CN102789145A - Toner and developer - Google Patents

Abstract

The invention provides a toner and a developer, the developer comprises a binder resin comprising a crystalline resin and a non-crystalline resin, a colorant, and a release agent, wherein the toner is provided with a flow starting temperature T1/2 equal to 1/2 of 120 DEG C-135 DEG C, and the ratio of the peak intensity obtained from the crystalline resin and the release agent to the peak intensity obtained from the binder resin via FTIR-ATR measurement is 0.10-0.20.

Description

Toner and developer

Background technology

The present invention relates to be used for image forming apparatus for example duplicating machine, facsimile recorder and printer toner and contain the developer of said toner.

Background technology

Electrofax or electrostatic recording image forming apparatus carry out image formation through manifest electric sub-image or magnetic sub-image with toner routinely.In electrofax, for example, on photoconductor, form electrostatic latent image, afterwards with the toner development electrostatic latent image to form toner image.Then toner image is transferred to recording medium for example on the paper, heat subsequently and melt with toner image on recording medium.

Recently, the demand in the market comprises the particle diameter that dwindles toner improving the image quality of output image, and the low-temperature fixing ability of improving toner is with energy-conservation.Dwindle through routine and mediate and the particle diameter of the toner that breaking method obtains is difficult, and the coating of particles of this toner is irregular, and its size-grade distribution is wide.In addition, this toner has the problem that fixing temperature need be set in high temperature and have difficulties aspect energy-conservation.Further, a large amount of release agent (wax) is present on the surface of toner-particle, because according to said kneading and breaking method, the product of in crushing process, mediating at the warp at the interface of said release agent is broken into fragment.Therefore, in photographic fixing, show stripping result, but on the other hand, said toner trends towards being deposited on carrier, photoconductor and the scraper plate.Said image forming course is considered as a whole the performance of said toner is not satisfied.

Simultaneously, the method for preparing toner that has proposed the use polymerization is to solve the problem in the breaking method.The toner of making through polymerization is minification easily, with compare through the toner of breaking method manufacturing, have the smaller particles diameter and have narrower size-grade distribution.Further, the toner through the polymerization manufacturing can be contained in wherein sealing with wax.

According to this polymerization, expectation be in order to improve the low-temperature fixing ability of toner for the purpose of energy-conservation.

Follow the low-temperature fixing ability, also expectation is to regulate toner not damage its heat-resisting storage stability and heat-resisting anti-seal property.

In order to solve foregoing problems, through having carried out various trials as follows: crystalline polyester is introduced in the conventional noncrystalline resin that uses the resin glue (referring to open (JP-A) No.2005-015589 of for example Japanese patent application, 2005-107387,2006-065025,2006-293338 and 2007-033773) as toner.Crystallized polyurethane resin in the toner has heat fusing character, makes under near photographic fixing begins temperature the temperature, demonstrates the rapid reduction of its viscosity owing to its crystallinity.That is, because the crystallinity of crystallized polyurethane resin, the heat-resisting storage stability of toner reaches fusion up to temperature, and to begin before the temperature all be excellent, and under fusion begins temperature, toner cause its viscosity rapid reduction (violent fusing) and by photographic fixing.As a result, can design the toner that has superior heat resistance storage stability and low-temperature fixing ability simultaneously.In addition, can design toner also excellent aspect heat-resisting anti-seal property.

With regard to being used for crystalline polyester is introduced with regard to the method for preparing toner of noncrystalline resin, disclosed following method.Said method comprises: the compound dissolution that can carry out chain extension or cross-linking reaction with binder resin precursor is in oil phase, and said oil phase passes to the major general and contains the resin glue of the binder resin precursor that is formed by crystallized polyurethane resin and modified polyester resin, colorant and release agent dissolving or be dispersed in the organic solvent and obtain; Said oil phase is dispersed in the water-bearing media that contains particle dispersants to obtain the dispersion liquid of emulsification; Make said binder resin precursor in the dispersion liquid of said emulsification, carry out cross-linking reaction and/or chain extending reaction; With remove said organic solvent.

As in the aforementioned manufacturing approach noncrystalline resin being introduced the low-temperature fixing ability that possibly be not enough to realize toner in the crystallized polyurethane resin.Even realized the low-temperature fixing ability, also possibly can't obtain desirable heat-resisting storage stability or heat-resisting anti-seal property.In order to obtain the low-temperature fixing ability, said crystallized polyurethane resin and the noncrystalline resin compatible temperature with the glass transition temperature (Tg) that reduces said toner and when reducing melt viscosity and beginning to reduce is important.But,, be important with said crystallized polyurethane resin and the mutual exclusive dispersion of said noncrystalline resin in order to ensure heat-resisting storage stability and heat-resisting anti-seal property.In order to realize low-temperature fixing ability, heat-resisting storage stability and heat-resisting anti-seal property simultaneously, realize that the compatible state that is in trade-off relation of said noncrystalline resin and crystallized polyurethane resin and incompatible state are important.For this reason; There is following the proposal, comprise the combination of using crystallized polyurethane resin and noncrystalline polyester resin and method for preparing toner (JP-ANo.2005-107387) or the toner (JP-ANo.2006-293338 and 2007-033773) of having stipulated to add the value of the endothermic peak of pining for through DSC.

Have aforementioned toner, wherein introduced crystallized polyurethane resin, and it can prevent the generation of the anti-seal of heat in the low-temperature fixing ability that obtains toner.Although possibly not cause the anti-seal of heat, be to use this toner to cause the problem of printing sheets coiling fixing roller, and can not obtain the excellent separating power of toner.In addition, improved said toner obtaining heat-resisting storage stability, but its effect is not enough.Therefore need the further improvement of heat-resisting storage stability.

Summary of the invention

The present invention aims to provide the toner of the separating property with excellent low-temperature fixing ability and heat-resisting storage stability and excellence and aims to provide the developer that contains said toner.

The means that solve foregoing problems are following.

Toner of the present invention contains:

The resin glue that contains crystalline resins and noncrystalline resin;

Colorant; With

Release agent,

Wherein said toner has 120 ℃-135 ℃ 1/2 flow starting temperature T1/2, and

Wherein the peak intensity ratio with FTIR-ATR peak intensity of measuring that derives from said crystalline resins and said release agent and the peak intensity that derives from said resin glue is 0.10-0.20.

The present invention has the excellent low-temperature fixing ability and the toner of heat-resisting storage stability and separating power through providing as follows: the first time of measuring through differential scanning calorimeter (DSC) except regulation is the heated glass transition temperature Tg1st; Also stipulated the heated glass transition temperature Tg2nd second time through dsc measurement; 1/2 flow starting temperature T1/2 of said toner and the peak intensity of measuring through FTIR-ATR that derives from said crystalline resins and said release agent and the peak intensity ratio of the peak intensity that derives from said resin glue.

Heated glass transition temperature Tg1st derives from the glass transition temperature of said crystalline polyester for the first time, and said crystalline polyester is as the resin that in being used to form the resin of toner, has lowest glass transition temperature.Under the situation that said crystalline polyester and said non-crystalline polyester become partially or completely compatible each other in manufacture process, said Tg1st is quite low.When said Tg1st was lower than 45 ℃, the heat-resisting storage stability of the toner that obtains was not enough.When said Tg1st was higher than 65 ℃, the temperature that said toner begins to melt was high and therefore can not obtain the low-temperature fixing ability.Therefore, Tg1st is adjusted to 45 ℃-65 ℃ the scope that falls into.

The glass transition temperature of being confirmed by heating for the second time (being the glass transition temperature Tg 2nd behind the toner heat fusing) is not to derive from the material that is used to form said toner, but since during aforementioned manufacture process the compatibility of resin and the new characteristic temperature that produces.When said Tg2nd is lower than 25C, be excessive in the compatibility of resin described in the fixing, this can worsen the separating power of said toner when photographic fixing.When said Tg2nd is higher than 35C, be not enough in the compatibility of resin described in the fixing, this can worsen the low-temperature fixing ability of said toner.Therefore, the Tg2nd with said toner is controlled to be in the scope that falls into 25 ℃-35 ℃.

1/2 flow starting temperature T1/2 of toner has also indicated the reduction of the viscosity of said resin; It is for example by through making sample fusing and the flow curve that obtains that flows is confirmed with the overhead system flow tester, and it is that stroke (stroke) variable quantity from the fusing flow starting temperature to the mobile end temp of fusing becomes 1/2 o'clock temperature.When said 1/2 flow starting temperature T1/2 was lower than 120 ℃, the separating power of said toner worsened when photographic fixing.When said 1/2 flow starting temperature T1/2 was higher than 135 ℃, the softening beginning temperature of said toner was high, so that can not obtain the low-temperature fixing ability of toner.Therefore, the T1/2 with said toner is controlled to be in the scope that falls into 120 ℃-135 ℃.

