CN101334597A - Polyester resin composition for toner and toner - Google Patents

Abstract

A toner resin composition, a toner containing the toner resin composition as adhereing resin, the toner resin composition comprising a linear polyester resin (A) containing a C3 to C10 aliphatic diol component and a linear polyester resin (B) containing a C3 to C10 aliphatic diol component which differs from the linear polyester resin (A), or further comprising a vinyl-based resin (C), and a toner containing the toner resin composition as a binding resin. A toner excellent in low temperature fixability, offset resistance, gloss, etc. and excellent in range of fixing temperature can be obtained.

Description

Polyester resin composition for toner and toner

The application is based on dividing an application of following Chinese patent application:

The original bill applying date: on Dec 17th, 2003

Original bill application number: 200380106424.6 (PCT/JP2003/016179)

Original bill application title: polyester resin composition for toner and toner

Technical field

The present invention relates to a kind of toner (toner) with vibrin and resin combination and contain these vibrin and resin combination as the toner of adhering resin.Especially, the invention provides a kind of development of electrostatic image and magnetic sub-image, toner of in xerography, electrostatic recording and videograph etc., being used to superior low-temperature fixing, un-offset property, glossiness etc.

Background technology

Obtaining according to electrophotographic printing method and development of static charge method in the method for image, be formed at electrostatic image on the photoreceptor in advance after the toner development by frictional electrification, carrying out the photographic fixing operation by allowing.About the photographic fixing mode, warm-up mill mode and noncontact photographic fixing mode are arranged, the former for the toner that will obtain by development with the roller after pressurization and the heating as photographic fixing, the latter is for using Electric heat oven and the light beam that glistens comes photographic fixing.Pass through smoothly for these programs are not gone wrong, toner at first must keep certain carried charge, secondly must have good fixation performance to paper.Again, have photographic fixing portion in the device,, must make toner be unlikely to caking because of temperature in installing rises as calandria.Recently, because energy-conservationization requirement, the warm-up mill mode is more and more to the low temperature development.For this reason, for toner, require it to have the fixing performance on paper under lower temperature, promptly the requirement of so-called low-temperature fixing is more and more stronger.Have again, recently,, begin to seek to form the toner of the image that has gloss along with popularizing of full color electronic photographing system.

Toner can bring very big influence to above-mentioned toner characteristic with adhering resin, and known, toner has polystyrene resin, styrene acrylic resin, vibrin, epoxy resin, polyamide etc. with adhering resin.Recently, vibrin be owing to can reach good balance on the transparency and fixation performance, and transparent superior, and the full color toner is had suitable characteristic, and therefore, vibrin is attracted attention especially.

But, for with the toner of polyester resin as adhering resin, for optimizing its fixation performance, open flat 4-12367 communique and special open clear 59-128558 communique and put down in writing as Japanese publication spy, proposition is by the scheme of monomer improvement fixation performance, but it is big that this scheme exists the molecular resin amount that obtains, and can not get the such problem of fixation performance of target call.

Again, open flat 7-140714 communique, spy as Japanese publication spy and open that 2002-287427 communique, spy are opened the 2002-202634 communique, the spy opens records such as flat 4-313760 communique, the method that proposal mixes softening temperature, the different vibrin of molecular weight, but, except being difficult to adjust the balance of fixation performance and un-offset property, the problem that this method exists high molecular weight components and is difficult to as the adjusting of the monomer component of the adjusting of bisphenol-a derivative composition, unsaturated fatty acid and so on and glossiness to carry out.

Again, open flat 4-362956 communique, spy Japanese publication spy and open in the flat 8-320593 communique etc., attempt in the non-linearity polyester, sneaking into low-melting linear polyesters and improve low-temperature fixing.Again, opening flat 10-339969 communique, spy Japanese publication spy opens in the 2000-305316 communique etc. and has studied the method for using linear polyesters.

Again, open in the flat 8-30027 communique Japanese publication spy, the resin of handling low-temperature fixing has well been proposed, but exist low-temperature fixing and comminuted between balance insufficient, and be the such problem of durability not insufficient of target with long-term wear resistance.

According to these technology etc., though existing people is at the improved resin for toner of exploitation fixation performance, but market is more and more higher for the requirement of fixation performance, according to above-mentioned technology, still untappedly go out such resin, described resin had both had necessary characteristics such as anti-caking capacity and un-offset property, simultaneously, can satisfy the low-temperature fixing and the glossiness of market demands again.

Recently, the consideration of energy-conservationization is become must condition, and photographic fixing portion is more and more to the low temperature development in the warm-up mill mode.Therefore, for toner under lower temperature the fixation performance on paper, be that the requirement of so-called low-temperature fixing is more and more stronger.Owing to require wide relatively opereating specification, therefore, also require more and more wideer as (value) amplitude of the fixing temperature of toner again.

For example, open in the flat 4-362956 communique, studied adhering resin non-linearity polyester and linear polyesters and usefulness Japanese publication spy.Concrete, the document disclosed with softening temperature 110～116 ℃ non-linearity polyester and softening point 85～102 ℃ linear polyesters and usefulness, the fixing temperature amplitude is at the toner more than 50 ℃.But though that the spy opens the fixing temperature amplitude of this toner of putting down in writing in the flat 4-362956 communique is wide, its minimum fixing temperature is up to more than 150 ℃, and low-temperature fixing still is insufficient.

Open in the flat 4-313760 communique Japanese publication spy, studied the adhering resin of 2 kinds of linear polyesters that softening point is different and usefulness.Concrete, disclosed with softening temperature 112～123 ℃ high softening-point linear polyesters and softening point 89～92 ℃ low softening point linear polyesters and with, fixing temperature amplitude at the toner more than 30 ℃.But the spy opens the minimum fixing temperature of this toner of putting down in writing in the flat 4-313760 communique up to more than 150 ℃, and low-temperature fixing still is bad.

Therefore, in view of high speed, miniaturization, energy-conservationization of nearest duplicating machine, expectation can have the expansion of better low-temperature fixing and fixing temperature amplitude.

Summary of the invention

Therefore, the objective of the invention is to, provide a kind of solve the problem points of above-mentioned conventional art, again can bring have superior low-temperature fixing, the polyester resin for toner and the resin combination of the toner of un-offset property, glossiness etc. and good fixing temperature amplitude, and the toner that uses these vibrin and resin combination.

Promptly, the 1st invention that the present invention relates to is the resin for toner composition and contains the toner of this resin for toner composition as adhering resin, described resin for toner composition contains linear polyester resin (A) and linear polyester resin (B), linear polyester resin A is that to contain carbon number be 3～10 aliphatic dihydroxy alcohol composition, and linear polyester resin B is that to contain carbon number be 3～10 aliphatic dihydroxy alcohol composition, the linear polyester resin that is different from linear polyester resin (A); All acid composition in each resin is 100 molar part, and (molar part of the aliphatic dihydroxy alcohol of carbon number 3～10 in the linear polyester resin (B))/(molar part of the aliphatic dihydroxy alcohol of carbon number 3～10 in the linear polyester resin (A)) is in 0.5～10 scope.

Again, the 2nd invention that the present invention relates to is the resin for toner composition and contains the toner of this resin for toner composition as adhering resin, described resin for toner composition contains linear polyester resin (A), linear polyester resin (B) and vinylite (C), it is 3～10 aliphatic dihydroxy alcohol composition that linear polyester resin A contains carbon number, and linear polyester resin B is that to contain carbon number be 3～10 aliphatic dihydroxy alcohol composition, the linear polyester resin that is different from linear polyester resin (A); All acid composition in each resin is 100 molar part, and (molar part of the aliphatic dihydroxy alcohol of carbon number 3～10 in the linear polyester resin (B))/(molar part of the aliphatic dihydroxy alcohol of carbon number 3～10 in the linear polyester resin (A)) is in 0.5～10 scope.

Again, the 3rd invention that the present invention relates to is toner with linear polyester resin (a1) and contains this toner with the toner of linear polyester resin as adhering resin, described toner is 100 molar part with linear polyester resin (a1) in whole carboxylic acid compositions, contains aliphatic dihydroxy alcohol 10～60 molar part of carbon number 3～10; Its glass temperature is at 50～75 ℃, and its quality average molecular weight Mw is 25,000～100,000 scope, and for there not being the resin of fusing point, and its softening temperature is 150～220 ℃ of scopes, and acid number is below 10mgKOH/g.

Again, the 4th invention that the present invention relates to is toner with linear polyester resin (b1) and contains this toner with the toner of linear polyester resin as adhering resin that described toner is the linear polyester resin that is made of dicarboxylic acid composition and glycol component with linear polyester resin (b1); Aromatic carboxylic acid is all accounting for 50 moles more than the % among the carboxylic acid composition, and reaching in whole carboxylic acid compositions is 100 molar part, and the aliphatic dihydroxy alcohol content of carbon number 4～8 is more than 60 molar part; This resin be glass temperature 40～70 ℃ of scopes, the quality average molecular weight Mw is 4,000～10,000 scope do not have the resin of fusing point, and softening temperature is 90～120 ℃ of scopes.

