paper transporting apparatus and fixing device, described to paper transporting apparatus by paper feeding tray paper feeding recording medium, described fixing device be in transfer printing after the recording medium of toner image separates from photoreceptor, with toner fixing on recording medium.So in the image processing system that constitutes, the surface of the photoreceptor of rotation by Charging system charged identical after, based on the laser beam of image information irradiation exposure device etc., on photoreceptor, form sub-image.Make charged toner attached on the electrostatic latent image that is formed on the photoreceptor by developing apparatus, form toner image.On the other hand, recording medium by to paper transporting apparatus by the paper feeding tray paper feeding, then be sent in the transfer printing portion of photoreceptor and transfer device subtend.Then, by transfer device to recording medium give with photoreceptor on the electric charge of toner image reversed polarity, the toner image that will be formed on the photoreceptor is transferred on the recording medium thus.Then, recording medium separates from photoreceptor, delivers in the fixing device, by toner fixing is obtained image on recording medium.

Wherein, Fig. 1 is the structure diagram of the developing apparatus 1 of the image processing system that relates to of present embodiment.Based on Fig. 1 the developing apparatus 1 that adopts in the above-mentioned image processing system is elaborated.This developing apparatus 1 has the side that is arranged on photoreceptor 8, contains the nonmagnetic development sleeve 7 of developer carrier of the two-component developing agent (following be also referred to as sometimes " developer ") of toner and magnetic carrier as load from the teeth outwards.These development sleeve 7 following installations: the peristome of photoreceptor 1 side that is formed on developing box is partly exposed, rotate along arrow b direction among the figure by not shown drive unit.As the material of development sleeve, so long as the material of using in the common developing apparatus gets final product, be not particularly limited, can use nonmagnetic substances such as stainless steel, aluminium, pottery or further they are coated with etc. and material of obtaining etc.In addition, the shape to development sleeve also is not particularly limited.In addition, at the not shown magnetic roller that by fixed magnet group constitute of the internal fixation of development sleeve 7 configuration as field generator for magnetic.In addition, developing apparatus 1 has the scraper of being made by rigid body 9 as the developer control assembly of the amount of the developer of control load on development sleeve 7.For this scraper 9, form the developer receptacle portion 4 take in developer at development sleeve 7 sense of rotation upstream sides, first and second agitating screw 5,6 of the developer that mixes this developer receptacle portion 4 is set.In addition, be provided with the toner replenishing mouth 23 of the top be configured in developer receptacle portion 4, developer receptacle portion 4 filled supplies toner toner hopper 2 with is connected the toner of toner replenishing mouth 23 and send and flow device 3 with toner hopper 2.

In the developing apparatus 1 of above-mentioned formation, the developer in the developer receptacle portion 4 is stirred in agitating screw 5,6 rotations by first and second, the mutual reversed polarity ground frictional electrification of toner and magnetic carrier.This developer is fed into along on the side face of the development sleeve 7 of arrow b direction rotation driving, and the developer carrying of supply by the rotation of development sleeve 7, is sent on its sense of rotation (arrow b direction) on the side face of development sleeve 7.Then, the developer of this transmission is by scraper 9 controlled quentity controlled variables, and the developer after the control is sent in the developing regional of photoreceptor 8 and development sleeve 7 subtends.In this developing regional, the toner electrostatic transfer in the developer to the electrostatic latent image on photoreceptor 8 surfaces, this electrostatic latent image as toner image by visual imageization.

Wherein, the interval (developing gap between image-carrier 8 and the development sleeve 7; Gp) be preferably 0.01mm～0.7mm.If above-mentioned gap is less than 0.01mm, the then transmission reduction of developer, the homogeneity of image reduces sometimes on the spot.On the other hand, if surpass 0.7mm, then electrical, the retentivity of the initial strip of developer reduces easily, so not preferred.

-intermediate transfer body-

An embodiment of the intermediate transfer body of the transferring system among the present invention is described with reference to Fig. 4.Be provided as around as the photoconductor drum of electrostatic image carrier (below be called photoreceptor) 10 Charging system charged roller 20, exposure device 30, have cleaning balde cleaning device 60, as neutralizer remove electric light 70, developing apparatus 40 and as the intermediate transfer body 50 of intermediate transfer body.These intermediate transfer body 50 following formations: be draped by a plurality of suspension rollers 51, and by not shown drive units such as motor along direction of arrow annular movement.The part of this suspension roller 51 has concurrently as effect from the transfer bias roller of transfer bias to the intermediate transfer body that supply with, is applied the transfer bias voltage of regulation by not shown power supply.In addition, also dispose the cleaning device 90 of cleaning balde with this intermediate transfer body 50.In addition, with these intermediate transfer body 50 subtends, transfer roll 80 is set as the transfer member that is used for the transfer printing developed image on the recording medium 100 as final transfer materials, this transfer roll 80 is supplied with transfer bias by not shown supply unit.And, at the corona charging device 52 that is provided as the electric charge member of imparting on every side of above-mentioned intermediate transfer body 50.

Above-mentioned developing apparatus 40 by as the strip-like developing pipe 41 of developer carrier and be arranged on simultaneously this strip-like developing pipe 41 around black (below be called Bk) developing parts 45K, yellow (below be called Y) developing parts 45Y, magenta (below be called magenta) developing parts 45M, cyan (below be called C) developing parts 45C constitute.In addition, this strip-like developing pipe 41 is hung by a plurality of band rollers,, roughly moves with speed at contact site and this photoreceptor 10 with above-mentioned photoreceptor 10 along direction of arrow annular movement by not shown driver parts such as motor.

Because the structure of each developing parts is common, below only Bk developing parts 45K is described, for other developing parts 45Y, 45M, 45C, in corresponding with the Bk developing parts 45K in the drawings part, after the sequence number of the part mark of these parts, enclose Y, M, C, omit its explanation.Developing parts 45K is by the developing trough 42K of the liquid developer of taking in the high viscosity that contains toner particle and carrier fluid composition, high concentration, is configured to the bottom and is immersed in drawing roller (scooping roller) 43K and will draw the developer thin layerization that roller 43 draws and the applicator roll 44K that is applied on the strip-like developing pipe 41 constitutes by this in the liquid developer in this developing trough 42K.This applicator roll 44K has electric conductivity, is applied the bias voltage of regulation by not shown power supply.

And the apparatus structure of the image processing system that relates to as present embodiment except apparatus structure shown in Figure 4, also can be provided with the apparatus structure of developing parts of all kinds as shown in Figure 5 simultaneously around a photoreceptor 10.

Then, the operation of the image processing system that present embodiment is related to describes.In Fig. 4, along direction of arrow rotation drive photoreceptor 10 and by charged roller 20 charged equably after, the optical system not shown by exposure device 30 usefulness will form electrostatic image from the reflected light imaging projection of original copy on this photoreceptor 10.This electrostatic image develops by developing apparatus 40, forms the toner image that develops.Developer thin layer on the strip-like developing pipe 41 is with 41 to peel off by contacting with photoreceptor with the state of thin layer from this in developing regional, transfers to the part of the formation sub-image on the photoreceptor 10.The toner image that develops by this developing apparatus 40 is transferred at the contact site (primary transfer zone) of photoreceptor 10 and the intermediate transfer body 50 of constant speed movement on the surface of intermediate transfer body 50 (primary transfer).When carrying out the transfer printing of overlapping three looks or four looks, respectively each color is repeated this process, on intermediate transfer body 50, form coloured image.

To be used for giving the sense of rotation of the above-mentioned corona charging device 52 of electric charge, be arranged on the downstream that contacts subtend portion of above-mentioned photoreceptor 10 and this intermediate transfer body 50 and on the position of this intermediate transfer body 50 and the upstream side that contacts subtend portion of recording medium 100 at this intermediate transfer body 50 to the overlapping toner image on the above-mentioned intermediate transfer body.Then, the true electric charge of charged polarity identical polar of the toner particle of this toner image is given and formed to this corona charging device 52 for this toner image, and giving to toner image can be to the required sufficient charge of recording medium 100 good transfer printings.Above-mentioned toner image by above-mentioned corona charging device 52 charged after, by transfer bias, be transferred on the recording medium 100 that transmits along the direction of arrow (secondary transfer printing) by not shown sheet feeding section is disposable from above-mentioned transfer roll 80.Then, transfer printing the recording medium 100 of toner image separate from photoreceptor 10 by not shown tripping device, after carrying out photographic fixing and handle with not shown fixing device, from install, arrange paper.On the other hand, the photoreceptor 10 after the transfer printing reclaims by cleaning device 60 and removes the toner of not transfer printing, removes residual charge to prepare next time charged by removing electric light 70.

As mentioned above, the coefficient of static friction of this intermediate transfer body is preferably 0.1～0.6, more preferably 0.3～0.5.The volume resistance of this intermediate transfer body is preferably several Ω cm～10 ³Ω cm.By making volume resistance is number Ω cm～10 ³Ω cm can prevent that intermediate transfer body itself is charged, and the electric charge of giving by the electric charge member of imparting is difficult for remaining on this intermediate transfer body simultaneously, the transfer printing inequality in the time of therefore can preventing secondary transfer printing.Applying of transfer bias when in addition, carrying out secondary transfer printing easily.

The material of intermediate transfer body is not particularly limited, and can use material known.An one example is shown below.(1) material that yang type modulus (tensile modulus of elasticity) is high as the composite material of the composite material of PC (polycarbonate), the PVDF (Kynoar) of single belt, PAT (polyalkylene terephthalates), PC (polycarbonate)/PAT (polyalkylene terephthalates), ETFE (ethene-zellon multipolymer)/PC, ETFE/PAT, PC/PAT, be dispersed with the Thermocurable polyimide of carbon black etc.The deflection of single belt counter stress when image forms that these Young moduluss are high is few, particularly when forming coloured image, has the advantage that is difficult for producing misregister (mis-registration).(2) with the high band of above-mentioned Young modulus as basic unit, on its periphery, give superficial layer or middle layer and the band of 2～3-tier architecture of obtaining, the band of these 2～3-tier architectures has and can prevent because the performance that the centre of the line image that the hardness of single belt produces comes off.(3) the lower band of Young modulus that uses rubber and elastic body to obtain, the advantage that the centre that these bands produce line image hardly owing to its flexibility has comes off.In addition, prevent bending, therefore can need not reinforcement (rib) or anti-bending device, thereby can realize low cost because the width that makes band greater than driven roller with hang roller, utilizes from the elastic force of the ear of the outstanding band of roller.

Up to now, intermediate transfer belt has used fluorine-type resin, polycarbonate resin, polyimide resin etc., but has used all layers that will band in recent years or the part be with is made the elastic webbing of elastomeric element.Use the transfer printing of the coloured image of resin strip to have following problem.

Coloured image usually by four looks colour toners form.In a coloured image, form toner layer from one deck to four layer.Toner layer is under pressure by primary transfer (being transferred on the intermediate transfer belt from photoreceptor) or secondary transfer printing (being transferred on the paper (sheet) from middle transfer belt), and the cohesiveness between the toner raises.If the cohesiveness between the toner raises, the centre that then easily produces literal comes off or the phenomenon that comes off of portion's edge of image on the spot.Transfer printing resin strip hardness height can not be out of shape corresponding to toner layer, therefore, compresses toner layer easily, thereby is easy to generate the middle obscission of literal.

In addition, on various paper, form full-colour image recently, for example at Japan paper or the requirement of having a mind to form on the additional concavo-convex paper image improve.But the paper of flatness difference is easy and toner generation space when transfer printing, comes off thereby be easy to generate transfer printing.If improve the transfer pressure of secondary transfer printing portion in order to improve adaptation, then the condensing power of toner layer increases, and the centre that produces above-mentioned literal comes off.

Therefore, when being transferred on the paper, elastic webbing is used for following purpose.Elastic webbing is out of shape corresponding to the paper of toner layer, flatness difference in transfer printing portion.That is,, can exceedingly not improve transfer pressure, obtain good adaptation, can obtain not having the centre of literal to come off, even for the yet excellent transferred image of the paper homogeneity of planarity difference to toner layer owing to elastic webbing is followed local concavo-convex the distortion.

Resin as above-mentioned elastic webbing, be not particularly limited, can suitably select according to purpose, can enumerate for example polycarbonate, fluorine-type resin (ETFE, PVDF), polystyrene, chlorinated polyphenyl ethene, poly alpha methylstyrene, Styrene-Butadiene, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, copolymer in cinnamic acrylic ester (for example, styrene-propene acid methyl terpolymer, styrene-propene acetoacetic ester multipolymer, the styrene-propene butyl acrylate copolymer, misery ester copolymer of styrene-propene and styrene-propene acid phenylester multipolymer etc.), styrene-methacrylate copolymer (for example, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-methacrylic acid phenylester multipolymer etc.), styrene-α-Lv Bingxisuanjiazhi multipolymer, styrene resins such as styrene-acrylonitrile-acrylate copolymer (homopolymer or the multipolymer that contain styrene or styrene substituent); Polymethyl methacrylate resin, the butyl methacrylate resin, the ethyl acrylate resin, the butyl acrylate resin, it is acrylic resin modified that (for example, silicone is acrylic resin modified, vestolit is acrylic resin modified, acrylic/polyurethane resin etc.), vestolit, styrene-vinyl acetate copolymer, vinyl chloride vinyl acetate copolymer, Abietyl modified maleic acid resin, phenolics, epoxy resin, vibrin, polyester polyurethane resin, tygon, polypropylene, polybutadiene, Vingon, ionomer resin, urethane resin, silicones, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, polyamide, modified polyphenylene ether resin etc.They can be used alone, and also can make up two or more uses.

As resilient material rubber or elastic body, can enumerate for example butyl rubber, fluorine class rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene (ABS) rubber natural rubber, isoprene rubber, styrene butadiene rubbers, butadiene rubber, ethylene-propylene rubber, the ethylene-propylene ter-polymers, chloroprene rubber, chlorosulfonated polyethylene, haloflex, urethane rubber, syndiotactic 1, the 2-polybutadiene, chloropropylene oxide class rubber, silicon rubber, fluororubber, thiokol, poly-norbornene rubber, hydrogenated nitrile rubber, thermoplastic elastomer (for example, polystyrene type, polyolefins, polyvinyl chloride, polyurethanes, polyamide-based, polyureas, polyesters, fluorine type resin) etc.They can be used alone, and also can make up two or more uses.

As the resistance value adjusting conductive agent, be not particularly limited, can suitably select according to purpose, for example can enumerate, the metal powder of carbon black, graphite, aluminium or nickel etc., tin oxide, titanium dioxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite oxides (ATO), indium oxide-tin oxide composite oxides conductive metal oxides such as (ITO), or on this conductive metal oxide, cover insulating fine particles such as barium sulphate, magnesium silicate, lime carbonate and conductive agent of obtaining etc.

Skin-material, top layer require to prevent pollution to photoreceptor by resilient material, and reduce the mantle friction resistance to the transfer belt surface, reduces the adhesion of toner, improves spatter property, thereby improve secondary transfer printing.For example, the material that can use one or more the combination that utilizes polyurethane, polyester, epoxy resin etc. to reduce surface energy and improve lubricity, for example with powder, the particle of one or more fluororesin, fluorine compounds, fluorocarbons, titania, silit etc., the powder of perhaps that particle diameter is different fluororesin, fluorine compounds, fluorocarbons, titania, silit etc., the combination of particle disperse to use.In addition, can also use such the passing through of fluorine class elastomeric material to heat-treat and form the layer of rich fluorine from the teeth outwards, thereby reduce the material of surface energy.

-Charging system-

Fig. 6 is the sketch of part-structure of the image processing system of the expression Charging system that uses contact.Drive as being rotated with the speed (processing speed) of regulation along the direction of arrow by the photoreceptor 140 of electrified body, electrostatic image carrier.Charged roller 160 as the live part that contacts with this photosensitive drums is a basic structure with mandrel with at the concentric conductive rubber layer that is formed on the roller of this mandrel periphery, keep rotation free at the two ends of mandrel with not shown parts of bearings etc., by not shown pressure-producing part the plus-pressure of photosensitive drums with regulation pushed simultaneously, under the situation of this figure, this charged roller 160 is driven in the rotation driving of photoreceptor 140 and rotates.Charged roller 160 is at the middle resistance rubber layer 522 about coating 100000 Ω cm on the mandrel of diameter 9mm, and the formation diameter is 16mm.

The mandrel of charged roller 160 is electrically connected with not shown power supply, charged roller is applied the bias voltage of regulation by power supply.Thus, similarly charged polarity, the current potential that is processed into regulation of the side face of photoreceptor 140.

The Charging system that uses among the present invention is not limited to the Charging system of above-mentioned contact, also can be non-contacting Charging system, but because the image processing system of the ozone that produces from Charging system of being reduced, preferably uses the Charging system of contact.

In addition, in the image processing system of the present invention, Charging system is applied alternating electric field.In DC (direct current) electric field,, form a large amount of O in order to make the charged one-tenth negative polarity of photoreceptor ₃ ^-And NO ₃ ^-This ozone, oxides of nitrogen are attached to making the photosensitive surface deterioration on the photoreceptor.Particularly make the photosensitive surface sclerosis and wearing and tearing are increased, in addition,, adhere to external additive easily, and the situation of generation film forming increases because friction factor reduces.Therefore, by applying the alternating electric field of superposeed AC (interchange), can suppress the generation of ozone etc. and make the photoreceptor uniform charged.Particularly, utilize the H of reversed polarity by forming alternating electric field ₃O ⁺Generation, can suppress the deterioration of the photoreceptor that ozone causes.