Being compared by the peak intensity according to peak intensity of in FTIR-ATR, measuring that derives from said crystallized polyurethane resin and said release agent and the peak intensity that derives from said resin glue can acquisition and crystalline polyester and the uneven distribution relevant index of release agent in the zone that the surface with said toner-particle is close to.When said peak intensity when low, its amount that shows the crystalline polyester that is present in around the toner-particle surface and release agent is low.If said peak intensity ratio is lower than 0.10, the separating power of said toner is not enough.When said peak intensity when high, its amount that shows the crystalline polyester that is present in the peripheral region, toner-particle surface and release agent is big.If said peak intensity ratio is greater than 0.20, the heat-resisting storage stability of the toner that obtains is not enough.When a large amount of release agents was present in the surperficial zone of contiguous toner-particle, the demoulding ability of said toner was improved, but on the other hand, heat-resisting storage stability worsens because said release agent trends towards being deposited on the parts on every side.When a large amount of crystalline polyesters was present in the surperficial zone of contiguous toner-particle, heat-resisting storage stability worsened.The reason of this deterioration is thought as follows.Said crystalline polyester has 0 ℃ or lower glass transition temperature and 100% or lower crystallinity usually, and the crystalline polyester that therefore disperses has the noncrystalline component that has 0 ℃ or lower glass transition temperature.Be present under the situation in the surperficial zone of contiguous toner-particle at the said crystalline polyester with this component, it is not enough that the heat-resisting storage stability of said toner becomes.In order to improve heat-resisting storage stability and to keep separating power, the aforementioned peak intensity that derives from said crystalline resins and release agent that will measure through FTIR-ATR is than being adjusted in the scope that falls into 0.10-0.20.

Like what show among the following embodiment, through satisfying the toner that aforementioned four conditions can obtain having excellent low-temperature fixing ability, heat-resisting storage stability and separating power.

The present invention can provide the toner with excellent low-temperature fixing ability, heat-resisting storage stability and separating power, and the developer that contains said toner is provided.

Description of drawings

Fig. 1 is the synoptic diagram of the instance of the explanation measurement mechanism that is used for measuring in an embodiment demolding performace.

Embodiment

(toner)

Toner of the present invention contains resin glue, colorant and the release agent that comprises crystalline resins and noncrystalline resin, and if necessary can further contain other component.

Through the said toner of following acquisition: oil phase is dispersed in the water-bearing media that contains particle dispersants to obtain the dispersion liquid of emulsification, wherein passes to major general's colorant, release agent (wax), the resin glue that comprises crystallized polyurethane resin and noncrystalline resin and other resin glue and be dispersed in and obtain said oil phase in the organic solvent; With from the dispersion liquid of said emulsification, remove said organic solvent.

In the present invention; Glass transition temperature Tg 1st by through the definite said toner of the heating first time of DSC is preferably 45 ℃-65 ℃; Glass transition temperature Tg 2nd by through the definite said toner of the heating second time of DSC is preferably 25 ℃-35 ℃; 1/2 flow starting temperature T1/2 of said toner is 120 ℃-135 ℃, and the peak intensity of measuring with FTIR-ATR that derives from said crystalline resins and said release agent and the peak intensity ratio of the peak intensity that derives from said resin glue are 0.10-0.20.

And; Said resin glue contains the binder resin precursor that is formed by modified polyester resin; And said resin glue is through obtain as follows: can with said binder resin precursor chain extension or crosslinked compound dissolution forming oil phase, and allow said binder resin precursor in emulsified dispersed liquid, to carry out cross-linking reaction and/or chain extending reaction.

The manufacturing approach that subsequently explanation is used to obtain the material of aforementioned toner and uses said material.

< organic solvent >

For said organic solvent; Can use and wherein to form homogeneous solution through crystallized polyurethane resin is dissolved in fully, and when being cooled to low temperature, cause and being separated of crystallized polyurethane resin to form the organic solvent of opaque heterogeneous solution.The instance of organic solvent comprises toluene, ethyl acetate, butyl acetate, methyl ethyl ketone and methyl isobutyl ketone.These can be used alone or in combination.

< crystalline resins >

Suitably select said crystalline resins and do not have any restriction, as long as it has crystallinity, but it is preferably crystallized polyurethane resin.Said crystallized polyurethane resin has the heat fusing character that viscosity reduces near the temperature of beginning photographic fixing.Promptly; Said crystallized polyurethane resin has good heat-resisting storage stability; Because it has crystallinity when just in time being lower than the temperature that crystallized polyurethane resin begins fusion, and it reduces its viscosity (character of violent fusing) rapidly in the temperature that crystallized polyurethane resin begins fusion, thereby is fixed.Therefore, in toner, use crystallized polyurethane resin to make it possible to design and have the excellent heat-resisting storage stability and the toner of low-temperature fixing ability.And, through using said crystallized polyurethane resin, can design the toner that aspect demoulding width (minimum fixing temperature and heat counter print and distribute the poor of living temperature), shows excellent results.

Lucubrate owing to the inventor carries out for the low-temperature fixing ability that satisfies toner and heat-resisting storage stability has been found that crystallized polyurethane resin preferably has 60 ℃-80 ℃ endotherm peak temperature.When endotherm peak temperature was lower than 60 ℃, the toner that obtains possibly have not enough heat-resisting storage stability.When endotherm peak temperature was higher than 80 ℃, the toner that obtains possibly have not enough low-temperature fixing ability.

Through the monomer of adjusting formation crystallized polyurethane resin and the weight-average molecular weight of this crystallized polyurethane resin, the endotherm peak temperature of scalable crystallized polyurethane resin.In order to reduce the difference between heat absorption shoulder temperature and the endotherm peak temperature; Regulate said monomer and form, particularly regulate: form acid and alcohol monomer composition to be increased in the probability of repetition same structure in the strand with analogue compounds through following mode to increase the crystallinity of said crystallized polyurethane resin.Alternatively, number-average molecular weight that it can be through reducing said crystallized polyurethane resin and the difference between the weight-average molecular weight are regulated.

The heat absorption value of said crystallized polyurethane resin can, for example, measure through differential scanning calorimeter (DSC) system (DSC-60, by Shimadzu Corporation make) in the method below.At first, about 5.0g vibrin is placed the aluminum sampling receptacle, said sampling receptacle is placed on the holder, be placed in the electric furnace subsequently.Afterwards, said sample is heated to 150 ℃ with the rate of heat addition of 10 ℃/min from 0 ℃ under nitrogen atmosphere, the cooldown rate with 10 ℃/min is cooled to 0 ℃ from 150 ℃ subsequently., said sample with the rate of heat addition of 10 ℃/min once more be heated to 150 ℃, measure the DSC curve through differential scanning calorimeter (DSC-60 is made by Shimadzu Corporation) subsequently thereafter.Use is stored in the DSC curve that the routine analyzer in the DSC-60 system heats from the DSC Curve selection that obtains for the first time, and through using " heat absorption shoulder temperature " in the said routine analyzer to confirm the heat absorption shoulder 1 and heat absorption shoulder 2 that heat the first time of said sample.Afterwards, select the DSC curve of heating for the second time, and confirm the heat absorption shoulder 1 and the heat absorption shoulder 2 of the heating second time of said sample through " the heat absorption shoulder temperature " in the said routine analyzer of use.The shoulder temperature is confirmed as heat absorption shoulder 1 and heat absorption shoulder 2 with the order that begins from lower temperature.And use is stored in the DSC curve that the routine analyzer in the DSC-60 system heats from the DSC Curve selection that obtains for the first time, and through using " endotherm peak temperature " in the said routine analyzer to confirm the endothermic peak that heat the first time of said sample.Select the DSC curve of heating for the second time, and use " endotherm peak temperature " in the said routine analyzer to confirm the endothermic peak that heat the second time of said sample.

Crystallized polyurethane resin is synthetic by alkoxide component and acid constituents.

The instance of said alkoxide component comprises C2-C12 radical of saturated aliphatic diol compound.The instance of said C2-C12 radical of saturated aliphatic diol compound comprises 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-ethohexadiol, 1,10-decanediol, 1, the derivant of 12-dodecanediol and aforementioned diol compound.

The instance of said acid constituents comprises C2-C12 dicarboxylic acid and the C2-C12 saturated dicarboxylic acid that contains the two keys (C=C) of carbon.

Contain the C2-C12 dicarboxylic acid of the two keys (C=C) of carbon or the instance of C2-C12 saturated dicarboxylic acid and comprise hexane diacid, fumaric acid, 1; 4-succinic acid, 1,6-hexane diacid, 1,8-suberic acid, 1; 10-decanedioic acid, 1, the derivant of 12-dodecanedioic acid and aforementioned acid.

In them, the crystalline polyester of preferably forming by C4-C12 saturated diols component and C4-C12 saturated dicarboxylic acid component, because can obtain the high crystalline of the crystalline polyester of gained, and the crystalline polyester of gained demonstrates rapid viscosity variation under near the temperature the fusing point; Said C4-C12 saturated diols component is for being selected from 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1; 8-ethohexadiol, 1,10-decanediol and 1, at least a in the 12-dodecanediol; Said C4-C12 saturated dicarboxylic acid component is for being selected from 1,4-succinic acid, 1,6-hexane diacid, 1; 8-suberic acid, 1,10-decanedioic acid and 1, at least a in the 12-dodecanedioic acid.

Method as for crystallinity that is used for the crystallization control vibrin and softening point; There is the method be used for the non-linearity polyester that design and use obtain through polycondensation; Said polycondensation is through carry out as follows: between the synthesis phase of polyester; In alkoxide component, add ternary or more polynary polyvalent alcohol (for example glycerine), or in acid constituents, add ternary or more polynary polybasic carboxylic acid (for example trimellitic anhydride).