Again, the 5th invention that the present invention relates to is that a kind of toner reaches the adhering resin that uses in this toner, toner is the toner that contains adhering resin and colorant, the major component of adhering resin by vibrin constitute, this vibrin contains vibrin (X) and vibrin (Y), the match ratio of vibrin (X) and vibrin (Y) is 5/95～95/5 (mass ratio), vibrin (X) is that the quality average molecular weight Mw is 25,000～100,000 scope, softening temperature are at 150～220 ℃ linear polyester resin; And vibrin (Y) be the quality average molecular weight Mw 2,000～10, the linear polyester resin in 000 scope; Minimum fixing temperature is below 130 ℃, and (value) amplitude of fixing temperature is more than 40 ℃.

According to the present invention, can obtain a kind of polyester resin for toner and resin combination, described polyester resin for toner and resin combination have superior low-temperature fixing, un-offset property, glossiness etc., toner with good fixing temperature amplitude can be provided, adopt that this polyester resin for toner can obtain to have superior low-temperature fixing, un-offset property, glossiness etc. and toner with good fixing temperature amplitude.

Embodiment

At first, do following explanation about the 1st～4 invention.

In the 1st～4 invention that the present invention relates in employed linear polyester resin (A) and the linear polyester resin (B), containing as carbon number that must composition is 3～10 aliphatic dihydroxy alcohol.

Owing to contain specific examples of such components, can make resulting toner have superior fixation performance for paper.Carbon number is that 3～10 aliphatic dihydroxy alcohol can suitably be selected as required, but preferably selects at least a from neopentyl glycol, propylene glycol and cyclohexanedimethanol.These compositions may be used alone, two or more kinds can also be used.

In linear polyester resin (A) and linear polyester resin (B), carbon number is the content of 3～10 aliphatic dihydroxy alcohol composition, count the occasion of 100 molar part at all acid composition of each resin, (molar part of the aliphatic dihydroxy alcohol of carbon number 3～10 in the linear polyester resin (B))/(molar part of the aliphatic dihydroxy alcohol of carbon number 3～10 in the linear polyester resin (A)) must be in 0.5～10 scope.This be because, if this ratio less than 0.5, the un-offset property of toner just has the tendency of variation.Above-mentioned ratio is preferably more than 0.9, and better is more than 1.Again, if this ratio surpasses 10, the un-offset property of toner just has the tendency of variation.Above-mentioned odds ratio is comparatively ideal to be below 7, it would be desirable below 6.

Linear polyester resin (A) if all acid composition is counted under the situation of 100 molar part, preferably contains aliphatic dihydroxy alcohol 10～60 molar part of carbon number 3～10.This be because, if this component content more than 10 molar part, then the fixation performance of toner just has the tendency of optimization.More than preferred 15 molar part of mentioned component content.Again, if mentioned component content below 60 molar part, then the fixation performance of toner just has the tendency of optimization.Below preferred 55 molar part of mentioned component content.

Linear polyester resin (B) as if the occasion of all acid composition being counted 100 molar part, preferably contains aliphatic dihydroxy alcohol 55～100 molar part of carbon number 3～10.This be because, if this component content more than 55 molar part, then the fixation performance of toner just has the tendency of optimization.More than preferred 60 molar part of mentioned component content.Again, if mentioned component content below 100 molar part, then the fixation performance of toner just has the tendency of optimization.Below preferred 95 molar part.

As operable other the glycol component of the constituent of linear polyester resin (A) and linear polyester resin (B), for example have, polyoxyethylene-(2.0)-2, two (4-hydroxy phenyl) propane of 2-, polyoxypropylene-(2.0)-2, two (4-hydroxy phenyl) propane of 2-, polyoxypropylene-(2.2)-polyoxyethylene-(2.0)-2, two (4-hydroxy phenyl) propane of 2-, polyoxypropylene-(6)-2, two (4-hydroxy phenyl) propane of 2-, polyoxypropylene-(2.2)-2, two (4-hydroxy phenyl) propane of 2-, polyoxypropylene-(2.4)-2, two (4-hydroxy phenyl) propane of 2-, polyoxypropylene-(3.3)-2, aromatic diol compositions such as two (4-hydroxy phenyl) propane of 2-, these compositions may be used alone, can also be two or more kinds in combination.Because the aromatic diol composition has the effect of the glass temperature that improves resin, it is used as constituent, the anti-caking capacity of the toner that obtains has the tendency of raising.Especially, the number n of preferred polyoxypropylene unit or polyoxyethylene unit is the polyoxypropylene of 2.1≤n≤8-(n)-2, and two (4-hydroxy phenyl) propane of 2-and/or n are the polyoxyethylene-(n)-2 of 2.0≤n≤3.0, two (4-hydroxy phenyl) propane of 2-.

On the other hand, these aromatic diol compositions, exist the possibility that the glossiness to the toner that obtains has a negative impact, therefore, its use amount, if in all acid composition is 100 molar part, below preferred 10 molar part of linear polyester resin (A), below preferred 50 molar part of linear polyester resin (B).

The glycol component of available other also can be exemplified below: ethylene glycol, hydrogenated bisphenol A etc.These compositions can be distinguished separately and use, and also can more than 2 kinds and use.

As the constituent of linear polyester resin (A) and linear polyester resin (B), available is exemplified below: the composition that is selected from terephthalic acid (TPA), m-phthalic acid or their lower alkyl esters etc.As the instantiation of terephthalic acid (TPA), m-phthalic acid and their lower alkyl esters, terephthalic acid (TPA) dimethyl esters, m-phthalic acid dimethyl esters, terephthalic acid (TPA) diethyl ester, m-phthalic acid diethyl ester, terephthalic acid (TPA) dibutyl ester, m-phthalic acid dibutyl ester etc. are arranged.But consider preferred terephthalic acid (TPA) and m-phthalic acid from operability and cost.These dicarboxylic acid and their lower alkyl esters can be distinguished separately and use, and also can make up more than 2 kinds and use.

Useful dicarboxylic acid composition as other can be exemplified below: phthalic acid, decanedioic acid, isodecyl succinic acid, dodecylene succinic acid, maleic acid, fumaric acid, hexane diacid or their monomethyl ester, single ethyl ester, dimethyl esters or diethyl ester and their acid anhydrides.These dicarboxylic acid compositions, because of relevant with the such fundamental characteristics of the fixation performance of toner and anti-caking capacity, therefore, in the scope of not damaging the object of the invention, performance is used aptly as requested.

The preferred softening temperature of linear polyester resin (A) is 150～220 ℃ of scopes.This be because, if softening temperature more than 150 ℃, then the un-offset property of toner just has the tendency of optimization.Be more preferably, softening temperature is more than 160 ℃, and best is that softening temperature is more than 170 ℃.Again, if softening temperature below 220 ℃, then the fixation performance of toner just has the tendency of optimization.Be more preferably, softening temperature is below 210 ℃, and best is that softening temperature is below 200 ℃.

Again, linear polyester resin (A) preferred glass temperature (to call Tg in the following text) is 50～75 ℃ of scopes.This be because, if Tg more than 50 ℃, the anti-caking capacity of toner just has the tendency of optimization.Preferred more than 52 ℃.On the other hand, if Tg below 75 ℃, the anti-caking capacity of toner just has the tendency of optimization.Preferred below 73 ℃.

The quality average molecular weight Mw of linear polyester resin (A) is preferably 25,000～10, in 000 scope.This be because, if the quality mean molecular weight more than 25,000, the un-offset property of toner just has the tendency of optimization.Preferably preferred more than 29,000.If the quality average molecular weight Mw is below 100,000, the un-offset property of toner just has the tendency of optimization.Preferably preferred below 90,000.

Again, the excellent resin that does not preferably have fusing point of linear polyester resin (A).If linear polyester resin (A) does not have fusing point, then the fixation performance of toner and glossiness just have the tendency of optimization.

Again, the acid number of linear polyester resin (A) is preferably below 10mgKOH/g.Thus, can make the image color of toner be difficult for reducing.

Particularly, the polyester resin for toner (a) that preferably has following characteristics: contain the aliphatic dihydroxy alcohol of the carbon number 3～10 of 10～60 molar part, glass temperature is at 50～75 ℃, the quality average molecular weight Mw is 25, in 000～100,000 scope, there is not fusing point.

More preferably, use has the polyester resin for toner (a1) of following characteristics: the aliphatic dihydroxy alcohol that contains the carbon number 3～10 of 10～60 molar part, glass temperature is at 50～75 ℃, the quality average molecular weight Mw is 25, in 000～100,000 scope, there is not fusing point, softening temperature is at 150～220 ℃, and acid number is below 10mgKOH/g.

By using linear polyester resin (a1), just can access the resin that the toner that photographic fixing face is level and smooth, fixation performance is good can be provided.

