CN1228685C

CN1228685C - Color mixing agent, developer and imaging method for electronic photograph

Info

Publication number: CN1228685C
Application number: CN 98125163
Authority: CN
Inventors: 中村正树; 吉田聪
Original assignee: Fuji Xerox Co Ltd
Current assignee: Fujifilm Business Innovation Corp
Priority date: 1998-11-30
Filing date: 1998-11-30
Publication date: 2005-11-23
Anticipated expiration: 2018-11-30
Also published as: CN1255650A

Abstract

The present invention relates to a toner containing an adhesive resin and a colourant. The adhesive resin has the characteristics that at a temperature ranging from a glass transition temperature Tg to loss elastic modulus G'=1*10<4> pascal, and the tandelta minimum value exists, and is below 1.2; under the temperature of the tandelta minimum value, storage elastic modulus is above G'=>5*10<5> pascal; under the temperature of G'=1*10<4> pascal, the tandelta value is above 3.0. Additionally, the same effect can also be obtained by adding a small amount of vinyl resin into polyester resin having the characteristics, or can be obtained by utilizing the copied body of the same resin to form images on a developing layer.

Description

Electrophoto-graphic toner, developer and formation method

Technical field

The present invention relates to utilize duplicating machine, printer, facsimile recorder to carry out the machine of electrophotographic processes, particularly relate to the manufacture method of the toner of the electrophoto-graphic toner that on color copy machine, uses (following only claim " toner "), electrophotography, the developer (following only be called " developer ") and the formation method of electrophotography.

Background technology

Electrophotographic processes is exactly on the photoreceptor that utilizes the photoconductivity material, utilize the whole bag of tricks, effect by electricity forms sub-image, utilize toner again, with this image development,, the toner image on the photoreceptor is duplicated after paper etc. is copied on the body by the middle copying body or by the middle copying body, this copy image photographic fixing is copied multiple working procedure on the body at paper etc., forms the photographic fixing image.In recent years, because enriching of the prosperity of the machinery of informationized society and communication network, electrophotographic processes not only utilizes duplicating machine, and printer also obtains widespread use, and is more and more stricter to miniaturization, lightweight and high-speedization, the high reliability request of institute's use device.

Particularly under the color electronography situation, require the image quality of drawing height of formation, colour rendering is good.In order to obtain the picture quality height, and the good image of colour rendering, from viewpoints such as light transmission and gloss, must make the abundant fusion of toner, the imaging surface after the photographic fixing is level and smooth.For this reason, the photographic fixing operation particular importance of electrophotographic processes.

As the widely used contact-type fixation method of fixation method, use the method (hereinafter referred to as " adding the thermo-compressed method ") of heat and pressure when generally being photographic fixing.Under this situation that adds thermal pressure welding method, because the surface of fixing member contacts adding to depress with toner image on being copied body, therefore, the thermal efficiency is very good, can carry out photographic fixing rapidly, and is particularly very effective to the high-velocity electrons photorepeater.

Yet, under the above-mentioned situation that adds thermal pressure welding method, because the surface and the toner image of fixing member add press contacts under the heating and melting state, probably can produce on the surface of a part attached to above-mentioned fixing member of toner image and shift, print through or circumvolution phenomenon take place.When particularly utilizing the color toner photographic fixing, with the black and white toner fixing relatively because must be, therefore must add the heat of q.s and pressure to toner with the toner fusion colour mixture of multiple color, make toner mobile better.Again because need be with molten condition, and the thick toner layer of multiple colour superimposition separates, unlikely generation print through or circumvolution phenomenon, thus the demoulding when utilizing the color toner photographic fixing, Billy's more difficult during with the black and white toner fixing.

As not making toner, can will be coated on the fixing member surface as silicone oil that prevents the liquid that print through is used etc. attached to the lip-deep short-cut method of fixing member.But, using under the wet goods situation, exist oil attached to the problem on body and the image of being copied after the photographic fixing.In addition, also need be provided with the fuel tank that is used to store wet goods in fixing device, this makes device be difficult to do lessly, and in addition, replenishing also of oil bothers, and restricted the reduction of cost etc.

In the past, when colored photographic fixing, above-mentioned wet goods reached about 8.0 * 10 at the general coating amount that is copied on the body ^-2Milligram/square centimeter.In contrast, black-and-white printer can need not be coated with unction fully, even will use, and 1/,100 8.0 * 10 of the oily coating amount when its coating amount also only is colored photographic fixing ^-4Below the milligram/square centimeter, therefore, above-mentioned shortcoming is a problem in practicality hardly.But, wish all generally that when colored photographic fixing identical oily coating amount in the time of also using with the black and white photographic fixing for this reason, has proposed that multiple it doesn't matter with fixing device, resin or the wax used by the improvement toner wait the method that improves the toner release property.

For example, in Jap.P. discloses No. 158340/1981 communique, announce the effect that contains resin and wax low-molecular-weight composition and high molecular composition, that widened molecular weight distribution by utilization, can bring into play the adaptive black and white toner of good oilless fixing.The resin that this black and white toner is used, the caoutchouc elasticity by the complexing of the high molecular composition that is diluted by the low-molecular-weight composition forms can bear the peeling force on the toner layer that is added on the fuser surface, can prevent that promptly print through from taking place.

But, during to the photographic fixing of coloured image, there are several problems in this technology popularization.That is, owing to use the material with the caoutchouc elasticity that is formed by the complexing of high molecular composition as binding resin, photographic fixing image glossiness reduces (1), and the colour rendering of coloured image is low; (2) even binding resin is flexible, because molecule contains the low-molecular-weight composition, the soft easily distortion of resin itself, thus as coloured image, when the toner bed thickness has 3 to 4 layers, peel off when being out of shape easy circumvolution on fuser, so the fissility reduction; (3) be under the situation of coloured image of multilayer at toner layer,, be easy to generate peeling off between the toner layer (being print through), the sort of effect that prevents print through when being difficult to obtain etc. between the different toner layer of tone as the black white image photographic fixing because wax oozes out.

Though, under the color toner situation, the various fixation methods that contain the fixation method of high molecular composition and use wax have been proposed,, address the above problem still relatively difficulty.Even the release property of toner has some to improve, but when using with the same oily coating amount of black and white toner fixing, it improves and does not also reach the practical no problem degree that.

In No. the 2595239th, Japanese patent laid-open publication gazette, the toner of using as the fixing device that adopts the photographic fixing heater of making by fluororesin, announced and a kind ofly be characterized as at viscoelasticity G ' (dynamically storage elastic modulus) when being 10000 handkerchiefs G " (dynamic loss elastic modulus) be the toner of 17000 to 30000 handkerchiefs.If be converted into viscosity, be about in viscosity under the state of the abundant fusion of toner of 100 to 1000 handkerchief seconds, this just expression be positioned at the existing color toner that has shown adhesion properties substantially, and the viscoelastic property between the black and white toner of the caoutchouc elasticity that constitutes by the high molecular composition based on low-molecular-weight resin.Disclose in this Japanese patent laid-open publication gazette, as the resin that satisfies this viscoelastic conditions, the vibrin and the Mw/Mn that have widened molecular weight distribution are little of below 3, and Mn is a resin at about styrene acrylic more than about 15000.

Therefore,, just can utilize this viscoelastic property, suppress a bit colored colour developing a little, and obtain the performance of heat-resisting print through as long as can prevent to be copied the circumvolution phenomenon of body on fuser by what cause adhering to of toner.But, owing to, enlarge the resin of molecular weight distribution, can not obtain aforesaid good demolding performace for being with high molecular composition and low-molecular-weight composition and usefulness, therefore,, must increase the coating amount of oil in order to prevent the circumvolution phenomenon.In addition, in the styrene-propene acid resin, even molecular weight increases, because the elastic modulus of the caoutchouc elasticity that the resin composition causes is low, also circumvolution can not get good demolding performace on fuser easily.

In addition, when interpolation wax was discussed, when adding wax in toner, release property can improve, but exists photopermeability and charging property, the tendency that the powder fluidity of toner etc. degenerates.Particularly, when the wax that utilizes comminuting method to obtain is exposed to lip-deep toner, exist the tangible tendency of the powder fluidity deterioration of charging property, toner.Disclose at Jap.P. that No. 61239/1993 communique, Jap.P. disclose No. 92736/1995 communique and Jap.P. discloses in No. 159178/1995 communique etc., announced a kind ofly utilizing suspension polymerization, the styrene-propene acid resin of restraining the wax exposing surface is the polymerization toner of main body.Therefore they can improve the flowability and the release property of toner powder owing to the surface texture that can prevent to be caused by wax reduces.But,, so as previously described, exist the tendency that causes the circumvolution phenomenon easily because the styrene-propene acid resin is a Main Ingredients and Appearance.Toner in multiple color is overlapping, and under the coloured image situation of toner layer thickening, this tendency can show more significantly, therefore is difficult to the demoulding stably.

In addition, general, in existing colored photographic fixing, exist because the low short big problem of the life-span of causing of the demolding performace of fixing roller.

As mentioned above, utilize existing technology, be difficult in and require in the higher color copy machine of picture quality, reach the oilless fixing adaptability of the toner that in the black and white copying machine, reaches now, therefore, must develop a kind of novel, toner that release property is good, that can obtain the high coloured image of picture quality.

Summary of the invention

The objective of the invention is to solve above-mentioned existing problem, provide a kind of in color toner, also the toner of Shi Yi electrophotography and utilize the formation method of this toner.

Promptly, first purpose of the present invention is to provide a kind of toner of electrophotography, it has the oilless fixing adaptability identical with the black and white toner fixing, can be without release agent or the coating amount that only utilizes minute quantity just can photographic fixing, the image quality height, colour rendering is good and the reliability height.

Second purpose of the present invention is to provide a kind of this electrophoto-graphic toner of use, fixing performance good, the developer of the high and electrophotography that colour rendering is good of picture quality.And then the 3rd purpose of the present invention provides a kind of this developer of use, can form the picture quality height, colour rendering is good and the formation method of the image of good luster.

In the past, as the manufacture method of toner, adopted a kind of mixing breaking method that is called the dry type manufacture method mostly.The mixing breaking method is with the colorant as in pigment or the dyestuff and also has release agent and charged controlling agent as required, carry out fusion with the binding resin that with the thermoplastic resin is representative, behind the mixing,, make the method for toner with desirable particle diameter again through pulverizing, classification.This method from improving the dispersiveness and the unrestricted viewpoint of binding resin kind of colorant binding resin and other adjuvant, is a kind of extraordinary method, and is generally with the most use at present.

But the toner of electrophotography of the present invention exists and uses the mixing comminuting method, is difficult to the tendency of pulverizing.Like this, owing to will carry out and the miniaturization work that improves the corresponding toner of picture quality, therefore, the crush efficiency of toner is low, produce sometimes can not miniaturization to the problem of desirable particle diameter.

Problem when solving this pulverize, proposed the method for producing toner and toner behind the mixing is made thin fibrous, the method of pulverizing (Jap.P. discloses communique No. 95246/1981), in method for producing toner and toner behind mixing, add inorganic fine particles, the method for pulverizing methods such as (Jap.P. disclose communique No. 142541/1981).But, the described method of communique is disclosed No. 95246/1981 for Jap.P., it is low that it makes efficient, and can not prevent that the toner fusion from sticking on the comminutor and toner fusion adhesion each other each other.In addition, the described method of communique is disclosed No. 142541/1981 for Jap.P., because inorganic particulate is inhomogeneous, and insecure anchoring on the surfaces of toner particles, therefore, to each other charged of toner particle has deviation, is difficult to obtain by pursuing the desired toner performance of the high viewpoint of picture quality in recent years.

In addition, disclose in the text of No. 127657/1990 communique, put down in writing in containing the vibrin of crosslinked composition, contain number-average molecular weight, can improve comminuted at other resin below 11000 at Jap.P..Utilize this method, comminuted certain improvement, but the fissility of binding resin itself is not so good.In addition, because the influence of the crosslinked composition in the polyester can not obtain high glossiness and form good colour.

In Jap.P. discloses No. 3856/1994 communique, also proposed a kind ofly to contain in vibrin that weight average molecular weight is 50000～150000, number-average molecular weight is 2000～10000 styrene-propene acid copolymer, has improved smashing black and white toner.It is comminuted to utilize this method also can improve, but poor as the release property of vibrin that mainly is binding resin, the toner that can not fully peel off multiple color is overlapped into thicker image.

As mentioned above, hope has a kind of except anti-print through, can satisfy the toner that manufacturing requires high-levelly.

Therefore, the 4th purpose of the present invention is toner and a kind of formation method that a kind of electrophotography that can address the above problem will be provided.Promptly, the 4th purpose of the present invention is that a kind of oilless fixing adaptability identical with the black and white toner fixing that has will be provided, just can carry out photographic fixing without release agent or with few coating amount, the picture quality height, colour rendering is good, reliability is high, make the also high electrophoto-graphic toner of efficient.

In the past, for purposes such as image demonstrations, extensively the method that adopts was, utilized the electrofax mode to form image on transparent film, and the transparent film that will have toner image is placed on and shoots high on the projector (following simple be " OHP "), and obtains projected image.But, on polyethylene terephthalate base materials such as (hereinafter to be referred as " PET "), when merely forming coloured image,, particularly can not form good colour on the intermediateness image at projected image, it is muddy that image becomes.This is because during photographic fixing, toner fixing partly is semiellipse shape protuberance, when from the light of base material aspect incident when toner layer sends, scattering causes on toner surface.

This phenomenon shows relatively significantly in the adjacent toner toner concentration zone, particularly intermediateness zone adhered to of not fusion each other, makes projected image become muddy.

When utilizing electrophoto-graphic toner of the present invention to form image, also there is influence, the situation that the colour developing on projected image is not so good owing to the image that forms.

In order to improve photopermeability, in disclosing No. 92964/1988 communique, Jap.P. proposed a kind ofly to have on the stable on heating base material, transparent resin bed is set, form the method for toner image thereon.The effect that this method is improved colour rendering is big, and method similar with it also repeatedly discloses No. 92965/1988 communique, Jap.P. at Jap.P. and disclose No. 263642/1990 communique, Jap.P. and disclose No. 198063/1991 communique, Jap.P. and disclose No. 125567/1992 communique and Jap.P. and disclose in No. 212168/1992 communique and disclosed.But, because any method in these methods all is when making up with the color toner with existing the sort of distinct performance, so the method for competence exertion effect is when do not apply the wet goods release agent on fuser, or coating amount after a little while, and its anti-print through is insufficient.

In addition, in Jap.P. discloses No. 104868/1993 communique, proposed on base material, to be provided with and contained the transparent heat moldable resin layer that fusing point is 90 ℃～170 ℃ a wax, improved the film that is copied of anti-print through.But, have employed resin in the color toner of existing the sort of distinct performance in utilization, form under the situation of the layer that develops, must contain wax in large quantities, diminish the permeability of light like this.In addition, owing in the layer that develops, used the styrene-propene acid resin, so release property is not very good.In order to have release property, need to increase molecular weight, will impair colour rendering like this.

In addition, disclose in No. 160278/1997 communique at Jap.P. and to have proposed a kind of method that improves fissility, it is to contain Tg at thermoplastic resin below 70 ℃ and release agent in the layer that develops, and making the polyflon band and the layer that develops, 180 degree peel strengths in the time of 150 ℃ reach below 0.1 newton/25 millimeter.But the situation that the heat time heating time during for actual photographic fixing is extremely short is in disbonded test, because the adhering resin band and the layer that develops need the time, during this section, the release agent in the layer that develops is exuded on the interface of resin strip, and the demoulding dosage that oozes out during with actual photographic fixing is different fully.Therefore, even the peel strength of the layer that develops is little, in most cases, anti-print through is also not very good.

Also announced a kind ofly by in the floor that develops in Jap.P. discloses No. 218527/1997 communique, the adding fusing point is 40 ℃～120 ℃ a release agent, and has improved the film that is copied of anti-print through.But, under the situation of the fissility that utilizes release agent to obtain to develop layer, when the overlapping image of the toner of multiple color is carried out photographic fixing, the thickness addition of the thickness of toner and the layer that develops, the distortion and the stress loss that are added in when peeling off on the toner are increased, as a result, anti-print through is also not very good.

In addition, in Jap.P. discloses No. 359258/1992 communique, proposed on base material, it be resin that the rubber that can see through light is set, particularly the method for the development layer that is made of the block elastomer rubber of styrene-butadiene system.In Jap.P. discloses No. 305066/1996 communique, proposed in the layer that develops, to contain styrene-butadiene block copolymer, the viscoelasticity scope that makes the layer that develops in particular value, thereby improve the method for anti-print through.But, when using crystalline polymkeric substance, because temperature variation causes the volume change of polymkeric substance, so toner is peeled off from the layer that develops easily,, can produce crystallization when in during fabrication the drying process etc. during heating, resin bed becomes gonorrhoea easily, creates conditions to be difficult to control.Under the situation of using the high resin of degree of crosslinking, the amount that toner embeds in the layer that develops reduces, and therefore, the colour rendering of the intermediateness of projected image is not very good.

In Jap.P. discloses No. 22136/1997 communique, a kind of method that improves colour rendering and anti-print through has also been proposed, it is in order to 2, carboxylic acid unit that selects in 6-naphthalene dicarboxylic acids and the terephthalic acid (TPA) and sulfo group benzene dicarboxylic acid are as sour composition, with ethylene glycol, triethylene glycol, bisphenol-A epoxy ethane addition product polyester, form the layer that develops as pure composition.But because the molecular resin amount of the layer that develops is little, under the situation of the coating amount that reduces oil, anti-print through also is difficult to improve.

In addition, in Jap.P. discloses No. 311497/1997 communique, announced the method that a kind of anti-print through and colour rendering are taken into account, the resin that constitutes the layer that develops in this method is in the molecular weight distribution of measuring with GPC, has the resin of at least two peaks or shoulder.This resin is made of macromolecule composition and low molecule composition, yet, as mentioned above, because the existence of intramolecular low-molecular-weight composition, when reducing the coating amount of oil, can produce the phenomenon of circumvolution to the fixing roller.

As mentioned above, requiring has a kind of characteristic of not damaging toner itself, though when oilless fixing, also can keep anti-print through, color developing good, forming can be through the method for the image of light.