The molecular structure of crystallized polyurethane resin can be for example confirms through following: in solution or measure and the measurement of using the crystallized polyurethane resin of X-ray diffraction, GC/MS, LC/MS and IR as the NMR of the crystallized polyurethane resin of solid.For example, simply in infrared absorption spectrum, at 965cm ^-1± 10cm ^-1And 990cm ^-1± 10cm ^-1The crystallized polyurethane resin of wavelength with absorption (based on the out-of-plane bending vibration (δ CH) of alkene) here describe as one of example.

Molecular weight for crystalline polyester; The inventor studies based on following comprehension: the low molecular crystalline polyester with sharp-pointed molecular weight distribution is excellent, and it has poor heat-resisting storage stability when crystalline polyester contains high low-molecular-weight molecule content.The result; Under following situation, can obtain the low-temperature fixing ability and the heat-resisting storage stability of said toner: in the molecular weight distribution of the gpc measurement of the solvend through o-dichlorobenzene, weight-average molecular weight is 5; 000-20; 000, have 500 or the ratio of the molecule of littler number-average molecular weight Mn be 0%-2.5%, and have 1000 or the ratio of the molecule of littler number-average molecular weight Mn be 0%-5.0%.More preferably, have 500 or the ratio of the molecule of littler number-average molecular weight Mn be 0%-2.0%, and have 1000 or the ratio of the molecule of littler number-average molecular weight Mn be 0%-4.0%.

Can for example under following condition, measure molecular weight distribution through gel permeation chromatography (GPC) measurement mechanism (GPC-8220GPC is made by TOSOHCORPORATION).

Post: TSKgel SuperHZM-H, 15cm, three connection posts (TOSOH CORPORATION)

Temperature: 40 ℃

Solvent: tetrahydrofuran (THF)

Flow velocity: 0.35mL/min

Sample: 0.15% sample of supplying with 0.4mL.

For said The pretreatment; Sample dissolution (is contained stabilizing agent at tetrahydrofuran (THF); Wako Chemical Industries, Ltd. system) in to reach the concentration of 0.15 quality %, then; Filtrator through having 0.2 μ m aperture filters gained solution, and the filtrating of inherent filtration in the future is as sample.Measure through supplying with 100 μ L tetrahydrofuran (THF) sample solutions.For the measurement of the molecular weight distribution of said sample, by the logarithm value of the calibration curve that obtains from some kinds of monodisperse polystyrene standard models and the molecular weight distribution that concerns calculation sample between the count value.As the polystyrene standard sample that is used to make said calibration curve; Use Showdex STANDARD Std.No.S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0 and the S-0.580 of SHOWA DENKO K.K., and toluene.As detecting device, use refractive index (RI) detecting device.

Relation below the acid number of crystallized polyurethane resin and hydroxyl value satisfy, wherein acid number is defined as A and hydroxyl value is defined as B:

10mgKOH/g＜A＜40mgKOH/g

0mgKOH/g＜B＜20mgKOH/g

20mgKOH/g＜A+B＜40mgKOH/g

When acid number A is 10mgKOH/g or when lower, the gained toner has for the compatibility as the difference of the paper of recording-member, and this possibly cause heat-resisting storage stability to worsen.When acid number A is that 40mgKOH/g or higher or hydroxyl value B are 20mgKOH/g or when lower, exist toner in high temperature and high humidity environment, to reduce the possibility of its charged ability.When acid number A and hydroxyl value B sum (A+B) are 20mgKOH/g or when lower, reduce with the compatibility of said noncrystalline polyester resin, and therefore possibly can't obtain the low-temperature fixing ability in some cases.When acid number A and hydroxyl value B sum (A+B) are 40mgKOH/g or when higher, the degree of the compatibility between crystallized polyurethane resin and the noncrystalline polyester resin becomes excessively, this can cause heat-resisting in some cases storage stability to worsen.

Said acid number is the index of carboxylic acid group's quantity in the resin, and said hydroxyl value is the index of hydroxyl quantity in the resin.These values are measured through the method according to JIS K0070-1992.

Be used in the method for organic solvent dissolving and the said crystallized polyurethane resin of recrystallization following.

Under 70 ℃, said crystallized polyurethane resin (10g) and organic solvent (90g) are mixed and stirred 1 hour.The solution that stirs the back acquisition was cooled off 12 hours down at 20 ℃, thereby make the crystallized polyurethane resin recrystallization.Use KIRIYAMA funnel (product of Kiriyama glass Co.) (wherein being provided with No. 4 filter paper (product of Kiriyama glass Co.) that are used for the KIRIYAMA funnel) to carry out suction filtration the dispersion in organic solvent of the crystallized polyurethane resin of recrystallization, thereby separate said crystallized polyurethane resin from said organic solvent through suction machine.The crystallized polyurethane resin that obtains through said separation descends dry 48 hours at 35 ℃, thereby obtains the recrystallized product of said crystallized polyurethane resin.

Under 70 ℃, crystalline polyester is preferably 10 mass parts or bigger to organic acid solubleness.When solubleness during less than 10 mass parts; Because the compatibility between organic solvent and the crystallized polyurethane resin is poor; Therefore be difficult in organic solvent, crystallized polyurethane resin is dispersed to the submicron order size; This can cause crystallized polyurethane resin to be provided to unevenly in the toner-particle, causes the image quality of not enough charged ability and the difference after long-term the use.

Under 20 ℃, crystalline polyester to the solubleness of organic solvent preferably less than 3.0 mass parts.When solubleness is 3.0 mass parts or when bigger, even the crystallized polyurethane resin that is dissolved in the organic solvent also was tending towards compatible with noncrystalline polyester resin before heating, this can cause heat-resisting storage stability, the pollution of developing cell or the deterioration of image of difference.

Crystallized polyurethane resin can be measured through following method the solubleness of organic solvent.

At first, under predetermined temperature, stirred 20g crystallized polyurethane resin and 80g organic solvent 1 hour.No. 4 filter paper (product of Kiriyama glass Co.) that will be used for the KIRIYAMA funnel are set to KIRIYAMA funnel (product of Kiriyama glass Co.).Use said KIRIYAMA funnel, the solution that obtains is carried out suction filtration with suction machine under predetermined temperature, thereby separate said crystallized polyurethane resin from said organic solvent.Under than the high 50 ℃ temperature of the boiling point of said organic solvent, will heat 1 hour through the organic solvent that said separation obtains, with the evaporation organic solvent.By the weight change before and after the heating, calculate the amount that is dissolved in the crystallized polyurethane resin in the organic solvent.

<binder resin precursor >

Said resin glue preferably contains binder resin precursor.

Said binder resin precursor is preferably the binder resin precursor that is formed by modified polyester resin, and the example comprises the polyester prepolyer with isocyanates or epoxy resin modification.Said polyester prepolyer and the compound (for example, amine) that contains active hydrogen group carry out the effect of chain extending reaction with the demoulding width that improves (minimum fixing temperature and heat is counter print and distribute between the living temperature poor).About the synthetic method of said polyester prepolyer, through making conventional isocyanation esterification reagent or epoxidation reagent and can easily synthesizing said polyester prepolyer as the vibrin reaction of basic thing (base).

The instance of isocyanation esterification reagent comprises: aliphatic polyisocyanate (for example, tetramethylene diisocyanate, hexamethylene diisocyanate and 2,6-two isocyanate group methyl caproates); Alicyclic polyisocyanates (for example, IPDI and cyclohexyl-methane diisocyanate); Aromatic diisocyanates (for example, toluene diisocyanate and methyl diphenylene diisocyanate); Aromatics aliphatic vulcabond (for example, α, α, α ', α '-tetramethylxylene diisocyanate); Isocyanuric acid ester; Aforementioned polyisocyanates with phenol derivatives, oxime or caprolactam blocking; And potpourri arbitrarily in the aforementioned polyisocyanates.The instance of epoxidation reagent comprises chloropropylene oxide.

The ratio of isocyanation esterification reagent is confirmed as equivalent proportion [NCO]/[OH] of isocyanate groups [NCO] and the hydroxyl [OH] of the polyester of waiting to become basic thing.The ratio of [NCO]/[OH] typically is 5/1-1/1, be preferably 4/1-1.2/1 and even 2.5/1-1.5/1 more preferably.When the ratio of [NCO]/[OH] greater than 5 the time, the gained toner possibly have not enough low-temperature fixing ability.When the mol ratio of [NCO] less than 1 the time, polyester prepolyer has low urea content, this can cause the heat-resisting anti-seal property of the deficiency of gained toner.

The amount of the isocyanation esterification reagent in the polyester prepolyer typically is 0.5 quality %-40 quality %, be preferably 1 quality %-30 quality % and 2 quality %-20 quality % more preferably.When the amount of isocyanation esterification reagent during, may not realize the heat-resisting storage stability and the low-temperature fixing ability of said toner simultaneously, and can not obtain enough heat-resisting anti-seal property less than 0.5 quality %.When it measured greater than 40 quality %, the gained toner can have not enough low-temperature fixing ability.

In the per molecule polyester prepolyer quantity of contained isocyanate groups typically be 1 or more, be preferably average 1.5-3 and more preferably average 1.8-2.5.When the quantity of the isocyanate groups of each molecule was less than 1, the urea modified polyester resin behind the chain extending reaction had little molecular weight, and this possibly cause not enough heat-resisting anti-seal property.