In the linear polyester resin (a1), carbon number is that 3～10 aliphatic dihydroxy alcohol composition has no particular limits, but preferably from neopentyl glycol, propylene glycol and cyclohexanedimethanol, select at least a.

The softening temperature of linear polyester resin (a1) is considered from the aspect of un-offset property, and is preferred more than 160 ℃, best preferred more than 170 ℃.Again, the softening temperature of linear polyester resin (a1) is considered from the aspect of fixation performance, and is preferred below 210 ℃, best preferred below 200 ℃.

Again, the glass temperature of linear polyester resin (a1) is considered from the aspect of anti-caking capacity, and is preferred more than 52 ℃, considers from the aspect of fixation performance, preferred below 73 ℃.

Again, the quality average molecular weight Mw of linear polyester resin (a1) is considered from the aspect of un-offset property, and is preferred more than 29,000, considers from the aspect of fixation performance, preferred below 90,000.

The preferred softening temperature of linear polyester resin (B) is at 70～110 ℃.This be because, softening temperature is more than 70 ℃, the un-offset property of toner just has the tendency of optimization.Preferable is more than 80 ℃, and the best is more than 90 ℃.Again, softening temperature is below 110 ℃, and the fixation performance of toner just has the tendency of optimization.Preferable is below 108 ℃, and the best is below 105 ℃.

Again, preferred 2,000～10,000 scope of the quality average molecular weight Mw of linear polyester resin (B).The quality average molecular weight Mw is more than 2,000, and the un-offset property of toner just has the tendency of optimization, and is preferred more than 3,000.The quality average molecular weight Mw is below 10,000, and the fixation performance of toner just has the tendency of optimization.

Again, linear polyester resin (B) does not preferably have fusing point.If linear polyester resin (A) does not have fusing point, the fixation performance of toner and glossiness just have the tendency of optimization.

The preferred Tg of linear polyester resin (B) is 40～70 ℃ of scopes.This be because, if Tg more than 50 ℃, the anti-caking capacity of toner just has the tendency of optimization, and is preferred more than 45 ℃.On the one hand, if Tg below 70 ℃, the anti-caking capacity of toner just has the tendency of optimization, and is preferred below 67 ℃.

Again, below the preferred 30mgKOH/g of acid number of linear polyester resin (B).Take this, can make the image color of toner be difficult for reducing.Preferable acid number is below the 20mgKOH/g.Especially, be dispersiveness that improves the charge control agent (electric charge adjusting resin) in the toner and the stability of improving image color, the acid number of preferred linear polyester resin (B) is higher than the acid number of linear polyester resin (A).

Especially, linear polyester resin (B) preferably has the linear polyester resin (b) of following characteristics: contain the aliphatic dihydroxy alcohol of the carbon number 3～10 of 55～100 molar part, glass temperature is at 40～70 ℃, the quality average molecular weight Mw is 2, in 000～10,000 scope, there is not fusing point.

Again, linear polyester resin (B) is the linear polyester resin that is made of dicarboxylic acid composition and glycol component, the aromatic dicarboxylic acid composition accounts for 50 moles of whole carboxylic acid compositions more than the %, and as if being 100 molar part in whole carboxylic acid compositions, then contain more than aliphatic dihydroxy alcohol 60 molar part of carbon number 4～8, glass temperature is at 40～70 ℃, the quality average molecular weight Mw is 4, in 000～10,000 scope, there is not fusing point.Preferred softening temperature is at 90～120 ℃ linear polyester resin (b1), at this moment, and low-temperature fixing performance the best.This linear polyester resin (B) can use separately, with other linear polyester resin (A) and with also reaching purpose of the present invention.

In this case, as the aromatic dicarboxylic acid composition, can enumerate and be selected from terephthalic acid (TPA), m-phthalic acid or their compositions such as lower alkyl esters.These compositions can be distinguished use separately and also can more than 2 kinds and use.

In the linear polyester resin (b1), as the dicarboxylic acid composition, the aromatic dicarboxilic acid composition accounts for the mole of all acid composition more than 50%, preferred 90 moles more than the %, preferably selects the amount of using 95 moles of % above.This be because, the aromatic dicarboxilic acid composition accounts for more than 50%, the resin that obtains has the tendency of optimization on the balance of physical propertys such as fixation performance, anti-caking capacity.

Again, the dibasic alcohol as the aliphatic dihydroxy alcohol composition that constitutes carbon number 4～8 has: neopentyl glycol, 1,2-butylene glycol, 1,3 butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, diglycol, triethylene glycol, 1,5-pentanediol etc.Wherein, preferred especially neopentyl glycol is because it can obtain having high-affinity with paper and have the resin of superior low-temperature fixing.

The glycol component of using in the linear polyester resin (b1) as if being 100 molar part in whole carboxylic acid compositions, then contains more than aliphatic dihydroxy alcohol 60 molar part of carbon number 4～8.This is because carbon number is that the composition consumption more than 4 reaches more than 60 molar part, can suppress the crystallization of vibrin, and the tendency of improving the transparency and glossiness is arranged.Carbon number is below 8, and the soft increase of the resin flexible that obtains has the tendency of the fixation performance that improves toner.More than preferred 70 molar part of the content of the aliphatic dihydroxy alcohol of carbon number 4～8.

Again, the quality mean molecular weight (Mw) of linear polyester resin (b1) is 4,000～10, in 000 scope.This be because, the quality mean molecular weight of linear polyester resin (b1) is more than 4,000, resin just trends towards enough intensity, and is preferred more than 5,000.Again, the Mw of linear polyester resin (b1) just has the tendency of improving low-temperature fixing below 10,000, and is preferred below 8,000.

Again, the softening temperature of linear polyester resin (b1) is at 90～120 ℃, and this is because softening temperature has the tendency of the anti-caking capacity of optimizing toner more than 90 ℃.The softening temperature of linear polyester resin (b1) is preferred more than 95 ℃.Again, the softening temperature of linear polyester resin (b1) has the tendency of the low-temperature fixing of optimizing toner below 120 ℃.Preferred below 110 ℃.

Again, the glass temperature of linear polyester resin (b1) is at 40～70 ℃.This is because glass temperature has the tendency of the anti-caking capacity of optimizing toner more than 40 ℃, and is preferred more than 50 ℃.Again, glass temperature has the tendency of the low-temperature fixing of optimizing toner below 70 ℃, and is preferred below 65 ℃.

Again, linear polyester resin (b1) acid number is preferably in 0.5～30mgKOH/g scope.This be because, the resin of the not enough 0.5mgKOH/g of acid number, but the low tendency of production efficiency is arranged, more preferably more than 1mgKOH/g.Again, acid number surpasses 30mgKOH/g, and the toner image stability that obtains has the tendency of reduction, more preferably below 25mgKOH/g.

Again, in the present invention, the softening temperature of preferred linear polyester resin (A) is higher more than 20 ℃ than linear polyester resin (B).Like this, the un-offset property of toner just has the tendency of optimization, preferable being chosen as, and the softening temperature of linear polyester resin (A) exceeds more than 40 ℃ than linear polyester resin (B), and optimal selection is for exceeding more than 50 ℃.

Linear polyester resin (A) and linear polyester resin (B) can be by esterification or ester exchange reaction, and polycondensation reactions, and the pure composition of the sour composition of above-mentioned dicarboxylic acid etc. and dibasic alcohol etc. is obtained through polymerization.In the time of polymerization, for example can use the polymerization catalyst of four titanium butoxide, Dibutyltin oxide, tin acetate, zinc acetate, stannic disulfide, antimony trioxide, germanium dioxide etc.Again, polymerization temperature is preferred 180～290 ℃.

Again, when making vibrin, the carrying out meeting of polyreaction is risen along with the increase of the molecular weight (viscosity, softening temperature) of resin in the reaction system, and can determine the degree that polyreaction is carried out according to the torque value of the agitator in the aggregation container (with certain speed rotation).During reaction, when torque value reaches the corresponding torque value of softening temperature with desirable resin, just this can be decided to be constantly the terminal point of polyreaction.

Especially, the reaction conditions of linear polyester resin (a1) is: allow dicarboxylic acid composition and glycol component after carrying out esterification under the pressure of the scope of the temperature of 250～280 ℃ of scopes and 200～500KPa, carry out polycondensation reaction under the condition particularly preferably in 250～300 ℃ and higher 5 ℃ than esterification simultaneously temperature, the low 1KPa of pressure.

This be because: esterification reaction temperature is decided to be more than 250 ℃, can increases the reactivity of dicarboxylic acid and dibasic alcohol, reduce unreacted amount of monomer easily.Esterification reaction temperature is preferred more than 260 ℃.Again, esterification reaction temperature is decided to be below 280 ℃, but the amount of the evaporation of the low boiling monomer (glycol component etc.) in the inhibitory reaction, the unreacted monomer of minimizing.More preferably, esterification reaction temperature is below 270 ℃.