Therefore, the 5th purpose of the present invention provides a kind of use electrophoto-graphic toner of the present invention, and then also is suitable for forming and can allows the formation method of image of light transmission.

The present inventor, aspect the release property problem of toner, be not limited to and the stripping result of toner on the fuser interface that produces by wax or oil, but attention toner layer integral body is peeled off the stripping result that the viscoelasticity when being out of shape causes, painstakingly studies.Found that, by not being that the scope that the high molecular composition in reflection research in the past exists is approximately 1 * 10 ⁴Viscoelastic property in the elastic modulus scope of the softness about handkerchief, but stipulated than 1 * 10 ⁵～1 * 10 ⁶The viscoelastic property that the elastic modulus of handkerchief is high, the method for may command release property, thus finish the present invention.

That is, electrophoto-graphic toner of the present invention is the electrophoto-graphic toner that contains binding resin and colorant, it is characterized in that having adopted at glass temperature (Tg)～loss elastic modulus G as above-mentioned binding resin "=1 * 10 ⁴In the temperature range of handkerchief, there is the minimal value of dissipation factor (tan δ) in this binding resin, and the minimal value of this tan δ is below 1.2, storage elastic modulus G '=5 * 10 under the minimum temperature of this tan δ ⁵More than the handkerchief, and at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is at the resin more than 3.

Toner of the present invention is an electrophoto-graphic toner, it is characterized in that, as binding resin, preferably adopting does not have the linear polyester of cross-linked structure resin in molecule.

As long as binding resin is the resin that satisfies the regulation of above-mentioned viscoelastic property physics value, can use a kind of resin, also can and with two or more resins, but under situation also with two or more resins, as the physics value of potpourri, must scope formerly in.As desirable resin combination, can enumerate two kinds of resins (A, B) in, the Tg of at least a resin (A) is 45 ℃～65 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is the minimal value of tan δ in this resin, and the minimal value of tan δ is below 1.0, and at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0, and the Tg of the resin of usefulness (B) is in the higher temperature scope than (Tg+5) of resin (A) ℃～(Tg+15) ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is tan δ minimal value in this resin.Under the situation of resin of combination more than three kinds, at least a resin must have the physics value of above-mentioned resin (A), and and the resin of usefulness also can have in resin (A) or the resin (B) any rerum natura.In this case, whole binding resin also requires to satisfy the physics value of described viscoelastic property.

In addition, the inventor finds, by controlling two viscoelastic properties of main binding resin, in order to improve manufacturing efficient, even contain a spot of other resin, does not also damage its fissility and colour rendering, thereby finish the present invention.

That is, electrophoto-graphic toner of the present invention is the electrophoto-graphic toner that contains binding resin and colorant, it is characterized in that containing in binding resin vibrin and vinyl resin.Vibrin is at glass temperature (Tg)～loss elastic modulus G "=1 * 10 ⁴In the temperature range of handkerchief, there is the minimal value of tan δ in this binding resin, and the minimal value of this tan δ is below 1.2, storage elastic modulus G '=5 * 10 under the minimum temperature of this tan δ ⁵More than the handkerchief, and at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is at the resin more than 3.0.The content of this resin in whole binding resin weight more than 70 weight %, and above-mentioned vinyl resin be weight average molecular weight (Mw) at the resin below 100000, the amount of this resin in whole binding resin weight is below the 20 weight %.

As long as vibrin is the resin of regulation that satisfies the physics value of above-mentioned viscoelastic property, can use a kind of resin, also can and with two or more resins, but under situation also with two or more resins, as the physics value of potpourri, must scope formerly in.As desirable resin combination, the Tg that wishes at least a resin (C) is at 45 ℃～65 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is the minimal value of tan δ in this resin, and the minimal value of this tan δ is below 1.0, at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0.And with the Tg of resin (D) in the scope of Tg+5 ℃ of resin (C)～Tg+15 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is tg δ minimal value in this resin.

Electrophoto-graphic toner of the present invention preferably adopts the manufacturing of wet type toner autofrettage, most preferably contains release agent.

The toner of electrophotography of the present invention can be used as the electrophotographic developer with the synthetic twenty percent part of vehicle group, or uses aptly as the developer of non magnetic single composition.When using two composition developers, as carrier preferably by resin-coated carrier.

Formation method of the present invention is characterized in that being included in the operation that forms sub-image on the latent image carrier; Use electrophotographic developer to make the operation of above-mentioned image development; The toner image that develops duplicated the operation on duplicating body and will duplicate in the formation method of photographic fixing operation that toner image on the body adds thermo-compressed, as the electrophotographic developer of developer use the invention described above of electrophotography.

The inventor studies relevant resin demoulding mechanism according to fixing, found that, toner has specific viscoelasticity scope with the development layer that is copied film, can take into account anti-print through and colour rendering, thereby finish the present invention.

That is, formation method of the present invention is characterized in that the operation that forms sub-image on the latent image carrier comprising; Use the developer of electrophotography, with the operation of above-mentioned image development; The toner image that develops duplicated the operation on duplicating body and will duplicate in the formation method of photographic fixing operation that toner image on the body adds thermo-compressed,, use electrophotographic developer of the present invention as the developer of electrophotography; As being copied body, reach in thermotolerance at least one face of the support more than 100 ℃, have the development layer that constitutes by thermoplastic resin.This thermoplastic resin is at glass temperature (Tg)～loss elastic modulus G "=1 * 10 ⁴In the temperature range of handkerchief, there is minimum tan δ in this binding resin, and the minimal value of this tan δ is below 1.2, storage elastic modulus G '=5 * 10 under the temperature of the tan δ that this is minimum ⁵More than the handkerchief, and at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is at the resin more than 1.0.In addition, thermoplastic resin is preferably does not have the linear polyester of cross-linked structure resin in molecule.

As long as thermoplastic resin is the resin of regulation that satisfies the physics value of above-mentioned viscoelastic property, can be only with a kind of, also can be also with two or more resins.And situation with two or more resins under, as the physics value of potpourri must scope formerly in.As desirable resin combination, two kinds of resins (E, F) in, the Tg of at least a resin (E) is at 45 ℃～65 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is minimum tan δ in this resin, and the minimal value of this tan δ is below 1.0, at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0.And the Tg of the resin of usefulness (F) is in the scope of Tg+5 ℃ of resin (E)～Tg+15 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, exist the minimal value of the tan δ of this resin.

In addition, in the layer that develops, preferably contain release agent.

The photographic fixing operation of formation method of the present invention preferably uses the heat-fixing device of the contact-type that contains fluororesin on the surface of fixing member to carry out.Yet, most preferably on the fixing member surface, be not coated with unction, or only use 8.0 * 10 ^-4The oily coating amount that milligram/square centimeter is following uses heat-fixing device to carry out.

Below, in the present invention, be 8.0 * 10 with the oily coating amount on fuser ^-4The following situation of milligram/square centimeter is called the oily coating amount identical with the photographic fixing of black and white toner, or the release agent coating amount identical with the black and white toner fixing.

Description of drawings

Fig. 1 is the key diagram of the viscoelastic property value of the binding resin that uses in the electrophoto-graphic toner of the present invention;

Fig. 2 is the concept map of the relation of the fissility of the binding resin that uses and temperature in electrophoto-graphic toner of the present invention;

Fig. 3 is the summary pie graph that is illustrated in the heat fixing device example of using in the formation method of the present invention;

Fig. 4 is used to illustrate the summary pie graph of example of the image output device of formation method of the present invention for expression.

Embodiment

Represented among Fig. 1 in the present invention, as the key diagram of the viscoelastic property value of the rerum natura of binding resin regulation.Among Fig. 1, G ' is storage elastic modulus (representing with dot-and-dash line), G " be loss elastic modulus (dotting), tan δ (tangent of loss is represented with solid line), tan δ=G "/G '.

These values are drawn by Measurement of Dynamic Viscoelasticity.In brief, during distortion, replying composition with respect to the elasticity of the elasticity coefficient of being out of shape the stress relation that produces is G ', and the energy of the work of deformation of this moment is stored relatively.It is G that the viscosity of above-mentioned elasticity coefficient is replied composition ", be heat with respect to the Conversion of energy of work of deformation at this moment, lost.Tan δ (=G "/G ') be their ratio, this is the yardstick with respect to the energy loss of work of deformation and the degree of storage.

Binding resin of the present invention has such viscoelastic property: at Tg～G "=1 * 10 ⁴In the scope of the temperature of handkerchief, have minimum tan δ, the minimal value of this tan δ is below 1.2, and under the temperature of this minimum tan δ, G ' is 5 * 10 ⁵More than the handkerchief, at G "=1 * 10 ⁴The value of tan δ under the temperature of handkerchief is more than 3.0.In other words, this viscoelastic property in the mid-term of photographic fixing operation, when during clamping, when binding resin is in molten condition, is found high viscous characteristics; Simultaneously, in the end during the peeling off of stage, show binding resin and be high elastic coefficient, and its elastic property is better than viscosity characteristic, or becomes the characteristic of same degree.

Viscoelastic property value of the present invention is to use Rotating Plates type galvanometer (Lei Oumeituolikusi Co., Ltd. system: RDA2, RHIOS system, 4.3 types), utilizing diameter is 8 millimeters parallel plate, in frequency is 1 radian per second, add the distortion below 20%, between about 40～150 ℃, with 1 ℃/minute programming rate, the test specimen of about 0.3 grammes per square metre heated up measure measured value.

By satisfying above-mentioned viscoelastic property, promptly use the oily coating amount identical to carry out photographic fixing with the black and white toner, the demoulding of toner is also good, can obtain distinct colored color developing, and its reason is illustrated below.

Usually, the photographic fixing clamping time of hot-rolling is 20～100 milliseconds, and the mensuration frequency of corresponding Measurement of Dynamic Viscoelasticity is approximately 10～100 radian per seconds.Owing to peel off instantaneous the causing of distortion, therefore, the mensuration frequency corresponding with peeling off distortion can reach and corresponding 1 figure place of frequency or the high-frequency of 2 figure places measured of clamping time.Because the photographic fixing of toner generally is to carry out under the viscosity of 1000 handkerchiefs about second, therefore, the elasticity coefficient corresponding with peeling off distortion can reach 1 * 10 ⁵About handkerchief.Thereby, can infer, for peeling off distortion, from vitreousness to 1 * 10 ⁴Viscoelastic property under the elasticity coefficient of handkerchief scope works.

Peeling off in the relevant viscoelastic property of distortion with above-mentioned, minimal value by making above-mentioned tan δ is below 1.2, when making polymer chain be subjected to being out of shape, can reach storage elastic modulus G ' than loss elastic modulus G " state of big or same degree value; promptly; as rubber; become flexible; the state that energy loss is few; if from the polymer molecule size, can obtain polymer chain from have very thick toner layer, even the polymer chain that exists on toner and the fuser interface also all can be delivered in the state of the power of non-migration between polymer molecule to polymer chain, and simultaneously, reach 5 * 10 by the G ' that makes this moment ⁵More than the handkerchief,, therefore can prevent the circumvolution distortion, the demolding performace of toner is improved because this rubbery state becomes the high rubber of elastic modulus.

Satisfying above-mentioned viscoelastic property simultaneously at 2 is the necessary condition that reaches effective release property of the present invention.More than 1.2, or the G ' under the minimizing temperature of this tan δ is less than 5 * 10 in the minimal value of tan δ ⁵Under any situation of handkerchief, all can produce the circumvolution phenomenon, can not get good demolding performace.When obtaining release property, under the minimizing temperature of tan δ, G ' reaches 6 * 10 ⁵Handkerchief is better above, and G ' is 7 * 10 ⁵Handkerchief is above better; And the minimal value of tan δ is better below 1.0, better below 0.9.

Moreover binding resin of the present invention must have at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is the viscoelastic property more than 3.0.It is the toner image of not photographic fixing, is passing through in the time of fuser, and its toner is in the fine mobile state of energy, thereby, be that toner image becomes good luster, the necessary condition that colour developing is good.Satisfy this condition and can make the toner image that obtains, even, also become painted image as the projected image of OHP.When the value of this tan δ did not reach 3.0, the photographic fixing image became tarnish, and it is also bad to develop the color, and the colour colour developing of OHP projected image is also bad.

The glass temperature of binding resin of the present invention (Tg) is preferably in 45 ℃～100 ℃ scopes, more preferably in 50 ℃～75 ℃ scopes, most preferably in 55 ℃～70 ℃ scopes.When Tg was lower than 45 ℃, toner was heated and blocks easily, and when Tg was higher than 100 ℃, fixing temperature was too high.

The glass temperature of resin (Tg), can be by universal method, (horse storehouse Sainz Co., Ltd. makes: DSC3110, thermal analysis system 001 for example to utilize differential scanning calorimetry, be designated hereinafter simply as " DSC "), be to measure under 5 ℃/minute the condition at programming rate.Can will go out the shoulder temperature of low temperature one side of the suitable decalescence point of Tg in the figure as Tg with gained.Tg of the present invention measures as described above.

In addition, the G of binding resin of the present invention "=1 * 10 ⁴The temperature of handkerchief is wished below 150 ℃.When higher than 150 ℃, fixing temperature is too high.

Below, in toner of the present invention, the binding resin that satisfies suitable viscoelastic property carries out specific description.

As the used binding resin of the present invention, want big viewpoint from the storage elastic modulus G ' under the minimum temperature of tan δ, be preferably polyamide, polycarbonate resin, polyether resin, polyacrylonitrile resin, polyacrylate resin, vibrin.Wherein, when adding melt temperature territory and glass temperature, during the viewpoint of the easy degree of charging property control, then to form be resin based on vibrin to the used comparatively ideal binding resin of the present invention.

When lifting the object lesson explanation, for example passing by widely used styrene-propene acid is that resin is exactly this resin.In molecular weight distribution narrow (Mw/Mn=3) and have under the situation of resin of high molecular (Mw=10 ten thousand), the viscoelastic property under the minimum temperature of tan δ is G '=1.1 * 10 ⁵Handkerchief, tan δ=0.9.In addition, same styrene-propene acid is that resin is formed, in existing black and white toner, also be extensive use of, contain under the situation of resin of more high molecular (Mw=20 ten thousand) of low-molecular-weight composition and high molecular composition (Mw/Mn=50), the viscoelastic property under the minimum temperature of tan δ is G '=1 * 10 ⁴Handkerchief, tan δ=0.67.That is, only contain the high molecular composition, or improve mean molecular weight, even the minimal value of tan δ reduces, and the G ' under the minimizing temperature of tan δ, also discontented unabridged version scope of invention.This tendency generally all can be seen in the good phenylethylene resin series of cohesiveness, and they all can not become the binding resin that uses in toner of the present invention.

In order to satisfy viscoelastic property of the present invention, in vibrin, preferably also adopt the vibrin of wire.

Below, describe desirable polyester in detail and form and molecular weight.

As the composition of the polyester of the above-mentioned suitable viscoelastic property of the bonding resin that satisfies toner of the present invention, the storage elastic modulus that proper is under the temperature that tan δ is minimum at least (G ') is by becoming forming of big tendency.From this viewpoint, as the dicarboxylic acid composition, preferably terephthalic acid (TPA), m-phthalic acid, cyclohexane dicarboxylic acid, naphthalene-2 particularly, 6-dicarboxylic acid, naphthalene-2, naphthalene dicarboxylic acids, diphenyldicarboxylic acids such as 7-dicarboxylic acid.In addition, as the glycol composition, be preferably ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol, any in the ethylene oxide adduct (compd A in the following formula) of the bisphenol-A of representing with following formula, the oxetanes addition product (compd B in the following formula) of bisphenol-A, or multiple be the glycol composition of main body.

Compd A: R=CH ₂CH ₂

Compd B: R=CH ₂CH ₂CH ₂

(in the formula: m and n represent 2～7 integer respectively independently)

For example, the propylene oxide adduct of bisphenol-A (Compound C in the above-mentioned formula) is the existing glycol composition that extensively is used in the vibrin that toner uses.When using it, and with above-mentioned desirable glycols comparison, the G ' value under the minimizing temperature of above-mentioned tan δ diminishes.Equally, as dicarboxylic acid, even use general adjacent phthalandione, the G ' value under the minimum temperature of above-mentioned tan δ also diminishes.Therefore, in the present invention, not desirable based on the composition of these two pure and mild dicarboxylic acid.

In addition, as the general vibrin binding resin of toner, that have cross-linked structure in the well-known molecule, with the linear polyester resin relatively, the G ' value under the minimum temperature of tan δ has the tendency of reduction, therefore, be unfavorable for binding resin of the present invention.This can infer is wide the diminishing of chain with strand of cross-linked structure, therefore, and with the strand comparison of wire, the cause of the transmission effect difference of its distortion.

Therefore, as carboxylic acid and glycol etc., getting the monomer with the above cross-linked structure of ternary is main body and bad.But in satisfying the scope of viscoelastic property of the present invention, in order to improve other rerum natura, polybasic carboxylic acid and the polyvalent alcohol more than the ternary that the ternary of employing denier (less than 2 moles of %) is above are also not serious.

As the standard of the molecular weight of the viscoelastic property that obtains binding resin suitable among the present invention, number-average molecular weight Mn is 6000～10000, weight average molecular weight Mw is 15000～25000, Z mean molecular weight Mz is 30000～70000, Mw/Mn is 3～5.Above-mentioned molecular weight and molecular weight distribution can utilize well-known method to measure, and general available gel infiltration chromatography (following be designated as briefly " GPC ") is measured.For example, can utilize HLC-802A that Japan Cao Da Co., Ltd. produces as the GPC device, be 40 ℃ at oven temperature, 1 milliliter of post flow per minute, and the sample injection rate IR is under 0.1 milliliter the condition, to carry out GPC and measure; Also can use and the pure medicine system of light: the THF that GPC uses is to carry out GPC for 0.5% time to measure at sample concentration.In addition, the polystyrene standard sample production lubber-line that for example can utilize Japan Cao Da Co., Ltd. to produce.Above-mentioned molecular weight of the present invention and molecular weight distribution come to this and measure.

So long as satisfy viscoelastic property scope of the present invention, except above-mentioned desirable monomer, can also and with the monomer shown in following.