Binder resin precursor preferably has 1 * 10 ⁴-3 * 10 ⁵Weight-average molecular weight." with binder resin precursor chain extension or crosslinked compound "

Comprise the compound that contains active hydrogen group with binder resin precursor chain extension or crosslinked examples for compounds, and its representative instance comprises amine.

The instance of amine comprises that the amino of any amine in diamine compound, ternary or more polynary polyamine compounds, alkamine compound, amineothiot compound, amino-acid compound and the aforementioned amine is by the end-caps of end-blocking.

The instance of diamine compound comprises: aromatic diamine (as phenylenediamine, diethyl toluene diamine and 4,4 '-diaminodiphenyl-methane); Alicyclic diamine (as 4,4 '-diamido-3,3 '-dimethyl dicyclohexyl methyl hydride, cyclohexane diamine and IPD); And aliphatic diamine (like ethylenediamine, tetra-methylenedimine and hexamethylene diamine).

The instance of ternary or more polynary polyamine compounds comprises diethylene triamine and trien.

The instance of alkamine compound comprises monoethanolamine and ethoxylaniline.

The amineothiot examples for compounds comprises aminoethyl mercaptan and aminopropyl mercaptan.

The instance of amino-acid compound comprises alanine and aminocaproic acid.

The amino of any amine in the aforementioned amine is comprised the ketimine compound and

isoxazoline compound that derives from amine and ketone (like acetone, methyl ethyl ketone and methyl isobutyl ketone) by the instance of the end-caps of end-blocking.In aforementioned amine, the potpourri of preferred diamine compound and diamine compound and a small amount of polyamine compounds.

< colorant >

Said colorant suitably selects not have any restriction according to intended purposes.The instance of said colorant comprises carbon black; Aniline black byestuffs; Iron black; Naphthol yellow S; Hansa yellow (10G; 5G and G); Cadmium yellow; Iron oxide yellow; Sil; Lead and yellow-collation; Titan yellow; Polyazo is yellow; Oil yellow; Hansa yellow (GR; A; RN and R); Pigment yellow L; Benzidine yellow (G and GR); Permanent yellow (NCG); Fu Erkan fast yellow (5G; R); Tartrazine lake; Quinoline yellow lake; The yellow BGL of anthracene azine; Iso-dihydro-indole is yellow; Colcother; The red lead; Plumbous bright red; Cadmium red; Cadmium mercury is red; Crimson antimony is red; Permanent bordeaux 4R; Para red; Red as fire; P-chloro-o-nitroaniline red; Lithol that fast scarlet G; Bright fast scarlet; Bright fuchsin BS; Permanent bordeaux (F2R; F4R; FRL; FRLL and F4RH); Fast scarlet VD; The strong rubine B of Fu Erkan; Brilliant scarlet G G; Lithol that rubine GX; Permanent bordeaux F5R; Bright fuchsin 6B; Pigment scarlet 3B; The red 5B of wine; The toluidine chestnut; Consolidate the red F2K of wine forever; The red BL of dust Leo wine; The red 10B of wine; Light BON chestnut; Middle BON chestnut; Eosine lake; Rhodamine color lake B; Rhodamine color lake Y; Alizarine lake; Thioindigo red B; The thioindigo chestnut; Oil red; Quinacridone is red; Pyrazolone red; Polyazo is red; Chrome vermilion; Benzidine orange; Pyrene ketone orange; The oil orange; Cobalt blue; Cerulean blue; Alkali blue lake; Peacock blue lake; The Victoria blue color lake; Metal-free phthalocyanine blue; Phthalocyanine blue; Fast sky blue; Indanthrene blue (RS and BC); Indigo-blue; The deep-sea is blue; Barba hispanica; Anthraquinone blue; Fast violet B; The methyl violet color lake; Cobalt violet; Manganese violet; Two the alkane purple; Anthraquinone is purple; Chrome green; Zinc green; Chromium oxide; Emerald green; Emerald green; Pigment green B; Naphthol green B; Green gold; The acid green color lake; The malachite green color lake; Phthalocyanine green; Anthraquinone green; Titanium dioxide; The zinc flower; Lithopone; And two kinds or more kinds of potpourris of aforementioned colorant.

The amount of colorant is preferably 1 quality %-15 quality %, more preferably 3 quality %-10 quality % with respect to toner.

Colorant can masterbatch form use, in said masterbatch, colorant and resin formation compound.The instance of the resin glue of in the manufacturing of masterbatch, mediating or mediating with masterbatch is except aforementioned modified polyester resin and unmodified polyester resin; Also comprise: the polymkeric substance of styrene or its substitution product (for example, polystyrene, gather) chlorostyrene and polyvinyl; Styrol copolymer (for example, styrene-right-chloro-styrene copolymer, styrene-propene multipolymer, styrene-ethylene base toluene multipolymer, styrene-ethylene base naphthalenedicarboxylate copolymer, styrene-propene acid methyl terpolymer, styrene-propene acetoacetic ester multipolymer, styrene-propene butyl acrylate copolymer, the misery ester copolymer of styrene-propene, styrene-methylmethacrylate copolymer, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl propylene acid methyl terpolymer, styrene-acrylonitrile copolymer, styrene-ethylene ylmethyl ketone copolymers, SB, styrene-isoprene multipolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer and styrene-maleic acid ester copolymer); And other material, comprise polymethylmethacrylate; Poly-n-butyl methacrylate; PVC; Polyvinyl acetate; Tygon; Polypropylene; Polyester; Epoxy resin; The epoxy polyol resin; Polyurethane; Polyamide; Polyvinyl butyral; Polyacrylic resin; Rosin; Modified rosin; Terpene resin; Aliphatic series or alicyclic hydrocarbon resin; Aromatic petroleum resin; Chlorinated paraffin; And paraffin.These can be used alone or in combination.

Masterbatch can be through will being used for masterbatch resin and colorant mix and mediate and prepare.In mixing and mediating, can be with an organic solvent to improve the interaction between colorant and the resin.And, can prepare said masterbatch through flash method (flashing method), in said flash method, the moisture thickener that contains colorant mixes with resin and organic solvent and mediates, and subsequently said colorant is transferred to resin and anhydrates and organic solvent to remove.Why preferably using this method, be because the wet cake of colorant can directly use, and the wet cake of drying-free colorant is with the preparation colorant.In the mixing and kneading of said colorant and resin, preferably use high shear dispersion machine (like triple-roller mill).

< release agent >

Said release agent is preferably the wax of the fusing point with 50 ℃-120 ℃.

Therefore the function that at the interface effectively play release agent of said wax between fixing roller and toner can be improved heat-resisting anti-seal property not applying under the situation of release agent (like oil) to the fixing roller.

Notice that the fusing point of said wax for example, is confirmed through the maximum endothermic peak of measuring said wax by the TG-DSCSystem TAS-100 (Rigaku Corporation system) as differential scanning calorimeter.

The material of listing below can be used as said release agent.

The instance of said wax comprises vegetable wax (for example Brazil wax, cotton wax, Japan tallow and rice wax); Animal wax (for example, beeswax and sheep oil); Mineral wax (for example, ceresine and ceresin); And pertroleum wax (for example, paraffin, microcrystalline wax and vaseline).

Instance divided by the wax outside the last natural wax comprises: synthetic chloroflo (for example, Fischer-Tropsch wax and Tissuemat E); And synthetic wax (for example, ester type waxes, ketone wax and ether wax).

In addition, other instance of said release agent comprises: fatty acid amide, for example, and 1,2-hydroxystearic acid acid amides, stearmide, phthalic anhydride acid imide and chlorinated hydrocabon; The low molecular crystalline polymkeric substance, for example, acrylic homopolymer (like positive stearyl ester of polymethylacrylic acid and the positive lauryl of polymethylacrylic acid) and acrylic copolymer (for example, the positive stearyl ester-ethyl methacrylate copolymers of acrylic acid); And has a crystalline polymer as the long alkyl of side chain.

< dispersing agent for wax >

For said toner, can use the dispersing agent for wax that is used to make the wax dispersion that comprises as release agent.Since wax with have low compatibility as the noncrystalline resin of resin glue, therefore, said wax is uneven distribution, so that it is positioned at the surface of contiguous toner-particle in a large number, only if use dispersing agent for wax.When using said dispersing agent for wax, said wax has increased the compatibility with said resin glue, so that said wax is dispersed in the interior section of said toner-particle.Said dispersing agent for wax has the effect that improves the dispersed of crystallized polyurethane resin and improve the dispersiveness of wax.Especially, said dispersing agent for wax has the function as the spreading agent of the dispersiveness that is used to improve crystallized polyurethane resin and release agent (wax).Through changing the amount of aforementioned dispersing agent for wax, may command is positioned at the crystalline polyester on contiguous toner-particle surface and the amount of wax.

Said dispersing agent for wax is for having following resin (B) as the graft polymer of side chain graft to the structure of the main chain of following resin (A).

Resin (A) is suitably selected from conventional release agent, but needs only graft resin (B) on it.For example, said resin (A) is a polyolefin resin, the polyolefin resin of preferably making through thermal decomposition.The instance that is used to form the alkene of polyolefin resin comprises ethene, propylene, 1-butylene, isobutylene, 1-hexene, 1-dodecylene and 1-vaccenic acid.