As the shape of the live part that uses among the present invention, except roller, can also adopt form arbitrarily such as magnetic brush, hairbrush, can select according to the specification or the form of image processing system.When using magnetic brush, magnetic brush for example is made of the non magnetic conducting sleeve of various ferrite particles such as support Zn-Cu ferrite and the magnetic roller that is encapsulated in this sleeve.In addition, use under the situation of brush, for example, use and carry out the material of the fur of conductive processing, again it is twined, is attached on the mandrel of metal or conductive processing and form Charging system as hairbrush by carbon black, copper sulfide, metal or metal oxide etc.

-tandem type coloured image formation device-

Fig. 7 illustrates the sketch that tandem type coloured image of the present invention forms the structure of device.

In the image processing system of tandem type, there is the device that transfer device 2 is transferred to the image on each photoreceptor 1 the direct transfer printing mode on the paper s that transmits with paper travelling belt 3 successively that passes through as shown in Figure 7, behind the passing through primary transfer device 2 and temporarily be transferred to the image on each photoreceptor 1 on the intermediate transfer body 4 successively as shown in Figure 8, by secondary transfer printing device 5 image on this intermediate transfer body 4 is transferred to once the device of the indirect transfer printing mode on the paper s again.Transfer device 5 is the transfer printing travelling belt, but the mode of roller shape is also arranged.

The device of direct transfer printing mode and the device of indirect transfer printing mode are compared, the former must exist in the shortcoming that the paper direction of transfer maximizes at the upstream side configuration paper feeding device 6 of the tandem type image processing system T that arranges photoreceptor 1, at downstream configuration fixing device 7.Relative therewith, the latter can more freely be provided with the secondary transfer printing position.Can be with paper feeding device 6 and fixing device 7 and tandem type image processing system T overlay configuration, the advantage that existence can miniaturization.

In addition, on the paper direction of transfer, maximize in order not make the former, be with fixing device 7 and tandem type image processing system T neighbor configuration.Therefore, has following shortcoming: can not have and to make the enough leeway of paper s bending dispose fixing device 7, because the impact (particularly especially remarkable at thick paper) the when top of paper s enters fixing device 7, the difference of the transfer rate of the paper that the transfer rate of paper and transfer printing travelling belt cause during perhaps by fixing device 7 form image to fixing device 7 at upstream side easily and exert an influence.Relative therewith, can dispose fixing device 7 in crooked enough leeway because the latter can have paper s, so fixing device 7 can formation brings influence to image hardly.

For above-mentioned reasons, the device of the particularly indirect transfer printing mode in the nearest tandem type image processing system receives publicity.Fig. 8 illustrates the sketch of structure that tandem type coloured image of the present invention forms the image processing system with intermediate transfer body of device.

Forming in device at this coloured image, as shown in Figure 8, utilize photoreceptor cleaning device 8 to remove the transfer printing remaining toner that remains in after the primary transfer on the photoreceptor 1, prepares for forming image once more in cleaning photoreceptor 1 surface.In addition, utilizing intermediate transfer body cleaning device 9 to remove the transfer printing remaining toner that remains in behind the secondary transfer printing on the intermediate transfer body 4, prepares for forming image once more in cleaning intermediate transfer body 4 surfaces.

Below, with reference to accompanying drawing embodiments of the present invention are described.

Fig. 9 is the sketch of structure of image processing system that the tandem type indirect transfer printing mode of an embodiment of the invention is shown.Symbol 100 is that copy device main body, the 200 paper feeding platforms for placement copy device main body, 300 are that the scanner, 400 that is installed on the copy device main body 100 is further original copy automatic conveyor (ADF) mounted thereto among the figure.Central authorities in copy device main body 100 are provided with endless belt-shaped intermediate transfer body 10.

As shown in Figure 9, be hung around in the illustrated example on three backing rolls 14,15,16, transmission can turn clockwise among the figure.

In this illustrated example, the left side of second backing roll 15 in three is provided with removes the intermediate transfer body cleaning device 17 that remains in the remaining toner on the intermediate transfer body 10 after the image transfer printing.

In addition, on the intermediate transfer body 10 that in three, hangs between first backing roll 14 and second backing roll 15, laterally dispose yellow, cyan, magenta, four kinds of image forming parts 18 of black side by side, constitute series connection image processing system 20 along its direction of transfer.

On this series connection image processing system 20, as shown in Figure 9, exposure device 21 is set further.On the other hand, has secondary transfer printing device 22 with series connection image processing system 20 opposite sides that accompany intermediate transfer body 10.In illustrated example, secondary transfer printing device 22 is to hang as the secondary transfer printing band 24 of endless belt to constitute between two rollers 23, is pressed in by intermediate transfer body 10 and disposes on the 3rd backing roll 16, and the image on the intermediate transfer body 10 is transferred on the paper.

Secondary transfer printing device 22 laterally, the fixing device 25 of the transferred image on the photographic fixing paper is set.Fixing device 25 is backer roll 27 is pressed on the photographic fixing band 26 of endless belt and constitutes.

In the above-mentioned secondary transfer printing device 22, also has the paper transmitting function that this fixing device 25 of the principal direction after the image transfer printing is transmitted.Certainly,, can dispose transfer roll or non-contacting charged device, under this situation, be difficult to have simultaneously this paper transmitting function as secondary transfer printing device 22.

In addition, in illustrated example, below this secondary transfer printing device 22 and fixing device 25, have parallel with above-mentioned series connection image processing system 20, at the paper turning device 28 of the paper of the two sides of paper upset document image.

When using this coloured image formation device to duplicate, original copy is installed on the document board 30 of original copy automatic conveyor 400.Perhaps, open original copy automatic conveyor 400, original copy is installed on the contact glass 32 of scanner 300, shut the original copy automatic conveyor and original copy is pressed in herein.

If press not shown beginning switch, when then on master copy automatic conveying device 400, placing original copy, original copy be transferred and move to the contact glass 32 on after, on the other hand, direct driven sweep device 300 when placing original copy on contact glass 32 moves the 1st moving body 33 and the 2nd moving body 34.And from source emissioning light, further reflection,, enters in the read sensor 36 by imaging len 35 with the specularly reflected of second moving body 34 towards second moving body 34 from the reflected light of original copy face simultaneously, reads the original copy content by first moving body 33.

In addition, if press not shown beginning switch, then by one in the not shown driving motor rotation driving backing roll 14,15,16, other two driven rotations of backing roll, rotation transmits intermediate transfer body 10.Simultaneously, in each image forming part 18, rotate this photoreceptor 40, on each photoreceptor 40, form the monochrome image of black, yellow, magenta and cyan respectively.Then, transmit intermediate transfer body 10, the while is these monochrome images of transfer printing successively, form combined color image on intermediate transfer body 10.

On the other hand, if press not shown beginning switch, then select in the feed roll 42 of rotation paper feeding platform 200, what multilayer had from paper storage device 43 sends paper successively in the middle of one in the carton 44, enter paper feeding path 46 after separating one by one with separate roller 45, transmit by transfer roller 47, import to the paper feeding path 48 in the duplicating machine main body 100, run into and stop after stopping roller 49.

In addition, rotation feed roll 50, send paper on the manual pallet 51 successively, separate the laggard manual paper feeding path 53 of going into one by one, similarly run into and stop after stopping roller 49 with separate roller 52.Then, synchronously rotate with combined color image on the intermediate transfer body 10 and to stop roller 49, between intermediate transfer body 10 and secondary transfer printing device 22, send into paper, by 22 transfer printings of secondary transfer printing device, record color image on paper.

Paper after the image transfer printing transmits by secondary transfer printing device 22, is sent to fixing device 25, applies heat and pressure by fixing device 25, after the transferred image photographic fixing, switches by switching pawl 55, discharges by distributing roller 56, is deposited on the discharge tray 57.In addition, enter into paper turning device 28,, import to transfer position once more, behind the document image, be discharged on the discharge tray 57 overleaf by distributing roller 56 in this upset by switching pawl 55 switchings.

On the other hand, the intermediate transfer body 10 after the image transfer printing is removed the remaining toner that residues in after the image transfer printing on the intermediate transfer body 10 by intermediate transfer body cleaning device 17, and the image of preparing once more by series connection image processing system 20 forms.

Wherein, stop roller 49 ground connection use mostly usually, but, also can apply bias voltage in order to remove the paper powder of paper.

In above-mentioned series connection image processing system 20, specifically, each image forming part 18 has Charging system 60, developing apparatus 61, primary transfer device 62, photoreceptor cleaning device 63, neutralizer 64 etc. as shown in Figure 9 around drum type photoreceptor 40.Though not record among Fig. 9 also has developer 65 on the development sleeve, paddle 68, dividing plate 69, toner concentration sensor 71, development sleeve 72, scraper 73, cleaning balde 75, cleaning brush 76, clearer 77, cleaning balde 78, toner discharge spiral drill 79, drive unit 80.

＜handle box 〉

The handle box that uses among the present invention has the electrostatic latent image carrier of load electrostatic latent image at least and uses developer will load on the latent electrostatic image developing on this electrostatic latent image carrier and form the developing parts of visual image, also has other parts of suitable selection as required.

As above-mentioned developing parts, at least have the developer receptacle device of taking in above-mentioned toner of the present invention or above-mentioned developer and load and transmit the toner taken in this developer receptacle device or the developer carrier of developer, the layer thickness control parts etc. that can also have in addition, the toner bed thickness that is used for control load.

Above-mentioned handle box can be installed on the image processing system main body with freely loading and unloading.

Wherein, Figure 10 is the structure diagram that the image processing system of the tandem type indirect transfer printing mode with handle box of the present invention is shown.In Figure 10,301 expression handle box integral body, 302 expression photoreceptors, 303 expression live parts, 304 expression developing parts, 305 expression cleaning members.

In the present invention, in the inscapes such as above-mentioned photoreceptor 302, live part 303, developing parts 304 and cleaning member 305, to major general's photoreceptor 302 and the developing parts 304 formation handle box that is combined as a whole, preferably constitute the structure that to load and unload this handle box to image processing system main bodys such as duplicating machine or printers.

Use contains the adhesive resin of polycondensation vibrin of the present invention and the toner for developing electrostatic latent image that obtains anti-adhesive and the low-temperature fixing under hot and humid degree environment is all excellent, even and under hot and humid environment or under the low temperature and low humidity environment and then under hi-vision area output As time goes on, use any one using method, can stably export high quality images, promptly, can not produce toner components cements on carrier or the development sleeve, problems such as the charged ability reduction of developer can stably be exported high quality image; In addition, storage stability, melt fluidity and charged characteristic are also excellent.In addition, though not on the environment for use in-problem tin compound also have good resin property as catalyzer.

In addition, in above-mentioned toner of the present invention, further contain charged controlling agent, particularly contain above-mentioned specific charged controlling agent and the toner that obtains, not produce down background is stained, charging property is excellent, charged environmental turbulence few and have a function of low-temperature fixing excellence because hot and humid, and since contain will not have bio-toxicity in-problem tin compound on environment as the toner binder of catalyzer, can realize low environmental load.

In addition, for the vibrin that in the presence of specific titanium-containing catalyst, forms as binder resin for toner of the present invention, use has the resin strip controling agent of specific constituent and constituent ratio and obtains the development of static charge toner, can obtain high carried charge and narrow carried charge distribution, initial strip is electrically excellent in addition, the stained excellence that waits of background, be not subjected to the influence of the variation of humiture, and also can prevent the pollution of development carrier (developer roll or sleeve) or development layer thickness control parts (scraper plate or roller) more than tens thousand of under long-term the use, and can prevent the photoreceptor film forming, in addition, comminuted good, the productivity height, and do not have problem on the environment, be very excellent toner for developing electrostatic latent image, be particularly suitable for panchromatic usefulness.

In addition, the present invention can provide dry type monocomponent toner, the two-component developing agent that contains above-mentioned toner, uses image forming method, the image processing system of this toner.

Embodiment

By the following examples the present invention is further specified, but the present invention is not limited by these embodiment.And, in following embodiment, " part " expression " mass parts ", " % " expression " quality % ".

In following embodiment and comparative example, the following mensuration of each rerum natura of toner.

The assay method of the softening point of＜toner 〉

Use flow tester constant heatingrate under the following conditions, its discharge is reached 1/2 temperature as softening point.

Device: Shimadzu Seisakusho Ltd. makes flow tester CTF-500D

Load: 20kgf/cm ²

Mould: 1mm φ-1mm

Programming rate: 6 ℃/min

Sample size: 1.0g

The particle size determination method of＜toner 〉

The size-grade distribution of toner particle uses Coulter counter TA-II (Beckman Coulter, Inc. makes) as the following mensuration of determinator.

At first, in 100～150ml electrolytic aqueous solution, add the surfactant (alkyl benzene sulfonate) of 0.1～5ml as spreading agent.Wherein, electrolytic solution is to use about 1%NaCl aqueous solution of sodium chloride preparation, uses ISOTON-II (Beckman Coulter, Inc. makes).Wherein, further add 2～20mg and measure sample.The used for electrolyte ultrasonic disperser that is suspended with sample carries out 1～3 minute dispersion treatment, by the said determination device, uses 100 μ m apertures as the aperture, measures volume, the number of toner particle or toner, calculates volume distributed median and number and distributes.Obtain volume average particle size, the number average particle diameter of toner by the distribution that obtains.

As passage (channel), use particle diameter 2.00 μ m above and less than 2.52 μ m, particle diameter 2.52 μ m are above and less than 3.17 μ m, particle diameter 3.17 μ m are above and less than 4.00 μ m, particle diameter 4.00 μ m are above and less than 5.04 μ m, particle diameter 5.04 μ m are above and less than 6.35 μ m, particle diameter 6.35 μ m are above and less than 8.00 μ m, particle diameter 8.00 μ m are above and less than 10.08 μ m, particle diameter 10.08 μ m are above and less than 12.70 μ m, particle diameter 12.70 μ m are above and less than 16.00 μ m, particle diameter 16.00 μ m are above and less than 20.20 μ m, particle diameter 20.20 μ m are above and less than 25.40 μ m, particle diameter 25.40 μ m are above and less than 32.00 μ m, particle diameter 32.00 μ m are above and less than ten triple channel of 40.30 μ m, with more than the particle diameter 2.00 μ m and less than the particle of 40.30 μ m as object.

The mensuration of the average circularity of＜toner 〉

Measure average circularity by flow-type particle picture analytical equipment FPIA-2100 (Sysmex Co. manufacturing).As concrete assay method, in container, remove in advance and add the surfactant (alkyl benzene sulfonate) of 0.3ml in the 120ml water of impure solid matter as spreading agent, add the mensuration sample about 0.2g again.The suspending liquid that is dispersed with sample is used about 2 minutes of ultrasonic disperser dispersion treatment, and making dispersion liquid concentration is 5000/μ L, measures the shape and the distribution of toner by said apparatus.

The shape coefficient SF-1 of＜toner and the mensuration of SF-2 〉

300 of the SEM image grab sample of the toner that will obtain by FE-SEM (S-4800) mensuration that the Hitachi makes import to this image information in the image analysis apparatus (LuzexAP, Nireco Co. make) by interface, analyze and try to achieve.

The mensuration of the condensation degree of＜toner 〉

Quicken in the assay method of condensation degree, the powder test instrument that uses Hosokawa Micro Co. manufacturing is installed appurtenances in the following sequence as determinator on shaking table.

(i) vibra shoot

(ii) filler

(iii) spacer ring

(iv) on the sieve (three kinds)＞in＞down

(v) depression bar

Then, fix, make shaking table work with spherical bolt.Condition determination is as described below.

Mesh size (on) 75 μ m

" (in) 45 μ m

" (descending) 22 μ m

Wide scale 1mm shakes

Sampling amount 2g

Time of vibration 15 seconds

After the mensuration, try to achieve condensation degree by following calculating.

The quality % of residual powder * 1 in the sieve of epimere ... (a)

The quality % of residual powder * 0.6 in the sieve in stage casing ... (b)

The quality % of residual powder * 0.2 in the sieve of hypomere ... (c)

With the summation of above-mentioned three calculated values as condensation degree (%).That is condensation number (%)=(a)+(b)+(c).

The mensuration of＜glass transition temperature (Tg) 〉

The Tg of toner uses following differential scanning type calorimeter, measures under the following conditions.

Differential scanning calorimeter: SEIKO1DSC100

SEIKO1SSC5040(Disk Station)

Condition determination:

Temperature range: 25～150 ℃

Programming rate: 10 ℃/min

Sample time: 0.5 second

Sample size: 10mg

The mensuration of the specific insulation of＜toner 〉

Specific insulation of the present invention is following value: be arranged on the toner that pushes on the particle between the parallel pole in 2mm gap, interval, between two electrodes, apply DC 1000V, with high resistance meter (for example TR8601 of the Advantest Co. manufacturing) resistance value of mensuration after 30 seconds, the value that obtains is converted by resistance value and grain thickness, is converted to the value (logarithm value) of specific insulation.

The mensuration of the apparent bulk density of＜toner 〉

Above-mentioned apparent bulk density for example can be measured by the powder test instrument PT-S that Hosokawa Micro Co. makes.