For example, carboxylic acid as binary, can use succinic acid, glutaric acid, hexane diacid, suberic acid, azelaic acid, decanedioic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), naphthalene-2,6-dicarboxylic acid, naphthalene-2, dibasic acid such as 7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid, mesaconic acid, and aliphatics unsaturated dicarboxylics such as their acid anhydride or rudimentary Arrcostab, maleic acid, fumaric acid, itaconic acid, citraconic acid etc.In addition,,, for example can adopt 1,2,4-benzene tricarbonic acid, 1,2,5-benzene tricarbonic acid, 1,2,4-naphthalene tricarboxylic acids etc., and their acid anhydride or its lower alkyl esters etc. as the carboxylic acid more than the ternary that can merge use if the amount of usefulness is very little.Also can use a kind of in them separately, also can and with two or more.

As dibasic alcohol, the oxirane of for example available bisphenol-A, hydrogenation bisphenol-A, bisphenol-A or (with) propylene oxide adduct, 1,4 cyclohexane diol, 1,4 cyclohexanedimethanols, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol etc.

In addition, if the amount of using is little, as can and alcohol more than the ternary of usefulness, for example, can use glycerine, trimethylolethane, trimethylolpropane, pentaerythrite etc.Can use a kind of in them separately, also can and with two or more.

As required, also can use monoacid such as acetic acid, benzoic acid or monohydroxy alcohols such as cyclohexanol, benzylalcohol to reach the purposes such as modulation of acid number and hydroxyl value.

Above-mentioned vibrin can be selected suitable composition combination from these monomer compositions, for example use, " polycondensation " (chemistry is published with people publishing house), described in " the macromolecule experiment is learned " (polycondensation and addition polymerization: upright altogether publishing house publishes) and " vibrin handbook " (Nikkan Kogyo Shimbun's volume), the existing method of knowing is synthetic.Particularly, can be used alone or in combination ester-interchange method or direct polycondensation method etc.Particularly, for the linear polyester of the suitable high polymerization degree among synthetic the present invention, must be noted that the purity that improves monomer, improve the vacuum tightness that is used for the cleaning reaction accessory substance, make the temperature of reaction optimization, make synthesis condition such as catalysts optimization.In addition, can also use the compound that contains diisocyanate etc., the vibrin of low polymerization degree be carried out high polymerization degree handle.In these methods, preferably use and contain the linear polyester resin that utilizes ester-interchange method polymerization resulting polyester resin.Directly carrying out under the situation of polycondensation reaction,, departing from the optimum value of monomer addition a little because monomer purity is low, just make that the polyester that will obtain high polymerization degree is exceedingly difficult, yet,, can obtain having the linear polyester resin of even molecular weight easily if utilize this ester-interchange method.

Ester-interchange method is a kind of like this synthetic method, promptly, it will use at least a kind ofly has volatile monomer under transesterification reaction temperature and decompression (being roughly its dummy status), for example, boiling point under reduced pressure such as ethylene glycol or neopentyl glycol is at the monomer below 250 ℃, as the phase one, under about 150 ℃～280 ℃ temperature, after carrying out the esterification of sour composition and pure composition, as subordinate phase, under about 180 ℃～380 ℃ temperature and decompression, volatile monomers eliminating to this system outside is gone, carry out transesterification simultaneously, improve the degree of polymerization.Even owing to used volatile monomers too much, also can it can be expelled to this system outside in subordinate phase, thus can not cause the one's share of expenses for a joint undertaking amount to reduce because of the monomer ratio deviation of acid and alcohol, therefore, easily and can be under narrow molecular weight distribution condition, the polyester of synthetic-highly polymerized degree.Particularly, under the situation of synthetic linear polyester, this is effectively.

He Cheng vibrin is to have hydroxyl endways in this way, is being used for as binding resin under the situation of toner, can utilize trihemellitic acid acid anhydride etc. to make the hydroxyl modification of terminal part or all, gives acid number, adjusts its negative charging amount.

And then, the preferred binding resin of the present invention be contain at least two kinds of resins as above-mentioned bonding resin (A, B).The Tg of at least a resin (A) is in 45 ℃～65 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is tan δ minimal value in this resin, and the minimal value of its tan δ is below 1.0, G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0.The Tg of the resin (B) that merge to use is in the scope of Tg+5 ℃ of resin (A)～Tg+15 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is tan δ minimal value in this resin.As the integral body of binding resin, binding resin of the present invention is the binding resin that satisfies the potpourri of above-mentioned viscoelastic property.

Like this, merging and use two or more resins, is good from viewpoint that fixing temperature is set in low-temperature zone and the viewpoint that improves heat-resisting obstructive.As shown in Figure 2, in satisfying the resin of viscoelastic property of the present invention, peel off the relation of energy needed and temperature, near Tg, have the peak,, peel off energy needed and reduce, peel off easily along with the rising of temperature.Form when noting changing with binding resin with onesize molecular weight, during fissility when changing Tg, with the resin of low Tg relatively, along with temperature rises, peeling off of the resin of high Tg can reduce, to high temperature one side shifting (shown in dotted line).Therefore, the setting of fixing temperature must move to high temperature one lateral deviation.

In contrast, by changing the composition of resin, the resin combination of the low-molecular-weight composition of the resin of the high molecular composition of low Tg and high Tg is used, can be improved fixing temperature, and obtain effect of the present invention.

In addition, when considering the low-molecular-weight composition,, form, improve the Tg of low-molecular-weight composition, can improve anti-obstructive by changing because the low-molecular-weight composition in the resin has disadvantageous effect to anti-obstructive.

Therefore, with the resin that utilizes single composition, the situation that satisfies above-mentioned viscoelastic property compares, and cooperates the degree of freedom of forming to improve.If the resin that composite design is general, it is lower to obtain cost easily, and the lower toner of fixing temperature.

The composition of the various vibrin that use in the mixing of above-mentioned binding resin and molecular weight, as long as it is from above-mentioned haplometrotic colony, select, just passable to obtain desirable Tg and viscoelasticity.

Toner of the present invention with this viscoelastic property, the release property of its bonding resin itself is good, particularly, even do not contain wax in toner is formed, also can use well.Yet, enlarging print through temperature range and the clean-up performance that improves without the print through toner of visual examination in order to reach, the wax that contains trace does not have any obstruction yet.In addition, adding an amount of wax, is useful to the efficient that improves fixing.

As the wax that can be used for toner of the present invention, for example, can enumerate paraffin, silicones, rosin based, Rice's wax, Carnauba wax of low-molecular-weight polypropylene or low-molecular-weight tygon etc. etc.Wherein, molten point is preferably in 40 ℃～150 ℃, and better is between 70 ℃～110 ℃.But, when the content of wax is too much, be present in colored photographic fixing imaging surface or inner wax, can make OHP projection mis-behave, when in the developer of two compositions, using, because the influence of friction, wax in the toner moves to carrier, make the chargeding performance time to time change of developer, when the developer as single composition used, because the influence of toner and supporting plate friction, wax moved to the supporting plate that produces charged usefulness, make the chargeding performance time to time change of developer, therefore, the flowability of toner degenerates etc., also has problems such as color image quality and reliability reduction also can occur.The amount of wax is preferably 0.1～7%, and better is 0.5～5%, is desirably 0.5～4% most.

The colorant that uses in toner of the present invention is had no particular limits, can use the colorant of knowing, for example, can adopt carbon black, dim, aniline blue, ultramarine blue, Ka Erkeluode indigo plant, methylene blue chloride, the copper phthalocyanine blue, quinoline yellow, chrome yellow, Du Pont's oil red, natural oil red, rose-red, the peacock green oxalates, aniline black byestuffs, C.I. pigment red 4 8:1, C.I. paratonere 57:1, C.I. pigment red 81: 1, C.I. pigment red 122, C.I. pigment yellow 97, C.I. pigment Yellow 12, C.I. pigment yellow 17, C.I. pigment blue 15: 1, C.I. pigment blue 15: 3 etc.

The content of the above-mentioned colorant in the electrophoto-graphic toner preferably accounts for 1～30 weight portion in 100 weight portions of above-mentioned binding resin, still, in the scope of the flatness of the imaging surface after not damaging photographic fixing, preferably some more as far as possible.When increasing the amount of colorant, when obtaining the image of same concentration, can the attenuate image thickness, for preventing that effectively print through from being favourable.In addition, according to the difference of above-mentioned colorant kind, can modulate yellow toner, magenta toner, cyan toner, black toner etc.

For improved characteristics, in the scope of not damaging effect of the present invention, can in toner of the present invention, merge and use various known additives.Have no particular limits as the adjuvant composition, can suitably select, for example can use various adjuvants well known in the art such as inorganic fine particles, organic particle, charged controlling agent, release agent according to the purpose difference.

As inorganic fine particles, for example can use: silicon dioxide, aluminium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, zinc paste, silica sand, clay, mica, rankinite, zeyssatite, cerium chloride, red iron oxide, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconia, silit, silicon nitride etc.In these inorganic fine particles, best is silicon dioxide particles, particularly best through the silicon dioxide particles of hydrophobization processing.Generally, using the purpose of above-mentioned inorganic fine particles is to improve flowability.The primary particle size of above-mentioned inorganic fine particles is preferably 1～1000 nanometer, as its addition, preferably accounts for 0.01～20 weight portion in 100 weight portions of toner.

As organic particle, for example can use: polystyrene, polymethacrylate, Kynoar.Generally, using the purpose of above-mentioned organic particle is will improve clean-up performance and duplicate performance.

As charged controlling agent, for example can use: salicylic acid metal salt, containing metal azo-compound, nigrosine or tetravalence ammonium salt etc.The purpose of using above-mentioned charged controlling agent is to improve charging property.

Electrophoto-graphic toner of the present invention can be according to manufacture method manufacturing well known in the art.As above-mentioned manufacture method, have no particular limits, according to the purpose difference, can suitably determine.For example, as the method for preparing toner of dry type, can enumerate the freezing comminuting method of mixing comminuting method and mixing.As the method for preparing toner of wet type, can enumerate at Jap.P. and disclose seasoning in the liquid described in No. 25664/1988 communique etc.; In indissolubility liquid, shear agitation is made atomic method with the toner of fusion, and binding resin and colorant are disperseed in solvent, utilizes spraying, makes atomic method etc.

The binding resin that in toner of the present invention, uses because with previous goods relatively, the G ' value under the minimum temperature of tan δ value is big, therefore exists to utilize to have widely used mixing comminuting method, the tendency that is difficult to pulverize now.But, in above-mentioned manufacture method, without limits to the intensity of binding resin.In the toner this point of making electrophotography easily, adopt the method for preparing toner of wet type best.

Below, as the object lesson of the toner autofrettage of wet type, describe seasoning in the liquid in detail.Seasoning is to comprise containing the toner constituent of binding resin and colorant at least in this liquid, in volatile solvent, disperses, dissolves, first operation of modulation dispersion soln; Second operation that above-mentioned dispersion soln is disperseed in water-medium; Method with the 3rd operation of from above-mentioned water-medium, removing above-mentioned volatile solvent.

In above-mentioned first operation, disperse, be dissolved in the toner constituent in the volatile solvent, contain binding resin and colorant at least, also can contain other composition as required.

As above-mentioned volatile solvent, as long as can dissolve and disperse the toner constituent, just be not particularly limited, for example, can adopt: halogenated hydrocarbon series solvents such as hydrocarbon system solvent, methylene chloride, chloroform, triclenes such as ketone series solvent, toluene, cyclohexanes such as ether series solvent, MEK, methyl isopropyl ketone, hexones such as ester series solvent, diethyl ether such as methyl acetate, ethyl acetate, propyl acetate etc.In these solvents, when carrying out industrial and agricultural production, from aspects such as security, cost and productivitys, cyclohexane, ethyl acetate are desirable especially.In addition, the ratio that above-mentioned volatile solvent is dissolved in the water is preferably about 0～30 weight %.

As the water-medium of second operation, for example, can use inorganic dispersant is disperseed in water, and the medium that macromolecule dispersing agent is dissolved equably.As inorganic dispersant, preferably hydrophilic, for example silicon dioxide, aluminium oxide, titania, lime carbonate, magnesium carbonate, tricalcium phosphate, clay, zeyssatite, bentonite etc.In these spreading agents, lime carbonate is best.

This inorganic dispersant best surfaces is covered with the polymkeric substance with carboxyl.As polymkeric substance with carboxyl, for example can use acrylic resin, methacrylate is a resin, and fumaric acid is a resin, and maleic acid is a resin etc.Use the such medium of bowl mill to send into dispersion machine and ultrasonic dispersing machine etc., inorganic dispersant is disperseed in above-mentioned water.

In the present invention, except above-mentioned polymkeric substance, also can use the co-polymer of the independent polymkeric substance of acrylic acid as the formation monomer of above-mentioned polymkeric substance, methacrylate, fumaric acid, maleic acid etc. and they and other vinyl monomer.In addition, above-mentioned carboxyl for example also can be slaines such as sodium salt, sylvite, magnesium salts.The mean grain size of above-mentioned inorganic dispersant is generally 1～1000 nanometer.

As macromolecule dispersing agent, it is desirable to hydrophilic spreading agent, particularly have the better of carboxyl, it would be desirable the spreading agent of lipophilic groups such as not having hydroxyl propoxyl group, methoxyl.As above-mentioned macromolecule dispersing agent, for example also use carboxymethyl cellulose, carboxyethyl cellulose etc.In these spreading agents, carboxymethyl cellulose is desirable especially.Macromolecule dispersing agent may be dissolved in the above-mentioned water, so that the viscosity of its water-medium was 1～10000 milli handkerchief second in the time of 20 ℃.Macromolecule dispersing agent, apparatus and method by adopting suitable selection etc. can be dissolved in the water equably.

Above-mentioned second operation generally will use the device of selling on market as mulser, dispersion machine that can produce strong shearing force to carry out.As the device that can use, particularly, for example can use: homogenizer (IKA Co., Ltd. system), Poly special grand (Port リトロ Application) (Kenai horse Supreme Being blocks Co., Ltd.'s system), TK automixer batch (-type) mulsers such as (Tokushu Kika Kogyo K.K's systems), Ai Balamailuda (エバラマイ Le ダ-) (ebara corporatlon system), TK pipeline type homogenizing mixer (Tokushu Kika Kogyo K.K's system), colloid mill (refreshing steel Pan Tektronix Co., Ltd system), slurries wet crushing mill (Mitsui Miike Engineering Corp.'s system), Ka Bitong (キャ PVC トロ Application) (excellent NTK Co., Ltd. system), meticulous mobile mill (Pacific Machinery ﹠ Engineering Co., Ltd.'s system) etc., the continuous emulsifying machine, Micro Fluid is counted instrument (Mi Zihuo Co., Ltd. system), second reduction machine (nano Mai Ze Co., Ltd. system), APV Gao Lin (go ウリ Application) high pressure mulsers such as (Gao Lin Co., Ltd. systems), film mulser film mulsers such as (Reika Kogyo's systems), oscillating blender oscillatory type mulsers such as (Reika Kogyo's systems), ultrasonic homogenizer ultrasonic emulsification machines such as (Blang pine Co., Ltd. systems) etc.

In the 3rd operation, by methods such as heating, decompressions, can remove the volatile solvent in the water-medium as required.As the temperature of heating, preferably be no more than the glass temperature of binding resin, remove volatile solvent after, remove water-medium again, clean, dehydration etc., can obtain the toner particle of electrophotography.When cleaning and dewater, carry out acid treatment to water-medium, according to circumstances different, after above-mentioned acid treatment, carry out alkali treatment.After the inorganic dispersant dissolving that makes interpolation, also can water clean, dehydration etc.

Making with seasoning in the liquid under the situation of toner, since with comminuting method such as mixing comminuting method relatively, the share of binding resin reduces, the dispersiveness of colorant and other composition reduces, therefore, it is desirable to especially, in advance with toner constituent fusion mixing, make the pigmentary resin constituent, then this binding resin composition is dissolved in volatile solvent.

Electrophoto-graphic toner of the present invention can shift towards the flow state fusion apace from solid state, and because release property is good, when using electrophoto-graphic toner of the present invention, when forming image, in the photographic fixing operation, can need the wet goods release agent hardly, just obtain the coloured image of the high distinctness of flatness height, picture quality height and colour rendering easily.

Electrophoto-graphic toner of the present invention because the value of the G ' under the minimizing temperature of tan δ is high, under the service condition that heat and pressure effect are arranged on the toner, has shown superior permanance.Electrophoto-graphic toner for example of the present invention can make the hot retentivity of toner improve, the retentivity of photographic fixing image improves, the flowability of powder improves, can prevent that external additive from entering in the electrophoto-graphic toner, the performance of keeping charging property improves, thereby can prevent because the firmly carrying of developer etc. or the electrophoto-graphic toner that causes that rubs are pulverized, electrophoto-graphic toner of the present invention can also make charged members such as carrier in the developer or supporting plate, because of strong stress frictional electrification, thereby make charging property uniform and stable, and can prevent to form on the photoreceptor thin film, improve clean-up performance etc.

Under the situation of the electrophoto-graphic toner of the spheroidal particle that the toner autofrettage of these effects wet type such as seasoning in utilizing above-mentioned liquid obtains, remarkable especially.That is, utilize the toner autofrettage of wet type, can obtain the toner of shape subglobular.Different with the atypic toner that has corner angle that draws by the mixing comminuting method, the electrophoto-graphic toner of spheroidal particle can obtain good frictional electrification equably, like this, not only to fixing performance, and to all favourable on the duplicating efficient when the toner xerox, the developing property.In addition, when in toner, adding wax, because the toner that draws in this way, the amount of its wax on toner surface lacks during than comminuting method, therefore can not weaken develop or when duplicating by effect that wax produced, can reduce because wax exists on the surface, and the flowability that causes reduces, attached to the pollution that causes in the device, charged shortcoming such as inhomogeneous, make use before the heat-resisting retentivity etc. of toner improve.

Owing to use vibrin as main binding resin, improved comminuted etc., below, detailed description is contained the electrophoto-graphic toner (below be sometimes referred to as the toner that contains vinylite) of vinyl resin.

The vibrin that uses in containing the toner of vinyl resin has the viscoelastic property same with above-mentioned binding resin, that is, and and at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, have the minimal value of tan δ, this tan δ minimal value is below 1.2, and the G ' under the temperature of this minimum tan δ is 5 * 10 ⁵More than the handkerchief, at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 3.0.Therefore, can use the vibrin that uses as above-mentioned binding resin fully.