The instance of polyolefin resin comprises: olefin polymer; The oxide of olefin polymer; The modified product of olefin polymer; And alkene and can with the multipolymer of other monomer of said olefin-copolymerization.

The instance of olefin polymer comprises tygon, polypropylene, ethylene-propylene copolymer, ethene-butene-1 copolymer and propylene-1-hexene copolymer.The instance of the oxide of olefin polymer comprises the oxide of aforementioned olefin polymer.The instance of the modified product of olefin polymer comprises the adduct of the maleic acid derivatives (for example maleic anhydride, monomethyl maleate, butyl maleate and dimethyl maleate) of aforementioned olefin polymer.Alkene with can comprise the for example multipolymer of unsaturated carboxylic acid (like (methyl) acrylic acid, itaconic acid and maleic anhydride), unsaturated carboxylic acid alkyl ester (like (methyl) acrylic acid alkyl (C1-C8) ester and maleic acid alkyl (C1-C8) ester) of alkene and monomer with the instance of the multipolymer of other monomer of olefin-copolymerization.

And in this embodiment, said monomer need not comprise alkene structures, as long as said polymer architecture has polyolefinic structure.For example, can use polymethylene (husky rope wax etc.).In these polyolefin resines, the oxide of preferred olefin polymers, olefin polymer and the modified product of olefin polymer; More preferably tygon, polymethylene, polypropylene, ethylene/propylene polymers, oxidic polyethylene, its chlorinated polypropylene and maleinization polypropylene; Even more preferably tygon and polypropylene.

The instance that is used to form the monomer of resin (B) comprises: the alkyl of unsaturated carboxylic acid (C1-C5) ester (for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-ethylhexyl acrylate); And vinyl ester monomers (for example vinyl acetate).Among them, preferred (methyl) alkyl acrylate, and more preferably (methyl) acrylic acid C1-C5 Arrcostab (B1).

Use instance to comprise styrene monomer with (B1) combination as the aromatic vinyl monomer (B2) of the monomer that is used to form resin (B), for example styrene, AMS, p-methylstyrene, a methyl styrene, to methoxy styrene, para hydroxybenzene ethene, to acetoxy-styrene, vinyltoluene, ethyl styrene, styryl phenyl and benzyl styrene.Among them, optimization styrene especially.

The particle diameter of dispersing agent for wax is for example measured through LA-920 (Horiba, Ltd. system).In the measurement of carrying out through LA-920, (Horiba Ltd.) is used for analyzing will to be used for the application program (Ver 3.32) of LA-920.

Particularly, after use has wherein disperseed the solvent adjustment optical axis of dispersing agent for wax, measure background., begin circulation, and wax dispersion is dropwise added wherein thereafter.After confirming that transmissivity is stable, under following condition, apply ultrasound wave.After applying ultrasound wave, measure the diameter of discrete particles under the condition in transmittance values falls into the scope of 70%-95%.Carrying out said measurement under the condition in the value of the transmissivity of LA-920 falls into the scope of 70%-95% is important for the repeatability of the measurement of the particle diameter of realizing carrying out through said measurement mechanism.After applying ultrasound wave, the value of transmissivity becomes not under the situation in aforementioned range, and said measurement need be carried out once more.In order to obtain the value of aforementioned transmissivity, need to regulate the amount of dripping of said dispersion liquid.

The condition setting that is used to measure and analyze is following:

The number of times that data read: 15

Relative index of refraction: 1.20

Circulation: 5

Ultrasonic intensity: 7

< charge control agent >

If necessary, said toner can further contain charge control agent.Said charge control agent is suitably selected according to intended purposes and is not had any restriction, and the example comprises aniline black byestuffs, triphenhlmethane dye, contains the slaine of metal complex dyes, molybdic acid chelate pigment, rhodamine dyes, alkoxyamine, quaternary ammonium salt (comprising the fluorine modified quaternary ammonium salt), alkylamide, phosphorus, phosphorus compound, tungsten, tungsten compound, fluorine active agent, salicylic slaine and the salicyclic acid derivatives of chromium.

For said charge control agent, can use commercial product.The instance of said commercial product comprises: aniline black byestuffs BONTRON 03, quaternary ammonium salt BONTRON P-51, metallic azo dyes BONTRON S-34, based on the metal complex E-82 of carbonaphthoic acid, based on salicylic metal complex E-84 and phenolic condensates E-89 (by ORIENT CHEMICAL INDUSTRIES CO., LTD makes); The molybdenum complex TP-302 of quaternary ammonium salt and TP-415 (by Hodogaya Chemical Co., Ltd. makes); Quaternary ammonium salt COPY CHARGE PSY VP 2038, triphenyl methane derivant COPYBLUE PR, quaternary ammonium salt COPY CHARGE NEG VP2036 and COPY CHARGE NX VP434 (making) by HoechstAG; LRA-901; Boron complex LR-147 (by Japan Carlit Co., Ltd. makes); Copper phthalocyanine; Perylene; Quinacridone; AZOpigments; And have the polymkeric substance as functional group such as sulfonic group, carboxyl, quaternary ammonium salt.

The amount of contained charge control agent can not be decided without exception, and the method for preparing toner (process for dispersing that comprises use) of its type according to used resin glue, the optional adjuvant that uses and use changes.The amount of charge control agent is preferably 0.1 mass parts-10 mass parts, 0.2 mass parts-5 mass parts more preferably with respect to 100 mass parts resin glues.When the amount of charge control agent during greater than 10 mass parts, the charged ability of said toner becomes excessively, this can reduce charge control agent effect, improve electrostatic force, cause the lazy flow of developer or the low image density of the image that obtains developer roll.These charge control agents can dissolve with masterbatch and/or resin fusion with after mediating and disperse.Certainly, charge control agent can directly join in the organic solvent when dissolving and disperse.Alternatively, can charge control agent be fixed on the surface of toner-particle after the toner-particle preparation.

< noncrystalline polyester resin >

Toner of the present invention contains the amorphous unmodified polyester resin as resin glue.Preferably the modified polyester resin and the unmodified polyester resin of the crosslinked and/or chain extending reaction acquisition through the binder resin precursor that formed by modified poly ester are compatible at least in part each other.Low-temperature fixing ability and the heat-resisting anti-seal property that can improve the toner that obtains used in the combination of these resins.Therefore, the polyvalent alcohol that is used to form unmodified polyester resin and polybasic carboxylic acid are preferably with to be used to form those of modified polyester resin identical or similar.For said unmodified polyester resin, also can use the noncrystalline polyester resin that is used in the said crystalline polyester dispersion liquid, as long as it is unmodified.

When the acid number that is defined as A and noncrystalline polyester resin when the acid number of crystalline polyester was defined as C, crystallized polyurethane resin and noncrystalline polyester resin preferably satisfied following relational expression:

-10mgKOH/g＜A-C＜10mgKOH/g，

When the difference of the acid number between crystalline polyester and the non-crystalline polyester is 10 or when bigger, compatibility and compatibility between crystalline polyester and the non-crystalline polyester are poor, this can cause the low-temperature fixing ability of the difference of gained toner.In addition, in this case, crystalline polyester is tending towards being exposed on the surface of toner-particle, and this is tending towards causing the pollution and the film forming of developing cell.

Notice that except unmodified polyester resin, the urea modified polyester resin also can use with the vibrin of using the chemical bond modification except the urea key (like the vibrin with the amino-formate bond modification).

Contain modified polyester resin for example under the situation of urea modified polyester resin at method for producing toner and toner, said modified polyester resin can pass through the single stage method manufacturing.

An instance of the manufacturing approach of urea modified polyester resin is described below.

At first, polyvalent alcohol and polybasic carboxylic acid are heated to 150 ℃-280 ℃ in the presence of catalyzer (like metatitanic acid four butoxy ester and dibutyl tin oxides), and remove the water (randomly under reduced pressure) of generation, thereby acquisition contains the vibrin of hydroxyl.Next, the vibrin and the polyisocyanates that contain hydroxyl are reacted at 40 ℃-140 ℃ down, thereby obtain to contain the polyester prepolyer of isocyanate groups.Then, the polyester prepolyer and the amine that contain isocyanate groups are reacted down at 0 ℃-140 ℃, thereby obtain the urea modified polyester resin.

The number-average molecular weight of urea modified polyester resin typically is 1000-10000 and is preferably 1500-6000.

Randomly solvent is used to contain the reaction of the vibrin and the polyisocyanates of hydroxyl, and the reaction that contains the polyester prepolyer and the amine of isocyanate groups.

Solvent is suitably selected according to intended purposes and is not had any restriction; And the example comprises the solvent to the isocyanate groups inertia, for example arsol (like toluene and xylene), ketone (like acetone, methyl ethyl ketone and methyl isobutyl ketone), ester (like ethyl acetate), acid amides (like dimethyl formamide and dimethyl acetamide) and ether (like tetrahydrofuran).

Under the situation of unmodified polyester resin and urea modified polyester resin combination use, can the vibrin made from the mode identical with the manufacturing of the vibrin that contains hydroxyl be added in the reaction solution afterwards that obtains said urea modified polyester resin and with this solution and mix.