[I] embodiment 1～12 and comparative example 1～4

＜evaluation machine 〉

The image that is used for estimating uses any one formation of following evaluation machine A, B, C, D and E.

＜evaluation machine A 〉

The fixation unit improvement of panchromatic laser printer (IPSiO Color 8000, Ricoh Co., Ltd make) of using the series system of the development section of the non magnetic bi-component class that will have four looks and the photoreceptor that four looks are used is as the oilless fixing unit and adjust the evaluation machine A that obtains and estimate.In print speed printing speed is to estimate under the high speed printing (20～50/minute/the A4 size).

＜evaluation machine B 〉

Use following evaluation machine B to estimate, described evaluation machine B improves the panchromatic laser printer of the series system of the development section of the non magnetic bi-component class with four looks and the photoreceptor that four looks are used (IPSiOColor 8000, Ricoh Co., Ltd make), change to primary transfer to the intermediate transfer body, again with the intermediate transfer mode of this toner image secondary transfer printing to the transfer materials, and fixation unit improvement is the oilless fixing unit, and adjusts and the evaluation machine B that obtains.In print speed printing speed is to estimate under the high speed printing (20～50/minute/the A4 size).

(estimating machine C)

Use following evaluation machine C to estimate, described evaluation machine C improves the fixation unit of panchromatic laser copier (IMAGIO Color 2800, Ricoh Co., Ltd make) for the oilless fixing unit and adjusts to obtain, the development section that described panchromatic laser copier is four looks carries out development of all kinds with bi-component class developer on a drum type photoreceptor, be transferred to successively on the intermediate transfer body, with the four looks disposable mode that is transferred on the recording medium.

(estimating machine D)

Use following evaluation machine D to estimate, described evaluation machine D adjusts the fixation unit improvement of panchromatic laser printer (IPSiO Color 5000, Ricoh Co., Ltd make) to obtain for the oilless fixing unit and under the state of printing ink application type, the development section of described panchromatic laser printer four looks develops to a banded photoreceptor successively with non-magnetic mono-component class developer is of all kinds, be transferred to successively on the intermediate transfer body, with the four looks disposable mode that is transferred on the recording medium.

(evaluation of two-component developing agent)

When carrying out picture appraisal with bi-component class developer, as described below, use is by the ferrite carrier of silicones with the mean grain size 50 μ m of the average thickness coating of 0.3 μ m, the rotary drum mixer of the pattern of using container to rotate and stirring evenly mixes 100 parts of carriers with 5 parts of each colour toners, make it charged, the preparation developer.

(preparation of carrier)

Core

Cu-Zn ferrite particle (mass mean diameter: 35 μ m) ... 5000 parts

Coating material

Toluene ... 450 parts

Silicones (SR2400, Toray Dow Corning Silicone Co. manufacturing, nonvolatile component 50%) ... 450 parts

Amino silane (SH6020, Toray Dow Corning Silicone Co. make) ... 10 parts

Carbon black ... 10 parts

Above-mentioned coating material was disperseed 10 minutes with stirrer, the preparation coating fluid, this coating fluid and core are put in the apparatus for coating that is coated with in the formation rotating flow that is provided with rotary plate disk and agitator in thermopnore, this coating fluid is applied on the core.To the coating thing that obtains in electric furnace in 250 ℃ of following sintering 2 hours, obtain above-mentioned carrier.

(assessment item)

1) carrier expendable

Figure for 50% image area, the control toner concentration is so that image color is 1.4 ± 0.2, use the variable quantity of carried charge (μ c/g) of 100000 developers after the output and the preliminary phase ratio before the output simultaneously, during with 0～30% reduction amount during as zero, 30%～50% reduction amount during as △, reduction amount more than 50% as * estimate.Carried charge is measured by the blowing method.

2) photographic fog

Under the environment of 10 ℃ of temperature, 15%RH, the toner contamination degree of using background portion on the recording medium after each toner is implemented continuously the long duration test of the figure of 100000 image area rates 0.5% of output is estimated by visual (magnifier).By the situation of excellence begin to be evaluated as successively ◎, zero, △, *.◎ is not for observing the state of the excellence of toner contamination fully, and zero for observing the degree of pollution a little, not becoming problem, and △ is a degree of observing a small amount of pollution, * very obviously pollute, become problem for existing outside the permissible range.

3) toner disperses

Under the environment of 40 ℃ of temperature, 90%RH, by visual to using the toner contamination degree in the duplicating machine after each toner is implemented continuously the long duration test of the figure of 100000 image area rates 10% of output to estimate.◎ is not for observing the state of the excellence of toner contamination fully, and zero for observing the degree of pollution a little, not becoming problem, and △ is a degree of observing a small amount of pollution, * very obviously pollute, become problem for existing outside the permissible range.

4) anti-adhesive (environment keeping quality)

Each measures in the glass container that the 10g toner joins 20ml, rap vial 100 times after, be placed in the calibration cell that is under 55 ℃ of temperature, the 80%RH after 48 hours, measure pen. with penetrometer.In addition, the toner that is kept under the low temperature and low humidity environment (10 ℃, 15%RH) is estimated pen. similarly, under hot and humid environment and low temperature and low humidity environment, adopt the littler value of pen. to estimate.Situation by excellence begins ◎: 20mm is above, zero: 15mm above and less than 20mm, △: 10mm above and less than 15mm, *: less than 10mm.

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

Transform image processing system (Ricoh Co., Ltd's manufacturing, imagio Neo 450), make band photographic fixing mode, go up with image on the spot with 1.0 ± 0.1mg/cm at the recording medium of common paper and ground paper (duplicating printing＜135 that Ricoh Co., Ltd makes, model 6200 and NBS Ricoh make 〉) ²The toner adhesion amount carry out the photographic fixing evaluation.The temperature that changes the photographic fixing band is carried out the photographic fixing test, will not produce the ceiling temperature of heat penetration seal as the photographic fixing ceiling temperature with common paper.In addition, measure the photographic fixing lower limit temperature with ground paper.The photographic fixing lower limit temperature is that the residual rate of the image color behind the photographic fixing image that will obtain with the thin paper wiping is that fixing roller temperature more than 70% is as the photographic fixing lower limit temperature.Preferred photographic fixing ceiling temperature is more than 200 ℃, the photographic fixing lower limit temperature is below 140 ℃.

[synthesizing of titanium-containing catalyst]

To having cooling tube, stirring machine and can be in liquid in the reactive tank of the nitrogen ingress pipe of bubbling, add 1617 parts of diisopropoxies two (triethanolamine) and close titanium and 126 parts of ion exchange waters, with nitrogen in liquid under the bubbling, slowly be warming up to 90 ℃, react (hydrolysis) 4 hours down at 90 ℃, obtain dihydroxy two (triethanolamine) thus and close titanium.

For later embodiment, also use same synthetic method, can obtain the titanium-containing catalyst that uses among the present invention respectively.

(embodiment 1)

[synthesizing of linear polyesters resin]

2 moles of PO addition products, 3 moles of PO addition products of 300 parts of bisphenol-As, 257 parts of terephthalic acid (TPA)s, 65 parts of m-phthalic acids, 10 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 430 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 220 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, take out during for 5mgKOH/g, pulverize behind the cool to room temperature, obtain linear polyesters resin (AX1-1) at acid number.

(AX1-1) do not contain the insoluble composition of THF, its acid number is 7mgKOH/g, and hydroxyl value is 12mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 6940, and peak molecular weight (Mp) is 19100.The ratio of the composition of molecular weight below 1500 is 1.2%.

[synthesizing of non-linear polyesters resin]

2 moles of EO addition products, 3 moles of PO addition products of 326 parts of bisphenol-As, 278 parts of terephthalic acid (TPA)s, 40 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 350 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g takes out when following at acid number, be cooled to 180 ℃, add 62 parts of trimellitic anhydrides, the airtight reaction down of normal pressure was taken out after 2 hours, pulverize after being cooled to room temperature, obtain non-linear polyesters resin (AX2-1).(AX2-1) do not contain the insoluble composition of THF, its acid number is 35mgKOH/g, and hydroxyl value is 17mgKOH/g, and glass transition temperature (Tg) is 69 ℃, and number-average molecular weight (Mn) is 3920, and peak molecular weight (Mp) is 112010.The ratio of the composition of molecular weight below 1500 is 0.9%.

[synthesizing of toner binder 1]

Utilize continuous kneader with 400 parts of polyester (AX1-1) and 600 parts of polyester (AX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain toner binder 1 of the present invention.

The preparation of-toner-

[black toner]

Water ... 1000 parts

The moisture filter cake of phthalocyanine green (solid constituent 30%) ... 200 parts

Carbon black (MA60, Mitsubishi chemical Co., Ltd make) ... 540 parts

Toner binder 1...1200 part

Above-mentioned starting material are mixed with Henschel mixer, obtain the potpourri in the water infiltration pigment condensation product.Be set at by roll surface temperature 130 ℃ two rollers to this potpourri carry out 45 minutes mixing, roll cooling, pulverize with comminutor, obtain rubber master batch material pigment.

Toner binder 1...100 part

Above-mentioned rubber master batch material ... 8 parts

Charged controlling agent (Orient Chemical Co. manufacturing, Bontron E-84) ... 2 parts

Wax (fatty acid ester wax, 83 ℃ of fusing points, viscosity 280mPas (90 ℃)) ... 5 parts

After above-mentioned material mixed with mixer, more than 3 times, mixing thing calendering is cooled off with two roller melting mixings.The comminutor of the impingement plate mode by utilizing jet mill (I formula mill then; Japan PneumaticMfg.Co. makes) and utilize air classification (the DS grader of rotating flow; Japan Pneumatic Mfg.Co. manufacturing), obtain the colored particles of the black of volume average particle size 5.5 μ m.Further add the hydrophobic silica (mean grain size of HDK H2000, Clariant Japan K.K. manufacturing, primary particle is 10nm) of 1.0% primary particle size 10nm, mix with Henschel mixer, by the sieve of aperture 50 μ m, remove condensation product, obtain black toner 1 thus.The toner rerum natura is as table 1-1 and table 1-2, and evaluation result is as shown in table 2.

[Yellow toner]

Water ... 600 parts

C.I. the moisture filter cake of pigment yellow 17 (solid constituent 50%) ... 1200 parts

Toner binder 1...1200 part

Above-mentioned starting material are mixed with Henschel mixer, obtain the potpourri in the water infiltration pigment condensation product.Be set at by roll surface temperature 130 ℃ two rollers to this potpourri carry out 45 minutes mixing, roll cooling, pulverize with comminutor, obtain rubber master batch material pigment.

Toner binder 1...100 part

Above-mentioned rubber master batch material ... 8 parts

Charged controlling agent (Orient Chemical Co. manufacturing, Bontron E-84) ... 2 parts

Wax (fatty acid ester wax, 83 ℃ of fusing points, viscosity 280mPas (90 ℃)) ... 5 parts

After above-mentioned material mixed with mixer, more than 3 times, mixing thing calendering is cooled off with two roller melting mixings.The comminutor of the impingement plate mode by utilizing jet mill (I formula mill then; Japan PneumaticMfg.Co. makes) and utilize air classification (the DS grader of rotating flow; Japan Pneumatic Mfg.Co. manufacturing), obtain the colored particles of the yellow of volume average particle size 5.5 μ m.Further the hydrophobic silica of the primary particle size 10nm of interpolation 1.0% (HDK H2000, Clariant Japan K.K. make) mixes with Henschel mixer, by the sieve of aperture 50 μ m, removes condensation product, obtains Yellow toner 1 thus.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.

[pinkish red toner]

Water ... 600 parts

C.I. paratonere 57 moisture filter cakes (solid constituent 50%) ... 1200 parts

Toner binder 1...1200 part

Above-mentioned starting material are mixed with Henschel mixer, obtain the potpourri in the water infiltration pigment condensation product.Be set at by roll surface temperature 130 ℃ two rollers to this potpourri carry out 45 minutes mixing, roll cooling, pulverize with comminutor, obtain rubber master batch material pigment.

Toner binder 1...100 part

Above-mentioned rubber master batch material ... 8 parts

Charged controlling agent (Orient Chemical Co. manufacturing, Bontron E-84) ... 2 parts

Wax (fatty acid ester wax, 83 ℃ of fusing points, viscosity 280mPas (90 ℃)) ... 5 parts

After above-mentioned material mixed with mixer, more than 3 times, mixing thing calendering is cooled off with two roller melting mixings.The comminutor of the impingement plate mode by utilizing jet mill (I formula mill then; Japan PneumaticMfg.Co. makes) and utilize air classification (the DS grader of rotating flow; Japan Pneumatic Mfg.Co. manufacturing), obtain the colored particles of the magenta of volume average particle size 5.5 μ m.Further the hydrophobic silica of the primary particle size 10nm of interpolation 1.0% (HDK H2000, Clariant Japan K.K. make) mixes with Henschel mixer, by the sieve of aperture 50 μ m, removes condensation product, obtains pinkish red toner 1 thus.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.

[cyan toner]

Water ... 600 parts

C.I. pigment blue 15: 3 moisture filter cakes (solid constituent 50%) ... 1200 parts

Toner binder 1...1200 part

Above-mentioned starting material are mixed with Henschel mixer, obtain the potpourri in the water infiltration pigment condensation product.Be set at by roll surface temperature 130 ℃ two rollers to this potpourri carry out 45 minutes mixing, roll cooling, pulverize with comminutor, obtain rubber master batch material pigment.

Toner binder 1...100 part

Above-mentioned rubber master batch material ... 8 parts

Charged controlling agent (Orient Chemical Co. manufacturing, Bontron E-84) ... 2 parts

Wax (fatty acid ester wax, 83 ℃ of fusing points, viscosity 280mPas (90 ℃)) ... 5 parts

After above-mentioned material mixed with mixer, more than 3 times, mixing thing calendering is cooled off with two roller melting mixings.The comminutor of the impingement plate mode by utilizing jet mill (I formula mill then; Japan PneumaticMfg.Co. makes) and utilize air classification (the DS grader of rotating flow; Japan Pneumatic Mfg.Co. manufacturing), obtain the colored particles of the cyan of volume average particle size 5.5 μ m.Further the hydrophobic silica of the primary particle size 10nm of interpolation 1.0% (HDK H2000, Clariant Japan K.K. make) mixes with Henschel mixer, by the sieve of aperture 50 μ m, removes condensation product, obtains cyan toner 1 thus.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 2)

[synthesizing of linear polyesters resin]

Except polycondensation catalyst being replaced with two (triethanolamine) network oxygen titanium, similarly react with (AX1-1) of embodiment 1, pulverize after being cooled to room temperature, obtain linear polyesters resin (AX1-2).

(AX1-2) do not contain the insoluble composition of THF, its acid number is 8mgKOH/g, and hydroxyl value is 10mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 6820, and peak molecular weight (Mp) is 20180.The ratio of the composition of molecular weight below 1500 is 1.1%.

[synthesizing of non-linear polyesters resin]

Close the titanium except polycondensation catalyst being replaced with two (triethanolamines), similarly react, be cooled to pulverize after the room temperature and obtain linear polyesters resin (AX2-2) with (AX2-1) of embodiment 1.

(AX2-2) do not contain the insoluble composition of THF, its acid number is 33mgKOH/g, and hydroxyl value is 14mgKOH/g, and glass transition temperature (Tg) is 70 ℃, and number-average molecular weight (Mn) is 4200, and peak molecular weight (Mp) is 11800.The ratio of the composition of molecular weight below 1500 is 0.8%.

[synthesizing of toner binder 2]

With Henschel mixer 500 parts of polyester (AX1-2) and 500 parts of polyester (AX2-2) are carried out powder 5 minutes, obtain toner binder 2 of the present invention.

The preparation of-toner-

Except in toner resin, rubber master batch material resin, using toner binder 2, similarly prepare toner, estimate with the black toner of embodiment 1.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 3)

[synthesizing of modified polyester resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 549 parts of bisphenol-A epoxy propane, 3 moles of addition products of 20 parts of bisphenol-A epoxy propane, 2 moles of addition products of 133 parts of bisphenol-A epoxy ethane, 5 moles of addition products of oxirane of 10 parts of phenol novolaks (average degree of polymerization is about 5), 252 parts of terephthalic acid (TPA)s, 19 parts of m-phthalic acids, 10 parts of trimellitic anhydrides and 2 parts of dihydroxy two (triethanolamine) and close titanium as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, react to acid number be below the 2mgKOH/g.Then, add 50 parts of trimellitic anhydrides, reaction is after 1 hour under normal pressure, under the decompression of 20～40mmHg, react, add 20 parts of bisphenol A diglycidyl ethers when softening point is 105 ℃, take out down for 150 ℃ at softening point, pulverize after being cooled to room temperature, obtain modified polyester resin (AY1-1).

(AY1-1) acid number is 52mgKOH/g, hydroxyl value is 16mgKOH/g, glass transition temperature (Tg) is 73 ℃, number-average molecular weight (Mn) is 1860, peak molecular weight (Mp) is 6550, the insoluble composition of THF is 32%, and the ratio of the composition of molecular weight below 1500 is 1.0%, used as toner binder 3.