Again, esterification reaction pressure is decided to be more than the 200KPa, can takes this low boiling monomer distillating outside reaction system in the inhibitory reaction, reduce the amount of unreacted monomer.On the other hand, esterification reaction pressure is decided to be below the 500KPa, can takes this to make particularly at the water that last stage reaction generates to be easy to outside reaction, distillate, thereby can improve the reaction rate of dicarboxylic acid and dibasic alcohol.Esterification reaction pressure is preferably below 450KPa.

Again, in the polycondensation reaction of after then esterification, carrying out, temperature of reaction is decided to be more than 250 ℃, this be because, take this to improve the reactivity of polycondensation reaction, can access softening temperature height, the superior resin for toner of un-offset property.The temperature of reaction of polycondensation reaction is preferably more than 260 ℃.Again, setting-up point being decided to be below 300 ℃, is because can suppress the thermal decomposition of resin like this, can access softening temperature height, the superior resin for toner of un-offset property.The temperature of reaction of polycondensation reaction is preferably below 290 ℃.

Again, the reaction pressure during with polycondensation fixes on below the 1KPa, takes this, and can improve the reactivity of polycondensation reaction, can access softening temperature height, the superior resin for toner of un-offset property.Below the preferred 0.8KPa of reaction pressure during polycondensation.

In the present invention, preferably under the temperature higher 5 ℃, carry out polycondensation reaction than esterification again.This is because carry out polycondensation reaction under the temperature higher 5 ℃ than esterification, can suppress the reactivity that distillates, improves the condensation polymerization reaction of oligomer and unreacted component, thereby can access softening temperature height, the superior resin for toner of un-offset property.The temperature of polycondensation reaction preferably exceeds esterification more than 7 ℃.

As the catalyzer of polyreaction, preferably from antimony, titanium, tin, zinc and manganese, select at least a above metallic atom, and the relative all acid composition of its consumption is 50～5000ppm again.This is because the polymerisation catalysts that uses metallic atom to reach the amount of 50ppm can obtain softening temperature height, the superior resin for toner of un-offset property.More than the preferred 80ppm of above-mentioned consumption.Again, use the following amount of 500ppm, can obtain the superior and non-staining resin for toner of glossiness.More preferably, above-mentioned consumption is below 4800ppm.

Resin for toner composition of the present invention is preferably, and contains linear polyester resin (A) 3～50 quality %, contains linear polyester resin (B) 50～97 quality %.

This is because linear polyester resin (A) content reaches more than the 3 quality %, can improve the un-offset property of toner.More than the preferred 5 quality % of linear polyester resin (A) content.On the other hand, linear polyester resin (A) content can improve the fixation performance of toner below 50 quality %, below the preferred 45 quality %.

Again, linear polyester resin (B) content reaches more than the 50 quality %, can improve the fixation performance of toner.More than the preferred 55 quality % of linear polyester resin (B) content.On the other hand, linear polyester resin (B) content can improve the un-offset property of toner below 97 quality %, below the preferred 95 quality %.

Toner of the present invention contains above-mentioned resin for toner composition as adhering resin.Preferably, 80～100 quality % of adhering resin resin for toner composition thus constitute, also can with other vinylite, cyclic olefin resin, epoxy resin etc. and use.

Wherein, preferred especially and vinylite (C) and usefulness are because can reduce print speed printing speed like this, improve HOS and be offset property.

When with vinylite (C) and time spent, resin for toner composition of the present invention preferably contains linear polyester resin (A) 3～50 quality %, linear polyester resin (B) 10～96 quality %, vinylite (C) 1～40 quality %.

As vinylite (C), can enumerate phenylethylene resin series, (methyl) acrylic resin, styrene-propene acid is resin etc., but consider from un-offset property and the aspect of improving charging property, wherein optimization styrene-acrylic resin and (methyl) acrylic resin.

Vinyl monomer as constituting vinylite (C) has: as styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, α-Jia Jibenyixi, to ethyl styrene, 2, the 4-dimethyl styrene, align butylstyrene (p- N one Block チ Le ス チ レ Application), to t-butyl styrene, to positive hexyl phenenyl ethene, to n-octyl styrene, align nonyl benzene ethene, align decyl styrene (p- N one デ Application シ Le ス チ レ Application), align dodecyl styrene, to the styrenic monomers of styryl phenyl, 3,4 two ring styrene etc.; (methyl) alkyl acrylate as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) propyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) acrylic acid-stearate etc. is a monomer; As unsaturated monocarboxylics such as (methyl) acrylic acid, cinnamic acids; Unsaturated dicarboxylic as maleic acid, fumaric acid, itaconic acid etc. is a monomer; Dicarboxylic acid monoesters as monomethyl maleate, ethyl maleate, butyl maleate, monomethyl fumarate, monomethyl ester, fumaric acid mono etc. is a monomer; Dicarboxylic diester as dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, DEF, dibutyl fumarate etc. is a monomer.

Above-mentioned monomer can be selected more than one uses aptly, but considers that from charging property and comminuted these aspects optimization styrene is a monomer, wherein optimization styrene.Especially, with being defined as 85 quality % on the usage rate of cinnamic vinylite (C), help further improving the image property of toner.

Again, consider preferred (methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) alkyl acrylate type monomer of (methyl) acrylic acid stearyl etc. from the fixation performance this point.

Vinylite (C) does not preferably have substantial gel component, and this gel component meaning is the insoluble composition of THF (tetrahydrofuran).Because, can optimize the fixation performance of toner if vinylite (C) does not have gel component.

Again, the preferred softening temperature of vinylite (C) is at 115～180 ℃, and this is because vinylite (C) softening temperature can improve the un-offset property of toner more than 115 ℃, and is preferred more than 120 ℃.Again, vinylite (C) softening temperature can be optimized the fixation performance of toner below 180 ℃, and is preferred below 170 ℃.

Again, the preferred Tg of vinylite (C) is at 50～70 ℃.This be because, Tg is more than 50 ℃, the anti-caking capacity of toner just has the tendency of optimization.Vinylite (C) Tg is preferred more than 52 ℃.Vinylite (C) Tg is below 70 ℃, and the fixation performance of toner just has the tendency of optimization, and is preferred below 68 ℃.

Again, the quality average molecular weight Mw of vinylite (C) is preferably 40,000～400, in 000 scope.More than 40,000, the un-offset property of toner just has the tendency of optimization as the quality average molecular weight Mw, and the quality average molecular weight Mw of vinylite (C) is preferred more than 50,000.The quality average molecular weight Mw of vinylite (C) is below 400,000, and the fixation performance of toner just has the tendency of optimization, and is preferred below 60,0000.

Again, below the preferred 40mgKOH/g of acid number of linear polyester resin (C).Because can there be the image color of toner to be difficult for the tendency that reduces like this, what acid number was preferable is below the 30mgKOH/g.

Linear polyester resin (C) can adopt methods such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization that above-mentioned vinyl monomer is obtained by polyreaction.The initiating agent that uses during polymerization can have been enumerated: superoxide series initiators, azo series initiators, redox series initiators etc.

Polymerization assistants such as emulsifying agent, spreading agent, disperse additive and solvent can be selected to use as required.

Toner of the present invention can contain release agent, colorant, charge control agent, flow ability modifying agent, magnetic etc.

Release agent, preference such as fusing point are at 60～100 ℃ release agent.This be because, use fusing point can optimize the anti-caking capacity of toner at the release agent more than 60 ℃, preferred more than 65 ℃.Again, use fusing point, can optimize the low-temperature fixing of toner at the release agent below 100 ℃.Preferred below 95 ℃.

Fusing point has Rice's wax (79 ℃ of fusing points), Brazil wax (83 ℃ of fusing points), alkene wax (60～90 ℃ of fusing points), a beeswax (64 ℃ of fusing points) etc. at 60～100 ℃.

These can select more than one uses as required aptly, but wherein, preferably pen. is below 3 in the time of 25 ℃.This is because use pen. in the time of 25 ℃ is the picture steadiness that the release agent below 3 can be optimized toner.

As the adjuvant of above-mentioned linear polyester resin (A) and linear polyester resin (B), release agent can prepare in advance, and under the condition that release agent exists, these vibrin also polymerization can take place.Especially, carry out polyreaction under the condition that the release agent that contains pure composition exists, a part and the monomer component of pure composition react, and can improve the mutual solubility between component of polymer and the release agent composition.Therefore, the dispersion that is contained in the release agent composition in the toner of the present invention directly can be reduced, improve the un-offset property of toner easily.

Pen. is below 3 in the time of 25 ℃, the release agent that contains pure composition has: Rice's wax, Brazil wax etc., wherein preferred Brazil wax is because it can improve fixation performance.

In the toner of the present invention, as required, can be used with other release agent again.Other release agent has: polypropylene-based wax, polyethylene-based wax, synthetic ester are that wax, fatty acid amide, silicon are wax etc.