For contained resin glue in the oil phase of making said toner; Can aforementioned crystallized polyurethane resin, noncrystalline polyester resin, binder resin precursor and unmodified resin combination be used, and said resin glue can further comprise the resin except that aforementioned resin.Resin glue preferably comprises vibrin, more preferably comprises the vibrin of 50 quality % or bigger amount.When the amount of vibrin was lower than 50 quality %, the gained toner can have not enough low-temperature fixing ability.Especially preferred is that the resin that comprises as resin glue all is a vibrin.

The instance of the resin glue except that vibrin comprises: the derive polymkeric substance of substituent of styrene polymer or styrene, for example polystyrene, gather (to chlorostyrene) and polyvinyl toluene; Styrol copolymer is styrene-right-chloro-styrene copolymer for example; The styrene-propene multipolymer; Styrene-ethylene base toluene multipolymer; Styrene-ethylene base naphthalenedicarboxylate copolymer; Styrene-propene acid methyl terpolymer; Styrene-propene acetoacetic ester multipolymer; The styrene-propene butyl acrylate copolymer; The misery ester copolymer of styrene-propene; Styrene-methylmethacrylate copolymer; Styrene-ethyl methacrylate copolymers; Styrene-butyl methacrylate copolymer; Styrene-α-chloromethyl propylene acid methyl terpolymer; Styrene-acrylonitrile copolymer; Styrene-ethylene ylmethyl ketone copolymers; SB; The styrene-isoprene multipolymer; Styrene-acrylonitrile-indene copolymer; Styrene-maleic acid copolymer; With the styrene-maleic acid ester copolymer; And other material polymethylmethacrylate for example; Poly-n-butyl methacrylate; PVC; Polyvinyl acetate; Tygon; Polypropylene; Epoxy resin; The epoxy polyol resin; Urethane resin; Polyamide; Polyvinyl butyral; Polyacrylic resin; Rosin; Modified rosin; Terpene resin; Aliphatic series or alicyclic hydrocarbon resin; Aromatic petroleum resin; Chlorinated paraffin; And paraffin.

<using the method for preparing toner of aqueous solvent >

The water-bearing media that is used to make toner of the present invention can be independent water or water with can with the combination of the miscible solvent of water.Can comprise alcohol (like methyl alcohol, isopropyl alcohol and monoethylene glycol), dimethyl formamide, tetrahydrofuran, cellosolve (like methyl cellosolve) and lower ketones (like acetone and methyl ethyl ketone) with the instance of the miscible solvent of water.

Add and be mixed for forming the material (also can be commonly referred to as " toner materials ") of toner-particle in the time of can in water-bearing media, forming dispersion (dispersed element); For example binder resin precursor, colorant, release agent, crystalline polyester, charge control agent and unmodified polyester resin; But more preferably these materials are mixed in advance, and add in the water-bearing media said mixtures of material and dispersed therein.In the manufacturing of the toner of this embodiment, when in water-bearing media, forming particle, needn't add the material that other is used to form said toner, for example colorant, release agent and charge control agent.These materials can add after forming particle.For example, after formation does not comprise the particle of colorant, can add colorant through the normal dyeing method.

Process for dispersing is suitably selected according to intended purposes and is not had any restriction, and the example comprises the dispersion by low velocity shear decollator, high speed shear decollator, friction decollator, high-pressure injection decollator and ultrasonic disperser.Among them, preferably use the high speed shear decollator, because the dispersion that obtains can obtain the particle diameter of 2 μ m-20 μ m.

Under the situation that the high speed shear decollator is used to disperse, rotational speed is suitably selected according to intended purposes and is not had any restriction, but is preferably 1000rpm-30000rpm, 5000rpm-20000rpm more preferably.The duration of disperseing does not receive special restriction, but in the situation of batch systems, it was typically 0.1 minute-60 minutes.The temperature that is used to disperse typically be preferably 0 ℃-80 ℃ (under pressure), more preferably 10 ℃-40 ℃.

The consumption of water-bearing media typically is 100 mass parts-1000 mass parts with respect to 100 mass parts toner materials.When the amount of water-bearing media during less than 100 mass parts, toner materials is desirably disperseed, so that possibly can't obtain the toner-particle of predetermined particle diameter.When it measured greater than 1000 mass parts, this was uneconomic.And, randomly use spreading agent.The use of spreading agent is preferred, because the particle that obtains has sharp-pointed size-grade distribution, and disperse state is stable.

For carrying out the method for polyester prepolyer with the reaction of the compound that contains active hydrogen group; Can be before being dispersed in toner materials in the water-bearing media; In water-bearing media, add the compound that contains active hydrogen group, make polyester prepolyer and the compound reaction that contains active hydrogen group subsequently.Alternatively, after being dispersed in toner materials in the water-bearing media, add the compound that contains active hydrogen group, thereby from the granular boundary initiation reaction.In this situation, the preferential modified poly ester that forms with polyester prepolyer that produces in the surface of the toner-particle of making, the result can provide concentration gradient in particle.

The instance that is used for will wherein being dispersed with the oil phase emulsification of toner materials and being dispersed in the spreading agent of the liquid that contains water comprises: anionic surfactant is alkyl benzene sulfonate, alpha-alkene sulfonate and phosphate for example; Amine salt such as alkylamine salt, amino alcohol fatty acid derivatives, polyamines derivative of fatty acid and imidazoline; Quaternary cationics such as alkyl trimethyl ammonium salt; Dialkyl dimethyl ammonium salt; Alkyl dimethyl benzyl ammonium salt; Pyridine

salt; Alkyl isoquinoline

salt and benzethonium chloride; Non-ionic surfactant is fatty acid amide derivant and polyol derivative for example; And amphoteric surfactant for example alanine, dodecyl two (aminoethyl) glycocoll, two (octyl group aminoethyl) glycocoll and N-alkyl-N, N-Dimethyl Ammonium betaine.

And, even the surfactant that contains fluoroalkyl is also can show its dispersion effect on a small quantity.The preferred embodiment that contains the anionic surfactant of fluoroalkyl comprises fluoroalkyl carboxylic acid or its slaine of C2-C10; PFO sulfonyl disodium glutamate; 3-[ω-fluoroalkyl (C6-C11) oxygen]-1-alkyl (C3-C4) sodium sulfonate; 3-[ω-fluothane acyl group (C6-C8)-N-ethylamino]-1-propane sulfonic acid sodium; Fluoroalkyl (C11-C20) carboxylic acid or its slaine; Perfluoro carboxylic acid (C7-C13) or its slaine; Perfluoroalkyl (C4-C12) sulphonic acid ester or its slaine; The PFOS diglycollic amide; N-propyl group-N-(2-hydroxyethyl) PFO sulfonamide; Perfluoroalkyl (C6-C10) sulfonamide oxypropyl trimethyl ammonium salt; Perfluoroalkyl (C6-C10)-N-ethylsulfonyl glycinate; With single perfluoroalkyl (C6-C16) ethyl phosphonic acid ester.

For the surfactant that contains fluoroalkyl, can use the commercially available prod.The instance of the name of product of said product comprises: SURFLON S-111, S-112, S-113 (Asahi Glass Co., Ltd. system); FRORARD FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Ltd. system); UNIDYNE DS-101, DS-102 (Daikin Industries, Ltd. system); MEGAFACE F-110, F-120, F-113, F-191, F-812, F-833 (DIC Corporation system); EFTOP EF-102,103,104,105,112,123A, 123B, 306A, 501,201,204 (Tohchem Products Co., Ltd. system); And FUTARGENT F-100, F-150 (NEOS COMPANY LIMITED system).

The instance of cationic surfactant comprises the aliphatic series primary that contains fluoroalkyl; The second month in a season or tertiary amine acid; Aliphatic quaternary ammonium salt (like perfluoroalkyl (C6-C10) sulfonamide oxypropyl trimethyl ammonium salt); The phenylmethane ammonium salt; Benzethonium chloride; Pyridine

salt and imidazoline

salt.For cationic surfactant, can use the commercially available prod.The instance of the name of product of said product comprises: SURFLON S-121 (Asahi Glass Co., Ltd. system); FRORARD FC-135 (Sumitomo 3M Ltd. system); UNIDYNE DS-202 (DaikinIndustries, Ltd. system); MEGAFACE F-150, F-824 (DIC Corporation system); EFTOP EF-132 (Tohchem Products Co., Ltd. system); With FUTARGENT F-300 (NEOS COMPANY LIMITED system).

For water-fast mineral compound spreading agent, can use tricalcium phosphate, lime carbonate, titanium dioxide, cataloid and hydroxyapatite.