The preparation of-toner-

Except in toner resin, rubber master batch material resin, using toner binder 3, similarly prepare toner with the black toner of embodiment 1, and estimate.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 4)

[synthesizing of non-linear polyesters resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 132 parts of bisphenol-A epoxy propane, 3 moles of addition products of 371 parts of bisphenol-A epoxy propane, 2 moles of addition products of 20 parts of bisphenol-A epoxy ethane, 5 moles of addition products of epoxypropane of 125 parts of phenol novolaks (average degree of polymerization is about 5), 201 parts of terephthalic acid (TPA)s, 25 parts of maleic anhydrides, 35 parts of dimethyl terephthalate (DMT) and 2 parts of two (triethanolamine) network oxygen titaniums as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g is cooled to 180 ℃ when following at acid number, adds 65 parts of trimellitic anhydrides, and the airtight reaction down of normal pressure was taken out after 2 hours, is cooled to pulverize after the room temperature to obtain non-linear polyesters resin (AX2-3).

The softening point of non-linear polyesters resin (AX2-3) is 144 ℃, acid number is 30mgKOH/g, hydroxyl value is 16mgKOH/g, glass transition temperature (Tg) is 59 ℃, number-average molecular weight (Mn) is 1410, and peak molecular weight (Mp) is 4110, and the insoluble composition of THF is 27%, the ratio of the composition of molecular weight below 1500 is 1.0%, used as toner binder 4.

The preparation of-toner-

Except in toner resin, rubber master batch material resin, using toner binder 4, similarly prepare toner with the black toner of embodiment 1 and estimate.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 5)

[synthesizing of non-linear polyesters resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 410 parts of bisphenol-A epoxy propane, 3 moles of addition products of 270 parts of bisphenol-A epoxy propane, 110 parts of terephthalic acid (TPA)s, 125 parts of m-phthalic acids, 15 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) and close titanium as condensation catalyst, under 220 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g is cooled to 180 ℃ when following at acid number, adds 25 parts of trimellitic anhydrides, and the airtight reaction down of normal pressure was taken out after 2 hours, pulverizes after being cooled to room temperature, obtains non-linear polyesters resin (AX2-4).

(AX2-4) do not contain the insoluble composition of THF, its acid number is 18mgKOH/g, and hydroxyl value is 37mgKOH/g, and glass transition temperature (Tg) is 62 ℃, and number-average molecular weight (Mn) is 2130, and number-average molecular weight (Mn) is 5350.The ratio of the composition of molecular weight below 1500 is 1.3%.

[synthesizing of modified polyester resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 317 parts of bisphenol-A epoxy ethane, 2 moles of addition products of 57 parts of bisphenol-A epoxy propane, 3 moles of addition products of 298 parts of bisphenol-A epoxy propane, 5 moles of addition products of epoxypropane of 75 parts of phenol novolaks (average degree of polymerization is about 5), 30 parts of m-phthalic acids, 157 parts of terephthalic acid (TPA)s, 27 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) and close titanium as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, at acid number is that 2mgKOH/g is cooled to 180 ℃ when following, then, adds 68 parts of trimellitic anhydrides, normal pressure reacts after 1 hour down, under the decompression of 20～40mmHg, react, add 25 parts of bisphenol A diglycidyl ethers when softening point is 120 ℃, take out down for 155 ℃ at softening point, pulverize after being cooled to room temperature, obtain modified polyester resin (AY1-2).(AY1-2) acid number is 11mgKOH/g, and hydroxyl value is 27mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 3020, and peak molecular weight (Mp) is 6030, and the insoluble composition of THF is 35%.The ratio of the composition of molecular weight below 1500 is 1.1%.

[synthesizing of toner binder 5]

Utilize continuous kneader with 500 parts (AX2-3) and 500 parts (AY1-2) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain toner binder 5 of the present invention.

The preparation of-toner-

Except in toner resin, rubber master batch material resin, using toner binder 5, similarly prepare toner with the black toner of embodiment 1 and estimate.The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 6)

Except following external additive mixed method being changed into when black toner 1 preparation of embodiment 1 wet type is prepared, estimate similarly to Example 1.

Be distributed in the water that contains 0.1% surfactant with Mono pump the hydrophobic silica (HDK H2000, Clariant Japan K.K. make) of the colored particles of the black of the volume average particle size 5.5 μ m of 10 parts of embodiment 1 and 2 parts of primary particle size 10nm and mix.By the monitoring of fluorescent X-ray method, the adhesion amount of monox takes out toner when being 1 quality % from water, by the sieve of aperture 50 μ m, remove condensation product, obtains black toner thus.

The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 7)

Except changing into when black toner 1 preparation of embodiment 1 following external additive mixed method is prepared, estimate similarly to Example 1.

In black toner 1, further mix 0.4 part of zinc stearate, by the sieve of aperture 50 μ m, remove condensation product once more, obtain black toner thus with Henschel mixer.

The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 8)

Except changing into when black toner 1 preparation of embodiment 1 following external additive mixed method is prepared, estimate similarly to Example 1.

In black toner 1, further mix the titanium dioxide (the mean grain size 15nm of STM-150AI, Tayca Co. manufacturing, primary particle) of 0.5 quality %, by the sieve of aperture 50 μ m, remove condensation product once more, obtain black toner thus.

The toner rerum natura is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 9)

Except making toner is the chemical toner of following preparation, estimates similarly to Example 1.

-organic fine particles emulsion synthetic-

In the reaction vessel that stirring rod and thermometer are installed, add the sodium salt (Eleminol RS-30, Sanyo Chemical Industries, Ltd. make) of 683 parts of water, 11 parts of methacrylic acid ethylene oxide adduct sulfuric esters, 166 parts of methacrylic acids, 110 parts of butyl acrylates, 1 part of ammonium persulfate, with 3800 rev/mins of stirrings 30 minutes, obtain the emulsion of white.Heat temperature raising 75 ℃ of temperature to the system were reacted 3 hours.Further add 30 part of 1% ammonium persulfate aqueous solution, 70 ℃ of following slakings 5 hours, obtain the aqueous liquid dispersion [particle dispersion liquid 1] of vinyl-based resin (multipolymer of the sodium salt of methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfuric ester).The volume average particle size that [particle dispersion liquid 1] mensuration is obtained with LA-920 is 75nm.Part to [particle dispersion liquid 1] is carried out drying, the separation resin composition.The glass transition temperature of this resinous principle (Tg) is 60 ℃, and weight-average molecular weight (Mw) is 110,000.

The preparation of-water-

48.3% aqueous solution (Eleminol MON-7, Sanyo Chemical Industries, Ltd. make) of 990 parts of water, 83 parts [particle dispersion liquid 1], 37 parts of dodecyl diphenyl ether sodium disulfonates, 90 parts of ethyl acetate are mixed stirring, obtain milky liquid.With it as " water 1 ".

-low molecular weight polycaprolactone ester synthetic-

2 moles of PO addition products, 3 moles of PO addition products of 300 parts of bisphenol-As, 257 parts of terephthalic acid (TPA)s, 65 parts of m-phthalic acids, 10 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 430 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 200 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 8 hours.Then, under the decompression of 5～20mmHg, react, after acid number takes out during for 7mgKOH/g, is cooled to room temperature, pulverize, obtain low molecular weight polycaprolactone ester resin 1.

Low molecular weight polycaprolactone ester resin 1 does not contain the insoluble composition of THF, and its acid number is 9mgKOH/g, and hydroxyl value is 12mgKOH/g, and glass transition temperature (Tg) is 52 ℃, and number-average molecular weight (Mn) is 4820, and peak molecular weight (Mp) is 17000.The ratio of the composition of molecular weight below 1500 is 0.8%.

-intermediate polyester synthetic-

In the reaction vessel that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 682 parts of bisphenol-A epoxy ethane, 2 moles of addition products of 81 parts of bisphenol-A epoxy propane, 283 parts of terephthalic acid (TPA)s, 22 parts of trimellitic anhydrides and 2 parts of Dibutyltin oxides, under the normal pressure, reacted 7 hours down at 230 ℃, further under the decompression of 10～15mmHg, reacted 5 hours, obtain [intermediate polyester 1].The number-average molecular weight of [intermediate polyester 1] is 2200, and the quality mean molecular weight is 9700, and glass transition temperature (Tg) is 54 ℃, and acid number is 0.5mgKOH/g, and hydroxyl value is 52mgKOH/g.

Then, in the reaction vessel that has cooling tube, stirring machine and nitrogen ingress pipe, add 410 parts [intermediate polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate, reacted 5 hours down, obtain [prepolymer 1] at 100 ℃.The free isocyanate quality % of [prepolymer 1] is 1.53%.

-ketimide-

In the reaction vessel that stirring rod and thermometer are installed, add 170 parts of isophorone diamine and 75 parts of MEKs, under 50 ℃, carry out half-reaction in 4 hours, obtain [ketimine compound 1].The amine value of [ketimine compound 1] is 417.

-masterbatch (MB) synthetic-

Add 600 parts of water, pigment blue 15: 3 moisture filter cakes (solid constituent 50%), 1200 parts of vibrin, mix with Henschel mixer (Mitsui Mining Co Ltd. BJ Offc's manufacturing), use two rollers with potpourri at 120 ℃ down after mixing 45 minutes, roll cooling, pulverize with comminutor, obtain [rubber master batch material 1].

The preparation of-oil phase-

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

1324 parts [raw material lysates 1] are transferred in the container, use ball mill (Ultra Visco mill, AIMEX Co. make), in liquor charging speed 1kg/hr, disk circumference speed 6m/ second, fill the 0.5mm zirconium oxide bead of 80 volume %, by under 3 times the condition, carry out the dispersion of pigment, wax.65% ethyl acetate solution that then adds 1324 parts [low molecular weight polycaprolactone esters] by 2 times, obtains [pigment-wax dispersion 1] with the ball mill of above-mentioned condition.The solid component concentration of [pigment-wax dispersion 1] (130 ℃, 30 minutes) is 50%.

-emulsification and desolventizing-

In container, add 749 parts of [pigment-wax dispersions 1], 115 parts [prepolymers 1], 2.9 parts [ketimine compound 1], with TK uniform mixer (special machine Co., Ltd. make) after mixing 2 minutes under the 5000rpm, in container, add 1200 parts [water 1], mixed 25 minutes under rotational speed 13000rpm with the TK uniform mixer, obtain [emulsification slurry 1].

In the container that stirring machine and thermometer are installed, drop in [emulsification slurry 1], after 8 hours, under 45 ℃, carry out slaking in 7 hours, obtain [dispersed paste 1] at 30 ℃ of following desolventizings.

-washing and drying-

Behind 100 parts of [dispersed paste 1] filtration under diminished pressure,

(1) in filter cake, adds 100 parts of ion exchange waters, after TK uniform mixer mixing (carrying out under the rotational speed 12000rpm 10 minutes), filter.

(2) in the filter cake of (1), add 100 part of 10% sodium hydrate aqueous solution, after TK uniform mixer mixing (carrying out under the rotational speed 12000rpm 30 minutes), filtration under diminished pressure.

(3) in the filter cake of (2), add 100 part of 10% hydrochloric acid, after TK uniform mixer mixing (carrying out under the rotational speed 12000rpm 10 minutes), filter.

(4) carry out twice and in the filter cake of (3), add 300 parts of ion exchange waters, mix the operation that filter (carrying out 10 minutes) back under rotational speed 12000rpm, obtain [filter cake 1] with the TK uniform mixer.

[filter cake 1] usefulness recirculating air dryer is following dry 48 hours at 45 ℃.

Then, be dispersed with in the hydrosolvent groove of following fluorine compounds (2) with 1 quality % concentration, the following fluorine compounds (2) that mix 0.1 quality % with respect to the toner parent, after making following fluorine compounds (2) adhere to (bonding), with the recirculating air dryer at 45 ℃ down after dry 48 hours, further with pallet 30 ℃ dry 10 hours down.Then, the sieve screening with aperture 75 μ m obtains [toner parent particle 1].

Fluorine compounds (2)

Then, mix, obtain toner with the hydrophobic silica (HDK H2000, Clariant JapanK.K. make) of Henschel mixer (Mitsui Mining Co Ltd. BJ Offc's manufacturing, FM20C) with 100 parts [toner parent particles 1], primary particle size 10nm.Mixing condition is peripheral speed 30m/sec, and triplicate rotated for 120 seconds, the setting in 60 seconds of stopping the rotation, and mixed, and obtained toner.

The rerum natura of the toner that obtains is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(embodiment 10～12)

Except using the black toner of embodiment 1 record in embodiment 1, each estimates machine in-service evaluation machine B, estimate machine C, estimate outside machine D estimates, and estimates similarly to Example 1.Evaluation result is as shown in table 2.

(comparative example 1)

The adhesive resin that uses in the black toner with embodiment 1 is changed into the following resin H2, similarly prepares toner with the black toner of embodiment 1, and estimates.

In the reaction vessel that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 229 parts of bisphenol-A epoxy ethane, 3 moles of addition products of 529 parts of bisphenol-A epoxy propane, 208 parts of terephthalic acid (TPA)s, 46 parts of hexane diacids and 2 parts of dibutyltin oxides, under the normal pressure, reacted 7 hours down at 230 ℃, further under the decompression of 10～15mmHg, reacted 5 hours, in reaction vessel, add 44 parts of trimellitic anhydrides then, reaction is 3 hours under 180 ℃, normal pressure, obtains vibrin H2.The number-average molecular weight of the vibrin H2 that obtains is 2300, and the quality mean molecular weight is 6700, and glass transition temperature (Tg) is 43 ℃, and acid number is 25mgKOH/g.And, in catalysts, mix 1 part of dibutyl tin and use.

The toner rerum natura that obtains is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(comparative example 2)

Except in the black toner of embodiment 1, make its particle diameter, size distribution, micro mist, meal content shown in table 1-1 outside the classification preparation, similarly prepare with the black toner of embodiment 1, and estimate.The toner rerum natura that obtains is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(comparative example 3)

Except in the black toner of embodiment 1, make its particle diameter, size distribution, micro mist, meal content shown in table 1-1 outside the classification preparation, similarly prepare with the black toner of embodiment 1, and estimate.The toner rerum natura that obtains is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

(comparative example 4)

Except in the black toner of embodiment 1, make its particle diameter, size distribution, micro mist, meal content shown in table 1-1 outside the classification preparation, similarly prepare with the black toner of embodiment 1, and estimate.The toner rerum natura that obtains is as table 1-1 and show 1-2, evaluation result is as shown in table 2.Evaluation machine in-service evaluation machine A.

[table 1-1]

[table 1-2]

[table 2]

[II] (embodiment 13～72 and comparative example 5～24)

(toner binder A's is synthetic)

[synthesizing of linear polyesters resin]

2 moles of PO addition products, 3 moles of PO addition products of 300 parts of bisphenol-As, 257 parts of terephthalic acid (TPA)s, 65 parts of m-phthalic acids, 10 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 430 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 220 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, after acid number takes out during for 5mgKOH/g, is cooled to room temperature, pulverize, obtain linear polyesters resin (AX1-1).

(AX1-1) do not contain the insoluble composition of THF, its acid number is 7mgKOH/g, and hydroxyl value is 12mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 6940, and peak molecular weight (Mp) is 19100.The ratio of the composition of molecular weight below 1500 is 1.2%.

[synthesizing of non-linear polyesters resin]

2 moles of EO addition products, 3 moles of PO addition products of 326 parts of bisphenol-As, 278 parts of terephthalic acid (TPA)s, 40 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 350 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g takes out when following at acid number, be cooled to 180 ℃, add 62 parts of trimellitic anhydrides, the airtight reaction down of normal pressure was taken out after 2 hours, pulverize after being cooled to room temperature, obtain non-linear polyesters resin (AX2-1).

(AX2-1) do not contain the insoluble composition of THF, its acid number is 35mgKOH/g, and hydroxyl value is 17mgKOH/g, and glass transition temperature (Tg) is 69 ℃, and number-average molecular weight (Mn) is 3920, and peak molecular weight (Mp) is 11200.The ratio of the composition of molecular weight below 1500 is 0.9%.

[toner binder A's is synthetic]

Utilize continuous kneader with 400 parts of polyester (AX1-1) and 600 parts of polyester (AX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain toner binder A of the present invention.

(toner binder B's is synthetic)

[synthesizing of linear polyesters resin]

Except polycondensation catalyst being replaced to two (triethanolamine) network oxygen titanium, similarly react with (AX1-1) in toner binder A synthetic, pulverize after being cooled to room temperature, obtain linear polyesters resin (AX1-2).

(AX1-2) do not contain the insoluble composition of THF, its acid number is 8mgKOH/g, and hydroxyl value is 10mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 6820, and peak molecular weight (Mp) is 20180.The ratio of the composition of molecular weight below 1500 is 1.1%.

[synthesizing of non-linear polyesters resin]

Except polycondensation catalyst being replaced with two (triethanolamine) network oxygen titanium, similarly react with (AX2-1) in toner binder A synthetic, be cooled to room temperature after pulverizing obtain linear polyesters resin (AX2-2).

(AX2-2) do not contain the insoluble composition of THF, its acid number is 33mgKOH/g, and hydroxyl value is 14mgKOH/g, and glass transition temperature (Tg) is 70 ℃, and number-average molecular weight (Mn) is 4200, and peak molecular weight (Mp) is 11800.The ratio of the composition of molecular weight below 1500 is 0.8%.

[toner binder B's is synthetic]

Utilize Henschel mixer that 500 parts of polyester (AX1-2) and 500 parts of polyester (AX2-2) were carried out powder 5 minutes, obtain toner binder B of the present invention.