In addition, (C D) forms vibrin by two kinds of resins at least.The Tg of resin (C) is at 45 ℃～65 ℃, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, have the minimal value of tan δ, this tan δ value is below 1.0, at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0.The Tg of resin D is in Tg+5 ℃～15 ℃ the scope of resin C, at Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is the minimal value of tan δ.As whole vibrin, preferably satisfy the resin of the mixing of above-mentioned viscoelastic property.

As the main binding resin that contains vinyl resin of the present invention, vibrin must account for more than the 70 weight % of whole binding resin weight.

Owing to be to have brought into play above-mentioned viscoelastic property by vibrin, when its content reduces, will inevitably reduce electrofax characteristics such as anti-print through, colour rendering, particularly heat-resisting print through significantly reduces.

In addition, in containing the toner of vinyl resin of the present invention, above-mentioned vinyl resin must be preferably 1 weight %～15 weight % all accounting for 0.5 weight %～20 weight % in the adhering resin weight, and that best is 1.5 weight %～10 weight %.Making under the situation of toner with the mixing comminuting method, vinyl resin helps to improve comminuted, under situation about making with seasoning in the liquid, helps to improve the solubility property to solvent.Therefore, when the content of ethene base system resin is very few, can not get improving the effect of manufacturing property, served as for a long time, make anti-print through and anti-circumvolution reduction.This is the characteristic that is had owing to as resin itself, and the G ' value of vinyl resin under the minimizing temperature of tan δ causes than the little of vibrin.

The weight average molecular weight of above-mentioned vinylite (Mw) need be below 100000, and preferably weight average molecular weight (Mw) is 1000～100000, more preferably 1000～50000, most preferably 12000～50000.When Mw was too high, the effect of comminuted raising weakened, and when Mw was low, volatile component was many, can product and foreign odor and safety issue during photographic fixing.

As the monomer that constitutes above-mentioned vinyl resin, for example can be used alone or in combination at the existing known monomer composition described in " macromolecule Fact Book: a basis piece of writing " (macromolecule association compiles, and training wind shop publishing house publishes).

Particularly, for example, can enumerate halogen-substituted styrene, the 4-fluorostyrene, 2 such as alkyl-substituted styrene, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene of alkyl chains such as styrene, α-Jia Jibenyixi, vinyl naphthalene or 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 2-ethyl styrene, 3-ethyl styrene, 4-ethyl styrene as styrenic monomers, fluorine substituted phenylethylenes such as 5-difluoro-benzene ethene.

As (partially) acrylic monomer, have: (partially) acrylic acid, (partially) methyl acrylate, (partially) ethyl acrylate, the toluene propyl acrylate, (partially) butyl acrylate, (partially) acrylic acid n-pentyl ester, (partially) ethyl acrylate, (partially) acrylic acid heptyl ester, (partially) 2-ethyl hexyl acrylate, (partially) decyl acrylate, (partially) acrylic acid dodecane ester, (partially) lauryl acrylate, (partially) acrylic acid tetradecane ester, (partially) acrylic acid hexadecane ester, (partially) acrylic acid octadecane ester, (partially) isopropyl acrylate, (partially) isobutyl acrylate, (partially) tert-butyl acrylate, (partially) acrylic acid isopentyl ester, (partially) acrylic acid pentyl ester, (partially) acrylic acid peopentyl ester, (partially) Isohexyl acrylate, (partially) acrylic acid isocyanate, (partially) Isooctyl acrylate monomer, (partially) acrylic acid 2-diethyl acetamidomalonate, (partially) phenyl acrylate, (partially) acrylic acid diphenyl ester, (partially) acrylic acid diphenyl ethyl ester, (partially) acrylic acid tert-butyl group phenyl ester, the many phenyl esters of (partially) acrylic acid, (partially) cyclohexyl acrylate, (partially) acrylic acid tert-butyl group cyclohexyl, (partially) acrylic acid dimethyl amyl group ethyl ester, (partially) diethyl amyl group ethyl ester, (partially) methoxyl ethyl ester, (partially) 2-hydroxy methacrylate, (partially) vinyl cyanide, (partially) acrylamide etc.

In addition, can enumerate divinyl aromatic compound as vinyl monomer composition, for example divinylbenzene, divinyl naphthalene etc.) with bridging property; Diacrylate ester type compound with the alkyl chain connection, for example with glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1, the acrylate of 5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate and above compound replaces into the compound of methacrylate.

With the diacrylate compounds of the alkyl chain connection that contains ehter bond, for example: the compound of the acrylate of diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyglycol #400 diacrylate, polyglycol #600 diacrylate, propylene glycol diacrylate and above compound being replaced by methacrylate.

With containing the diacrylate compounds that chain that aromatic series base and etherificate close connects, have: for example with polyoxyethylene (2)-2, two (4-hydroxy phenyl) the propane diacrylates of 2-, polyoxyethylene (4)-2, the acrylate of two (4-hydroxy phenyl) propane diacrylates of 2-and above compound is replaced by the compound of metering system ester.

As multi-functional crosslinking chemical, pentaerythritol triacrylate, Pehanorm triacrylate, three hydroxypropyl alkane triacrylates, four hydroxyls, four methylmethane tetraacrylate, low-polyacrylate, and the acrylate of above compound can be replaced by metering system ester etc.But because the color developing that a large amount of crosslinked compositions is exchanged toner has infringement, therefore preferably with molal weight than using below the % at 10 moles.

Because styrene base system monomer, even the effect that the heat-resisting obstructive in ethene base system monomer improves is also big, therefore, above-mentioned ethene base system resin preferably includes into as component unit with styrenic monomers.Particularly, the amount of styrenic monomers in whole monomers of vinyl resin by the mole anharmonic ratio, is preferably 10 moles of %～90 mole %, and best is at 20 moles of %～80 mole %.

Owing to have the carbonyl key in the monomer, making propylene is that the intermiscibility of monomer and vibrin is superior, because the toner of the inhibition turbid effect that bleaches is arranged, therefore, above-mentioned vinyl resin is that monomer includes as the formation monomer with propylene preferably again.Particularly, propylene is the amount of monomer in whole monomers of vinyl resin, by the mole weight ratio, is preferably 2 moles of %～80 mole %; Best is at 5 moles of %～60 mole %.When the content of propylene base system monomer was very few, intermiscibility worsened; And served as for a long time, then mix excessively, can not get adding the effect that causes.

Particularly, when the Mw of vinyl resin 30000 when above, the effect that contains propylene base system monomer is remarkable.In addition, from the effect of the manufacturing property that improves toner, propylene is (partially) esters of acrylic acid of (partially) acrylic acid pentyl ester, (partially) Hexyl 2-propenoate, (partially) isobutyl acrylate, (partially) tert-butyl acrylate etc. preferably in the monomer.

The glass temperature of above-mentioned vinyl resin is preferably in more than 50 ℃ in the scope.When Tg below 50 ℃ the time, toner container is subject to thermal chokes.

In not damaging effect limit of the present invention, can in containing the toner of the present invention of vinyl resin, use colorant and the adjuvant that is used for improved characteristics.Can use above-mentioned compound as colorant and adjuvant.

Can contain the manufacturing of the toner of the present invention of vinyl resin according to the above-mentioned existing method of knowing.The feature that contains the toner of the present invention of vinyl resin is, owing to added vinyl resin, can not damage because of limiting the effect that viscoelastic property causes, the comminuted of toner materials can be improved, and obtains the rerum natura that the mixing breaking method also is suitable for.Therefore, seasoning is best suited in as containing the manufacture method of the toner of the present invention of vinyl resin in mixing comminuting method and the liquid.

The toner of the present invention that contains vinyl resin, identical with the toner of above-mentioned electrophotography, can shift to the flow state fusion apace from solid state, and release property is good, so when using electrophoto-graphic toner of the present invention to generate image, in the photographic fixing operation, almost can not need the wet goods release agent, just can easily obtain the coloured image of the good distinctness of flatness height, picture quality height and colour rendering.In addition because the G ' value under the minimizing temperature of tan δ is high, toner be heated and the service condition of pressure effect under, also can obtain enough permanance.

More than Shuo Ming electrophoto-graphic toner of the present invention (below, also include the toner of vinyl resin in the occasion of the said electrophoto-graphic toner) toner that can be used as electrophotographic developer suitably uses.

Below, electrophotographic developer of the present invention is described.Electrophotographic developer of the present invention comprises above-mentioned electrophoto-graphic toner.

Electrophotographic developer of the present invention can be the electrophotographic developer that contains the single composition of electrophoto-graphic toner of the present invention, also can be the electrophotographic developer that contains two compositions of the toner of this electrophotography and carrier.

Under the situation of the quiet electrophotographic developer of single composition, because the G ' height of the binding resin that uses in the toner of the present invention, endurance to heat and friction is strong, therefore, when as the time,, has uniform charging property with the rub resistance height of member with the non magnetic single composition developer of charged member electrification by friction such as supporting plate, and change for a short time in time by the charging property that friction causes, can obtain the developer of good heat resistance.

Under the situation of the electrophotographic developer of two compositions, have no particular limits as merging the carrier that uses with toner, can enumerate suitable well-known carrier, for example, the carrier of coated with resin.The carrier of coated with resin is lining one deck resin on the surface of material core.Can use as the material core, for example magnetic powders such as iron powder, ferrite, nickel powder etc.As coated with resin, for example can act on: fluororesin, vinyl resin, silicon are resin etc.

Under the situation of the two composition electrophotographic developers that use toner of the present invention, same with the developer of single composition, good with the wear-resisting wiping of carrier.Because problems such as the carrier surface that is not caused by wax adheres to can be kept uniform charging property, therefore, can obtain development property, duplicating property, electrophotographic developer that permanance is all good.

In addition, according to the purpose difference, electrophotographic developer of the present invention also can contain the adjuvant of suitable selection etc.For example, if purpose is in order to obtain magnetic, then can to comprise with the iron class headed by iron, ferrite, the tri-iron tetroxide; Nickel, cobalt etc. have ferromagnetic metal, alloy or contain the compound of metal; Magnetic material and the magnetized material of possibility.

Because electrophotographic developer of the present invention contains above-mentioned electrophoto-graphic toner of the present invention, therefore, the advantage of electrophoto-graphic toner of the present invention also can be used as the advantage of electrophotographic developer of the present invention.So when using electrophotographic developer of the present invention to form image, it is good to obtain flatness, the coloured image of the distinctness that picture quality height and colour rendering are good.

In addition, the electrophotographic developer of the invention described above also can suitably use in various formation methods.

Being characterized as of formation method of the present invention uses electrophotographic developer of the present invention as electrophotographic developer.As the process of image generating method of the present invention, also can adopt the process that comprises well-known imaging process, for example on latent image carrier, form the operation of sub-image; Use electrophotographic developer to make the operation of above-mentioned image development; The toner image that has developed duplicated duplicating the duplicating operation on the body and will duplicate the operation etc. of toner image on the body.

As the employed fixing device of formation method of the present invention, can use contact heat-fixing device with well-known coating device of demoulding agent.For example, can use, have rubber elastic layer is arranged on the heated rollers of fixing member superficial layer and the core iron, have as required the heat roller fixation device that the backer roll of fixing member superficial layer constitutes as required by rubber elastic layer is arranged on the core iron; Or the combination of this roller and roller is changed into the fixing device of the combination of the combination of roller and belt or belt and belt.

As rubber elastic layer, can use heat-resisting rubber such as silicon rubber or fluororubber.

As the fixing member superficial layer, can use the layer of making by low materials of surface energy such as silicon rubber, fluororubber, fluorine latex, fluororesin.Toner of the present invention because release property is good, under the situation of using these fixing member superficial layers, can obtain good reliability.Wherein, use fluororesin, can obtain the high fixing performance of reliability for a long time.

As the fluororesin of using on the fixing member surface, can use the teflon that contains PFA (perfluor alkyl ethide ether copolymer) etc., the soft fluorine resin of fluoridizing ethenylidene etc.With silicon rubber or fluororubber relatively do not reduce because fluororesin is besmirched to wait to adhere to or precipitate the release property that causes by toner, therefore, if the release property of toner is good, the life-span of its fixing member is with regard to length.

For the base material (material core) of above-mentioned fixing member, should select good heat resistance for use, for the intensity height of distortion, the material that heat conductivity is good.Under the situation of roller-type fixing device, but for example aluminium, iron, copper etc.; Under the situation of banding pattern fixing device, for example can select the band of Kapton and stainless steel etc.

According to the purpose difference, above-mentioned fixing member also can contain various adjuvants.For example, be purpose to improve wearing quality and controlling resistance value, then can contain the ceramic particle of carbon black or metal oxide, SiC etc. etc.

Now utilize Fig. 3 to describe the photographic fixing operation of using developer of the present invention in detail.

The thermo-compression bonding device that adds shown in Figure 3 is the device that fixing member uses roller, and it has hot-rolling 1, the crimping roller 2 of relative configuration with it, the release agent feedway 9 that is used to heat the heating source 10 of hot-rolling 1 and supplies with release agent 15 to the fixing member superficial layer 11 of hot-rolling 1.On the surface of hot-rolling 1, form elastic layer 12.With formed toner image 13 be copied body 14; When between crimping roller 2 and thermo roll 1, passing through, be copied body heating, pressurization, with image fixing.

As required, the thermo-compression bonding device that adds shown in Figure 3 can also have and is used for the cleaning element removed attached to thermo roll 1 lip-deep toner, is used to pawl (hook) that heats the heating source 10 of crimping roller 2 and peel off recording materials from thermo roll 1 etc.In addition, the heating source that adds thermo-compression bonding device 10 shown in Figure 3 can not controlled by temperature control equipment (illustrating among the figure).

On thermo roll 1 and/or crimping roller 2, preferably has the elastic layer 12 of single or multiple lift stepped construction.As the thickness of elastic layer, be 0.1～3 millimeter preferably, best is 0.5～2 millimeter.Can use thermotolerance rubber such as silicon rubber or fluororubber on elastic layer 12, rubber hardness is preferably in below 60.When fixing member elasticity layer 12, along with being copied the concavo-convex of toner image 13 on the body 14, above-mentioned fixing member distortion improves the flatness of the imaging surface after the photographic fixing.But when the thickness of elastic layer surpassed 3 millimeters thick, the thermal capacity of fixing member increased, and the heat fixer member needs the long period to temperature desired, and the energy of Xiao Haoing also increases like this, and this is bad.When the thickness of elastic layer below 0.1 millimeter, when too thin, then fixing member can not be out of shape along with the concavo-convex of toner image, it is inhomogeneous to produce fusion, and when peeling off, elastic layer can not be out of shape effectively, this is also bad.

In formation method of the present invention, owing to use the good developer of release property, therefore have under the situation of fixing member of the superficial layer that the material low by surface energy make in application, do not need adding the fixing member surface applied release agent of thermo-compressed especially, but from the permanance of raising fixing member and the viewpoint of release property, at fixing member surface applied release agent also is good, its coating amount same release agent coating amount during preferably with the black and white toner fixing, promptly 1.6 * 10 ^-5～8.0 * 10 ^-4Milligram/square centimeter.

From viewpoints such as the flatness of the image that drawn and gloss, the coating amount of release agent is better less, but, when the quantity delivered of release agent is 0 milligram/square centimeter, because in the photographic fixing operation, when above-mentioned fixing member and paper etc. are copied body and contact, the fixing member wear extent increases, the permanance of fixing member is reduced, therefore, still preferably a spot of release agent is supplied with fixing member in the practicality.

When the quantity delivered of release agent surpasses 8.0 * 10 ^-4During milligram/square centimeter (each opens A4 paper is 0.5 milligram), remain in the release agent on the imaging surface after the photographic fixing, make image quality decrease, particularly utilizing seeing through under the situation of light of OHP one class more obvious, can produce release agent attached to being copied problems such as producing adhesion on the body.In addition, if the release agent quantity delivered is big, the capacity that then stores the case of release agent also wants big, and the fixing device size is increased.

The quantity delivered of release agent can followingly be measured.That is, when making the common paper used on the general duplicating machine (be typically the copy paper that Fuji Xerox Co., Ltd produces, commodity are called " J paper ") when having supplied with the fixing member of release agent from the teeth outwards, decolorant is attached on the common paper.Can the release agent on this common paper be extracted with Soxhlet's extractor.Solvent is to use hexane.Release agent that this hexane contains can carry out quantitatively making the amount attached to the release agent on the common paper in atomic absorption spectrum analysing arrangement.This amount is defined as the demoulding dosage of supplying with to fixing member.

The release agent that uses is had no particular limits, can use thermotolerance oil, for example, modification wet goods liquid release agents such as dimethyl silicon oil, fluorocarbon oil, fluoro silicone oil or amino-modified silicone oil.

As release agent, all be to use some high-performance, and the high fluorocarbon oil of price, fluoro silicone oil etc.But under the situation of formation method of the present invention,, therefore in practicality aspect the cost, do not have problem because the quantity delivered of release agent is few.

Method for supply with from release agent to the thermo roll surface that adds thermo-compression bonding device has no particular limits, and for example can use: contain the puddling mode of immersion fluid release agent, web joint mode, roller mode or contactless spray mode (spray regime) etc.In these modes, from can supplying with release agent equably, and control the viewpoint of quantity delivered easily, preferably web joint mode and roller mode.In addition, utilize the spray mode when the integral body of above-mentioned fixing member is supplied with above-mentioned release agent equably, needing the supporting plate of other purposes of use etc.

Be copied body (recording materials) as what in formation method of the present invention, use, for example can use: the paper of on common paper of using on the duplicating machine of electrofax mode and the printer etc. and OHP, using etc.In order to improve the flatness of the imaging surface after the photographic fixing, the preferably above-mentioned surface that is copied body is also level and smooth as much as possible.For example, can will the coated paper on surface of common paper and the art paper of printing usefulness etc. have been applied with resin etc. as the above-mentioned body that is copied.

Under the situation that forms the permeable image of light, as being copied body (recording materials), can use on matrixes such as transparent plastic film or transparent plastic film, the tracing paper of the development layer of being made by thermoplastic resin etc. is arranged.