And the drop usable polymers protecting colloid of dispersion or water-fast organic granular are stable.The instance of the dispersion stabilizer that uses comprises: acid is acrylic acid, methacrylic acid, alpha-cyanoacrylate, alpha-cyano methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride for example; (methyl) acryl monomer that contains hydroxyl is propenoic acid beta-hydroxy ethyl ester for example; Jia Jibingxisuanβ-Qiang Yizhi; The propenoic acid beta-hydroxy propyl ester; Methacrylic acid β-hydroxypropyl acrylate; Acrylic acid γ-hydroxypropyl acrylate; Methacrylic acid γ-hydroxypropyl acrylate; Acrylic acid 3-chloro-2-hydroxypropyl acrylate; Methacrylic acid 3-chloro-2-hydroxypropyl acrylate; Single acrylic acid diglycol ester; Monomethyl acrylic acid diglycol ester; Single acrylic acid glyceride; Monomethyl acrylic acid glyceride; N hydroxymethyl acrylamide and N-methylol methacrylamide; Vinyl alcohol or with the ether of vinyl alcohol, for example vinyl methyl ether, EVE and vinyl propyl ether; Vinyl alcohol and the ester that contains the compound of carboxyl, for example vinyl acetate, propionate and vinyl butyrate; Acrylic amide, the for example methylol compound of acrylic amide, Methacrylamide, DAAM or aforementioned acid amides; Acid chloride is acryloyl chloride and methacrylic chloride for example; The homopolymer or the multipolymer that contain nitrogen-atoms or its heterocycle, for example vinylpyridine, vinyl pyrrolidone, vinyl imidazole and aziridine; Polyoxyethylene, for example polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl amine, polyoxypropylene alkyl amine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylplenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene octadecyl phenylester and polyoxyethylene nonyl phenylester; And cellulose, for example methylcellulose, hydroxyethyl cellulose and hydroxypropyl cellulose.

In the time will dissolving in acid or alkaline bleach liquor soluble compound (like calcium phosphate) as dispersion stabilizer, use the used calcium phosphate of acid (example hydrochloric acid) dissolving, use water washing subsequently, thereby in formed fine grained (toner-particle), remove calcium phosphate.And calcium phosphate can decompose through enzyme to be removed.

Alternatively, used spreading agent can be retained on the toner-particle surface.But, consider the charged ability of the toner that obtains, spreading agent is preferably removed through washing.

In addition, in order to reduce the viscosity of method for producing toner and toner, can use solvent, solubilized has the modified poly ester through the reaction acquisition of polyester prepolyer in this solvent.The preferred solvent that uses is because the toner that obtains has sharp-pointed size-grade distribution.

Said solvent is preferably volatile, and has and be lower than 100 ℃ boiling point, because it can be easy to remove.Said solvent does not have any restriction according to suitable selection of intended purposes; And the example comprises toluene, xylene, benzene, phenixin, methylene chloride, 1; 2-ethylene dichloride, 1; 1,2-trichloroethanes, triclene, chloroform, monochloro benzene, vinylidene chloride, methyl acetate, ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone.These can be used alone or in combination.

Among them, preferred especially arsol (like toluene and xylene) and halogenated hydrocarbons (like methylene chloride, 1,2-ethylene dichloride, chloroform and phenixin).

With respect to 100 mass parts polyester prepolyers, the amount of solvent is preferably 0-300 mass parts, more preferably 0-100 mass parts and even 25 mass parts-70 mass parts more preferably.When using solvent, through under normal pressure or decompression, heating after chain extension and/or the cross-linking reaction except that desolvating.

The duration of chain extension and/or cross-linking reaction is selected according to polyester prepolyer and the reactivity that contains between the compound of active hydrogen group, but its typically be 10 minutes-40 hours, be preferably 30 minutes-24 hours.Temperature of reaction typically is 0 ℃-100 ℃, is preferably 10 ℃-50 ℃.And, if necessary, can conventional catalyst be used for chain extension and/or cross-linking reaction.The instantiation of catalyzer comprises: tertiary amine (for example triethylamine) and imidazoles.

In order from the emulsified dispersed liquid that is obtained, to remove organic solvent, can use following method.Said method comprises: whole system is heated gradually, so that contained organic solvent evaporates fully in the drop.Alternatively, the dispersion liquid of the said emulsification of spraying in dry atmosphere is removed to form toner-particle, to evaporate simultaneously and remove the water-fast organic solvent that comprises in the drop fully and is contained water dispersant.Dispersion liquid for emulsification is sprayed to dry atmosphere wherein, uses the gas (for example, air, nitrogen, carbon dioxide and burning gases) through heating usually, the various airflows that especially under the temperature of the maximum boiling point that is equal to or higher than solvent, heat.The processing of using spray dryer, belt dryer or rotary kiln to carry out the short time can fully obtain the quality of expecting.

In emulsification and dispersion process, have wide size-grade distribution in dispersion, and the particle that obtains with keep this size-grade distribution wash with dry situation under, can said size-grade distribution be adjusted to the size-grade distribution of expection through classification.

As the progressive operation of in liquid, carrying out, can remove fine grained through cyclone separator, decanter or centrifugal separator.Certainly, can after the particle of the powder type that obtains to obtain, carry out classification by drying.But, consider efficient, more preferably in liquid, carry out classification.Can unnecessary fine grained or coarse particle that collect be turned back to kneading process, so that they are used to form particle.In this cycling, said fine grained or coarse particle can be hygrometric state.

The spreading agent that uses is preferably removed from said dispersion liquid as much as possible, and removing preferably of spreading agent carried out in progressive operation.

Toner powder through obtaining and warp is dry mixes with other particle (for example release agent particle, electric charge control particle, plasticizer particle and coloring agent particle); Perhaps apply physical shock to mixture of powders; Aforementioned other granulopexy is also fused on the surface of the composite particles that obtains, thereby stop other particle to come off from the surface of said composite particles.

The concrete grammar that is used to mix or applies impact comprises: the method that applies impulsive force through the blade of high speed rotating to potpourri; And potpourri added in the high-speed air flow and increase flow velocity, thereby make particle bump against other particle, or make the method for composite particles and suitable impingement plate collision.The instance of the device that uses comprises: ANGMILL (product of Hosokawa Micron Corporation); Through the equipment of I type mill (Nippon Pneumatic Mfg.Co., the product of Ltd.) being retrofited making so that it pulverizes the air pressure reduction; Hybrid system (Nara Machinery Co., the product of Ltd.); Kryptron system (Kawasaki Heavy Industries, the product of Ltd.); And automatic mortar.

< external additive >

Said toner can contain and is useful on the external additive that auxiliary block post is stated the flowability of toner, development capability or charged ability.

For said external additive, preferably use inorganic particle.The primary particle size of inorganic particle is preferably 5nm-2 μ m, 5nm-500nm more preferably.Its BET specific surface area is preferably 20m ²/ g-500m ²/ g.

The amount of inorganic particle is preferably 0.01 quality %-5.0 quality %, 0.01 quality %-2.0 quality % more preferably with respect to toner.The instance of inorganic particle comprises silicon dioxide, aluminium oxide, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanates, zinc paste, tin oxide, silica sand, clay, mica, wollastonite, zeyssatite, chromium oxide, cerium oxide, iron oxide red, antimony trioxide, magnesium oxide, zirconia, barium sulphate, barium carbonate, lime carbonate, silit and silicon nitride.

Other instance of external additive comprises: polymer beads, the particle of for example making through no soap emulsion polymerization, suspension polymerization or dispersin polymerization (like granules of polystyrene, (methyl) acrylate copolymer particle); Through the polymer beads of polycondensation manufacturing, for example organic silicon granule, benzoguanamine particle and nylon particle; And the polymer beads of thermoset resin.

Can carry out surface treatment with the raising hydrophobicity to being used to give mobile external additive, and prevent flowing property or chargeding performance variation in high humidity environment.

The instance of surface conditioning agent comprises silane coupling agent, sillylation reagent, contains the silane coupling agent of fluoroalkyl, based on the coupling agent of organic titanate, coupling agent, silicone oil and modified silicon oil based on aluminium.

Being used to remove the instance that remains in the cleaning improver of the developer on photoconductor and the primary transfer parts after the transfer printing comprises: fatty acid metal salts, for example zinc stearate, calcium stearate, stearic acid; And the polymer beads that passes through no soap emulsion polymerization manufacturing, for example poly methyl methacrylate particle and granules of polystyrene.For polymer beads, preferred use has narrow relatively size-grade distribution and the equal particle diameter of body is the polymer beads of 0.01 μ m-1 μ m.

(developer)

Toner of the present invention can be used as single component magnetic or the non magnetic developer that does not use carrier.Toner of the present invention also can be used for containing the two-component developing agent of carrier.

Be used at said toner under the situation of two-component developing agent, use said toner through mixing with magnetic carrier.For the ratio of carrier in the developer with toner, said toner preferably is included in the said developer with the amount of 1-10 mass parts with respect to 100 mass parts carriers.For magnetic carrier, can use conventional carrier, for example particle diameter is iron powder, ferrite powder, MAG powder and the magnetic resin carrier of about 20 μ m-200 μ m.

The carrier granular that constitutes said carrier can apply with coated with resins.The instance of coated with resins comprises: amide resin, for example urea-formaldehyde resins, melamine resin, benzoguanamine resin, Lauxite, polyamide; Epoxy resin; Polyvinyl resin, for example acrylic resin, polymethylmethacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol (PVA) and polyvinyl butyral; Polyvinylidene base resin; Polystyrene resin, for example polystyrene, styrene-propene acyl group copolymer resin; Alkenyl halide resin, for example PVC; Vibrin, for example polyethylene terephthalate and polybutylene terephthalate; And other material polycarbonate resin for example, tygon, PVF; PVDF gathers trifluoro-ethylene, polyhexafluoropropylene; The multipolymer of vinylidene fluoride and acrylic monomer; The multipolymer of vinylidene fluoride and PVF, the terpolymer of zellon, vinylidene fluoride and non-fluoridate monomer, and organic siliconresin.