(toner binder C's is synthetic)

[relatively synthesizing] with the linear polyesters resin

Except polycondensation catalyst is replaced with the tetraisopropoxy titanium, similarly react with (AX1-1) in toner binder A synthetic.Because catalyst deactivation, be reflected at Halfway Stopping, owing to produce the problem that water does not distill out that generates, append 2 parts tetraisopropoxy titanium midway 4 times in reaction, relatively used linear polyesters resin (CAX1-1).

(CAX1-1) do not contain the insoluble composition of THF, its acid number is 7mgKOH/g, and hydroxyl value is 12mgKOH/g, and glass transition temperature (Tg) is 58 ℃, and number-average molecular weight (Mn) is 6220, and peak molecular weight (Mp) is 18900.The ratio of the composition of molecular weight below 1500 is 2.2%.

[relatively synthesizing] with non-linear polyesters resin

Except polycondensation catalyst is replaced with the tetraisopropoxy titanium, similarly react with (AX2-1) in toner binder A synthetic.Reaction is 8 hours under reaction 16 hours under normal pressure, the decompression.Because reaction velocity is slow, append 2 parts tetraisopropoxy titanium midway 3 times in reaction, relatively used non-linear polyesters resin (CAX2-1).

(CAX2-1) do not contain the insoluble composition of THF, its acid number is 34mgKOH/g, and hydroxyl value is 16mgKOH/g, and glass transition temperature (Tg) is 68 ℃, and number-average molecular weight (Mn) is 3420, and peak molecular weight (Mp) is 12100.The ratio of the composition of molecular weight below 1500 is 2.1%.

[toner binder C's is synthetic]

Utilize continuous kneader with 400 parts of polyester (CAX1-1) and 600 parts of polyester (CAX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain comparison toner binder C.Toner binder C is the resin of dark purple brown.

(embodiment 13)

After using Henschel mixer [Mitsui Miike Engineering Corp. makes, FM10B] with 100 parts of toner binder A of the present invention, 5 parts of Brazil waxs [Brazil wax C1,84 ℃ of fusing points, add Co., Ltd. of rattan foreign firm make], 4 parts of yellow uitramarines [Clariant Co. makes, toner yellow HG VP2155] and 3 parts of salicylic acid zinc salts [Orient Chemical Co. makes, Bontron E-84] premixed, [Co., Ltd.'s pond shellfish manufacturing, PCM-30] is mixing with the twin shaft mixing roll.

Then, use supersonic velocity comminutor lab jet[Japan Pneumatic Mfg.Co. to make] carry out micro mist broken after, with gas flow sizing machine [Japan Pneumatic Mfg.Co. makes, MDS-1] classification, obtain the toner particle that particle diameter D50 is 8 μ m.Then, utilize the sample mill in 100 parts of toner particles, to mix 0.5 part of cataloid [Nippon Aerosil Co. manufacturing, Aerosil R972], obtain toner (T13).

(embodiment 14)

Except changing to quaternary ammonium salt [Orient Chemical Co. manufacturing, Bontron P-51] by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84] and changing to [Wacker Chemical Co. manufacturing, H30TA] by cataloid [NipponAerosil Co. manufacturing, Aerosil R972], operation obtains toner (T14) similarly to Example 13.

(embodiment 15)

Except [1-(5-chloro-2-hydroxy phenyl azo-beta naphthal] chromium (III) acid that changed to two by salicylic acid zinc salt [Orient Chemical Co. make, Bontron E-84], operation obtains toner (T15) similarly to Example 13.

(embodiment 16)

Except changing to nigrosine [Orient Chemical Co. manufacturing, Nigrosine Base EX] by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84] and changing to [Wacker Chemical Co. manufacturing, H30TA] by cataloid [NipponAerosil Co. manufacturing, Aerosil R972], operation obtains toner (T16) similarly to Example 13.

(embodiment 17)

Except being changed to the fluorine compounds [Clariant Co. manufacturing, Copy Charge NX VP 434] by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T17) similarly to Example 13.

(embodiment 18)

Except being changed to the perfluoroalkyl trimethyl ammonium iodide [Neos Co. manufacturing, FT-310] by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T18) similarly to Example 13.

(embodiment 19)

Except changing to the styrene-propene acid copolymer that contains quaternary ammonium salt [Fujikura Kasei Co., Ltd makes, FCR-77PR] by salicylic acid zinc salt [Orient Chemical Co. make, Bontron E-84] and changing to [Wacker ChemicalCo. makes, H30TA] by cataloid [Nippon Aerosil Co. makes, Aerosil R972], operation obtains toner (T19) similarly to Example 13.

(embodiment 20)

Except being changed to the Cr azo dyes [AstraZeneca manufacturing, CCA-7] by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T20) similarly to Example 13.

(embodiment 21)

Except being changed to the Fe azo dyes [Hodogaya Chemical Co. manufacturing, T-77] by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T21) similarly to Example 13.

(embodiment 22)

Except being changed to the polyhydroxyalkanoatefrom by salicylic acid zinc salt [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T22) similarly to Example 13.

Wherein, shown in the preparation method of PHA for example descends.

[polyhydroxyalkanoatefrom preparation method]

The bacterium colony of the tabular strain of seed agar was cultivated 30 hours down at 30 ℃ in 500mL volume vibration flask on the 200mL nutrient culture media of the 5-phenyl sulfanilamide (SN) valeric acid that contains 0.5% poly-peptone and 0.1%.After the cultivation,, use the methanol wash postlyophilization by centrifuging results thalline.Behind the dry thalline of weighing, add acetone, stirred 72 hours down in room temperature (about 23 ℃), thus extracting polymer.Polymkeric substance is filtered by the acetone that extracting goes out, after concentrating by evaporator, solidify with the cold methanol precipitation, the part that collecting precipitation solidifies, drying under reduced pressure obtains subject polymer.The quality of dry thalline is 215mg, and the quality of the polymkeric substance that obtains is 76mg.

(embodiment 23)

Except toner binder A is changed to the toner binder B, operation obtains toner (T23) similarly to Example 13.

(embodiment 24)

Except toner binder A is changed to the toner binder B, operation obtains toner (T24) similarly to Example 14.

(embodiment 25)

Except toner binder A is changed to the toner binder B, operation obtains toner (T25) similarly to Example 15.

(embodiment 26)

Except toner binder A is changed to the toner binder B, operation obtains toner (T26) similarly to Example 16.

(embodiment 27)

Except toner binder A is changed to the toner binder B, operation obtains toner (T27) similarly to Example 17.

(embodiment 28)

Except toner binder A is changed to the toner binder B, operation obtains toner (T28) similarly to Example 18.

(embodiment 29)

Except toner binder A is changed to the toner binder B, operation obtains toner (T29) similarly to Example 19.

(embodiment 30)

Except toner binder A is changed to the toner binder B, operation obtains toner (T30) similarly to Example 20.

(embodiment 31)

Except toner binder A is changed to the toner binder B, operation obtains toner (T31) similarly to Example 21.

(embodiment 32)

Except toner binder A is changed to the toner binder B, operation obtains toner (T32) similarly to Example 22.

(embodiment 33)

Except change to 3 parts of salicylic acid zinc salts [Orient Chemical Co. makes, Bontron E-84] and 2 part two [1-(5-chloro-2-hydroxy phenyl azo-beta naphthal] chromium (III) acid by 3 parts of salicylic acid zinc salts [Orient Chemical Co. make, Bontron E-84], operation obtains toner (T33) similarly to Example 13.

(embodiment 34)

Except changing to by 3 parts of quaternary ammonium salts [Orient Chemical Co. manufacturing, Bontron P-51] 3 parts of quaternary ammonium salts [Orient Chemical Co. manufacturing, Bontron P-51] and the 2 parts of nigrosines [Orient ChemicalCo. manufacturing, Nigrosine Base EX], operation obtains toner (T34) similarly to Example 14.

(embodiment 35)

Except [1-(5-chloro-2-hydroxy phenyl azo-beta naphthal) chromium (III) acid changes to 3 part of two [1-(5-chloro-2-hydroxy phenyl azo-beta naphthal] chromium (III) acid and the 2 parts of salicylic acid zinc salts [Orient ChemicalCo. manufacturing, Bontron E-84] by 3 part two, operation obtains toner (T35) similarly to Example 15.

(embodiment 36)

Except changing to by 3 parts of nigrosines [Orient Chemical Co. manufacturing, Nigrosine Base EX] 3 parts of nigrosines [Orient Chemical Co. manufacturing, Nigrosine Base EX] and the 2 parts of quaternary ammonium salts [OrientChemical Co. manufacturing, Bontron P-51], operation obtains toner (T36) similarly to Example 16.

(embodiment 37)

Except changing to by 3 parts of fluorine compounds [Clariant Co. manufacturing, Copy Charge NX VP 434] 3 parts of fluorine compounds [Clariant Co. manufacturing, Copy Charge NX VP 434] and the 2 parts of salicylic acid zinc salts [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T37) similarly to Example 17.

(embodiment 38)

Except changing to by 3 parts of perfluoroalkyl trimethyl ammonium iodides [Neos Co. manufacturing, FT-310] 3 parts of perfluoroalkyl trimethyl ammonium iodides [Neos Co. manufacturing, FT-310] and the 2 parts of salicylic acid zinc salts [OrientChemical Co. manufacturing, Bontron E-84], operation obtains toner (T38) similarly to Example 18.

(embodiment 39)

Except the styrene-propene acid copolymer that contains quaternary ammonium salt by 3 parts [Fujikura Kasei Co., Ltd makes, FCR-77PR] changes to 3 parts of styrene-propene acid copolymers that contain quaternary ammonium salt [Fujikura Kasei Co., Ltd makes, FCA-77PR] and 2 parts of quaternary ammonium salts [Orient Chemical Co. manufacturing, Bontron P-51], operation obtains toner (T39) similarly to Example 19.

(embodiment 40)

Except changing to by 3 parts of Cr azo dyess [AstraZeneca manufacturing, CCA-7] 3 parts of Cr azo dyess [AstraZeneca manufacturing, CCA-7] and the 2 parts of salicylic acid zinc salts [Orient Chemical Co. manufacturing, Bontron E-84], operation obtains toner (T40) similarly to Example 20.

(embodiment 41)

Except changing to by 3 parts of Fe azo dyess [Hodogaya Chemical Co. manufacturing, T-77] 3 parts of Fe azo dyess [Hodogaya Chemical Co. manufacturing, T-77] and the 2 parts of salicylic acid zinc salts [OrientChemical Co. manufacturing, Bontron E-84], operation obtains toner (T41) similarly to Example 21.

(embodiment 42)

Except changed to 3 parts of polyhydroxyalkanoatefroms and 2 parts of salicylic acid zinc salts [Orient Chemical Co. manufacturing, Bontron E-84] by 3 parts of polyhydroxyalkanoatefroms, operation obtains toner (T42) similarly to Example 22.

(comparative example 5)

Except toner binder A is changed to the toner binder C, operation similarly to Example 13 obtains toner (T5 ').

(comparative example 6)

Except toner binder A is changed to the toner binder C, operation obtains toner (T6 ') similarly to Example 14.

(comparative example 7)

Except toner binder A is changed to the toner binder C, operation similarly to Example 15 obtains toner (T7 ').

(comparative example 8)

Except toner binder A is changed to the toner binder C, operation similarly to Example 16 obtains toner (T8 ').

(comparative example 9)

Except toner binder A is changed to the toner binder C, operation similarly to Example 17 obtains toner (T9 ').

(comparative example 10)

Except toner binder A is changed to the toner binder C, operation similarly to Example 18 obtains toner (T10 ').

(comparative example 11)

Except toner binder A is changed to the toner binder C, operation similarly to Example 19 obtains toner (T11 ').

(comparative example 12)

Except toner binder A is changed to the toner binder C, operation similarly to Example 20 obtains toner (T12 ').

(comparative example 13)

Except toner binder A is changed to the toner binder C, operation similarly to Example 21 obtains toner (T13 ').

(comparative example 14)

Except toner binder A is changed to the toner binder C, operation similarly to Example 22 obtains toner (T14 ').

(toner binder D's is synthetic)

[synthesizing of modified polyester resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 549 parts of bisphenol-A epoxy propane, 3 moles of addition products of 20 parts of bisphenol-A epoxy propane, 2 moles of addition products of 133 parts of bisphenol-A epoxy ethane, 5 moles of addition products of oxirane of 10 parts of phenol novolaks (average degree of polymerization is about 5), 252 parts of terephthalic acid (TPA)s, 19 parts of m-phthalic acids, 10 parts of trimellitic anhydrides and 2 parts of dihydroxy two (diethanolamine) and close titanium as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, react to acid number be below the 2mgKOH/g.Then, add 50 parts of trimellitic anhydrides, normal pressure reacts after 1 hour down, under the decompression of 20～40mmHg, react, when softening point is 105 ℃, add 20 parts of bisphenol A diglycidyl ethers, take out down for 150 ℃ at softening point, pulverize after being cooled to room temperature, obtain modified polyester resin (AY1-1).

(AY1-1) acid number is 52mgKOH/g, hydroxyl value is 16mgKOH/g, glass transition temperature (Tg) is 73 ℃, number-average molecular weight (Mn) is 1860, peak molecular weight (Mp) is 6550, the insoluble composition of THF is 32%, and the ratio of the composition of molecular weight below 1500 is 1.0%, used as toner binder (D).

(toner binder E's is synthetic)

[synthesizing of modified polyester resin]

Except polycondensation catalyst being replaced with four titanium butoxide, modified polyester resin (CAY1-2) is relatively used in reaction similarly to Example 15.

(CAY1-2) softening point is 150 ℃, acid number is 53mgKOH/g, hydroxyl value is 17mgKOH/g, glass transition temperature (Tg) is 71 ℃, number-average molecular weight (Mn) is 1660, and peak molecular weight (Mp) is 6340, and the insoluble composition of THF is 34%, the ratio of the composition of molecular weight below 1500 is 3.1%, used as toner binder (E).

(toner binder F's is synthetic)

[synthesizing of non-linear polyesters resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 132 parts of bisphenol-A epoxy propane, 3 moles of addition products of 371 parts of bisphenol-A epoxy propane, 2 moles of addition products of 20 parts of bisphenol-A epoxy ethane, 5 moles of addition products of epoxypropane of 125 parts of phenol novolaks (average degree of polymerization is about 5), 201 parts of terephthalic acid (TPA)s, 25 parts of maleic anhydrides, 35 parts of dimethyl terephthalate (DMT) and 2 parts of dihydroxy two (triethanolamine) network oxygen titaniums as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g is cooled to 180 ℃ when following at acid number, adds 65 parts of trimellitic anhydrides, and the airtight reaction down of normal pressure was taken out after 2 hours, pulverizes after being cooled to room temperature, obtains non-linear polyesters resin (AX2-3).

The softening point of non-linear polyesters resin (AX2-3) is 144 ℃, acid number is 30mgKOH/g, hydroxyl value is 16mgKOH/g, glass transition temperature (Tg) is 59 ℃, number-average molecular weight (Mn) is 1410, and peak molecular weight (Mp) is 4110, and the insoluble composition of THF is 27%, the ratio of the composition of molecular weight below 1500 is 1.0%, used as toner binder (F).

(toner binder G's is synthetic)

[synthesizing of non-linear polyesters resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 410 parts of bisphenol-A epoxy propane, 3 moles of addition products of 270 parts of bisphenol-A epoxy propane, 110 parts of terephthalic acid (TPA)s, 125 parts of m-phthalic acids, 15 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) and close titanium as condensation catalyst, under 220 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g is cooled to 180 ℃ when following at acid number, adds 25 parts of trimellitic anhydrides, and the airtight reaction down of normal pressure was taken out after 2 hours, pulverizes after being cooled to room temperature, obtains non-linear polyesters resin (AX2-4).

(AX2-4) do not contain the insoluble composition of THF, its acid number is 18mgKOH/g, and hydroxyl value is 37mgKOH/g, and glass transition temperature (Tg) is 62 ℃, and number-average molecular weight (Mn) is 2130, and peak molecular weight (Mp) is 5350.The ratio of the composition of molecular weight below 1500 is 1.3%.

[synthesizing of modified polyester resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 317 parts of bisphenol-A epoxy ethane, 2 moles of addition products of 57 parts of bisphenol-A epoxy propane, 3 moles of addition products of 298 parts of bisphenol-A epoxy propane, 5 moles of addition products of epoxypropane of 75 parts of phenol novolaks (average degree of polymerization is about 5), 30 parts of m-phthalic acids, 157 parts of terephthalic acid (TPA)s, 27 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) and close titanium as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g is cooled to 180 ℃ when following at acid number.Then, add 68 parts of trimellitic anhydrides, normal pressure reacts after 1 hour down, under the decompression of 20～40mmHg, react, add 25 parts of bisphenol A diglycidyl ethers when softening point is 120 ℃, take out down for 155 ℃ at softening point, pulverize after being cooled to room temperature, obtain modified polyester resin (AY1-2).

The acid number of (AY1-2) that obtains is 11mgKOH/g, and hydroxyl value is 27mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 3020, and peak molecular weight (Mp) is 6030, and the insoluble composition of THF is 35%.The ratio of the composition of molecular weight below 1500 is 1.1%.

[toner binder G's is synthetic]

Utilize continuous kneader with 500 parts of polyester (AX2-3) and 500 parts of polyester (AY1-2) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain toner binder of the present invention (G).

(embodiment 43)

Except toner binder A is changed to the toner binder D, operation obtains toner (T43) similarly to Example 13.