As matrix, can use heat resisting temperature particularly at the pet film more than 100 ℃ (hereinafter to be referred as " PET "), polyethylene naphthalenedicarboxylate dioctyl phthalate second two ester films (hereinafter to be referred as " PEN "), polysulphone film, polyphenylene oxide film, Kapton, polycarbonate film, cellulose ester film, polyamide film etc.Wherein, best with the thermotolerance and the transparency of PET and PEN.When heat resisting temperature is crossed when low, during photographic fixing, the matrix distortion, circumvolution is on fuser.Utilizing in the scope of electrofax, heat resisting temperature does not have special higher limit, but when considering formability and again during problem such as utilization, hope can be about 250 ℃ time fusion.

The thickness of matrix preferably is about 20～200 microns.When matrix was blocked up, photopermeability was poor.Because the thermal capacitance quantitative change during photographic fixing is big, fixing temperature is raise.On the other hand, during photographic fixing, even matrix thickness is thin also no problem, but according to present matrix material characteristic, when matrix thickness was too thin, because the easy deformation of matrix own, therefore easy circumvolution, need have a lower limit during photographic fixing on fuser.

Generally, owing under the situation of the black and white copying that oilless fixing is used, on the thermoplastic resin that forms the layer that develops, do not need colour rendering, therefore, can use the high resins of elasticity such as styrene butadiene resin.Under situation,, therefore, can use the vibrin of the viscosity same etc. with having the toner resin of rapid meltbility owing to need colour developing with oily photographic fixing color photocopying.But when wishing that melting characteristic under the low temperature is good, wish that its release property might as well this put, preferably use the identical resin of binding resin with the toner of formation electrophotography of the present invention.In addition, if on the layer that develops, use the resin that has with the similar composition of binding resin of toner, because almost there is not refractive index, or the difference of solubility parameter (SP value), therefore, intermiscibility.This puts not damaging colour rendering and photopermeability, also is good.

Specifically, preferably utilize resin to form the layer that develops with following properties, that is, and at glass temperature (Tg)～loss elastic modulus G "=1 * 10 ⁴In the temperature range of handkerchief, there is tan δ minimal value in this binding resin, and the minimal value of this tan δ is below 1.2, storage elastic modulus G '=5 * 10 under the minimizing temperature of this tan δ ⁵More than the handkerchief, and at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0.

Necessary viscoelasticity scope is at expression G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is in 1.0 above this point, and is different with above-mentioned toner.The reasons different with the situation of above-mentioned toner are, because the layer that develops passes through smoothing processing in advance, therefore, do not need the toner must be from the granular required flowability of smoothed image that flow to during photographic fixing.

These numerical ranges are necessary minimum scopes.Because the minimal value of tan δ is little, favourable to peeling off, therefore preferably should be worth below 1.1, the most desirable is below 1.0.From peeling off viewpoint, tan δ does not have lower limit, but from viewpoint such as coating manufacturing etc., preferably dissolubilities such as solvent required more than 0.3.In addition, show that at tan δ the G ' under the minimizing temperature is preferably in 6 * 10 ⁵More than the handkerchief, better is 7 * 10 ⁵More than the handkerchief.In addition, G " be 1 * 10 ⁴Tan δ under the temperature of handkerchief is preferably in more than 2.0, and the most desirable is more than 3.0.

When reaching this viscoelasticity scope, in the shear history of photographic fixing, the marginal portion of toner image becomes viscosity, embeds in the layer that develops, and does flexible action when peeling off, and can obtain good stripping performance.Embed in the layer that develops by marginal portion, the projected image of half tone image part is developed the color brightly toner image.In addition, G " be 1 * 10 ⁴Temperature during handkerchief is good below 180 ℃ making fixing temperature reduce on this aspect.

The glass temperature of binding resin of the present invention (Tg) is preferably in 45 ℃～85 ℃ scopes, and more satisfactory is in 50 ℃～75 ℃ scopes, and the most desirable is in 55 ℃～70 ℃ scopes.When Tg was lower than 45 ℃, toner was heated and blocks easily; When Tg was higher than 100 ℃, fixing temperature can be too high.

As the molecular weight standard that obtains viscoelastic property of the present invention, the molecular weight of measuring with GPC is Mn=5000～10000, Mw=13000～25000; Mz=20000～70000; Mw/Mn=3～5.

As long as satisfy above-mentioned condition, form the thermoplastic resin of the layer that develops, can use the spendable resin of binding resin all as the electrophoto-graphic toner of the invention described above.

Use two or more resins as the above-mentioned thermoplastic resin that forms above-mentioned development layer from fixing temperature being set in the viewpoint of lower temperature side and the heat-resisting obstructive of raising, preferably merging.Specifically, best above-mentioned thermoplastic resin contain at least two kinds of resins (E, F), wherein, the Tg of at least a resin (E) is 45 ℃～65 ℃, Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is tan δ minimal value in this resin, and this tan δ minimal value is below 1.0, G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is more than 1.0.The Tg of the resin (F) that merge to use in Tg+5 ℃～Tg+15 of resin (E) ℃ scope, Tg～G "=1 * 10 ⁴In the temperature range of handkerchief, there is the tan δ minimal value of this resin.

Form the G of the thermoplastic resin of the layer that develops in season "=1 * 10 ⁴The temperature of handkerchief is Tf, makes the G of toner "=1 * 10 ⁴When the temperature of handkerchief was Tt, best Tf and Tt poor (Tf-Tt) in-30 ℃～30 ℃ scopes, the most desirable was in-20 ℃～20 ℃ scopes.When this difference was bigger than above-mentioned scope, the viscosity during two kinds of resin fusions was significantly different, and this can impair colour rendering and anti-print through performance.

The available existing known method of above-mentioned development layer forms.

Generally can enumerate thermoplastic resin and other adjuvants are dissolved in the solvent, apply with rotation coater or rod-type coater etc. and dry method and apply latex again, heating and melting carries out the method for smoothing processing etc.

In addition,, tack coat can be set, on matrix surface, carry out processing such as Cement Composite Treated by Plasma or corona discharge in order to improve matrix and the cohesiveness of the layer that develops.The applied thickness of development layer is preferably in 1 micron～20 microns.When the layer that develops was too thin, the effect that colour rendering is improved was little; When blocked up, anti-print through reduction.

In order to improve performance, can also in above-mentioned development layer, add existing well-known various adjuvants.

In order to improve release property, in above-mentioned development layer, can also contain release agent.Contained release agent can use the release agent identical with release agent contained in above-mentioned toner.When release agent content is too much, favourable to fissility, but because photopermeability is had infringement, therefore, it preferably accounts for below the 5 weight % in the layer resin that develop.

If from the viewpoint of resin intermiscibility, as long as suitably select, then in the layer that develops, the dispersion diameter of release agent can improve photopermeability below 1.0 microns the time.Under release agent is dissolved in situation in the solvent, can directly apply, be not dissolved in the solvent at release agent, to in advance release agent be ground into below 0.5 micron, preferably below 0.3 micron, it be dispersed in the solvent, apply, drying, dispersion diameter can be diminished.From preventing the viewpoint of release agent aggegation, drying at this moment is preferably under the following temperature of the fusing point of release agent and carries out.

In addition, in order to control friction factor, can also contain particulate in the above-mentioned development layer.As contained particulate, preferably with the refringence of the layer resin that develop at the particulate below 0.2.Specifically, can use organic particles such as inorganic fine particles such as silicon dioxide, aluminium oxide, lime carbonate, polystyrene, polymethylmethacrylate.Its content is preferably in 0.1～10 weight % scope.

In addition, the surface resistance of above-mentioned development layer is preferably 10 ⁷～10 ¹³Ohm-sq centimetre.When surface resistance than 10 ¹³When ohm-sq is centimetre high, is easy to generate the picture quality that discharge causes and degenerates; When resistance ratio 10 ⁷When ohm-sq was centimetre low, the charged reduction that is used to keep toner degenerated picture quality.

Can utilize charged controlling agent to control the surface resistance of above-mentioned development layer.Charged controlling agent can be included in the layer that develops, and perhaps also can newly form a layer that contains charged controlling agent on the layer that develops.

As charged controlling agent, be preferably water white, for example, can use: Sulfonates, ammonium salt class, sulfosalt class or metal oxide microparticle etc.When these charged controlling agents disperse when bad, owing to can cause the surface resistance deviation, become the main cause that picture quality degenerates, therefore, working medium comminutor etc., these charged controlling agents are ground into particulate, re-use.Preferably in resin of the present invention,, by in working procedure of coating, using dispersed very high charged controlling agent etc., improve dispersiveness then in advance with charged controlling agent mixing.

Moreover, can carry out the mensuration of surface resistance according to the method for JIS-K6911.At this moment, can be with test specimen at 20 ℃, 65%RH places after 24 hours down, utilizes resistance measurer " R8340 (liking moral Bandaid Si Te Co., Ltd. system) " etc., measures under 100 volts.

When adopting the formation method of the present invention that uses electrophoto-graphic toner of the present invention and electrophotographic developer, because release agent is hardly attached to being copied on the body, therefore, stull processing, the function admirable of revising, and, when double-sided copying, also can prevent part in the machine, for example adhere to the wet goods phenomenon on feeder roller and the duplicating member etc. and take place.

As mentioned above, adopt electrophoto-graphic toner of the present invention, because toner adhesive has above-mentioned viscoelastic property, therefore, when in fuser, passing through, can flow fast, and when peeling off, have strong polymerization between the cementing agent molecule, become flexible, like this, even the amount of image toner is many, thick again, also can peel off well, make picture quality height after the photographic fixing, colour rendering is good.In addition, owing to have strong polymerization between the cementing agent molecule, even the toning dosage at image is many, under the situation of toner bed thickness, during photographic fixing owing to peel off distortion, also make the demonstrate flexibility character of body of toner adhesive, and it is peeled off fully, and therefore, the picture quality height after the photographic fixing, colour rendering is good, and photopermeability might as well.In addition, because the fissility of toner adhesive self is good, the amount of the release agent that uses in fuser is significantly reduced, therefore the stull processability of copy and revise function admirable, and can prevent when double-sided copying, part in the duplicating machine, for example feeder roller or duplicating member etc. adhere to the wet goods dirt.And then, owing to improved anti-print through performance,, only need very little some demoulding dosage even when in toner, containing release agent, just can bring into play effect, therefore, can will make the reduction of the various characteristics of toner be controlled at Min. owing to containing release agent.In addition, because the tan δ minimal value of toner adhesive is littler than 1.2, it is the intensity height of toner adhesive, therefore, except fissility, can expect that also having after the photographic fixing image intensity improve the copy keeping quality that causes improves, toner reduces to the infiltration of recording materials such as paper, toner permanance in the developer improves, and photoreceptor pollutes effects such as reduction and clean-up performance raising.

Below, embodiments of the invention and comparative example are described, but the present invention not only is confined to this.

(synthesis example 1 of vibrin)

As shown in table 1, with the cyclohexane dicarboxylic acid dimethyl ester of the dimethyl isophthalate of the dimethyl terephthalate (DMT) of the cyclohexanedimethanol of 72.1 weight portions, 67.9 weight portions, 87.3 weight portions, 40.0 weight portions and as the tetrabutyl oxygen titanium of 1.0 weight portions of catalyzer join have stirrer, in the reaction vessel of thermometer, condenser and nitrogen ingress pipe, in reaction vessel with behind the nitrogen drying, in the bell-type well heater, heat, under stream of nitrogen gas, about 5 hours of about 190 ℃ of following stirring reactions.Then, cool to room temperature adds the tetrabutyl oxygen titanium of the ethylene glycol and 0.5 weight portion of 124 weight portions again, and then, flow down at nitrogen, stir down at about 190 ℃, reacted about 5 hours.Continue on one side to stir, be cooled to about 100 ℃ on one side, after confirming there is not residual acid composition monomer with silica gel thin-layer chromatography (TLC), with about 0.6 mm Hg that reduces pressure in the reaction vessel, make temperature in the reaction vessel, in about 10 ℃/5 minutes ratio, rise to about 230 ℃, under 230 ℃ of constant situations, reacted about 2 hours, obtain faint yellow transparent amorphous polyester resin A.The physics value of amorphous polyester resin A is as shown in table 2.

(synthesis example 2 of vibrin)

Press shown in the table 1, with the cyclohexane dicarboxylic acid dimethyl ester of the dimethyl isophthalate of the dimethyl terephthalate (DMT) of the cyclohexanedimethanol of 72.1 weight portions, 77.6 weight portions, 87.3 weight portions, 30.0 weight portions with as the tetrabutyl oxygen titanium of 1.0 weight portions of catalyzer, join in the reaction vessel identical with vibrin synthesis example 1, in reaction vessel with behind the nitrogen drying, in the bell-type well heater, heat, under stream of nitrogen gas, at about 190 ℃, stir, reacted about 5 hours.Then, be cooled to room temperature, add the tetrabutyl oxygen titanium of the ethylene glycol and 0.5 weight portion of 124 weight portions, under stream of nitrogen gas, under about 190 ℃, about 5 hours of stirring reaction.Continue on one side to stir, be cooled to about 100 ℃ on one side, after confirming there is not residual acid composition monomer with silica gel thin-layer chromatography (TLC), with about 1.0 mm Hg that reduce pressure in the reaction vessel, make the temperature in the reaction vessel, rise to about 230 ℃ with about 10 ℃/5 minutes ratio, under 230 ℃ of constant situations, reacted about 1 hour, and can obtain water white amorphous polyester resin B.The physics value of amorphous polyester resin B is as shown in table 2.

(synthesis example 3 of vibrin)

Press shown in the table 1, dimethyl terephthalate (DMT) with 116.4 weight portions, 77.6 the dimethyl isophthalate of weight portion, 211.3 2 moles of addition products of the bisphenol-A epoxy ethane of weight portion, 24.1 the ethylene glycol of weight portion and as catalyzer, 2.0 the dibutyl tin oxide of weight portion, join and have stirrer, thermometer, in the reaction vessel of condenser and nitrogen ingress pipe, in reaction vessel, behind nitrogen drying, under stream of nitrogen gas, stir down at about 200 ℃, reacted about 5 hours, again temperature is increased to about 240 ℃, about 5 hours of stirring reaction can obtain water white amorphous polyester resin C.The physics value of amorphous polyester resin C is as shown in table 2.

(synthesis example 4 of vibrin)

According to the ratio of components shown in the table 1, add excessive ethylene glycol, utilize and vibrin synthesis example 1 and 2 same methods, change decompression degree and reaction time, can obtain non-crystalline vibrin D.The physics value of amorphous polyester resin D is as shown in table 2.

(synthesis example 5 of vibrin)

According to the ratio of components shown in the table 1, identical with vibrin synthesis example 3, change the reaction time, can obtain non-crystalline vibrin E.The physics value of amorphous polyester resin E is as shown in table 2.

(synthesis example 6 of vibrin)

According to the ratio of components shown in the table 1, excessively add ethylene glycol, utilize and vibrin synthesis example 1 and 2 identical methods, change decompression degree and reaction time, can obtain non-crystalline vibrin F.The physics value of amorphous polyester resin F is as shown in table 2.

(synthesis example 1 of styrene-propene acid copolymer resins)

After with this system of nitrogen drying, the tetrahydrofuran (hereinafter referred to as THF) of fully removing 780 weight portions of moisture content is added in the reaction vessel as the styrene of solution, the 265.2 weight portions n-butyl acrylate as monomer and 57.6 weight portions, add the about 1/100 mole N of molal quantity that accounts for all monomers again, N '-azoisobutyronitrile (hereinafter referred to as AIBN), system is warming up to 60 ℃, under the uniform temp, reacted about 48 hours.After reaction finished, in the methyl alcohol of about 7000 weight portions, stirred on one side with solution, slowly makes under the drips of solution on one side, behind the sediment filtration drying, obtains water white amorphism styrene-propene acid copolymer resins G.The physics value of amorphism styrene-propene acid copolymer resins G is as shown in table 2.

(synthesis example 1 of vinyl resin)

The cumene of 500 weight portions is added in the reaction vessel, in reaction vessel, replace, be heated to about 150 ℃ with nitrogen.In reaction vessel, the mixed solution of the benzoyl peroxide of the styrene of 250 weight portions and 5 weight portions has been dissolved in dropping, reach 3 hours, under about 150 ℃, after carrying out about 2 hours polymerization, under reduced pressure, slowly be warming up to 190 ℃, remove cumene, obtain Mw and be 15000, Mn is 3000, Tg is 72.1 ℃ water white styrene resin H.

(synthesis example 2 of vinyl resin)

Select monomer, so that the copolymerization ratio of styrene, tert-butyl group acrylate and n-butyl acrylate is 6: 3: 1, utilize the method same, obtain Mw and be 36000, Mn is 12000, Tg is 71.1 ℃ water white styrene-propene acid copolymer resins K with the synthesis example 1 of vinyl resin.

(synthesis example 3 of vinyl resin)

Select monomer, so that the copolymerization of styrene and n-butyl acrylate ratio is 9: 1, utilize the method identical, obtain Mw and be 110000, Mn is 7000, Tg is 68.8 ℃ the sour copolymer resins L of water white styrene-propene with the synthesis example 1 of vinyl resin.

Following table 1 is to represent as the vibrin A～F of binding resin use and the composition of styrene-propene acid resin G with addition.Numeric representation adds the numeric representation molal quantity in fashionable weight portion, the parantheses.