These release agents, the content in toner of the present invention are preferably in 1～10 quality % scope.This is because more than 1 quality %, then the un-offset property of toner just has the tendency of optimization, more than the preferred 1.5 quality % of the content of release agent composition as the content of release agent composition.Again, below 10 quality %, then the stability of the glossiness of toner and image just has the tendency of optimization as the release agent component content, below the preferred 9 quality %.

As employed colorant in the toner of the present invention, can enumerate: carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine series pigments, chrome yellow, quinacridone, benzidine yellow, rose iron oxide red (ロ one ズ ベ Application ガ Le), triarylmethane series pigments, Monoazo type system, two azos system, polycondensation azo based dye or pigment etc.These pigment and dyestuff can use separately also can mix use more than 2 kinds.In the full color toner,, benzidine yellow, monoazo based dye pigment, monoazo based dye pigment, polycondensation azo based dye pigment etc. can be arranged as yellow.As red (magenta) look, quinacridone, rhodamine based dye pigment, monoazo based dye pigment etc. can be arranged, as cyanic colours, phthalocyanine blue etc. can be arranged.Consider from tone, image color, the thermodynamic behaviour aspect of toner, preferably in toner, use the painted dosage of 2～10 quality % degree.

As employed charge control agent in the toner of the present invention, the positively charged controlling agent has: the organism of quaternary amine, alkalescence or the sub-property of powering; Electronegative controlling agent has: the organism of metallo-chelate class, metalliferous dye, acidity or electrophilic.Under the situation of color toner, charged controlling agent is colourless or light color, importantly can not the tone of toner be exerted an influence.Described charge control agent has, for example, and slaines such as the chromium of salicylic acid or alkyl salicylate, zinc, aluminium, metal complex, amino-compound, oxybenzene compound, naphthol compound etc.Again, styrenic, acrylic acid series polymeric compounds, metha crylic polymer, have sulfonic ethene polymers and also can be used as charge control agent and use.These charge control agents are the preferred amount of using 0.5～5 quality % in toner.This is because above more than the 0.5 quality %, carried charge just can reach sufficient level as charge control agent; Be lower than 5 quality %, just can suppress the reduction of the carried charge that the aggegation owing to charge control agent produces.

Adjuvant as flow ability modifying agent that can use in toner of the present invention etc. has: as the flow enhancing agent of the silicon of micronized, aluminium oxide, titania etc.; Inorganic micro powder end as tri-iron tetroxide, ferrite, cerium oxide, strontium titanates, electric conductivity titania etc.; As the impedance adjustment agent of styrene resin, acryl resin etc., lubricant etc.These both can be used as inner additive and also can be used as the external additive use.These adjuvants can use by the amount of 0.05～10 quality % in toner.These adjuvant use amounts reach 0.05 quality % when above, can obtain good modified effect, and can easily improve the stability of image below 10 quality %.

Toner of the present invention can use any developer in magnetic single component developer, non-magnetic mono-component developer, the two-component developing agent.Under situation about using as the magnetic single component developer, contain magnetic, magnetic is except there being the ferromagnetic alloy for the iron content of representative, cobalt, nickel etc. such as for example ferrite, tri-iron tetroxide etc., though do not contain compound or ferromagnetism element in addition but will not show ferromagnetic alloy through suitable thermal treatment, for example manganese-copper-aluminium, manganese-copper-Xi etc. contain so-called whistler (manganese aluminum bronze) magnetic alloy, chromium dioxide of manganese and copper etc.These magnetics can preferably use by the scope of 40～60 quality % in toner.Reach more than the 40 quality % as the magnet consumption, then the carried charge of toner will reach sufficient level; And below 60 quality %, then can optimize the fixation performance of toner.Again, under the situation of using the magnetic two-component developing agent, the mode of employing and carrier and usefulness.As carrier is exactly surface-coated resinous coat at magnetic materials such as iron powder, tri-iron tetroxide powder, ferrite powders, can use known carriers such as magnetic carrier.The coating resin that is used for the resinous coat carrier, can use: known have phenylethylene resin series, acrylic resin, styrene acrylic copolymer are that resin, silicon are that resin, modification silicon are the potpourri of resin, fluorine resin and these resins.

Toner of the present invention for example can adopt: after above-mentioned toner is mixed with composition and release agent, colorant, charge control agent, flow ability modifying agent, magnet etc., with melting mixings such as two-axis extruders, carry out that coarse crushing, fine powder are broken, progressive operation makes.As required, can carry out the outer interpolation processing etc. of inorganic particulate.Especially, in the operation of mixing, preferably under being higher than the softening temperature condition of vibrin, the cylinder temperature of extruder mixes.In aforesaid operations, also can after the broken and classification of micro mist, exchange toner particle and carry out spheroidization and handle again.

In the toner of the present invention, the preferred Tg of Tg is at 45～70 ℃.This be because, Tg is more than 45 ℃, the anti-caking capacity of toner just has the tendency of optimization, and is preferred more than 47 ℃.Tg is below 70 ℃, and the fixation performance of toner just has the tendency of optimization, and is preferred below 68 ℃.

Again, toner of the present invention, softening temperature are preferably at 90～140 ℃.This is because softening temperature can improve the un-offset property of toner more than 90 ℃.What above-mentioned softening temperature was preferable is chosen as more than 95 ℃, and optimal selection is more than 100 ℃.Again, above-mentioned softening temperature can be optimized the fixation performance of toner below 140 ℃, and preferable is chosen as below 130 ℃, and optimal selection is below 120 ℃.

Again, toner of the present invention, the melt viscosity in the time of 120 ℃ is preferably in 100～5000PaS scope.This is because melt viscosity can improve the un-offset property of toner more than 100PaS, more than the preferred 200PaS.Melt viscosity can be optimized the fixation performance and the glossiness of toner below 5000PaS, below the preferred 4600PaS.

Again, toner of the present invention, the quality average molecular weight Mw is 8,000～60, in 000 scope.This be because, the quality average molecular weight Mw can be improved the un-offset property of toner more than 8,000.Preferred more than 10,000.The quality average molecular weight Mw can be improved the low-temperature fixing of toner below 60,000, and is preferred below 50,000.

Again, toner of the present invention, preferred glossiness is in 10～40 scopes.This be because, glossiness can be improved the color development of toner more than 10, and the image glossiness that obtains is improved.Preferable glossiness is chosen as more than 20, and optimal selection is more than 30.Again, glossiness is below 40, can suppress the color development of excessive toner, and image quality is improved.

Again, toner of the present invention is below the preferred mean grain size 7 μ m.This be because, the mean grain size of toner can be improved the un-offset property of toner below 7 μ m, simultaneously can obtain glossiness and the superior image of resolution.

Below, the 5th invention is described.

The 5th invention that the present invention relates to, because vibrin (X) is to use average molecular weight Mw 25,000～100,000 scope, softening temperature are at 150～220 ℃ linear polyester resin, and vibrin (Y) is to use average molecular weight Mw 2,000～10, linear polyester resin in 000 scope, and vibrin (X) and vibrin (Y) are 5: 95～95: the 5 interior and usefulness of scope with mass ratio, thus, can obtain minimum fixing temperature below 130 ℃, fixing temperature amplitude at the toner more than 40 ℃.

Generally, have such tendency: the slow more fixing temperature scope of roller speed is just narrow more.Therefore, use low-speed machine, the fixing temperature scope just has the tendency that narrows down.The 5th invention that the present invention relates to is even use low-speed machine also can guarantee sufficient fixing temperature amplitude.About said minimum fixing temperature in the 5th invention, use is with the improved device of duplicating machine " PAGERRESTN4-612II " (production of カ シ オ Electronics Industry Company), reduce the design temperature of warm-up mill successively, the image adhesion that will be printed on common A4 paper top simultaneously is on roller, range estimation confirms that the bottom blank parts of paper has or not spot, and the lowest set temperature that does not produce spot is exactly minimum fixing temperature.Again, the fixing temperature amplitude refers to the difference of the highest fixing temperature and minimum fixing temperature.The highest fixing temperature of what is called is represented: the design temperature of the above-mentioned hot-rolling that raises successively, measure the glossiness of photographic fixing image simultaneously, and represented temperature was exactly the highest fixing temperature when glossiness was maximum.

The minimum fixing temperature of toner surpasses under 130 ℃ the situation, and the design temperature of hot-rolling will uprise, and therefore the power consumption of printer also can increase, so such situation is unsatisfactory.

Again, shift phenomenon takes place less than under 40 ℃ the situation in the fixing temperature amplitude of toner easily when heat roller temperature changes, and therefore such situation is unsatisfactory.

In the 5th invention that the present invention relates to, vibrin (X) preferred mass average molecular weight Mw is 25,000～100, and in 000 scope, softening temperature is at 150～220 ℃ linear polyester resin.Though be not particularly limited preferred aforementioned linear polyester resin (A).Again, vibrin (Y) be the quality average molecular weight Mw 2,000～10, the linear polyester resin in 000 scope is though be not particularly limited preferred aforementioned linear polyester resin (B).