(embodiment 44)

Except toner binder A is changed to the toner binder D, operation obtains toner (T44) similarly to Example 14.

(embodiment 45)

Except toner binder A is changed to the toner binder D, operation obtains toner (T45) similarly to Example 15.

(embodiment 46)

Except toner binder A is changed to the toner binder D, operation obtains toner (T46) similarly to Example 16.

(embodiment 47)

Except toner binder A is changed to the toner binder D, operation obtains toner (T47) similarly to Example 17.

(embodiment 48)

Except toner binder A is changed to the toner binder D, operation obtains toner (T48) similarly to Example 18.

(embodiment 49)

Except toner binder A is changed to the toner binder D, operation obtains toner (T49) similarly to Example 19.

(embodiment 50)

Except toner binder A is changed to the toner binder D, operation obtains toner (T50) similarly to Example 20.

(embodiment 51)

Except toner binder A is changed to the toner binder D, operation obtains toner (T51) similarly to Example 21.

(embodiment 52)

Except toner binder A is changed to the toner binder D, operation obtains toner (T52) similarly to Example 22.

(embodiment 53)

Except toner binder A is changed to the toner binder F, operation obtains toner (T53) similarly to Example 13.

(embodiment 54)

Except toner binder A is changed to the toner binder F, operation obtains toner (T54) similarly to Example 14.

(embodiment 55)

Except toner binder A is changed to the toner binder F, operation obtains toner (T55) similarly to Example 15.

(embodiment 56)

Except toner binder A is changed to the toner binder F, operation obtains toner (T56) similarly to Example 16.

(embodiment 57)

Except toner binder A is changed to the toner binder F, operation obtains toner (T57) similarly to Example 17.

(embodiment 58)

Except toner binder A is changed to the toner binder F, operation obtains toner (T58) similarly to Example 18.

(embodiment 59)

Except toner binder A is changed to the toner binder F, operation obtains toner (T59) similarly to Example 19.

(embodiment 60)

Except toner binder A is changed to the toner binder F, operation obtains toner (T60) similarly to Example 20.

(embodiment 61)

Except toner binder A is changed to the toner binder F, operation obtains toner (T61) similarly to Example 21.

(embodiment 62)

Except toner binder A is changed to the toner binder F, operation obtains toner (T62) similarly to Example 22.

(embodiment 63)

Except toner binder A is changed to the toner binder G, operation obtains toner (T63) similarly to Example 13.

(embodiment 64)

Except toner binder A is changed to the toner binder G, operation obtains toner (T64) similarly to Example 14.

(embodiment 65)

Except toner binder A is changed to the toner binder G, operation obtains toner (T65) similarly to Example 15.

(embodiment 66)

Except toner binder A is changed to the toner binder G, operation obtains toner (T66) similarly to Example 16.

(embodiment 67)

Except toner binder A is changed to the toner binder G, operation obtains toner (T67) similarly to Example 17.

(embodiment 68)

Except toner binder A is changed to the toner binder G, operation obtains toner (T68) similarly to Example 18.

(embodiment 69)

Except toner binder A is changed to the toner binder G, operation obtains toner (T69) similarly to Example 19.

(embodiment 70)

Except toner binder A is changed to the toner binder G, operation obtains toner (T70) similarly to Example 20.

(embodiment 71)

Except toner binder A is changed to the toner binder G, operation obtains toner (T71) similarly to Example 21.

(embodiment 72)

Except toner binder A is changed to the toner binder G, operation obtains toner (T72) similarly to Example 22.

(comparative example 15)

Except toner binder A is changed to the toner binder E, operation similarly to Example 13 obtains toner (T15 ').

(comparative example 16)

Except toner binder A is changed to the toner binder E, operation similarly to Example 14 obtains toner (T16 ').

(comparative example 17)

Except toner binder A is changed to the toner binder E, operation similarly to Example 15 obtains toner (T17 ').

(comparative example 18)

Except toner binder A is changed to the toner binder E, operation similarly to Example 16 obtains toner (T18 ').

(comparative example 19)

Except toner binder A is changed to the toner binder E, operation similarly to Example 17 obtains toner (T19 ').

(comparative example 20)

Except toner binder A is changed to the toner binder E, operation similarly to Example 18 obtains toner (T20 ').

(comparative example 21)

Except toner binder A is changed to the toner binder E, operation similarly to Example 19 obtains toner (T21 ').

(comparative example 22)

Except toner binder A is changed to the toner binder E, operation similarly to Example 20 obtains toner (T22 ').

(comparative example 23)

Except toner binder A is changed to the toner binder E, operation similarly to Example 21 obtains toner (T23 ').

(comparative example 24)

Except toner binder A is changed to the toner binder E, operation similarly to Example 22 obtains toner (T24 ').

[evaluation method (just charged toner)]

＜assessment item 〉

(1) low-temperature fixing (tape stripping)

Utilize rotary drum mixer that 4 mass parts toners and 96 mass parts silicone coated ferrite carriers (Kanto Electrization Industrial Co., Ltd's manufacturing, mean grain size 100 μ m) were mixed 5 minutes, obtain developer.Then, in that duplicating machine (imagio105, Ricoh Co., Ltd make) is transformed into and can in the device of photographic fixing outside device developer be installed, the toner adhesion amount is adjusted into 0.5mg/cm ², obtain the uncertain image of 2cm * 12cm.Further make the temperature of fixing roller be elevated to 250 ℃ successively from 100 ℃ with per 5 ℃, simultaneously with linear velocity 1500mm/ second with uncertain image photographic fixing, carry out the photographic fixing test.Photographic fixing paper uses " RICOPY PPC paper TYPE6000 " (Ricoh Co., Ltd's manufacturing).

On the image that obtains under each fixing temperature, paste adhesive tape (manufacturing of Sumitomo 3M Co., Ltd.), place stripping tape after 3 hours, transfer on the blank sheet of paper, measure attached to the uncertain image concentration on the adhesive tape with X-Rite938 (manufacturing of X-Rite company), to be to be evaluated as not photographic fixing more than 0.150 with the difference of blank, the temperature that surpasses 0.150 fixing roller at first as minimum fixing temperature, is estimated low-temperature fixing according to following metewand.

[metewand]

◎: minimum fixing temperature is less than 140 ℃

Zero: minimum fixing temperature is more than 140 ℃ and less than 150 ℃

*: minimum fixing temperature is more than 150 ℃

(2) the stained property of background evaluation

With above-mentioned (1) similarly, develop down 10000 on the spot behind the image with the toner for preparing in embodiment and the comparative example hot and humid with duplicating machine, partly paste adhesive tape (manufacturing of Sumitomo 3M Co., Ltd.) at the basal surface of photoreceptor, stripping tape is transferred on the blank sheet of paper, measure attached to the stained concentration of the background on the adhesive tape with X-Rite938 (X-Rite corporate system), will being to be evaluated as more than 0.050 that to produce background stained with the difference of blank, be the stained excellence of 0.005 anti-background when above less than 0.010, less than 0.005 o'clock stained property of anti-background very excellence come the stained property of anti-background is estimated.

[metewand]

◎: the stained property of anti-background is very excellent

Zero: the stained property of anti-background excellence

*: it is stained to produce background

[evaluation method (negative charging toner)]

＜assessment item 〉

Utilize rotary drum mixer that 4 mass parts toners and 96 mass parts ferrite carriers (Powder TecCo. manufacturing, F-150) were mixed 5 minutes, obtain developer.Then, in that duplicating machine (imagio Neo C385, Ricoh Co., Ltd make) is transformed into and can in the device of photographic fixing outside device developer be installed, the toner adhesion amount is adjusted into 0.5mg/cm ², obtain the uncertain image of 2cm * 12cm.Further make the temperature of fixing roller be elevated to 250 ℃ successively from 100 ℃ with per 5 ℃, simultaneously with linear velocity 1500mm/ second with uncertain image photographic fixing, carry out the photographic fixing test.Photographic fixing paper uses " RICOPY PPC paper TYPE6000 " (Ricoh Co., Ltd's manufacturing).

On the image that obtains under each fixing temperature, paste adhesive tape (manufacturing of Sumitomo 3M Co., Ltd.), place stripping tape after 3 hours, transfer on the blank sheet of paper, measure attached to the uncertain image concentration on the adhesive tape with X-Rite938 (X-Rite corporate system), to be to be evaluated as not photographic fixing more than 0.150 with the difference of blank, the temperature that surpasses 0.150 fixing roller at first as minimum fixing temperature, is estimated low-temperature fixing according to following metewand.

[metewand]

◎: minimum fixing temperature is less than 140 ℃

Zero: minimum fixing temperature is more than 140 ℃ and less than 150 ℃

*: minimum fixing temperature is more than 150 ℃

(2) the stained property of background evaluation

With above-mentioned (1) similarly, develop down 10000 on the spot behind the image with the toner for preparing in embodiment and the comparative example hot and humid with duplicating machine, partly paste adhesive tape (manufacturing of Sumitomo 3M Co., Ltd.) at the basal surface of photoreceptor, stripping tape is transferred on the blank sheet of paper, measure attached to the stained concentration of the background on the adhesive tape with X-Rite938 (manufacturing of X-Rite company), will being to be evaluated as more than 0.050 that to produce background stained with the difference of blank, be the stained excellence of 0.005 anti-background when above less than 0.010, less than 0.005 o'clock stained property of anti-background very excellence come the stained property of anti-background is estimated.

[metewand]

◎: the stained property of anti-background is very excellent

Zero: the stained property of anti-background excellence

*: it is stained to produce background

[table 3-1]

	Low-temperature fixing	The stained property of anti-background
			Embodiment 13	○	○
Embodiment 14	○	○
			Embodiment 15	◎	○
Embodiment 16	○	○
			Embodiment 17	◎	○
Embodiment 18	○	○
			Embodiment 19	○	○
Embodiment 20	○	○
			Embodiment 21	◎	○
Embodiment 22	○	◎
			Embodiment 23	○	○
Embodiment 24	○	○
			Embodiment 25	◎	◎
Embodiment 26	○	○
			Embodiment 27	○	○
Embodiment 28	○	○
			Embodiment 29	◎	○
Embodiment 30	○	○
			Embodiment 31	○	○
Embodiment 32	◎	◎
			Embodiment 33	○	○
Embodiment 34	◎	○
			Embodiment 35	○	○
Embodiment 36	○	○
			Embodiment 37	○	○
Embodiment 38	◎	○
			Embodiment 39	○	○
Embodiment 40	○	○
			Embodiment 41	◎	○
Embodiment 42	○	◎

[table 3-2]

	Low-temperature fixing	The stained property of anti-background
			Embodiment 43	○	○
Embodiment 44	◎	◎
			Embodiment 45	◎	○
Embodiment 46	○	○
			Embodiment 47	◎	○
Embodiment 48	○	○
			Embodiment 49	◎	◎
Embodiment 50	○	○
			Embodiment 51	◎	○
Embodiment 52	◎	◎
			Embodiment 53	○	◎
Embodiment 54	◎	○
			Embodiment 55	◎	◎
Embodiment 56	○	○
			Embodiment 57	◎	◎
Embodiment 58	◎	○
			Embodiment 59	○	◎
Embodiment 60	◎	○
			Embodiment 61	○	◎
Embodiment 62	◎	◎
			Embodiment 63	○	○
Embodiment 64	○	○
			Embodiment 65	◎	◎
Embodiment 66	◎	○
			Embodiment 67	○	◎
Embodiment 68	◎	◎
			Embodiment 69	○	○
Embodiment 70	◎	○
			Embodiment 71	○	○
Embodiment 72	◎	◎

[table 3-3]

	Low-temperature fixing	The stained property of anti-background
			Comparative example 5	△	△
Comparative example 6	○	×
			Comparative example 7	○	×
Comparative example 8	△	△
			Comparative example 9	△	×
Comparative example 10	×	△
			Comparative example 11	△	△
Comparative example 12	△	×
			Comparative example 13	△	△
Comparative example 14	○	×
			Comparative example 15	△	×
Comparative example 16	×	△
			Comparative example 17	△	×
Comparative example 18	△	△
			Comparative example 19	△	△
Comparative example 20	△	×
			Comparative example 21	×	△
Comparative example 22	△	△
			Comparative example 23	△	×
Comparative example 24	△	△

Even it is stained that toner of the present invention as can be known has excellent low-temperature fixing and also do not produce the background of toner under hot and humid degree.

[III] (embodiment 73～74 and comparative example 25)

(synthesis example 1)

[synthesizing of linear polyesters resin]

2 moles of PO addition products, 3 moles of PO addition products of 300 parts of bisphenol-As, 257 parts of terephthalic acid (TPA)s, 65 parts of m-phthalic acids, 10 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 430 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 220 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, after acid number is taking-up in 5 o'clock, is cooled to room temperature, pulverize, obtain linear polyesters resin (AX1-1).

[synthesizing of non-linear polyesters resin]

2 moles of EO addition products, 3 moles of PO addition products of 326 parts of bisphenol-As, 278 parts of terephthalic acid (TPA)s, 40 parts of anhydride phthalic acids and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 350 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, react under the decompression of 5～20mmHg, take out during for 2mgKOH/g at acid number, be cooled to 180 ℃, add 62 parts of trimellitic anhydrides, the airtight reaction down of normal pressure was taken out after 2 hours, pulverized after being cooled to room temperature, obtained non-linear polyesters resin (AX2-1).

[synthesizing of toner binder resin (TB1)]

Utilize continuous kneader with 400 parts of polyester (AX1-1) and 600 parts of polyester (AX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain toner binder resin of the present invention (TB1).

The molecular weight 5 * 10 of the toner binder resin (TB1) that obtains ²Following content is 3.5%, and the molecular weight main peak is 7.5 * 10 ³, glass transition temperature (Tg) is 62 ℃, and the Mw/Mn ratio is 5.1, and acid number is 2.3mgKOH/g, and the apparent viscosity that obtains by flow tester is 10 ³Temperature during Pas is 112 ℃.In addition, do not contain the insoluble composition of THF.

(synthesis example 2)

[synthesizing of linear polyesters resin]

Except polycondensation catalyst being replaced with two (triethanolamine) network oxygen titanium, similarly react with (AX1-1) of synthesis example 1, pulverize after being cooled to room temperature, obtain linear polyesters resin (AX1-2).

[synthesizing of non-linear polyesters resin]

Except polycondensation catalyst being replaced with two (triethanolamine) network oxygen titanium, similarly react with (AX2-1) of synthesis example 1, pulverize after being cooled to room temperature, obtain linear polyesters resin (AX2-2).

[synthesizing of toner binder resin (TB2)]

Utilize Henschel mixer that 500 parts of polyester (AX1-2) and 500 parts of polyester (AX2-2) were carried out powder 5 minutes, obtain toner binder resin of the present invention (TB2).

The molecular weight 5 * 10 of the toner binder resin (TB2) that obtains ²Following content is 3.0%, and the molecular weight main peak is 8 * 10 ³, glass transition temperature (Tg) is 62 ℃, and the Mw/Mn ratio is 4.7, and acid number is 0.5mgKOH/g, and the apparent viscosity that obtains by flow tester is 10 ³Temperature during Pas is 116 ℃.In addition, do not contain the insoluble composition of THF.

(synthesis example 3)

[relatively synthesizing] with the linear polyesters resin

Except polycondensation catalyst is replaced with the tetraisopropoxy titanium, similarly react with (AX1-1) of synthesis example 1.Because catalyst deactivation, be reflected at Halfway Stopping, produce the problem that water does not distill out that generates, so append 2 parts tetraisopropoxy titanium midway 4 times, relatively used linear polyesters resin (CAX1-1) in reaction.

[relatively synthesizing] with non-linear polyesters resin

Except polycondensation catalyst is replaced with the tetraisopropoxy titanium, similarly react with (AX2-1) of synthesis example 1.Reaction is 8 hours under reaction 16 hours under normal pressure, the decompression.Because reaction velocity is slow, append 2 parts tetraisopropoxy titanium midway 3 times in reaction, relatively used non-linear polyesters resin (CAX2-1).

[relatively using the synthetic of toner binder resin (CTB1)]

Utilize continuous kneader with 400 parts of polyester (CAX1-1) and 600 parts of polyester (CAX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain comparison toner binder resin (CTB1).(CTB1) be the resin of dark purple brown.

The molecular weight 5 * 10 of the toner binder resin (CTB1) that obtains ²Following content is 5.1%, and the molecular weight main peak is 9.2 * 10 ³, glass transition temperature (Tg) is 71 ℃, and the Mw/Mn ratio is 4.6, and acid number is 10.0mgKOH/g, and the apparent viscosity that obtains by flow tester is 10 ³Temperature during Pas is 117 ℃.In addition, do not contain the insoluble composition of THF.Used as toner binder (CTB1).

(synthesis example 4)

[synthesizing of modified polyester resin]

In the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe, add 2 moles of addition products of 549 parts of bisphenol-A epoxy propane, 3 moles of addition products of 20 parts of bisphenol-A epoxy propane, 2 moles of addition products of 133 parts of bisphenol-A epoxy ethane, 5 moles of addition products of oxirane of 10 parts of phenol novolaks (average degree of polymerization is about 5), 252 parts of terephthalic acid (TPA)s, 19 parts of m-phthalic acids, 10 parts of trimellitic anhydrides and 2 parts of dihydroxy two (diethanolamine) and close titanium as condensation catalyst, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, react to acid number be below 2.Then, add 50 parts of trimellitic anhydrides, normal pressure reacts after 1 hour down, under the decompression of 20～40mmHg, react, add 20 parts of bisphenol A diglycidyl ethers when softening point is 105 ℃, take out down for 150 ℃ at softening point, pulverize after being cooled to room temperature, obtain modified polyester resin (AY1-1).