Table 1: the composition of the vibrin of use (addition)

Monomer	A	B	C	D	E	F	Monomer	G
Monomer	A	B	C	D	E	F	Monomer	G	EG	124(2.00)	124(2.00)	24.1(0.39)	93(1.50)	4.34(0.07)	93(1.50)	ST	265.2(2.55)
CHDM	72.1(0.50)	72.1(0.50)					n-BAc	57.6(0.45)	EG	124(2.00)	124(2.00)	24.1(0.39)	93(1.50)	4.34(0.07)	93(1.50)	ST	265.2(2.55)
CHDM	72.1(0.50)	72.1(0.50)					n-BAc	57.6(0.45)	BPA-EO			211.3(0.65)	211.3(0.65)	113.5(0.35)
BPA-PO					260.6(0.75)	243.6(0.70)			BPA-EO			211.3(0.65)	211.3(0.65)	113.5(0.35)
BPA-PO					260.6(0.75)	243.6(0.70)			TPA	67.9(0.35)	77.6(0.40)	116.4(0.60)	116.4(0.60)	145.5(0.75)	116.4(0.60)
IPA	87.3(0.45)	87.3(0.45)	77.6(0.40)	77.6(0.40)		77.6(0.40)			TPA	67.9(0.35)	77.6(0.40)	116.4(0.60)	116.4(0.60)	145.5(0.75)	116.4(0.60)
IPA	87.3(0.45)	87.3(0.45)	77.6(0.40)	77.6(0.40)		77.6(0.40)			CHDA	40.0(0.20)	30.0(0.15)
DSA					46.8(0.15)				CHDA	40.0(0.20)	30.0(0.15)
DSA					46.8(0.15)				TMA					25.2(0.10)
Catalyzer	Ti 1.5	Ti 1.5	Sn 2.0	Ti 1.5	Sn 3.0	Ti 1.5			TMA					25.2(0.10)

Numerical value is weight portion, numerical value in the parantheses is molal quantity, simple number is EG: ethylene glycol, CHDM: cyclohexanedimethanol, BPA-EO: 2.2 moles of addition products of bisphenol-A epoxy ethane, BAP-PO: 2.0 moles of addition products of bisphenol-A epoxy propane, TPA: dimethyl terephthalate (DMT), IPA: dimethyl isophthalate, CHDA: cyclohexane dicarboxylic acid dimethyl ester, DSA: dodecanol dimethyl succinate, TMA: trihemellitic acid trimethyl, catalyzer Ti: tetrabutyl oxygen titanium, catalyst S n: dibutyl tin oxide, ST: styrene monomer, n-BAc: n-butyl acrylate monomer

Resin A～G that expression draws in the above-mentioned synthesis example in the table 2 and these resins are made up the physics value of the resin of use with two kinds.Below, with the various resins of resin numbering expression of (1)～(10).The resin numbering contrast of using in these embodiment and comparative example is as follows.

Resin numbering (3): comparative example 1,5,10

Resin numbering (4): embodiment 4,8,12,18,22

Resin numbering (5): comparative example 2,6,11

Resin numbering (6): comparative example 3,7,12

Resin numbering (7): comparative example 4,8,13

Resin numbering (7):

embodiment

1,5,15,19

Resin numbering (8):

embodiment

2,6,13,14,16,20

Resin numbering (9):

embodiment

3,7,9,10,11,17,21, comparative example 9

The physics value of the vibrin that table 2: embodiment and comparative example use

The resin numbering	Use resin	1	Use resin 2	Mw (×1000)	Mn (×1000)	Tg (℃)	The temperature of expression Tan δ min (℃)	Tanδ min	G ' (* 10 during expression Tan δ min ⁵) (handkerchief)	10 ⁴Temperature during handkerchief δ (℃)	10 ⁴Tan δ during handkerchief δ
The resin numbering	Use resin	1	Use resin 2	Mw (×1000)	Mn (×1000)	Tg (℃)	The temperature of expression Tan δ min (℃)	Tanδ min	G ' (* 10 during expression Tan δ min ⁵) (handkerchief)	10 ⁴Temperature during handkerchief δ (℃)	10 ⁴Tan δ during handkerchief δ	(1)	A(100)	-	35.0	15.5	60.5	77.0	0.47	8.9	136.0	8.3
(2)	B(100)	-	14.3	7.2	56.2	71.0	0.97	6.6	104.5	17.6		(1)	A(100)	-	35.0	15.5	60.5	77.0	0.47	8.9	136.0	8.3
(2)	B(100)	-	14.3	7.2	56.2	71.0	0.97	6.6	104.5	17.6	(3)	C(100)	-	9.5	4.6	65.1	76.5	1.49	4.5	97.5	20.9
(4)	D(100)	-	17.3	7.3	67.3	85.0	0.91	6.5	113.0	10.2	(3)	C(100)	-	9.5	4.6	65.1	76.5	1.49	4.5	97.5	20.9
(4)	D(100)	-	17.3	7.3	67.3	85.0	0.91	6.5	113.0	10.2	(5)	E(100)	-	88.9	5.1	69.9	91.0	0.91	3.8	127.0	1.6
(6)	F(100)	-	17.4	6.6	68.2	85.5	1.13	4.5	111.0	12.7	(5)	E(100)	-	88.9	5.1	69.9	91.0	0.91	3.8	127.0	1.6
(6)	F(100)	-	17.4	6.6	68.2	85.5	1.13	4.5	111.0	12.7	(7)	G(100)	-	63.3	26.6	65	90.0	0.9	1.5	122.0	3.4
(8)	A(30)	B(70)	18.5	8.3	57.8	73.0	0.83	6.0	112.0	9.8	(7)	G(100)	-	63.3	26.6	65	90.0	0.9	1.5	122.0	3.4
(8)	A(30)	B(70)	18.5	8.3	57.8	73.0	0.83	6.0	112.0	9.8	(9)	A(50)	B(50)	23.4	9.6	58.6	73.5	0.72	6.2	117.0	7.9
(10)	A(50)	C(50)	18.1	6.7	65.2	77.0	0.89	6.6	111.0	9.6	(9)	A(50)	B(50)	23.4	9.6	58.6	73.5	0.72	6.2	117.0	7.9

Embodiment 1

(modulation 1 of toner)

According to the composition table of table 3, with the vibrin A of 28.8 weight portions, the vibrin B of 67.2 weight portions and the green pigment (dark blue-4933M: the Co., Ltd. that refines big day produces) of 4 weight portions, with Banbury mixing type mixing roll fusion mixing.Mixing thing is made thickness with stack be about tabular about 1 centimetre, this mill type comminutor coarse crushing of expense is to several millimeters level size again, and it is broken to carry out micro mist with IDS type comminutor successively again, carries out classification with the bent tube type grader, obtains toner.Use the hydrophobic silica powder (R972: Japanese Ai Luojielu Co., Ltd. system) add in the resulting toner, toner is modulated of 3 weight % again.

Equally, change colorant into magenta pigment (セイカ Off ア one スト fuchsin 1476T-7 from green pigment (dark blue-4933M: the Co., Ltd. that refines big day produces); Co., Ltd. that refines big day produces), yellow uitramarine (セイカ Off ア one スト Huang 2400; The Co., Ltd. that refines produced in big day) and carbon black (carbon black #25; Mitsubishi chemical Co., Ltd produces), make pinkish red toner, black toner and Yellow toner respectively, can obtain the four-color full-color colour toners.With resulting toner as toner A1.The size-grade distribution of toner can be measured with Coulter-counter TA-II type machine (Coulter Corporation's system).

Embodiment 2～4

According to the ratio of components shown in the table 3, the same with embodiment 1, make toner A2～A4.

Embodiment 5

Composition table according to table 3, the vibrin B of the vibrin A of 28.5 weight portions, 66.5 weight portions and the green pigment of 4 weight portions is (dark blue-4933M: Co., Ltd.'s system of refining big day), fusion mixing in Banbury mixing type mixing roll, from mixing, add the wax of 1 weight portion after 7 minutes, melting mixing is 8 minutes again.It is tabular about 1 centimetre that mixing thing is pressed into thickness with stack, and this grinding machine type comminutor coarse crushing of expense is to several millimeters level size again, and it is broken and carry out classification with the bent tube type grader to carry out micro mist with IDS type comminutor successively again, can obtain toner A5.With the hydrophobic silica powder of 3 weight % (R972: Japanese Ai Luojielu Co., Ltd. system) add in the resulting toner, toner is modulated.

Equally, from green pigment (dark blue-4933M: Co., Ltd. refines big day), change colorant into magenta pigment (セイカ Off ア one スト fuchsin 1476T-7; Big day Co., Ltd.'s system of refining), yellow uitramarine (セイカ Off ア one スト Huang 2400; Co., Ltd.'s system of refining big day) and carbon black (carbon black #25; Mitsubishi chemical Co., Ltd's system), makes pinkish red toner, black toner and Yellow toner respectively, can obtain the four-color full-color colour toners.

Embodiment 6～9

According to the ratio of components shown in the table 3, the same with embodiment 5, can make toner A6～A9.

Embodiment 10

Composition table according to table 3, the green pigment of the styrene resin H of the vibrin C of the vibrin A of 46.5 weight portions, 46.5 weight portions, 3.0 weight portions and 4 weight portions is (dark blue-4933M: Co., Ltd.'s system of refining big day), with Banbury mixing type mixing roll fusion mixing, it is tabular about 1 centimetre that mixing thing is pressed into thickness with stack, this grinding machine type comminutor coarse crushing of expense is to several millimeters level size then, it is broken to carry out micro mist with IDS type comminutor successively again, carry out classification with the bent tube type grader, can obtain toner A10.

Again with the hydrophobic silica powder of 3 weight % (R972: Japanese Ai Luojielu Co., Ltd. system), be added in the resulting toner, toner is modulated.

Equally, from green pigment (dark blue-4933M: Co., Ltd. refines big day), change colorant into magenta pigment (セイカ Off ア one スト fuchsin 1476T-7; Big day Co., Ltd.'s system of refining), yellow uitramarine (セイカ Off ア one スト Huang 2400; Co., Ltd.'s system of refining big day) and carbon black (carbon black #25; Mitsubishi chemical Co., Ltd's system), makes pinkish red toner, black toner and Yellow toner respectively, can obtain the four-color full-color colour toners.The size-grade distribution of toner is measured with the counter TA-II of Coulter Corporation type machine (Coulter Corporation's system).

Embodiment 11

Composition table according to table 3, the green pigment of the styrene-propene acid copolymer H of the vibrin C of the vibrin A of 45.5 weight portions, 45.5 weight portions, 4.0 weight portions and 4 weight portions is (dark blue-4933M: Co., Ltd.'s system of refining big day), with Banbury mixing type mixing roll fusion mixing, from mixing beginning after 7 minutes, the wax that adds 1 weight portion, melting mixing is 8 minutes again.Utilize stack, it is tabular about 1 centimetre that mixing thing is pressed into thickness, and this grinding machine type comminutor coarse crushing of expense is to several millimeters level size again, and it is broken to carry out micro mist with IDS type comminutor successively again, carries out classification with the bent tube type grader, can obtain toner A11.

Equally, from green pigment (dark blue-4933M: Co., Ltd. refines big day), change colorant into magenta pigment (セイカ Off ア one スト fuchsin 1476T-7; Big day Co., Ltd.'s system of refining), yellow uitramarine (セイカ Off ア one スト Huang 2400; Co., Ltd.'s system of refining big day) and carbon black (carbon black #25; Mitsubishi chemical Co., Ltd's system), makes pinkish red toner, black toner and Yellow toner respectively, then can obtain the four-color full-color colour toners.

Embodiment 12～14

According to the ratio of components shown in the table 3,, make toner A12～A14 with embodiment 11 the same carrying out.

Comparative example 1～4

According to the ratio of components shown in the table 4, the same with embodiment 1, make toner B1～B4.

Comparative example 5～8

According to the ratio of components shown in the table 4, the same with embodiment 5, make toner B5～B8.

Comparative example 9

According to the ratio of components shown in the table 4, the same with embodiment 11, make toner B9.

The pigment concentration of following table 3 and table 4 all is 4 weight %, and the wax in the table is the Carnauba wax that wild field wax Co., Ltd. makes.

Table 3: the photographic fixing test composition of toner

	The toner name	Use vibrin 1	Use vibrin 2	Use vinylite	Wax	Particle diameter (micron)	Reference resin numbering (table 2)
	The toner name	Use vibrin 1	Use vibrin 2	Use vinylite	Wax	Particle diameter (micron)	Reference resin numbering (table 2)	Embodiment 1	Toner A1	A(28.8)	B(67.2)	-	-	8.8	(8)
Embodiment 2	Toner A2	A(48.0)	B(48.0)	-	-	9.8	(9)	Embodiment 1	Toner A1	A(28.8)	B(67.2)	-	-	8.8	(8)
Embodiment 2	Toner A2	A(48.0)	B(48.0)	-	-	9.8	(9)	Embodiment 3	Toner A3	A(48.0)	C(48.0)	-	-	8.0	(10)
Embodiment 4	Toner A4	D(96.0)	-	-	-	10.3	(4)	Embodiment 3	Toner A3	A(48.0)	C(48.0)	-	-	8.0	(10)
Embodiment 4	Toner A4	D(96.0)	-	-	-	10.3	(4)	Embodiment 5	Toner A5	A(28.5)	B(66.5)	-	(1.0)	8.9	(8)
Embodiment 6	Toner A6	A(47.5)	B(47.5)	-	(1.0)	10.1	(9)	Embodiment 5	Toner A5	A(28.5)	B(66.5)	-	(1.0)	8.9	(8)
Embodiment 6	Toner A6	A(47.5)	B(47.5)	-	(1.0)	10.1	(9)	Embodiment 7	Toner A7	A(47.5)	C(47.5)	-	(1.0)	8.2	(10)
Embodiment 8	Toner A8	D(95.5)		-	(1.0)	10.5	(4)	Embodiment 7	Toner A7	A(47.5)	C(47.5)	-	(1.0)	8.2	(10)
Embodiment 8	Toner A8	D(95.5)		-	(1.0)	10.5	(4)	Embodiment 9	Toner A9	A(47.75)	C(47.75)	-	(0.5)	8.0	(10)
Embodiment 10	Toner A10	A(46.5)	C(46.5)	H(3.0)	-	7.3	(10)	Embodiment 9	Toner A9	A(47.75)	C(47.75)	-	(0.5)	8.0	(10)
Embodiment 10	Toner A10	A(46.5)	C(46.5)	H(3.0)	-	7.3	(10)	Embodiment 11	Toner A11	A(45.5)	C(45.5)	K(4.0)	(1.0)	7.6	(10)
Embodiment 12	Toner A12	D(88.0)	-	K(7.0)	(1.0)	7.5	(4)	Embodiment 11	Toner A11	A(45.5)	C(45.5)	K(4.0)	(1.0)	7.6	(10)
Embodiment 12	Toner A12	D(88.0)	-	K(7.0)	(1.0)	7.5	(4)	Embodiment 13	Toner A13	A(41.0)	B(41.0)	K(11.0)	(3.0)	7.3	(9)
Embodiment 14	Toner A14	A(43.5)	B(43.5)	L(8.0)	(1.0)	9.5	(9)	Embodiment 13	Toner A13	A(41.0)	B(41.0)	K(11.0)	(3.0)	7.3	(9)

Pigment concentration all is 4 weight %.Wax is refining Carnauba wax (wild field wax Co., Ltd. system)

Table 4: the photographic fixing test composition of toner

	The toner name	Use vibrin	1	Use vibrin 2	Use vinylite	Wax	Particle diameter (micron)	Reference resin numbering (table 2)
	The toner name	Use vibrin	1	Use vibrin 2	Use vinylite	Wax	Particle diameter (micron)	Reference resin numbering (table 2)	Comparative example 1	Toner B1	C(96.0)	-	-	-	7.6	(3)
Comparative example 2	Toner B2	E(96.0)	-	-	-	7.9	(5)		Comparative example 1	Toner B1	C(96.0)	-	-	-	7.6	(3)
Comparative example 2	Toner B2	E(96.0)	-	-	-	7.9	(5)	Comparative example 3	Toner B3	F(96.0)	-	-	-	8.8	(6)
Comparative example 4	Toner B4	G(96.0)	-	-	-	7.5	(7)	Comparative example 3	Toner B3	F(96.0)	-	-	-	8.8	(6)
Comparative example 4	Toner B4	G(96.0)	-	-	-	7.5	(7)	Comparative example 5	Toner B5	C(93.0)	-	-	(3.0)	7.6	(3)
Comparative example 6	Toner B6	E(93.0)	-	-	(3.0)	7.9	(5)	Comparative example 5	Toner B5	C(93.0)	-	-	(3.0)	7.6	(3)
Comparative example 6	Toner B6	E(93.0)	-	-	(3.0)	7.9	(5)	Comparative example 7	Toner B7	F(93.0)	-	-	(3.0)	8.9	(6)
Comparative example 8	Toner B8	G(93.0)	-	-	(3.0)	7.5	(7)	Comparative example 7	Toner B7	F(93.0)	-	-	(3.0)	8.9	(6)
Comparative example 8	Toner B8	G(93.0)	-	-	(3.0)	7.5	(7)	Comparative example 9	Toner B9	A(37.0)	C(37.0)	H(21.0)	(1.0)	6.8	(10)

The various toners that draw in the embodiment of 7 weight portions and the comparative example and the carrier of 93 weight portions are mixed, make electrophotographic developer.Carrier be resin-coated type carrier it be that will contain amino polyvinyl is overlayed on the ferrite iron core with the potpourri that contains the polyvinyl of fluorinated alkyl.

The image output device summary is introduced

Image output device uses the device of transforming A colour-635 (Fuji Xerox Co., Ltd's system) and drawing.The summary situation of Fig. 4 presentation video output unit.This image output device is for having photoreceptor 21, charged device 22, exposure device 23, middle copying body 24, four look developer 25a, 25b, 25c, 25d; The general full-color image output unit of dubs electrical equipment 26 and clearer 27.

Concrete experiment condition is: adopt Organophotoreceptor (diameter is 84 millimeters) as photoreceptor 21; Adopt LE400dpi as ROS; Processing speed is 160 mm/second; The sub-image current potential is-550 volts at the background position, and the image position is-150 volts; Developer roll (first to fourth developer is shared) is fixed for magnet, the sleeve revolution, and the magnetic flux density of magnet is 500 Gausses (on the sleeves), and sleeve diameter is 25 millimeters, and the sleeve speed of gyration is 300 mm/second; Photoreceptor 21 is spaced apart 0.5 millimeter with developer roll (first to fourth developer is shared); The interval (first to fourth developer is shared) that the bed thickness of developer layer limits member and developer roll is 0.5 millimeter; Development bias voltage (first to fourth developer is shared), DC (direct current) composition is-500 volts, AC (interchange) composition is 1.5kVP-P (8 kilo hertzs); Copy mode is that corona tube duplicates mode (diameter of wire is 85 microns), exports the image of not photographic fixing.

The making of uncertain image

Utilize above-mentioned image output device, the top ends of the chromatics paper of making in Fuji Xerox Co., Ltd (J paper), with the toning dosage of 1.0 milligrams/square centimeter and 2.5 milligrams/square centimeter, make the toner solid-state image of 50 millimeters * 50 millimeters sizes respectively, i.e. the image of photographic fixing not.