Again, vibrin (Y), if and with its at least one distinguishing two or more vibrin and using in composition, weight average molecular weight, softening temperature, Tg, can on the balance of optimizing between minimum fixing temperature and the fixing temperature amplitude, be optimized especially, therefore, vibrin (Y) preferably uses 2 kinds of vibrin at least.

Again, preferably use at least under the situation of 2 kinds of vibrin at vibrin (Y), preferably the softening temperature difference of these 2 kinds of vibrin is more than 5 ℃.As vibrin (Y), when contain more than 2 kinds at least, the softening temperature difference is during at the vibrin more than 5 ℃, its fixing temperature amplitude may broaden.The higher limit of this softening temperature difference, though be not particularly limited, preferably below 20 ℃.When the softening temperature difference below 20 ℃ the time, the fixing temperature amplitude of toner will be optimized.

The combination ratio of vibrin (X) and vibrin (Y) is 5/95～95/5 (mass ratio).In the present invention, vibrin (X) and vibrin (Y) and usefulness, proportioning adopts aforementioned proportion, can obtain minimum fixing temperature below 130 ℃, and the fixing temperature amplitude is at the toner more than 40 ℃.What this proportioning was more satisfactory is 10: 90～90: 10, it is desirable to 15: 85～85: 15 especially.

Again, about the content of vibrin (X) and vibrin (Y), though be not particularly limited, preferably both total amounts account in the adhering resin more than the 50 quality %.

Below enumerate embodiments of the invention, the present invention is not limited to any one condition in the illustrated embodiment.

Again, the evaluation method of resin that is presented among these embodiment and toner is as follows.

The evaluation method of resin/toner

1) softening temperature

The measurement of rate of flow instrument CFT-500 that uses Shimadzu Seisakusho Ltd.'s (strain) to produce, under the at the uniform velocity intensification of 3 ℃/minute of loading 294N (30Kgf), programming rate, the temperature when measuring 1/2 in the 1.0 gram samples and in the nozzle of 1mm φ * 10mm, flowing out.

2) acid number

The measured value that records according to titrimetry with KOH solution.

3) quality mean molecular weight

The mensuration of quality mean molecular weight adopts gel permeation chromatography (HCL-8200 that eastern Cao company produces), is undertaken by following condition determination.

Chromatographic column condition: G4000Hx1 * 1 * G2000Hx1

Column oven temperature: 40 ℃

Eluant, eluent: tetrahydrofuran

Flow velocity: 1ml/ branch

Sample concentration: 0.4 quality %

Sample size: 100 μ L

Detecting device: RI

4) fusing point

Use differential scanning formula calorimeter, the endothermic peak in the time of will measuring under the condition of 5 ℃/minute of programming rates is decided to be fusing point.

5) glass temperature

Use differential scanning formula calorimeter, the intersection point temperature of the baseline of the collection of illustrative plates when under the condition of 5 ℃/minute of programming rates, measuring and the line of the endothermic curve near Tg.

6) melt viscosity

The flow stream velocity meter DynalyserDAR-100 that uses REOLGICA company to produce concentrates the 1g sample, sandwiches in the parallel flat of 25mm φ, after adjusting thickness to 0.5～1.0mm under 150 ℃, be warming up to 80～250 ℃ with 3 ℃/minute speed,, measure under the condition of 1% strain at frequency 1Hz.

7) evaluation method of un-offset property

7) evaluation method 1 (medium speed printer evaluation method)-1

Use the fixing roller that contains uncoated silicone oil, roller speed setting as printing the 100mm/ second and the printer (manifolder that カ シ オ Electronics Industry Company is produced " the improved device of PAGEPREST N4-612II) that can change temperature, carry out the evaluation of un-offset property.Again, toner maximum temperature when mobile on fixing roller is decided to be the skew occurrence temperature during with photographic fixing, judges un-offset property according to following standard.

◎ (very good): the skew occurrence temperature is more than 230 ℃

Zero (well): the skew occurrence temperature is more than 220 ℃, less than 230 ℃

△ (can use): the skew occurrence temperature is more than 200 ℃, less than 220 ℃

* (poor): the skew occurrence temperature is less than 200 ℃

7) evaluation method 2 (middling speed low temperature printer evaluation method)-2.

Use the fixing roller that contains uncoated silicone oil, roller speed setting as printing the 100mm/ second and the printer (duplicating machine that カ シ オ Electronics Industry Company is produced " the improved device of PAGEPREST N4-612II) that can change temperature, carry out the evaluation of un-offset property.Again, toner maximum temperature when mobile on fixing roller is decided to be the skew occurrence temperature during with photographic fixing, judges un-offset property according to following standard.

◎ (very good): the HOS occurrence temperature is more than 200 ℃

Zero (well): the HOS occurrence temperature is more than 185 ℃, less than 200 ℃

△ (can use): the HOS occurrence temperature is more than 175 ℃, less than 185 ℃

* (poor): the HOS occurrence temperature is less than 175 ℃

7) evaluation method 3 (low speed printer evaluation method)-3.

Use the fixing roller that contains uncoated silicone oil, roller speed setting as printing the 50mm/ second and the printer (duplicating machine that カ シ オ Electronics Industry Company is produced " the improved device of PAGEPRESTN4-612II) that can change temperature, carry out the evaluation of un-offset property.Again, toner maximum temperature when mobile on fixing roller is decided to be the skew occurrence temperature during with photographic fixing, judges un-offset property according to following standard.

◎ (very good): the skew occurrence temperature is more than 230 ℃

Zero (well): the skew occurrence temperature more than 220 ℃ less than 230 ℃

△ (can use): the skew occurrence temperature more than 200 ℃ less than 220 ℃

* (poor): the skew occurrence temperature is less than 200 ℃

7) evaluation method 4 (middle low speed printer evaluation method)-4.

" the improved device of PAGEPREST N4-612II (production of カ シ オ Electronics Industry Company), the uncertain image that draws carries out the test in fixing temperature field with duplicating machine in use.Fixing roller used herein is the fixing roller that is not coated with silicone oil, sets pincers and holds the wide 3mm of portion, linear velocity 70mm/s.The design temperature of hot-rolling raises successively with per 5 ℃, and the image adhesion that will be printed on common A4 paper (big Zhao is with System Zhi System BM64T) top simultaneously is on roller, and range estimation confirms that the bottom blank parts of paper has or not spot, is raised to till 200 ℃ until temperature repeatedly.About this photographic fixing image, the glossmeter-PG-1 that uses Japanese electric look Industrial Co., Ltd to produce measures incident angle and is 75 gloss values when spending.Glossiness increases with the rising of temperature, is that turning point begins to descend when reaching certain temperature.Like this, the temperature design temperature when glossiness is begun to descend is considered as the occurrence temperature of thermal migration, and the temperature when glossiness is maximum is decided to be the highest fixing temperature.

8) evaluation assessment of fixation performance

8) evaluation method 1 (medium speed printer evaluation method)-1.

With the same condition of the evaluation method 1 of un-offset property under, make toner photographic fixing on paper, the minimum temperature of toner when photographic fixing begins on paper is decided to be fixing temperature, according to following standard determination.

◎ (very good): fixing temperature is less than 120 ℃

Zero (well): fixing temperature more than 120 ℃ less than 130 ℃

△ (can use): fixing temperature more than 130 ℃ less than 160 ℃

* (poor): fixing temperature is more than 160 ℃

8) evaluation method 2 (middling speed low temperature printer evaluation method)-2.

With the same condition of the evaluation method 2 of un-offset property under, make toner photographic fixing on paper, the minimum roll temperature so that cold skew not to take place is decided to be photographic fixing and begins temperature, judges low-temperature fixing according to following standard.

◎ (very good): photographic fixing begins temperature less than 125 ℃

Zero (well): photographic fixing begin temperature more than 125 ℃ less than 135 ℃

△ (can use): photographic fixing begin temperature more than 135 ℃ less than 145 ℃

* (poor): photographic fixing begins temperature above 145 ℃

8) evaluation method 3 (low speed printer evaluation method)-3.

With the same condition of the evaluation method 3 of un-offset property under, make toner photographic fixing on paper, the minimum temperature when beginning photographic fixing with toner on paper is decided to be fixing temperature, according to following standard determination.

◎ (very good): fixing temperature is less than 120 ℃

Zero (well): fixing temperature more than 120 ℃ less than 130 ℃

△ (can use): fixing temperature more than 130 ℃ less than 160 ℃

* (poor): fixing temperature is more than 160 ℃

8) evaluation method 4 (middle low speed printer evaluation method)-4.

The benchmark that is determined as with the evaluation method 4 of un-offset property, with toner as transfer printing, handle with above-mentioned heat roller fixation machine photographic fixing, the design temperature of hot-rolling reduces successively with per 5 ℃, the image adhesion that will be printed on common A4 paper (big Zhao is with System Zhi System BM64T) top simultaneously is on roller, range estimation confirms that the bottom blank parts of paper has or not spot, and the lowest set temperature when not producing spot is decided to be minimum fixing temperature.