(AY1-1) molecular weight 5 * 10 ²Following content is 2.8%, and the molecular weight main peak is 6.9 * 10 ³, glass transition temperature (Tg) is 64 ℃, and the Mw/Mn ratio is 5.5, and acid number is 8.1mgKOH/g, and the apparent viscosity that obtains by flow tester is 10 ³Temperature during Pas is 102 ℃.In addition, do not contain the insoluble composition of THF.Used as toner binder resin (TB3).

(synthesis example 5)

[relatively synthesizing] with modified polyester resin

Except polycondensation catalyst being replaced with four titanium butoxide, similarly react with synthesis example 4, relatively used modified polyester resin (CAY1-2).

(CAY1-2) molecular weight 5 * 10 ²Following content is 6.1%, and the molecular weight main peak is 10.7 * 10 ³, glass transition temperature (Tg) is 74 ℃, and the Mw/Mn ratio is 7.2, and acid number is 10.6mgKOH/g, and the apparent viscosity that obtains by flow tester is 10 ³Temperature during Pas is 122 ℃.In addition, the insoluble composition of THF is 12%.Used as toner binder resin (CTB2).

(synthesis example of resin strip controling agent)

(synthesis example 1)

With 350 part 3,4-dichlorophenyl maleimide and 100 parts of 2-acrylamide-2-methyl propane sulfonic acids under boiling point, are initiating agent copolymerization 8 hours with the di-t-butyl peroxide in dimethyl formamide (DMF).Then, adding 500 parts of n-butyl acrylates, 50 parts of styrene, is initiating agent graft polymerization after 4 hours with the di-t-butyl peroxide, removes DMF by the drying under reduced pressure distillation, and obtaining specific insulation is that 10.5Log Ω cm, quality mean molecular weight are 1 * 10 ⁴, apparent viscosity is 10 ⁴Temperature during Pas is 96 ℃, quality mean molecular weight 1 * 10 ³Following polymer content is 6% resin strip controling agent 1.

(synthesis example 2)

Is initiating agent copolymerization 8 hours with the di-t-butyl peroxide with 600 parts of m-nitro base maleimides and 100 parts of perfluorooctane sulfonates under boiling point in DMF.Then, adding 250 parts of 2-EHAs, 30 parts of styrene, is initiating agent graft polymerization after 4 hours with the di-t-butyl peroxide, removes DMF by the drying under reduced pressure distillation, and obtaining specific insulation is that 9.5Log Ω cm, quality mean molecular weight are 5.5 * 10 ³, apparent viscosity is 10 ⁴Temperature during Pas is 85 ℃, quality mean molecular weight 1 * 10 ³Following polymer content is 8% resin strip controling agent 2.

(synthesis example 3)

With 500 part 3,4-dichlorophenyl maleimide and 150 parts of 2-acrylamide-2-methyl propane sulfonic acids are initiating agent copolymerization 8 hours with the di-t-butyl peroxide under boiling point in dimethyl formamide (DMF).Then, add 350 parts of n-butyl acrylates, 250 parts of α-Jia Jibenyixi, be initiating agent graft polymerization after 4 hours with the di-t-butyl peroxide, remove DMF by the drying under reduced pressure distillation, obtaining specific insulation is that 11.5Log Ω cm, quality mean molecular weight are 9.6 * 10 ⁴, apparent viscosity is 10 ⁴Temperature during Pas is 110 ℃, quality mean molecular weight 1 * 10 ³The resin strip controling agent 3 of following polymer content 5%.

(synthesis example 4)

With 400 part 3,4-dichlorophenyl maleimide and 200 parts of perfluorooctane sulfonates are initiating agent copolymerization 8 hours with the di-t-butyl peroxide under boiling point in DMF.Then, adding 300 parts of n-butyl acrylates, is initiating agent graft polymerization after 4 hours with the di-t-butyl peroxide, removes DMF by the drying under reduced pressure distillation, and obtaining specific insulation is that 10.4Log Ω cm, quality mean molecular weight are 1.5 * 10 ⁴, apparent viscosity is 10 ⁴Temperature during Pas is 105 ℃, quality mean molecular weight 1 * 10 ³Following polymer content is 6% resin strip controling agent 4.

(synthesis example 5)

With 400 part 3,4-dichlorophenyl maleimide and 100 parts of 2-acrylamide-2-methyl propane sulfonic acids are initiating agent copolymerization 8 hours with the di-t-butyl peroxide under boiling point in DMF.Then, add 500 parts of n-butyl acrylates, the dissolving of 100 parts of styrene after, be initiating agent graft polymerization after 4 hours with the di-t-butyl peroxide, remove DMF by the drying under reduced pressure distillation, obtaining specific insulation is that 9.3Log Ω cm, quality mean molecular weight are 3 * 10 ⁴, apparent viscosity is 10 ⁴Temperature during Pas is 101 ℃, quality mean molecular weight 1 * 10 ³Following polymkeric substance is the resin strip controling agent 5 of content 6%.

(embodiment 73)

Carry out the processing of colorant by following prescription.

Yellow based colorant prescription:

Adhesive resin TB1...100 part

C.I. pigment yellow 180...100 part

The pink group colorant formulations:

Adhesive resin TB1...100 part

C.I. pigment red 122 ... 100 parts

Cyan based colorant prescription:

Adhesive resin TB1...100 part

C.I. pigment blue 15 .3...100 part

Black based colorant prescription:

Adhesive resin TB1...100 part

Carbon black ... 100 parts

To of all kinds, with above-mentioned material join mix in the Henschel mixer after, potpourri is put in air cooled two rollers, dropped into the back melting mixing 15 minutes.Then, mixing thing is rolled cooling, carry out coarse crushing, obtain adhesive resin and handle colorant with beating crusher.

Then, by following formulation toner.

The Yellow toner prescription:

Adhesive resin TB1...91 part

Adhesive resin TB1 handles yellow based colorant ... 12 parts

Resin strip controling agent 1...3 part

Pinkish red toner formulation:

Adhesive resin TB1...92 part

Adhesive resin TB1 handles the pink group colorant ... 10 parts

Resin strip controling agent 1...3 part

The cyan toner prescription:

Adhesive resin TB1...94 part

Adhesive resin TB1 handles the cyan based colorant ... 6 parts

Resin strip controling agent 1...3 part

The black toner prescription:

Adhesive resin TB1...90 part

Adhesive resin TB1 handles the black based colorant ... 12 parts

Adhesive resin TB1 handles the cyan based colorant ... 2 parts

Resin strip controling agent 1...3 part

To of all kinds, above-mentioned material joined in the Henschel mixer mix, the potpourri that obtains put in the roller mill that is heated to 110 ℃, dropped into the back melting mixing 30 minutes.Then, cool off mixing thing, carry out coarse crushing with beating crusher, it is broken to carry out micro mist with air jet mill comminutor.Further remove micro mist, obtain each colour toners by air classifier.And the T1/T2 of adhesive resin TB1 and resin strip controling agent 1 is 1.16.

With respect to 100 parts of each colour toners that obtains, mix following additives with Henschel mixer and make monocomponent toner.

Hydrophobic silica (primary particle size=0.02 μ m) ... 2.5 parts

Hydrophobicity titania (primary particle size=0.015 μ m, specific surface area=90mg/cm ²) ... 0.8 part

The monocomponent toner that obtains is installed in the commercially available digital panchromatic printer (Ricoh Co., Ltd's manufacturing, IPSiOColor 6500), forms image.The image distinctness that obtains, background not occur stained etc. unusual.During by the visualization developer roll, the toner thin layer homogeneous on the roller.Measure behind the carried charge on the developer roll as can be known by the attraction method, yellow developer is that-35 μ C/g, pinkish red developer are that-30 μ C/g, blue developer are that-31 μ C/g, black reagent are-32 μ C/g.Under 27 ℃, the hot and humid condition of 80%RH with 10 ℃, the low temperature and low humidity condition of 15%RH under imaging similarly, find to change, form excellent image.Continuously amount to 40,000 endurancing under normal temperature, low temperature and low humidity, hot and humid, each environment of normal temperature by full-colour image after, do not find marked change in the photographic fixing image, the 40,000 image also is the image that does not have the stained distinctness of background.During by the visualization developer roll, do not find significant the variation in the toner thin layer on roller, the carried charge of the developer of this moment is stable, and yellow developer is that-31 μ C/g, pinkish red developer are that-29 μ C/g, blue developer are that-29 μ C/g, black reagent are-27 μ C/g.When visualization developer roll, scraper plate, photoreceptor, do not find film forming.

(embodiment 74)

Carry out the processing of colorant by following prescription.

Yellow based colorant prescription:

Adhesive resin TB2...100 part

C.I. pigment yellow 180...100 part

The pink group colorant formulations:

Adhesive resin TB2...100 part

C.I. pigment red 146 ... 100 parts

Cyan based colorant prescription:

Adhesive resin TB3...100 part

C.I. pigment blue 15 .3...100 part

Black based colorant prescription:

Adhesive resin TB3...100 part

Carbon black ... 100 parts

To of all kinds, with above-mentioned material join mix in the Henschel mixer after, potpourri is put in air cooled two rollers, dropped into the back melting mixing 15 minutes.Then, mixing thing is rolled cooling, carry out coarse crushing, obtain adhesive resin and handle colorant with beating crusher.

Then, by following formulation toner.

The Yellow toner prescription:

Adhesive resin TB2...91 part

Adhesive resin TB2 handles yellow based colorant ... 12 parts

Resin strip controling agent 2...3 part

Pinkish red toner formulation:

Adhesive resin TB2...92 part

Adhesive resin TB2 handles the pink group colorant ... 10 parts

Resin strip controling agent 2...3 part

The cyan toner prescription:

Adhesive resin TB3...94 part

Adhesive resin TB3 handles the cyan based colorant ... 6 parts

Resin strip controling agent 3...3 part

The black toner prescription:

Adhesive resin TB3...90 part

Adhesive resin TB3 plastic resin treatment black based colorant ... 12 parts

Adhesive resin TB3 plastic resin treatment cyan based colorant ... 2 parts

Resin strip controling agent 4...3 part

To of all kinds, above-mentioned material joined in the Henschel mixer mix, the potpourri that obtains is put in the dual-axle continuous pugging machine that is heated to 80 ℃, carry out melting mixing.Then, cool off mixing thing, carry out coarse crushing with beating crusher, it is broken to carry out micro mist with jet mill.Further remove micro mist, obtain each colour toners by air classifier.And the T1/T2 of adhesive resin TB2 and resin strip controling agent 2 is 1.11, and the T1/T2 of adhesive resin TB3 and resin strip controling agent 3 is 1.15, and the T1/T2 of adhesive resin TB3 and resin strip controling agent 4 is 1.21.With respect to 100 parts of each colour toners that obtains, mix following additives with Henschel mixer.

Hydrophobic silica (primary particle size=0.02 μ m) ... 2.1 parts

Hydrophobicity titania (primary particle size=0.015 μ m, specific surface area=120mg/cm ²) ... 1.0 parts

6 parts of toners that obtain and 94 parts of silicone resin coated carriers are mixed and made into two-component developing agent.The two-component developing agent that obtains is installed in the commercially available digital panchromatic printer (Ricoh Co., Ltd's manufacturing, IPSiOColor 7100), forms image.It is stained, distinct that the image that obtains does not have background.Image under hot and humid, the low temperature and low humidity, charged all no abnormal.Even carry out 10,000 endurancing by full-colour image after, find to disperse after in the also no abnormal image, viewing test machine etc., also not to adhering to of photoreceptor etc.

(comparative example 25)

Carry out the processing of colorant by following prescription.

Yellow based colorant prescription:

Adhesive resin CTB1...100 part

C.I. pigment yellow 180...100 part

The pink group colorant formulations:

Adhesive resin CTB1...100 part

C.I. pigment red 122 ... 100 parts

Cyan based colorant prescription:

Adhesive resin CTB2...100 part

C.I. pigment blue 15 .3...100 part

Black based colorant prescription:

Adhesive resin CTB2...100 part

Carbon black ... 100 parts

To of all kinds, with above-mentioned material join mix in the Henschel mixer after, potpourri is put in air cooled two rollers, dropped into the back melting mixing 15 minutes.Then, mixing thing is rolled cooling, carry out coarse crushing, obtain adhesive resin and handle colorant with beating crusher.

Then, by following formulation toner.

The Yellow toner prescription:

Adhesive resin CTB1...91 part

Adhesive resin CTB1 handles yellow based colorant ... 12 parts

Resin strip controling agent 1...3 part

Pinkish red toner formulation:

Adhesive resin CTB1...92 part

Adhesive resin CTB1 handles the pink group colorant ... 10 parts

Resin strip controling agent 3...3 part

The cyan toner prescription:

Adhesive resin CTB2...94 part

Adhesive resin CTB2 handles the cyan based colorant ... 6 parts

Resin strip controling agent 5...3 part

The black toner prescription:

Adhesive resin CTB2...90 part

Adhesive resin CTB2 handles the black based colorant ... 12 parts

Adhesive resin CTB2 handles the cyan based colorant ... 2 parts

Resin strip controling agent 5...3 part

To of all kinds, above-mentioned material joined in the Henschel mixer mix, the potpourri that obtains is put in the roller mill that is heated to 100 ℃, dropped into the back melting mixing 20 minutes.Then, cool off mixing thing, carry out coarse crushing with beating crusher, it is broken to carry out micro mist with air jet mill comminutor.Further remove micro mist, obtain each colour toners by air classifier.And the T1/T2 of adhesive resin CTB1 and resin strip controling agent 1 is 1.20, and the T1/T2 of adhesive resin CTB1 and resin strip controling agent 3 is 1.11, and the T1/T2 of adhesive resin CTB2 and resin strip controling agent 5 is 1.34.

With respect to 100 parts in the bonding agent of all kinds that obtains, mix following additives with Henschel mixer and make monocomponent toner.

Hydrophobic silica (primary particle size=0.02 μ m) ... 2.5 parts

Hydrophobicity titania (primary particle size=0.015 μ m, specific surface area=90mg/cm ²) ... 0.8 part

The monocomponent toner that obtains is installed in the commercially available digital panchromatic printer (Ricoh Co., Ltd's manufacturing, IPSiOColor 6500), forms image.The image distinctness that obtains, do not find that background is stained etc. unusual.During by the visualization developer roll as can be known, the toner thin layer homogeneous on the roller.Measure behind the carried charge on the developer roll as can be known by the attraction method, yellow developer is that-43 μ C/g, pinkish red developer are that-36 μ C/g, blue developer are that-38 μ C/g, black reagent are-35 μ C/g.When under 27 ℃, the hot and humid condition of 80%RH, forming image, form and have unclear image.In addition, under 10 ℃, the low temperature and low humidity condition of 15%RH, during imaging similarly, obtain the low blurred picture of ID.Continuously after carrying out endurancing by full-colour image under normal temperature, low temperature and low humidity, hot and humid, each environment of normal temperature, produce that background is stained, the striped on the dust, image etc. is unusual.This moment, the toner thin layer on the roller produced striped in a circumferential direction by the visualization developer roll as can be known.When measuring the carried charge of developer, yellow developer is that-28 μ C/g, pinkish red developer are that-22 μ C/g, blue developer are that-25 μ C/g, black reagent are-21 μ C/g, all variation.

[synthesizing of titanium-containing catalyst]

To have cooling tube, stirring machine and can be in liquid bubbling the reactive tank of nitrogen ingress pipe in add 1700 parts of diisopropoxies two (triethanolamine) and close titanium and 130 parts of ion exchange waters, with nitrogen in liquid under the bubbling, slowly be warming up to 90 ℃, react (hydrolysis) 4 hours down at 90 ℃, obtain dihydroxy two (triethanolamine) thus and close titanium.

Also use same synthetic method for later embodiment, can obtain the titanium-containing catalyst that uses among the present invention respectively.

[the synthesizing 1 of linear polyesters resin]

2 moles of PO addition products, 3 moles of PO addition products of 300 parts of bisphenol-As, 257 parts of terephthalic acid (TPA)s, 65 parts of m-phthalic acids, 10 parts of maleic anhydrides and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 430 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 220 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, under the decompression of 5～20mmHg, react, after acid number takes out during for 5mgKOH/g, is cooled to room temperature, pulverize, obtain linear polyesters resin (AX1-1).

(AX1-1) do not contain the insoluble composition of THF, its acid number is 7mgKOH/g, and hydroxyl value is 12mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 6940, and peak molecular weight (Mp) is 19100.The ratio of the composition of molecular weight below 1500 is 1.2%.

[the synthesizing 1 of non-linear polyesters resin]

2 moles of EO addition products, 3 moles of PO addition products of 326 parts of bisphenol-As, 278 parts of terephthalic acid (TPA)s, 40 parts of anhydride phthalic acids and 2 parts of dihydroxy two (triethanolamine) as condensation catalyst of adding 350 parts of bisphenol-As in the reactive tank that has cooling tube, stirring machine and nitrogen ingress pipe close titanium, under 230 ℃ under stream of nitrogen gas distillation remove the water of generation, and reacted 10 hours.Then, reacting under the decompression of 5～20mmHg, is that 2mgKOH/g is cooled to 180 ℃ when following at acid number, adds 62 parts of trimellitic anhydrides, and the airtight reaction down of normal pressure was taken out after 2 hours, pulverizes after being cooled to room temperature, obtains non-linear polyesters resin (AX2-1).