The evaluation of toner fixing

Use lining thickness on metal-cored is 2 millimeters silastic-layer, the external diameter that 25 microns PFA resin bed is arranged on its top layer is 50 millimeters a warm-up mill, with lining thickness on metal-cored be that the external diameter of one 25 microns PFA resin bed is arranged is the fuser that 50 millimeters pressure roll constitutes for silastic-layer, its top layer of 1 millimeter, getting shearing width is 6 millimeters, and photographic fixing pressure is that 6 kilogram/square centimeters are as condition.

Silicone oil is to be installed on the warm-up mill by the roller with impregnation silicone oil to carry out in the coating on the fuser.Utilize scraper plate control coating amount, its coating amount is opened A4 paper 0.1 milligram (1.7 * 10 for each ^-4Milligram/square centimeter).The silicone oil coating amount is to measure like this: blank sheet of paper by fuser, is utilized Soxhlet's extractor, and fuel-displaced with hexane as solvent extraction, utilize atomic absorption spectrum analysing arrangement to measure oil mass quantitatively again.

Use this fuser, the temperature of appropriate change fuser, uncertain image photographic fixing with various toners, the heat penetration of glossiness, the heat penetration of the image after the photographic fixing being printed and distributed living temperature again and being surpassed 40 temperature from glossiness is printed and distributed living temperature province and is defined as the photographic fixing tolerance, estimates the fixing performance of various toners.

Image glossiness after the photographic fixing can be utilized gloss tolerance line GM-26D (Co., Ltd. of color technical institute system in the village), measures penetrating under the angle of light on the test specimen is 75 ° condition.Heat penetration is not printed on and produces, and can at uncertain image after passing through on the blank sheet of paper blank sheet of paper be sent into fuser, the situation that toner adheres on the blank sheet of paper that detects by an unaided eye, and judge whether the heat penetration seal takes place.

Represented the result in following table 5 and the table 6.In " peeling off bad occurrence temperature " hurdle of table 5 and table 6, one " not peeling off " arranged is that expression is wound on the state on the fuser.

Table 5: photographic fixing test findings

		1.0 milligrams/square centimeter of toning dosage			2.5 milligrams/square centimeter of toning dosage
		1.0 milligrams/square centimeter of toning dosage			2.5 milligrams/square centimeter of toning dosage			Peel off bad temperature	The maximum glossiness that obtains	Tolerance	Peel off bad temperature	The maximum glossiness that obtains	Tolerance
		Embodiment						Peel off bad temperature	The maximum glossiness that obtains	Tolerance	Peel off bad temperature	The maximum glossiness that obtains	Tolerance
1	Toner A1	Embodiment	195	88	50	175	83	30
1	Toner A1	Embodiment 2	195	88	50	175	83	30	Toner A2	200	86	55	185	82	40
Embodiment 3	Toner A3	Embodiment 2	190	88	40	180	78	30	Toner A2	200	86	55	185	82	40
Embodiment 3	Toner A3	Embodiment 4	190	88	40	180	78	30	Toner A4	190	83	40	165	71	15
Embodiment 5	Toner A5	Embodiment 4	More than 220	85	More than 70	195	95	50	Toner A4	190	83	40	165	71	15
Embodiment 5	Toner A5	Embodiment 6	More than 220	85	More than 70	195	95	50	Toner A6	More than 220	86	More than 70	200	96	55
Embodiment 7	Toner A7	Embodiment 6	More than 220	84	More than 70	195	95	45	Toner A6	More than 220	86	More than 70	200	96	55
Embodiment 7	Toner A7	Embodiment 8	More than 220	84	More than 70	195	95	45	Toner A8	More than 220	85	More than 70	190	93	40
Embodiment 9	Toner A9	Embodiment 8	More than 220	83	More than 70	190	92	40	Toner A8	More than 220	85	More than 70	190	93	40
Embodiment 9	Toner A9	Embodiment 10	More than 220	83	More than 70	190	92	40	Toner A10	185	86	35	175	92	25
Embodiment 11	Toner A11	Embodiment 10	210	88	60	195	96	45	Toner A10	185	86	35	175	92	25
Embodiment 11	Toner A11	Embodiment 12	210	88	60	195	96	45	Toner A12	205	87	55	185	90	35
Embodiment 13	Toner A13	Embodiment 12	210	83	60	195	91	40	Toner A12	205	87	55	185	90	35
Embodiment 13	Toner A13	Embodiment 14	210	83	60	195	91	40	Toner A14	200	83	50	185	80	35

Table 6: photographic fixing test findings

		1.0 milligrams/square centimeter of toning dosage			2.5 milligrams/square centimeter of toning dosage
		1.0 milligrams/square centimeter of toning dosage			2.5 milligrams/square centimeter of toning dosage			Peel off bad temperature	The maximum glossiness that obtains	Tolerance	Peel off bad temperature	The maximum glossiness that obtains	Tolerance
		Comparative example 1	Toner B1	Unstripped	-	Do not have	Unstripped	Peel off bad temperature	The maximum glossiness that obtains	Tolerance	Peel off bad temperature	The maximum glossiness that obtains	Tolerance	-	Do not have
Comparative example 2	Toner B2	Comparative example 1	Toner B1	Unstripped	-	Do not have	Unstripped	Unstripped	-	Do not have	Unstripped	-	Do not have	-	Do not have
Comparative example 2	Toner B2	Comparative example 3	Toner B3	165	77	20	Unstripped	Unstripped	-	Do not have	Unstripped	-	Do not have	-	Do not have
Comparative example 4	Toner B4	Comparative example 3	Toner B3	165	77	20	Unstripped	Unstripped	-	Do not have	Unstripped	-	Do not have	-	Do not have
Comparative example 4	Toner B4	Comparative example 5	Toner B5	180	78	35	Unstripped	Unstripped	-	Do not have	Unstripped	-	Do not have	-	Do not have
Comparative example 6	Toner B6	Comparative example 5	Toner B5	180	78	35	Unstripped	175	78	35	Unstripped	-	Do not have	-	Do not have
Comparative example 6	Toner B6	Comparative example 7	Toner B7	180	54	20	Unstripped	175	78	35	Unstripped	-	Do not have	-	Do not have
Comparative example 8	Toner B8	Comparative example 7	Toner B7	180	54	20	Unstripped	Unstripped	-	Do not have	Unstripped	-	Do not have	-	Do not have
Comparative example 8	Toner B8	Comparative example 9	Toner B9	190	83	45	Unstripped	Unstripped	-	Do not have	Unstripped	-	Do not have	-	Do not have

So-called unstrippedly be meant that circumvolution is on the photographic fixing machine.

Toner fixing performance evaluation result

The fixing performance evaluation result of various toners is shown in above-mentioned table 5, table 6.

Minimal value (following be tan δ (min) value simply) at the tan δ of embodiment 1 to embodiment 4 resulting toner is littler than 1.2, and the polymerization density height owing to the strand of cementing agent makes the elasticity composition effect increase of the viscoelastic property of cementing agent.Because be added in the effect of the distortion on the toner when peeling off, toner vibrates as elastic body, therefore, image toning dosage much less after a little while, even in the toner bed thickness, also can peel off fully.

In addition, under the situation that contains micro-wax of embodiment 5 to embodiment 9, tolerance has also enlarged.As the tolerance of photographic fixing, generally, be preferably in more than 25 ℃ more than 15 ℃.The result of embodiment can be fully durable in practicality.

The toner of comparative example 1 is exactly the cementing agent that the existing toner of generally using as color copy machine uses.Because its tan δ (min) value is bigger than 1.2, the viscosity composition role of the viscoelastic property of cementing agent is big, therefore, when peeling off, be added in the distortion on the toner, toner is vibrated as elasticity, like this, even containing (comparative example 5) under the situation of wax, can not peel off, toner can be wound on the fixing roller.

Again, the toner of comparative example 3 has the toner molecular weight about equally with embodiment 4.Simultaneously,, make tan δ (min) value bigger than 1.2 owing to constitute the difference of the monomer of cementing agent, therefore, because the reason same with the toner of comparative example 1 can not be peeled off.The toner that contains the comparative example 7 of wax also because of same reason, under the few situation of image toning dosage, can be peeled off, and under the many situations of image toning dosage, can not peel off.

The toner of comparative example 2 has than 1.2 little tan δ (min), but cementing agent intermolecular be not polymerization, but form by cross-linked structure, therefore, by having the very wide distribution of forming in the cementing agent.Like this, when peeling off, because more than tan δ (min) value, viscoid plays vibration, when image toning dosage can not be peeled off for a long time.In addition, because its crosslinked composition, at G "=1 * 10 ⁴Tan δ value under the temperature of handkerchief is 1.6 little value, so glossiness can not rise.The toner that contains the comparative example 6 of wax also owing to same reason, under the few situation of image toning dosage, can be peeled off, and under the many situations of image toning dosage, can not peel off.

The tan δ (min) of the toner of comparative example 4 value is little than 1, is the influence of 1.5 little value owing to the G ' value under the temperature of tan δ (min), even the effect of the elasticity composition in the viscoelastic property of cementing agent is big, but because its absolute value is little, a little less than the bounce, therefore, can not peel off.The toner that contains the comparative example 8 of wax also owing to same reason, can not be peeled off.

The toner that is drawn among the embodiment 10 to 14 compares with the toner that does not contain vinyl resin, can do the diameter of sized particles very small.

In addition, the comminuted of the toner of the comparative example 9 that vinyl resin content is many improved greatly, but because the content of vibrin very little, can not effectively utilize the viscoelasticity that vibrin has, therefore, stripping performance significantly reduces.

Embodiment 15～22 and comparative example 10～13

The modulation 2 of toner

The same with the situation of the modulation 1 of toner, according to table 7, make toner A15～A22 of embodiment, the toner B10～B13 of comparative example.Relevant to table 3, as to repeat in table 4 and the table 5 toner can directly utilize the toner of modulating in (modulation 1 of toner).

The pigment concentration of following table 7 all is 4 weight %, and the wax PE in the table represents tetracontane.

Table 7: the photographic fixing test composition of toner

	The toner name	Use vibrin 1	Use vibrin 2	Use vinylite	Wax	Particle diameter (micron)	Reference resin numbering (table 2)
	The toner name	Use vibrin 1	Use vibrin 2	Use vinylite	Wax	Particle diameter (micron)	Reference resin numbering (table 2)	Embodiment 15	Toner A15	A(28.5)	B(66.5)	-	PE(1.0)	8.9	(8)
Embodiment 16	Toner A16	A(47.5)	B(47.5)	-	PE(1.0)	10.1	(9)	Embodiment 15	Toner A15	A(28.5)	B(66.5)	-	PE(1.0)	8.9	(8)
Embodiment 16	Toner A16	A(47.5)	B(47.5)	-	PE(1.0)	10.1	(9)	Embodiment 17	Toner A17	A(47.5)	C(47.5)	-	PE(1.0)	8.2	(10)
Embodiment 18	Toner A18	D(95.0)	-	-	PE(1.0)	10.2	(4)	Embodiment 17	Toner A17	A(47.5)	C(47.5)	-	PE(1.0)	8.2	(10)
Embodiment 18	Toner A18	D(95.0)	-	-	PE(1.0)	10.2	(4)	Embodiment 19	Toner A19	A(27.9)	B(65.1)	-	PE(3.0)	9.0	(8)
Embodiment 20	Toner A20	A(46.5)	B(46.5)	-	PE(3.0)	10.2	(9)	Embodiment 19	Toner A19	A(27.9)	B(65.1)	-	PE(3.0)	9.0	(8)
Embodiment 20	Toner A20	A(46.5)	B(46.5)	-	PE(3.0)	10.2	(9)	Embodiment 21	Toner A21	A(46.5)	C(46.5)	-	PE(3.0)	8.3	(10)
Embodiment 22	Toner A22	D(93.0)	-	-	PE(3.0)	10.6	(4)	Embodiment 21	Toner A21	A(46.5)	C(46.5)	-	PE(3.0)	8.3	(10)
Embodiment 22	Toner A22	D(93.0)	-	-	PE(3.0)	10.6	(4)	Comparative example 10	Toner B10	C(93.0)	-	-	PE(3.0)	7.6	(3)
Comparative example 11	Toner B11	F(93.0)	-	-	PE(3.0)	7.9	(5)	Comparative example 10	Toner B10	C(93.0)	-	-	PE(3.0)	7.6	(3)
Comparative example 11	Toner B11	F(93.0)	-	-	PE(3.0)	7.9	(5)	Comparative example 12	Toner B12	E(93.0)	-	-	PE(3.0)	8.8	(6)
Comparative example 13	Toner B13	G(93.0)	-	-	PE(3.0)	7.5	(7)	Comparative example 12	Toner B12	E(93.0)	-	-	PE(3.0)	8.8	(6)

The evaluation 2 of the fixing performance of toner

Except not being coated with on the fuser the unction fully, the same with the situation of (fixing performance of toner estimates 1), come the fixing performance of each toner of evaluation table 7.The result is illustrated in the table 8.In " peeling off bad occurrence temperature " hurdle in the table 8, not " not peeling off ", same with the situation of table 6, be the state of expression circumvolution on fuser.

Table 8: photographic fixing test findings

		1.0 milligrams/square centimeter of toning dosage			2.5 milligrams/square centimeter of toning dosage
		1.0 milligrams/square centimeter of toning dosage			2.5 milligrams/square centimeter of toning dosage			Peel off bad temperature	The maximum glossiness that obtains	Tolerance	Peel off bad temperature	The maximum glossiness that obtains	Tolerance
		Embodiment						Peel off bad temperature	The maximum glossiness that obtains	Tolerance	Peel off bad temperature	The maximum glossiness that obtains	Tolerance
15	Toner A15	Embodiment	200	85	55	190	83	30
15	Toner A15	Embodiment 16	200	85	55	190	83	30	Toner A16	205	86	60	195	82	40
Embodiment 17	Toner A17	Embodiment 16	195	84	45	190	78	30	Toner A16	205	86	60	195	82	40
Embodiment 17	Toner A17	Embodiment 18	195	84	45	190	78	30	Toner A18	195	85	45	190	71	15
Embodiment 19	Toner A19	Embodiment 18	More than 220	83	More than 70	195	95	50	Toner A18	195	85	45	190	71	15
Embodiment 19	Toner A19	Embodiment 20	More than 220	83	More than 70	195	95	50	Toner A20	More than 220	87	More than 70	200	96	55
Embodiment 21	Toner A21	Embodiment 20	More than 220	82	More than 70	200	95	45	Toner A20	More than 220	87	More than 70	200	96	55
Embodiment 21	Toner A21	Embodiment 22	More than 220	82	More than 70	200	95	45	Toner A22	More than 220	84	More than 70	195	93	40
Comparative example 10	Toner A10	Embodiment 22	165	75	35	Unstripped	-	Do not have	Toner A22	More than 220	84	More than 70	195	93	40
Comparative example 10	Toner A10	Comparative example 11	165	75	35	Unstripped	-	Do not have	Toner A11	170	45	10	Unstripped	-	Do not have
Comparative example 12	Toner A12	Comparative example 11	190	82	40	Unstripped	-	Do not have	Toner A11	170	45	10	Unstripped	-	Do not have
Comparative example 12	Toner A12	Comparative example 13	190	82	40	Unstripped	-	Do not have	Toner A13	Unstripped	-	Do not have	Unstripped	-	Do not have

The fixing performance evaluation result 2 of toner

The evaluation result of the fixing performance of various toners is as shown in table 8.The various toners that draw among the embodiment even do not using the demoulding with under the oil condition, have also obtained and the same good result of the evaluation result in (fixing performance of toner estimates 1).On the other hand, each toner that draws in the comparative example, the same with described in the fixing performance of the toner (estimate 1) particularly under the situation more than the image toning dosage, print through does not take place, but the fissility that is wound on the fuser is bad.

Embodiment 23

The making of toner

(1) adjustment of vibrin

With the vibrin A of 50 weight portions and the vibrin B of 50 weight portions, fusion mixing in Banbury type mixing roll, the vibrin AB that obtains mixing.

(2) making of dispersible pigment dispersion

With the hybrid polyester resin AB of 50 weight portions and the green pigment of 50 weight portions, dissolving and dispersion add beaded glass, in the dispersion machine of the puddle mixer formula of packing into again in the ethyl acetate of 150 weight portions.Cool off around the dispersion cup on one side, with high-speed stirred mode disperse 3 hour on one side.Continue on one side to stir, Yi Bian add an amount of ethyl acetate, adjusting pigment concentration is the dispersible pigment dispersion of 10 weight % again.

(3) making of the wax of corpusculed

The wax of 10 weight portions that will pulverize with mortar etc. in advance, in the ethyl acetate of 90 weight portions, disperse, in APV GAULIN HOMOGENIZER 15MR type high-pressure emulsification machine, use this dispersion liquid, at pressure is under 500 kilograms/square centimeter, carries out the corpusculed of wax.In micronize is carried out, suitably append the ethyl acetate that has volatilized.With resulting little dispersion liquid,, carry out corpusculed once more by same processing.Utilize laser diffraction/scattering particle size distribution device LA-700 (the hole field makes made), measure the wax granularity in resulting little dispersion liquid, be about 0.9 micron.

The dispersion liquid of the wax of the corpusculed made from the ethyl acetate dilution, makes the weight concentration of wax reach the concentration of 10 weight %.

(4) making of oil phase

The hybrid polyester resin AB of 87 weight portions is dissolved in the ethyl acetate of 200 weight portions, again with dispersible pigment dispersion (the resin concentration 10 weight % of this lysate and 40 weight portions, pigment concentration 10 weight %), and the dispersion liquid (wax concentration is 10 weight %) of the corpusculed wax of 50 weight portions is put into homogenizing mixer (Ai Si homogenizer, Japan Precise Machine Co., Ltd makes) in, speed rotation with 15000 rev/mins was stirred 2 minutes, modulated uniform oil phase.

(5) making 1 of water

With the lime carbonate (0.03 micron of mean grain size) of 60 weight portions and the pure water of 40 weight portions, stirred 4 days with bowl mill, make calcium carbonate aqueous solution.Utilize above-mentioned laser diffraction/scattering particle size distribution device LA-700 (the hole field makes made), measure the particle mean size of lime carbonate, be about 0.08 micron.

(6) making 2 of water

Utilize the pure water of 98 weight portions to dissolve the carboxymethyl cellulose (plug Lip river root BSH, Di-ichi Kogyo Seiyaku Co., Ltd.'s system) of 2 weight portions, make carboxymethyl cellulose aqueous solution.