9) fixing temperature amplitude

The difference of the highest fixing temperature and minimum fixing temperature is decided to be the fixing temperature amplitude.

10) anti-caking capacity

Take by weighing the about 5g of toner and put into sample bottle, put in the exsiccator that keeps 50 ℃ and placed 24 hours, estimate the index of the aggegation degree of toner as anti-caking capacity.Evaluation criterion is as follows.

◎ (well): as long as the sample bottle upset just can be spread out

Zero (can use):, beat 2～3 times and just can spread out with the sample bottle upset

* (poor):, beat more than 4 times and just can spread out with sample bottle upset

11) glossiness

150 ℃, make image photographic fixing in toner, the glossmeter-PG-1 that uses Japanese electric look Industrial Co., Ltd to produce measures, and is 75 measured values when spending according to incident angle, estimates by following standard.

◎ (very good): glossiness is more than 30 below 40

Zero (well): glossiness more than 20 less than 30

△ (can use): glossiness more than 10 less than 20

* (poor): glossiness is less than 10

12) 145 ℃ fixation performance

145 ℃ fixation performance

With JIS 512 sand rubbers, the fixing roller temperature is set in 145 ℃ of image wipings after the photographic fixing 9 times, surely test the image color of front and back with the image color instrumentation that マ Network ベ ス company produces, calculate the photographic fixing rate, estimate according to (image color before the image color/test after the test) * 100 (%) by following standard.

◎ (very good): the photographic fixing rate is more than 80%

Zero (well): the photographic fixing rate is more than 75%, less than 80%

△ (can use): the photographic fixing rate is more than 70%, less than 75%

* (poor): the photographic fixing rate is less than 70%, or at 145 ℃ COS takes place, and can't measure

The Production Example of Production Example 1 linear polyester resin (A)

The monomer component that feeding intake shown in the table 1 formed and be equipped with in the reaction vessel of distillation column with respect to the antimony trioxide input of all acid composition 2000ppm.Then, keeping the velocity of rotation of agitator in the reaction vessel is 120rpm, begins to heat up, and the temperature that is heated in the reaction system reaches 265 ℃, keeps this temperature.Water distillates from reaction system, and esterification began the back about 7 hours, and water no longer distillates, and reaction finishes.Next, reduce the temperature of reaction system, keep 285 ℃,, make vacuum tightness reach 1.0mmHg, allow diol component when reaction system distillates, carry out polycondensation reaction reaction vessel decompression 40 minutes.The viscosity of reaction system and the carrying out of reaction rise synchronously, gas clean-up when viscosity rises, when the torque that polycondensation reaction proceeds to agitator reaches the pairing value of the softening temperature of hope till.Then, the moment when arriving torque that demonstration is decided, make reaction system return to normal pressure, stop heating, about 40 minutes of nitrogen pressure is taken out reactant, obtains resin HA～HL.

To carry out constituent analysis by gas-liquid chromatography with resin HA～HL that this method obtains, its result forms the resin shown in the table 1 and forms.Again, the characteristic value of resin is also listed in table 1.

The Production Example of Production Example 2 linear polyester resins (B)

The monomer component that feeding intake shown in the table 2 formed, adjuvant and be equipped with in the reaction vessel of distillation column with respect to the Dibutyltin oxide input of all acid composition 1000ppm.Then, the agitator velocity of rotation begins to heat up at 120rpm in the maintenance reaction vessel, and the temperature that is heated in the reaction system reaches 260 ℃, keeps this temperature.Water distillates from reaction system, and esterification began the back about 8 hours, and water no longer distillates, and reaction finishes.Next, reduce the temperature of reaction system, keeps 235 ℃, reaction vessel was reduced pressure 40 minutes, make vacuum tightness reach 1.0mmHg, allow glycol component when reaction system distillates, contract and react.The viscosity of reaction system and the carrying out of reaction rise synchronously, gas clean-up when viscosity rises, when the torque that polycondensation reaction proceeds to agitator reaches the pairing value of the softening temperature of hope till.Then, when arrive to show moment of fixed torque, reaction system is returned to normal pressure, stop heating, about 40 minutes of nitrogen pressure is taken out reactant, obtains resin LA～LN.

To carry out constituent analysis by gas-liquid chromatograph with resin LA～LN that this method obtains, its result forms the resin shown in the table 2 and forms.Again, the characteristic value of resin is also listed in table 2.

Embodiment 1

Use the resin that obtains as stated above, the thinner of mixing colours respectively.In the preparation of toner, with the linear polyester resin (A) of the amount of Table 3, linear polyester resin (B) simultaneously, use quinacridone pigment (Network ラ リ ア Application ト company produces E02) 5 mass parts, Brazil wax (East ocean ペ ト ロ ラ イ De company produces) 5 mass parts, electronegativity charge control agent (オ リ エ Application ト chemical company produces E-84) 2 mass parts were mixed 30 minutes in Henschel mixer.Then, the potpourri that obtains mixes 2 times with the fusion of twin shaft muller.Fusion is mixed and is carried out under 180 ℃ of conditions of internal temperature.After mixing, cooling obtains the toner piece, and broken with air-flow atomizer micro mist, the particle diameter of putting toner with pelletizing machine in order becomes 5 μ m..In the micropowder that obtains, add 0.25% silicon (the Japanese ア エ ロ ジ Le production R-972 of company), mix that in Henschel mixer it is adhered to, finally obtain toner 1～18.

The toner 1～18 that just obtains uses said method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 1) to carry out the toner evaluation.The evaluation result of these toners is as shown in table 3.

Embodiment 2

In the preparation of toner, except the vibrin that uses the amount of Table 4, all the other are all equally operated with embodiment 1, obtain toner 19～20.About the toner 19～20 that obtains, above-mentioned evaluation method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 1) is carried out the toner evaluation.The evaluation result of these toners is as shown in table 4.

Embodiment 3

In the preparation of toner, except using the vibrin of the amount of Table 5, the use amount of Brazil wax changes to beyond 15 mass parts, and all the other obtain toner 21～23 as embodiment 1 operation.

The toner 21～23 that just obtains is used commentary valency method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 1) and is carried out the toner evaluation.The evaluation result of these toners is as shown in table 5.

Comparative example 1

In the preparation of toner, except the linear polyester resin (A) that uses the amount of Table 6, linear polyester resin (B), all the other obtain toner C1～C4 as embodiment 1 operation.

Toner C1～the C4 that just obtains carries out the toner evaluation by above-mentioned evaluation method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 1).The evaluation result of these toners is as shown in table 6.

Comparative example 2

In the preparation of toner, except the linear polyester resin (A) that uses the amount of Table 7, linear polyester resin (B), all the other obtain toner C5～C6 as embodiment 3 operations.

Toner C5～the C6 that just obtains carries out the toner evaluation by aforementioned evaluation method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 1).The evaluation result of these toners is as shown in table 7.

The Production Example of Production Example 3 vinylites (C)

In the polymer reactor that is provided with stirring machine, thermometer, reflux condenser, add the deionized water of 200 mass parts and the polyvinyl alcohol (PVA) of 0.2 mass parts, stir, after the polyvinyl alcohol (PVA) dissolving, monomer component shown in the input table 8 and initiating agent.Speed of agitator keeps 200rpm, with about 10 minutes the temperature in the polymer reactor is elevated to 80 ℃.For making reactor temperature can remain on 80 ℃, control the outside wall temperature of polymer reactor, be higher than reactor temperature from outside wall temperature and begin meter, allow reaction continue about 2 hours.Next, heat up, make the temperature in the polymer reactor reach 90 ℃, kept one hour.Afterwards, cooling drops to below 40 ℃ the temperature in the polymer reactor, takes out resin in polymer reactor, and is fully clean with deionized water, obtains vinylite M1～M5.The characteristic value of gained M1～M5 is as shown in table 8.

Embodiment 4

Use the resin that obtains as stated above, the thinner of mixing colours respectively.In the preparation of toner, use linear polyester resin (A), linear polyester resin (B), the vinylite (C) of the amount of Table 9, simultaneously, use quinacridone pigment (Network ラ リ ア Application ト company produces E02) 5 mass parts, Brazil wax (East ocean ペ ト ロ ラ イ De company to produce) 5 mass parts, electronegativity charge control agent (オ リ エ Application ト chemical company produces E-84) 2 mass parts, in Henschel mixer, mixed 30 minutes.Then, the potpourri that obtains is mixed 2 times with the fusion of twin shaft muller.Fusion is mixed and is carried out under 180 ℃ of conditions of internal temperature.Cooling obtains the toner piece after mixing, and it is broken to make micro mist with the air-flow atomizer, and the particle diameter of putting toner with pelletizing machine in order becomes 5 μ m..In the micropowder that obtains, add 0.25% silicon (the Japanese ア エ ロ ジ Le production R-972 of company), in Henschel mixer, mix, it is adhered to, finally obtain toner 24～35.