(AX2-1) do not contain the insoluble composition of THF, its acid number is 35mgKOH/g, and hydroxyl value is 17mgKOH/g, and glass transition temperature (Tg) is 69 ℃, and number-average molecular weight (Mn) is 3920, and peak molecular weight (Mp) is 11200.The ratio of the composition of molecular weight below 1500 is 0.9%.

[the synthesizing 1 of toner binder]

Utilize continuous kneader with 400 parts (AX1-1) and 600 parts (AX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain toner binder of the present invention (Resin A).

[relatively using the Synthetic 2 of linear polyesters resin]

Except polycondensation catalyst is replaced with the tetraisopropoxy titanium, similarly react with (AX1-1) of synthesis example 1.Because catalyst deactivation, in the reaction Halfway Stopping, produce the problem that water does not distill out that generates, therefore append 2 parts tetraisopropoxy titanium midway 4 times in reaction, relatively used linear polyesters resin (CAX1-1).

(CAX1-1) do not contain the insoluble composition of THF, its acid number is 7mgKOH/g, and hydroxyl value is 12mgKOH/g, and glass transition temperature (Tg) is 58 ℃, and number-average molecular weight (Mn) is 6220, and peak molecular weight (Mp) is 18900.The ratio of the composition of molecular weight below 1500 is 2.2%.

[relatively using the Synthetic 2 of non-linear polyesters resin]

Except polycondensation catalyst is replaced with the tetraisopropoxy titanium, similarly react with (AX2-1) of synthesis example 1.Reaction is 8 hours under reaction 16 hours under normal pressure, the decompression.Because reaction velocity is slow, append 2 parts four titanium propanolates midway 3 times in reaction, relatively used non-linear polyesters resin (CAX2-1).

(CAX2-1) do not contain the insoluble composition of THF, its acid number is 34mgKOH/g, and hydroxyl value is 16mgKOH/g, and glass transition temperature (Tg) is 68 ℃, and number-average molecular weight (Mn) is 3420, and peak molecular weight (Mp) is 12100.The ratio of the composition of molecular weight below 1500 is 2.1%.

[the relatively Synthetic 2 of toner binder]

Utilize continuous kneader with 400 parts (CAX1-1) and 600 parts (CAX2-1) in 150 ℃ of jacket temperatures, following melting mixing of 3 minutes hold-up times.Pulverize after using the steel band cooler that molten resin was cooled to 30 ℃ with 4 minutes, obtain comparison toner binder (resin B).Resin B is the resin of dark purple brown.

[the synthesizing 3 of linear polyesters resin]

Except polycondensation catalyst being replaced with two (triethanolamine) network oxygen titanium, similarly react with (AX1-1) of synthesis example 1, be cooled to pulverize after the room temperature and obtain linear polyesters resin (AX1-2).

(AX1-2) do not contain the insoluble composition of THF, its acid number is 8mgKOH/g, and hydroxyl value is 10mgKOH/g, and glass transition temperature (Tg) is 60 ℃, and number-average molecular weight (Mn) is 6820, and peak molecular weight (Mp) is 20180.The ratio of the composition of molecular weight below 1500 is 1.1%.

[the synthesizing 3 of non-linear polyesters resin]

Except polycondensation catalyst being replaced with two (triethanolamine) network oxygen titanium, similarly react with (AX2-1) of synthesis example 1, pulverize after being cooled to room temperature, obtain linear polyesters resin (AX2-2).

(AX2-2) do not contain the insoluble composition of THF, its acid number is 33mgKOH/g, and hydroxyl value is 14mgKOH/g, and glass transition temperature (Tg) is 70 ℃, and number-average molecular weight (Mn) is 4200, and peak molecular weight (Mp) is 11800.The ratio of the composition of molecular weight below 1500 is 0.8%.

[the synthesizing 3 of toner binder]

Utilize Henschel mixer that 500 parts (AX1-2) and 500 parts (AX2-2) were carried out powder 5 minutes, obtain toner binder of the present invention resin (resin C).

[preparation example of toner A]

Prescription:

Resin A ... 100 parts

Magenta pigment (C.I. paratonere 269) ... 5 parts

Charged controlling agent (Orient Chemical Co. manufacturing, E-84) ... 2 parts

In the above-mentioned material, pigment, vibrin and pure water are mixed with the ratio of 1: 1: 0.5 (mass ratio), mixing by two rollers.Carry out mixingly under 70 ℃, then, rising roll temperature to 120 ℃ evaporates the water, preparation rubber master batch material.

Use the rubber master batch material of preparation, with above-mentioned prescription composite material in the same manner, by two rollers 50 ℃ of following melting mixings 40 minutes, after the cooling, after carrying out coarse crushing with beating crusher, spraying mixing comminutor with air, to carry out micro mist broken, and the micropowder classification that obtains is obtained the toner parent that volume average particle size (D4) is 6.8 μ m.Further add 0.15 part of zinc stearate (Sakai Chemical Industry Co., Ltd.'s manufacturing), 1 part of hydrophobic silica (Clariant Japan K.K. manufacturing), 1 part of hydrophobic titanium oxide (Tayca Co. manufacturing), mix, preparation toner A with mixer.

Volume average particle size (Dv)=6.8 μ m of the toner A that obtains, than (Dv/Dn)=1.38, shape coefficient SF-1=151, SF-2=142.

[preparation example of toner B]

Except in the preparation example of toner A, magenta pigment is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner B.

Yellow uitramarine (C.I. pigment yellow 180) ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner B that obtains, than (Dv/Dn)=1.35, shape coefficient SF-1=150, SF-2=141.

[preparation example of toner C]

Except in the preparation example of toner A, magenta pigment is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner C.

Yellow uitramarine (C.I. pigment yellow 155) ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner C that obtains, than (Dv/Dn)=1.38, shape coefficient SF-1=158, SF-2=150.

[preparation example of toner D]

Except in the preparation example of toner A, magenta pigment is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner D.

Magenta pigment [C.I. paratonere 184 (mixture of C.I. pigment red 146 and C.I. paratonere 147)] ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner D that obtains, than (Dv/Dn)=1.36, shape coefficient SF-1=150, SF-2=142.

[preparation example of toner E]

Except in the preparation example of toner A, magenta pigment is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner E.

Yellow uitramarine (C.I. pigment yellow 17) ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner E that obtains, than (Dv/Dn)=1.35, shape coefficient SF-1=154, SF2=148.

[preparation example of toner F]

Except in the preparation example of toner A, magenta pigment is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner F.

Green pigment (C.I. pigment blue 15: 2) ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner F that obtains, than (Dv/Dn)=1.36, shape coefficient SF-1=151, SF-2=145.

[preparation example of toner G]

Except in the preparation example of toner A, Resin A is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner G.

Resin B ... 100 parts

Volume average particle size (Dv)=6.8 μ m of the toner G that obtains, than (Dv/Dn)=1.32, shape coefficient SF-1=153, SF-2=149.

[preparation example of toner H]

Except in the preparation example of toner B, Resin A is changed to outside the following material, similarly operate with the preparation example of toner B, obtain toner H.

Resin B ... 100 parts

Volume average particle size (Dv)=6.8 μ m of the toner H that obtains, than (Dv/Dn)=1.33, shape coefficient SF-1=159, SF-2=148.

[preparation example of toner J]

Except in the preparation example of toner A, following appending outside the wax similarly operated with the preparation example of toner A, obtains toner J.

Brazil wax ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner J that obtains, than (Dv/Dn)=1.32, shape coefficient SF-1=152, SF-2=145.

[preparation example of toner K]

Except in the preparation example of toner B, following appending outside the wax similarly operated with the preparation example of toner B, obtains toner K.

Brazil wax ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner K that obtains, than (Dv/Dn)=1.37, shape coefficient SF-1=151, SF-2=149.

[preparation example of toner L]

Except in the preparation example of toner F, following appending outside the wax similarly operated with the preparation example of toner F, obtains toner L.

Brazil wax ... 5 parts

Volume average particle size (Dv)=6.8 μ m of the toner L that obtains, than (Dv/Dn)=1.34, shape coefficient SF-1=155, SF-2=144.

[preparation example of toner M]

Except in the preparation example of toner A, Resin A is changed to outside the following material, similarly operate with the preparation example of toner A, obtain toner M.

Resin C...100 part

Volume average particle size (Dv)=6.8 μ m of the toner M that obtains, than (Dv/Dn)=1.31, shape coefficient SF-1=159, SF-2=142.

＜evaluation method 〉

(1) L ^*a ^*b ^*The color specification system aberration

Use the evaluation machine of image processing system, by the image color of X-Rite938 (manufacturing of X-Rite company) to 100% image area under the monochromatic mode of yellow (Y), pinkish red (M), cyan (C), and measure under the condition spent at the observation visual angle 2 of observing light D50 (JIS Z-8720 (1983)) of each image color of the Neutral colour of yellow (Y), pinkish red (M) and each 50% colour mixture of cyan (C) and the blueness (B) that obtains, green (G) and red (R), be a of the image portion of " 1.0 " to image color ID (Log reflectivity) ^*, b ^*Measure.Its result such as Figure 11～shown in Figure 15.And Figure 13 is the part enlarged drawing of Figure 12, and Figure 15 is the part enlarged drawing of Figure 14.

During overlapping two-tone toner, on paper with the nearest layer of distance paper be followed successively by magenta, then be cyan, be the order overlapping imaging of yellow once more.

(embodiment 75～78 and comparative example 26～29)

The toner Cartridge that uses in the evaluation of the toner of embodiment 75～78 and comparative example 26～29 is as shown in table 4.

[table 4]

	Pinkish red toner	Yellow toner	Cyan toner
				Embodiment 75	Toner A	Toner B	Toner F
Embodiment 76	Toner A	Toner C	Toner F
				Embodiment 77	Toner J	Toner K	Toner L
Embodiment 78	Toner M	Toner B	Toner F
				Comparative example 26	Toner G	Toner B	Toner F
Comparative example 27	Toner A	Toner H	Toner F
				Comparative example 28	Toner D	Toner B	Toner F
Comparative example 29	Toner A	Toner E	Toner F

In addition, evaluation result such as table 5, table 6 and Figure 11～shown in Figure 15.

Drawing L ^*a ^*b ^*The a of color specification system pigment ^*b ^*Figure in, the wide ranges of surrounding with Y/R/M/B/C/G six looks means the colorrendering quality excellence.

By Figure 12 and Figure 13 as can be known, embodiment 75,78, compare with comparative example 26,27, and the color reproduction zone of R and M is obviously wide.The width excellence in the color reproduction zone among the R particularly.

Relative therewith, though comparative example 26 has the color reproduction zone of the ratio broad of G/C, R/M is narrow.Though M is wide in the comparative example 27, G/Y/R is obviously narrow.

So as can be known, embodiments of the invention 75,78 have wide color reproduction zone in Zone Full, and particularly R is wide.

In addition, by Figure 14 and Figure 15 as can be known, R regional wide and do not sacrifice other zone particularly among the embodiment 76, though be not the width in the color reproduction zone of embodiment 76 such degree for R among the embodiment 77, the color reproduction zone of M/B is wide.

＜picture appraisal 〉

The toner 5% of as above preparation is mixed with the copper that is coated with the mean grain size 40 μ m of silicone resin-Zn ferrite carrier 95%, the two-component developing agent that use obtains, utilize the transformation apparatus of duplicating machine (Ricoh Co., Ltd's manufacturing, imagio Neo C385), containing under the original copy photo of the colour of skin with the full color photographs pattern, under 400dpi, carry out 1000 developments, allow 50 people carry out visual valuation, carry out grade evaluation by following benchmark.The result is as shown in table 5.

＜colour of skin photo official can estimate 〉

The evaluation result of the excellent degree of the broca scale picture that obtains by above people's visual valuation is carried out grade evaluation with following five grades.

Colour of skin photo official can metewand: 100 fens full marks, minimum 0 minute, carry out grade evaluation respectively with 50 people's average mark.

◎: very excellent more than 80 minutes

Zero: excellent 60～79 minutes

: common 40～59 minutes

△: differed from 20～39 fens

*: non-constant is below 19 minutes

[table 5]

	Colour of skin photo official can evaluation result (grade)
		Embodiment 75	○
Embodiment 76	○
		Embodiment 77	◎
Embodiment 78	○
		Comparative example 26	△
Comparative example 27	△
		Comparative example 28	□
Comparative example 29	□

[table 6]

Industrial applicibility

Toner of the present invention is because the stained property of anti-adhesive, anti-background under hot and humid degree environment and low-temperature fixability are excellent, even and under hot and humid environment or under the low temperature and low humidity environment and then under high quality image area output As time goes on, adopt any one using method, can export high-quality image, not having namely that toner components is bonded on carrier or the development sleeve, the problems such as band power reduction of developer, is useful as toner for developing electrostatic latent image.

Toner Cartridge of the present invention is owing to yellow, pinkish red color reproduction zone broaden, the colour of skin that particularly can the broadening Neutral colour, red color reproduction zone, the interior toner of image processing system that further can reduce pinkish red toner, Yellow toner disperses, and is useful as the toner for developing electrostatic latent image box.

Claims (12)

1. toner, it contains colorant and adhesive resin at least, wherein,

Described adhesive resin contains at least a vibrin, described vibrin be at least a following general formula (I) and the titanium-containing catalyst (II) in the presence of polycondensation form,

The volume average particle size of described toner is 2.0～10.0 μ m, and the ratio (Dv/Dn) of this volume average particle size (Dv) and number average particle diameter (Dn) is 1.00～1.40,

Ti(-X)m(-OH)n (I)

O＝Ti(-X)p(-OR)q (II)

Above-mentioned general formula (I) and (II) in, X removes the H of an OH base and the residue that obtains from any one of the monoalkanolamine of carbon number 2～12 and many alkanolamines, other OH base of these many alkanolamines can carry out polycondensation and form ring structure with the OH base of Direct Bonding on same Ti atom in molecule, also can carry out polycondensation and form repetitive structure intermolecular with the OH base of Direct Bonding on other Ti atom, the degree of polymerization when in addition, forming repetitive structure is 2～5;

R represents that hydrogen atom and the optional carbon number that contains 1～3 ehter bond are any one in 1～8 the alkyl;

M is that 1～4 integer, n are that 0～3 integer, m and n sum are 4, and p is that 1～2 integer, q are that 0～1 integer, p and q sum are 2, and m and p are 2 when above, and X separately is identical or different.

2. the described toner of claim 1, wherein, vibrin contains at least a in the following vibrin, described vibrin be at general formula (I) and the titanium-containing catalyst of the residue that obtains for the H that from any one of two (three alkanolamines) and three alkanolamines, removes an OH base of the X (II) in the presence of polycondensation form.

3. each described toner in the claim 1～2, wherein, vibrin contains at least a in the following vibrin, described vibrin be m in general formula (I) and (II) or p are more than 2, all X are identical group titanium-containing catalyst in the presence of polycondensation form.

4. each described toner in the claim 1～3 wherein, contains at least a by the polyepoxide modified resins to the small part vibrin.

5. each described toner in the claim 1～4, wherein, vibrin does not contain the insoluble composition of THF, and molecular weight is 5 * 10 in the molecular weight distribution of gel permeation chromatography ²The content of following composition is below the 4 quality %, in mass molecular weight 3 * 10 ³～9 * 10 ³The zone have main peak.

6. each described toner in the claim 1～5, wherein, the endothermic peak that adhesive resin obtains by differential scanning calorimeter (DSC) is 60～70 ℃.

7. each described toner in the claim 1～6, wherein, the weight-average molecular weight of adhesive resin (Mw) is 2≤Mw/Mn≤10 with the ratio (Mw/Mn) of number-average molecular weight (Mn).

8. each described toner in the claim 1～7, wherein, the acid number of adhesive resin is below the 10mgKOH/g.

9. each described toner in the claim 1～8, wherein, adhesive resin reaches 10 by the apparent viscosity that flow tester obtains ³Temperature during Pas is 95～120 ℃.

10. toner Cartridge, it contains each described toner in the claim 1～9, and contains Yellow toner, pinkish red toner and cyan toner at least, wherein,

Described pinkish red toner contains the organic pigment shown in the following structural formula (1),

Described Yellow toner contains the organic pigment that has two following structural frameworks (A) in the molecule and do not have halogen atom,

Above-mentioned formula (1) and (A) in ,=C=N-NH-comprises=situation of CH-N=N-.

11. the described toner Cartridge of claim 10, wherein, the organic pigment that has two described structural frameworks (A) and do not have a halogen atom is the organic pigment shown in any one at least in following structural formula (2) and (3),

12. an image processing system, it comprises at least: electrostatic latent image carrier; The electrostatic latent image that forms electrostatic latent image on this electrostatic latent image carrier forms parts, use each described toner Cartridge in the claim 10～11 described latent electrostatic image developing to be formed at least three developing parts of visual image; Described visual image is transferred to transfer member on the recording medium; With fixing member with the transferred image photographic fixing of transfer printing on described recording medium.

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