(7) manufacture method of toner

With the oil phase (4) of 60 weight portions, the calcium carbonate aqueous solution (5) of 10 weight portions, the carboxymethyl cellulose aqueous solution of 30 weight portions (6) drops in the colloid mill (Japan Precise Machine Co., Ltd's manufacturing), is 1.5 millimeters in clearance gap, speed is 8000 rev/mins of rotations down, carries out 20 minutes emulsification.Secondly, above-mentioned emulsion is dropped in the rotary evaporator, under the decompression of room temperature 300 mm Hg, the desolventizing that carried out 3 hours is handled.Then, add 12 newton's hydrochloric acid, to the pH value be 2, remove lime carbonate from toner surface, add newton's NaOH again, to the pH value be 10, then, in ultrasonic cleaning bath, stir with stirring machine, continue to stir 1 hour.Carry out centrifugation again, its clarification part is carried out carrying out drying after three exchanges are cleaned, can obtain pigment content is 4 weight %, and wax content is 5% toner.

In the toner that is drawn, add the hydrophobic silica powder (R972: Japanese Ai Luojielu Co., Ltd. system), adjust toner of 3 weight %.The toner that draws is as toner A23.

Embodiment 24

Except replacing the vibrin B with vibrin C, the same with embodiment 23, make toner A24.

Embodiment 25

In the oil phase of (4) is made, except the dispersion liquid with hybrid polyester resin AC, dispersible pigment dispersion and corpusculed wax changes to 85 weight portions, 40 weight portions and 70 weight portions respectively, make that wax content reaches beyond the 7 weight % in the toner, similarly to Example 24, make toner A25.

Embodiment 26

In the oil phase of (4) is made, except respectively hybrid polyester resin AC, dispersible pigment dispersion and corpusculed wax dispersion being changed to 82 weight portions, 40 weight portions and 100 weight portions, wax content in the toner is reached beyond the 10 weight %, similarly to Example 24, make toner A26.

Toner duplicates the evaluation of efficient

When the duplicating efficient of measuring from photoreceptor to the middle copying body 1, with transparent splicing tape, take the toner image on the photoreceptor, utilize the color reflection of the concentration to measure this image then.Secondly, make toner image again, and toner image is duplicated to the middle copying body the same, utilize splicing tape, take this toner image, measure the concentration of this image.

Duplicating efficient can calculate as follows:

Duplicate efficient 1=(duplicating the toner image concentration that body is taked from the centre)/(the toner image concentration of taking from photoreceptor)

Equally, duplicating body from the centre can followingly calculate to the duplicating efficient of photocopying materials.

Duplicate efficient 2=(from duplicating the toner image concentration that body is taked)/(duplicating the toner image concentration that body is taked from the centre)

Final duplicating efficient is calculated as follows:

Final efficient=duplicating efficient 1 * duplicating the efficient 2 of duplicating

According to above formula, can estimate and utilize toner A20, toner A21 that mixing comminuting method makes and with the duplicating efficient of toner A23, toner A24, toner A25 and the toner A26 of seasoning making in the liquid.The composition of toner is illustrated in the table 9.The PE of the wax in the table 9 represents tetracontane.

Table 9: the photographic fixing test composition and the evaluation of toner

	The toner name	Use vibrin	1	Use vibrin 2	Duplicate efficient 1	Duplicate efficient 2	2.5 milligrams/square centimeter of toning dosage			Reference resin numbering (table 2)
							2.5 milligrams/square centimeter of toning dosage				Peel off bad occurrence temperature	The maximum glossiness that obtains	Tolerance
							Embodiment 20	Toner A20	A(46.5)		Peel off bad occurrence temperature	The maximum glossiness that obtains	Tolerance	B(46.5)	95	98	200	93	50	(9)
Embodiment 21	Toner A21	A(46.5)	C(46.5)	97	95	200	Embodiment 20	Toner A20	A(46.5)	93	45	(10)		B(46.5)	95	98	200	93	50	(9)
Embodiment 21	Toner A21	A(46.5)	C(46.5)	97	95	200	Embodiment 23	Toner A23	A(45.5)	93	45	(10)	B(45.5)	99	99	210	95	55	(9)
Embodiment 24	Toner A24	A(45.5)	C(45.5)	98	98	210	Embodiment 23	Toner A23	A(45.5)	94	55	(10)	B(45.5)	99	99	210	95	55	(9)
Embodiment 24	Toner A24	A(45.5)	C(45.5)	98	98	210	Embodiment 25	Toner A25	A(44.5)	94	55	(10)	C(44.5)	98	99	210	92	50	(10)
Embodiment 26	Toner A26	A(43.0)	C(43.0)	98	98	205	Embodiment 25	Toner A25	A(44.5)	89	45	(10)	C(44.5)	98	99	210	92	50	(10)

Duplicate the evaluation result of efficient

The evaluation result of duplicating efficient is as shown in table 9.Toner A20 that makes of mixing comminuting method and toner A21's, the duplicating efficient from photoreceptor 1 to middle copying body 4 is 95～97%, and duplicating body 4 to the duplicating efficient that is copied material 10 from the centre is 95～98%, and total duplicating efficient is 90～95%.This value does not have special problem on degenerating for picture quality, and residual toner can be removed with cleaning balde etc., and is no problem in the practicality.

On the other hand, the duplicating efficient from photoreceptor 1 to middle copying body 4 with toner A23, toner A24, toner A25 and the toner A26 of seasoning making in the liquid is 98～99%, duplicating body 4 to the duplicating efficient that is copied material 10 from the centre is 98～99%, total duplicating efficient reaches 96～98%, has shown very high duplicating efficient.This be because, when making toner with seasoning in the liquid, globulate can be roughly done in the formation of toner, so just can reduce the contact area of photoreceptor and duplicating body.In addition, even under the situation of toner A23, toner A24, toner A25 and toner A26, also, has sufficient photographic fixing tolerance with (fixing performance of toner estimates 2) the same evaluation.

The thermal chokes and the OHP light transmission of the various toners shown in the present evaluation table 9.

The evaluation of thermal chokes

The toners of 5 grams were placed 17 hours in 40 ℃, the container of 50%RH.After returning back to room temperature, it is in 45 microns the screen cloth that the toners of 2 grams are dropped into mesh sizes, vibration under certain condition.Measure residual toner weight on the screen cloth, calculate weight ratio with respect to charge weight.With the thermal chokes index of this numerical value as toner.Table 10 has been represented evaluation result.

The OHP light transmission is estimated

In (the fixing performance evaluation of toner), except use OHP (Fuji Xerox Co., Ltd's system) conduct with the black and white toner by fixing member, getting toner is monochromatic cyan toner, image toning dosage is 0.7 milligram/square centimeter, the processing speed of fuser is beyond 50 mm/second, the same with (fixing performance of toner estimates 1), various toners are carried out photographic fixing.Utilize spectrophotometer U-3210 (Hitachi's system, wavelength 480 nanometers) to measure the transmittance of photographic fixing image.Measure the transmittance of resulting high gloss.Evaluation result is listed in the table 10.

Table 10: the photographic fixing test composition and the evaluation of toner

	The toner name	Use vibrin	1	Use vibrin 2	Wax	Particle diameter (micron)	Thermal chokes index (%)	OHP light transmission (%)	Reference resin numbering (table 2)
	The toner name	Use vibrin	1	Use vibrin 2	Wax	Particle diameter (micron)	Thermal chokes index (%)	OHP light transmission (%)	Reference resin numbering (table 2)	Embodiment 20	Toner A20	A(46.5)	B(46.5)	PE(3.0)	10.2	5.7	92	(9)
Embodiment 21	Toner A21	A(46.5)	C(46.5)	PE(3.0)	8.3	4.9	93	(10)		Embodiment 20	Toner A20	A(46.5)	B(46.5)	PE(3.0)	10.2	5.7	92	(9)
Embodiment 21	Toner A21	A(46.5)	C(46.5)	PE(3.0)	8.3	4.9	93	(10)	Embodiment 23	Toner A23	A(45.5)	B(45.5)	PE(5.0)	7.3	4.1	89	(9)
Embodiment 24	Toner A24	A(45.5)	C(45.5)	PE(5.0)	7.6	3.3	88	(10)	Embodiment 23	Toner A23	A(45.5)	B(45.5)	PE(5.0)	7.3	4.1	89	(9)
Embodiment 24	Toner A24	A(45.5)	C(45.5)	PE(5.0)	7.6	3.3	88	(10)	Embodiment 25	Toner A25	A(44.5)	C(44.5)	PE(7.0)	7.5	3.1	86	(10)
Embodiment 26	Toner A26	A(43.0)	C(43.0)	PE(10.0)	7.6	3.3	80	(10)	Embodiment 25	Toner A25	A(44.5)	C(44.5)	PE(7.0)	7.5	3.1	86	(10)

The evaluation result of thermal chokes and OHP light transmission

Can find out that from table 10 thermal chokes of various toners is all very good.When the thermal chokes index 10% when above, on actual machine, use the problem that has.Yet toner of the present invention has shown the practical extraordinary value that.Particularly more excellent with the thermal chokes exponential quantity of the toner of seasoning making in the liquid.On the other hand, for the OHP light transmission, when the wax that contains is when 10 weight % are above, the OHP light transmission begins to reduce, if in the practicality more than 80%, just no problem.Each toner in the table 10 has all shown the practical well value that goes up.

Durability evaluation

The toner A3 that uses embodiment 3 to draw carries out consecutive image output and photographic fixing.Image output device and fixing device use and (toner fixing performance evaluation 1) same device, the two is connected use.After 100,000 images were exported continuously, confusion did not take place in image yet, did not change than almost having with preliminary phase, and image is fine.In addition, when photographic fixing, phenomenons such as print through and circumvolution do not take place yet, fixing roller is also pollution-free.

Secondly, utilize the toner A11 that draws among the embodiment 11 again, same, carry out image output and photographic fixing continuously.After exporting 5000 images continuously, confusion does not take place in image yet, does not change than almost having with preliminary phase, and image is fine.In addition, phenomenons such as print through and circumvolution do not take place during photographic fixing yet, fixing roller is pollution-free.

Embodiment 27

The PET film that will not form the development layer of 100 micron thickness is directly used in picture appraisal.For control surface resistance, using the alkyl acid phosphate with 1 weight portion is surfactant, and the solution that dissolving obtains in the toluene of 100 weight portions spreads upon on the PET film with the rod-type coater, carries out drying, produces and is copied film.This film that is copied is called film A.The sheet resistance value of film A is 8.0 * 10 ¹⁰Ohm-sq centimetre.

Embodiment 28

Utilize the rod-type coater, amorphous polyester resin A, the amorphous polyester resin B of 14 weight portions that 6 weight portions are drawn in the synthetic example of vibrin and the alkyl acid phosphate of 1 weight portion are surfactant, in the toluene of 100 weight portions, dissolve, the solution that draws, spread upon on the PET film, after the drying, produce and be copied film B.The viscoelastic property value of the resin of development layer is the same with the resin numbering (8) of table 2.

Embodiment 29

Except the amorphous polyester resin A that uses 10 weight portions and the amorphous polyester resin B of 10 weight portions, the same with embodiment 24 beyond the thermoplastic resin that forms the layer that develops, making and evaluation are copied film C.The viscoelastic property value of the development layer resin of film C is the same with the resin of table 2 numbering (9).

Embodiment 30

Except the amorphous polyester resin B with 20 weight portions, the same with embodiment 24 beyond the thermoplastic resin that forms the layer that develops, making and evaluation are copied film D.The viscoelastic property value of the development layer resin of film D is the same with the resin of table 2 numbering (2).

Embodiment 31

Except the thermoplastic resin of amorphous polyester resin F as formation development layer with 20 weight portions, the same with embodiment 24, making and evaluation are copied film E.The viscoelastic property value of the development layer resin of film E is the same with the resin of table 2 numbering (6).

Anti-print through evaluation

Utilize the toner A6 that draws among the embodiment 6 as toner, the same with above-mentioned image output method, with 2.5 milligrams/square centimeter toning dosage, on each film that in embodiment 27～embodiment 31, draws, make solid-state uncertain image.The fuser that use is used in above-mentioned toner fixing performance evaluation, and same release agent application are 50 mm/second in the feed rate of paper, under 170 ℃, the film that forms uncertain image are carried out photographic fixing.After film passes through, blank sheet of paper is passed through, under the situation of adhering toner on the blank sheet of paper, judge whether to produce print through.Whether layer be transparent because develop, and can't with the naked eye confirm on blank sheet of paper, therefore, sees on the film surface after the photographic fixing whether produce fluctuating, or have debase phenomenon such as streak to confirm the print through that film develops layer on the layer that develops.

Light transmission is estimated

The toner A6 that use draws in embodiment 6 is as toner, and is the same with above-mentioned image output method, with 0.7 milligram/square centimeter toning dosage, makes the image area rate and reach 20% the uncertain image of shadow tone on film.The same with above-mentioned OHP light transmission evaluation, carry out the evaluation of light transmission.

The evaluation result of anti-print through and light transmission

The evaluation result of table 11 anti-print through of expression and light transmission.Because half tone image is different with solid-state image, the marginal portion of toner is many, and therefore, the light transmission of half tone image portion is lower than solid-state image usually.Therefore, in the half tone image portion, light transmission is being lowest term more than 70%, when 80% when above, can obtain and original equal colour rendering characteristic.On the contrary, reduce to 70% when following, projected image grizzle and color muddiness when transmittance.

Table 11: the anti-print through and the light transmission evaluation result that are copied film

	Film	Print through	Light transmission (%)	Reference resin numbering (table 2)
	Film	Print through	Light transmission (%)	Reference resin numbering (table 2)	Embodiment 27	A	Do not have	76	Do not have
Embodiment 28	B	Do not have	88	(8)	Embodiment 27	A	Do not have	76	Do not have
Embodiment 28	B	Do not have	88	(8)	Embodiment 29	C	Do not have	88	(9)
Embodiment 30	D	Do not have	85	(2)	Embodiment 29	C	Do not have	88	(9)
Embodiment 30	D	Do not have	85	(2)	Embodiment 31	E	Do not have	86	(6)

When considering the above, as can be seen from Table 11, under the situation that is copied film A that in using the embodiment 27 that does not form the layer that develops, draws, some muddiness of projected image when forming half tone image, and using by forming the film that develops layer with toner identical materials of the present invention, carry out under the situation of imaging (embodiment 28～embodiment 31), the image light transmission that is drawn is good, can obtain not having the projected image of muddy distinctness.

In addition, can find out that as long as use toner of the present invention, no matter how be copied film, anti-print through is all good from embodiment 27～embodiment 31.Can on image, not produce in addition because the problem that photographic fixing or the picture quality that causes such as charged degenerate.

Electrophoto-graphic toner of the present invention goes for color toner, can be with carrying out photographic fixing with the same release agent coating amount of black and white toner fixing, and the picture quality height, colour rendering is good, and reliability and permanance are all good.In addition, use the picture quality of electrophotographic developer of toner of this electrophotography also high, colour rendering is good.

In addition, in the scope of the characteristic of not damaging vibrin,, can further improve manufacturing property by contain vinyl resin auxiliaryly.

In addition, this electrophotographic developer of the application of the invention is as the formation method of developer, can obtain picture quality height, image that colour rendering is good.Because release agent is little to the influence that is copied body, so the processability of recording materials is also superior.

Claims

1. electrophoto-graphic toner, it contains binding resin and colorant, it is characterized in that, above-mentioned binding resin with respect to 100 weight portions, colorant is 1～30 weight portion, above-mentioned binding resin by (1) with from terephthalic acid (TPA), m-phthalic acid, cyclohexane dicarboxylic acid, naphthalene dicarboxylic acids, the dicarboxylic acid composition that chooses in the xenyl dicarboxylic acid and from ethylene glycol, propylene glycol, own cycloalkanes dimethanol, the glycol composition of selecting in the ethylene oxide adduct of bisphenol-A is a main body, do not have the linear polyester resin of cross-linked structure to account for the styrene of binding resin general assembly (TW) 0.5～20 weight % and the copolymer resins formation of n-butyl acrylate or the formation of tert-butyl group acrylate with (2) in molecule, this binding resin is at glass temperature Tg～loss elastic modulus G "=1 * 10 ⁴Have the minimal value of dissipation factor in the temperature range of being afraid of, this dissipation factor minimal value is 0.47～1.2, and the storage elastic modulus under the minimizing temperature of this dissipation factor is G '=5 * 10 ⁵～8.9 * 10 ⁵Handkerchief, and, at G "=1 * 10 ⁴Loss factor values under the temperature of handkerchief is 3.0～20.9, and the number-average molecular weight Mn of above-mentioned polyester is 6,000～10,000, and weight-average molecular weight Mw is 15,000～25,000, the weight-average molecular weight of above-mentioned copolymer resins is 1,000～50,000.

2. electrophoto-graphic toner as claimed in claim 1 is characterized in that, above-mentioned electrophoto-graphic toner is made of wet type toner autofrettage.

3. electrophoto-graphic toner as claimed in claim 1 is characterized in that it also contains the wax of 0.1～7 weight %.

4. electrophotographic developer, it is characterized in that, it contains described electrophoto-graphic toner of claim 1 and carrier, and described carrier is resin-coated carrier, and this carrier is by the polyvinyl that contains fluorinated alkyl and contains amino polyvinyl lining and form.

5. formation method, it is included in the operation that forms sub-image on the latent image carrier; Use the operation of electrophotographic developer with above-mentioned image development; Duplicate the toner image that develops in the operation that is copied body and will be copied the photographic fixing operation that toner image on the body adds thermo-compressed; It is characterized in that above-mentioned electrophotographic developer is the described electrophotographic developer of claim 4.

6. formation method as claimed in claim 5 is characterized in that, above-mentioned development layer contains wax.

7. formation method as claimed in claim 5, it is characterized in that, above-mentioned photographic fixing operation is to use the contact-type heat-fixing device that contains fluororesin on the fixing member surface to carry out, and this fluororesin is selected from perfluor alkyl ethide ether copolymer resin or fluorinated vinylidene resin.

8. formation method as claimed in claim 5 is characterized in that, above-mentioned photographic fixing operation is to use heat-fixing device, not oiling on the fixing member surface, or with 1.6 * 10 ^-5～8.0 * 10 ^-4The oily coating amount of milligram/square centimeter carries out.