The toner 24～35 that just obtains uses said method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 3) to carry out the toner evaluation.The evaluation result of these toners is as shown in table 9.

Ratio of components: with all acid composition total amount is 100 Mil's part timing,

(molar part of the aliphatic dihydroxy alcohol composition of carbon number 3～10 in the linear polyester resin (B))/(molar part of the aliphatic dihydroxy alcohol composition of carbon number 3～10 in the linear polyester resin (A)) ratio

Comparative example 3

In the preparation of toner, except the linear polyester resin (A) that uses the amount of Table 10, linear polyester resin (B), vinylite (C), all the other obtain toner C10 as embodiment 5 operations.

The toner C10 that just obtains is by carrying out the toner evaluation with embodiment 4 same evaluation methods (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 3).The evaluation result of these toners is as shown in table 10.

The Production Example of Production Example 4 linear polyester resins (B)

The monomer component that feeding intake shown in the table 11 formed, adjuvant and be equipped with in the reaction vessel of distillation column with respect to the antimony trioxide input of all acid composition 500ppm.Then, the agitator velocity of rotation begins to heat up at 120rpm in the maintenance reaction vessel, and the temperature that is heated in the reaction system reaches 260 ℃, keeps this temperature.Water distillates from reaction system, and esterification began the back about 8 hours, and water no longer distillates, and reaction finishes.Next, reduce the temperature of reaction system, keep 230 ℃,, make vacuum tightness reach 1.0mmHg, allow diol component when reaction system distillates, carry out polycondensation reaction reaction vessel decompression 40 minutes.The viscosity of reaction system and the carrying out of reaction rise synchronously, the softening temperature of resin in the following response system, when polycondensation reaction proceeds to the pairing value of the softening temperature that reaches hope till.Then, when arrive indication moment of fixed softening temperature, reaction system is returned to normal pressure, stop heating, about 2 hours of nitrogen pressure is taken out reactant, slowly cools off 2 hours again, obtains resin LO～LV.To carry out constituent analysis by gas-liquid chromatography with resin LO～LV that this method obtains, the physical characteristics matter value of its result and resin is listed in table 11 together.

Embodiment 5

Use the resin that obtains as stated above, the thinner of mixing colours respectively.In the preparation of toner, use linear polyester resin 93 mass parts, quinacridone pigment (Network ラ リ ア Application ト company produces E02) 3 mass parts, Brazil wax (East ocean ペ ト ロ ラ イ De company produces) 3 mass parts, electronegativity charge control agent (オ リ エ Application ト chemical company produces E-84) 1 mass parts was mixed 30 minutes in Henschel mixer.Then, the potpourri that obtains mixes 2 times with the fusion of twin shaft muller.Fusion is mixed and is carried out under 180 ℃ of conditions of internal temperature.After mixing, cooling obtains the toner piece, and it is broken to make micro mist with the air-flow atomizer, becomes 5 μ m. with pelletizing machine arrangement toner particle diameter.In the micropowder that obtains, add 0.25% silicon (the Japanese ア エ ロ ジ Le production R-972 of company), in Henschel mixer, mix, it is adhered to, obtain toner 36～39.The toner 24～35 that just obtains uses said method (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 2) to carry out the toner evaluation.The evaluation result of these toners is as shown in table 12.

Comparative example 4

Except vibrin being transformed into resin LS～LV, all the other make toner C11～C14 as embodiment 5 operations, and evaluation result is as shown in table 12.

The Production Example of Production Example 5 linear polyester resins (X)

The monomer component that feeding intake shown in the table 13 formed and be equipped with in the reaction vessel of distillation column with respect to the antimony trioxide input of all acid composition 1500ppm.Then, begin to heat up, the temperature that is heated in the reaction system reaches 265 ℃, keeps this temperature.Till reaction is performed until water and no longer distillates from reaction system.Next, the temperature change that makes reaction system is 285 ℃, will reduce pressure in the reaction vessel, carries out polycondensation reaction when allowing diol component distillate from reaction system.The viscosity of reaction system and the carrying out of reaction rise synchronously, when the torque that agitator is carried out in polycondensation reaction reaches the pairing value of the softening temperature of hope till.Then, when arrive indication moment of fixed torque, take out reactant, cooling obtains resin 1a～1f.The physical property values of each vibrin is as shown in table 13.

The Production Example of Production Example 6 linear polyester resins (Y)

The monomer component that feeding intake shown in the table 14 formed, release agent composition (Brazil wax) and be equipped with in the reaction vessel of distillation column with respect to the Dibutyltin oxide input of all acid composition 1000ppm.Then, begin to heat up, the temperature that is heated in the reaction system reaches 265 ℃, keeps this temperature.Till reaction is performed until water and no longer distillates from reaction system.Next, make the temperature of reaction system remain on 235 ℃, will reduce pressure in the reaction vessel, carry out polycondensation reaction when allowing diol component distillate from reaction system.The viscosity of reaction system and the carrying out of reaction rise synchronously, and sampling is repeatedly carried out in the process in reaction, when polycondensation reaction proceeds to the pairing value of the softening temperature that reaches hope till.Then, when arrive indication moment of fixed softening temperature, take out reactant, cooling obtains resin 2a～2g.The physical property values of vibrin is as shown in table 14.

Embodiment 6

As adhering resin, the vibrin of composition and combined amount shown in the table 15 is amounted to 93 mass parts, quinacridone pigment (Network ラ リ ア Application ト company produces E02) 3 mass parts, Brazil wax (East ocean ペ ト ロ ラ イ De company produces) 3 mass parts, electronegativity charge control agent (the Japanese カ production LR-147 of one リ Star ト company) 1 mass parts is pre-mixed, and the potpourri that obtains mixes 160 ℃ of following fusions with the twin shaft muller.After the coarse crushing, it is broken to make micro mist in the air-flow atomizer, with pelletizing machine toner is carried out whole grain, and making its mean grain size is 5 μ m.In the micro mist grain that obtains, add the silicon (the Japanese エ ア ロ ジ Le production R-972 of company) of 0.2 quality %, mix that in Henschel mixer it is adhered to, finally obtain toner 40～47.This toner is installed in the non-magnetic mono-component dry copier, obtains the initial stage image, its performance is estimated (but the evaluation method of un-offset property and the evaluation method of fixation performance are with evaluation method of evaluation assessment 4) carry out the toner evaluation.The evaluation result of the toner 40～47 that obtains is shown in table 16.

As can be seen from the above results, toner 40～47 of the present invention is even on-line velocity is under the low-medium speed degree of 70mm/s, any can both have 130 ℃ of good low-temperature fixings down, simultaneously, high thermal migration temperature and the highest fixing temperature are arranged all also, demonstrate wide fixing temperature amplitude.

Comparative example 5

Except the vibrin as composition and combined amount shown in the adhering resin use table 15 amounts to 93 mass parts, obtain toner C15～C17 by embodiment 6 same methods.The result is shown in table 16 for its performance evaluation (but the evaluation method of un-offset property is identical with evaluation assessment 4 with the evaluation method of fixation performance).

Toner C15 since the softening temperature of vibrin (X) less than 150 ℃, the quality mean molecular weight is less than 25,000, un-offset temperature and the highest fixing temperature step-down, its result, fixing temperature amplitude are reduced into 35 ℃.

Toner C16 since the combined amount of vibrin (X) less than 5 mass parts, thermal migration temperature and the highest fixing temperature step-down, its result, fixing temperature amplitude are reduced into 10 ℃.

Toner C17 is because vibrin (X) the quality mean molecular weight that uses surpasses 10,000, so minimum fixing temperature up to 150 ℃, is the toner of fixation performance difference.

Industrial utilizability

The present invention is applicable to the aobvious of electrostatic image in xerography, electrostatic recording and the videograph or magnetic sub-image The shadow technology.

Claims (5)

1. toner linear polyester resin b1, described toner is the linear polyester resin that is made of dicarboxylic acid composition and glycol component with linear polyester resin b1, it is characterized in that, wherein, aromatic dicarboxylic acid content is 50 moles of whole carboxylic acid compositions more than the %, reaching in whole carboxylic acid compositions is 100 molar part, and the aliphatic dihydroxy alcohol content of carbon number 4～8 is more than 60 molar part; Described linear polyester resin b1 be glass temperature in 40～70 ℃ of scopes, its quality average molecular weight Mw 4,000～10,000 scope, do not have the resin of fusing point, and its softening temperature is 90～120 ℃.

2. toner linear polyester resin b1 as claimed in claim 1 is characterized in that the aliphatic dihydroxy alcohol of carbon number 4～8 is a neopentyl glycol.

3. toner linear polyester resin b1 as claimed in claim 1 or 2 is characterized in that acid number is in 0.5～30mgKOH/g scope.

4. a toner is characterized in that, described toner is any one described toner linear polyester resin b1 in the claim 1～2 that contains in toner more than the 5 quality %.

5. a toner is characterized in that, described toner is the described toner of the claim 3 linear polyester resin b1 that contains in toner more than the 5 quality %.