If necessary, said coated with resins can contain conductive powder (like metal powder, carbon black, titanium dioxide, tin oxide and zinc paste).Conductive powder preferably has 1 μ m or lower average particulate diameter.When the average particulate diameter of conductive powder during, be difficult to controlling resistance greater than 1 μ m.

The measuring method and the value of the character of the toner that obtains with aforementioned manner will be described below.

In this embodiment, the size-grade distribution of toner is measured through the Coulter-counter method.

For measurement mechanism, Coulter Counter TA-II and Coulter Multisizer II (both by Beckman Coulter, Inc. system) have been listed according to the size-grade distribution of Coulter-counter method.

In this embodiment, Coulter Counter TA-II measurement mechanism is connected with the interface (I-JUSE) of PC-9801 PC (NEC Corporation system) via output distributed number and volume distributed median, thereby carries out the measurement of size-grade distribution.

Specifically, the surfactant as spreading agent (preferred alkyl benzene sulfonate) that in the electrolytic solution of 100mL-150mL, adds 0.1mL-5mL.Notice that said electrolytic solution is the WS through the about 1 quality % that uses grade sodium chloride preparation, and (Beckman Coulter is Inc.) as said electrolytic solution for example to use ISOTON-II.Next, in the gained potpourri, add the 2mg-20mg sample and make its suspension, and this potpourri was disperseed 1 minute-3 minutes through ultrasonic disperser.Use has the aforementioned measurement mechanism in 100 μ m holes, by the volume and the quantity of gained dispersion liquid measurement toner-particle, then, calculates the volume distributed median and the distributed number of toner.

Note,, use following 13 passages: 2.00 μ m or bigger but less than 2.52 μ m as passage; 2.52 μ m or bigger but less than 3.17 μ m; 3.17 μ m or bigger but less than 4.00 μ m; 4.00 μ m or bigger but less than 5.04 μ m; 5.04 μ m or bigger but less than 6.35 μ m; 6.35 μ m or bigger but less than 8.00 μ m; 8.00 μ m or bigger but less than 10.08 μ m; 10.08 μ m or bigger but less than 12.70 μ m; 12.70 μ m or bigger but less than 16.00 μ m; 16.00 μ m or bigger but less than 20.20 μ m; 20.20 μ m or bigger but less than 25.40 μ m; 25.40 μ m or bigger but less than 32.00 μ m; And 32.00 μ m or bigger but less than 40.30 μ m.The target particles of this measurement is to have 2.00 μ m or bigger but less than the particle of the diameter of 40.30 μ m.

The equal particle diameter of the body of said toner is preferably 3 μ m-7 μ m, and the ratio of the equal particle diameter of the body of said toner and the number average particle diameter of said toner is preferably 1.2 or littler.In addition, preferred said toner contains the particle with 2 μ m or littler particle diameter of 1 quantity %-10 quantity %.

The acid number of the toner of this embodiment is measured through the method according to JIS K0070-1992.

Specifically, in 120mL toluene, add 0.5g sample (ethyl acetate soluble substance: 0.3g), and stir about 10 hours of the potpourri that obtains down with dissolving at 23 ℃.Next, to wherein adding ethanol (30mL), thus the preparation sample solution.Especially; When said sample is insoluble to toluene, use other solvent for example two

alkane or tetrahydrofuran.Then, use potential measurement autotitrator (DL-53Titrator, Mettler-Toledo K.K. system) and electrode DG113-SC (product of Mettler-Toledo K.K.) to measure said acid number down at 23 ℃.Analyze this measurement result with analysis software LabX Light 1.00.000 version.

Note, use the solvent mixture of toluene (120mL) and ethanol (30mL) to carry out the calibration of this equipment.

Said measuring condition is identical with those conditions of measuring the hydroxyl value setting.

Can measure said acid number in the above described manner.Specifically, use warp standardized 0.1N potassium hydroxide/alcoholic solution titration sample solution in advance, use following equation to calculate said acid number then by titer:

Acid number [KOHmg/g]=titer [mL] * N * 56.1 [mg/mL]/sample quality [g], wherein N is the coefficient of 0.1N potassium hydroxide/alcoholic solution.

The acid number of toner is the low-temperature fixing ability of toner and the important indicator of heat-resisting anti-seal property, and it derives from the terminal carboxyl group of unmodified polyester resin.In order to control low-temperature fixing ability (for example minimum fixing temperature and heat counter print and distribute living temperature), the acid number of toner is preferably 0.5mgKOH/g-40mgKOH/g.When the acid number of toner was higher than 40mgKOH/g, the chain extending reaction of the reactive polyester resin of modification and/or cross-linking reaction were carried out insufficiently, the heat-resisting anti-seal property of the deficiency of the toner that this possibly cause obtaining.When the acid number of toner is lower than 0.5mgKOH/g, the effect of the dispersion stabilization during the improvement that possibly can't obtain to be brought by alkali is made, perhaps, chain extending reaction and/or cross-linking reaction are very easily carried out, and this can reduce makes stability.

In this embodiment, the glass transition temperature of toner can for example pass through differential scanning calorimeter (DSC) system (DSC-60, Shimadzu Corporation system) and measure.

Specifically, at first, the aluminum sampling receptacle of about 5mg sample of will having packed into places on the holder, subsequently said holder is put into electric furnace.Next, sample is heated to 150 ℃ with 10 ℃/minute the rate of heat addition from 10 ℃, to confirm the glass transition temperature of said toner, i.e. T1.After heating for the first time, sample was left standstill under 150 ℃ 10 minutes, be cooled to 10 ℃ with 10 ℃/minute cooldown rate subsequently, left standstill afterwards 10 minutes.Sample was heated for second time to confirm the glass transition temperature of toner with 10 ℃/minute the rate of heat addition once more, and it is measured as T2.Use the routine analyzer in the said system, calculate the glass transition temperature of said toner by the contact point of the tangent line of the endothermic curve of adjacent glass transition temperature and baseline.

The glass transition temperature Tg 1st that is confirmed by heating for the first time derives from the glass transition temperature as the said crystalline polyester of the resin that in being used to form each resin of toner, has lowest glass transition temperature.When partially or completely becoming mutual when compatible in said crystalline polyester and the process of said non-crystalline polyester in aforementioned manufacturing approach, Tg1st significantly reduces on the contrary.When Tg1st was lower than 45 ℃, the heat-resisting storage stability of said toner worsened.When the Tg1st of toner was higher than 65 ℃, the temperature when toner begins to melt uprised, so that can not obtain the low-temperature fixing ability of toner.Therefore, the Tg1st of toner is controlled to be in the scope that falls into 45 ℃-65 ℃.

The glass transition temperature of being confirmed by heating for the second time (being the glass transition temperature Tg 2nd behind the said toner heat fusing) does not derive from the material that is used to form said toner, but since in the process of aforementioned manufacturing approach the compatibility of resin and the new characteristic temperature that produces.When Tg2nd was lower than 25 ℃, the compatibility of said resin was excessive in fixing, the separating power of toner when this can worsen photographic fixing.When said Tg2nd is higher than 35 ℃, be not enough in the compatibility of resin described in the fixing, this can worsen the low-temperature fixing ability of said toner.Therefore, the Tg2nd of toner is controlled to be in the scope that falls into 25 ℃-35 ℃.

In this embodiment, can pass through the 1/2 flow starting temperature T1/2 that overhead system flow tester (CFT500 is made by Shimadzu Corporation) is measured toner.Specifically, 1/2 flow starting temperature T1/2 can be by through making sample fusing and the flow curve that obtains that flows is confirmed, and it is that flow from the fusing flow starting temperature to the fusing stroke variable quantity of end temp becomes 1/2 o'clock temperature.

The reduction of the viscosity of the 1/2 flow starting temperature T1/2 indication resin of toner.When said 1/2 flow starting temperature T1/2 was lower than 120 ℃, the separating power of said toner worsened when photographic fixing.When said 1/2 flow starting temperature T1/2 was higher than 135 ℃, the softening beginning temperature of said toner was high, so that can not obtain the low-temperature fixing ability of toner.Therefore, the T1/2 with toner is controlled to be in the scope that falls into 120 ℃-135 ℃.

In this embodiment, can for example pass through the strength ratio (P2850/P828) of the toner of FTIR device (Avatar 370, Thermo Fisher Scientific K.K. system) beasurement base FTIR-ATR.

Specifically; 3g is put into automatic cuber (Type M No.50BRP-E as the toner of sample; Maekawa Testing Machine Mfg.Co.Ltd.) in, and with the load of 6t compacting 1 minute, thereby preparation has 40mm diameter (thickness: compressing tablet about 2mm).The surface of the toner compressing tablet that obtains through aforementioned FTIR measurement device.The condition that is used to measure is following:

Measuring condition

Measurement range: 4,000 [cm ^-1]-675 [cm ^-1]

The window material that uses: Ge

Gain 4:4.0

Mirror speed: 0.6327

Aperture: 100

Beam splitter: KBr

The peak that derives from wax and crystallized polyurethane resin and obtain (2,850cm ^-1) with derive from the peak (828cm of resin glue ^-1) strength ratio (P2850/P828) confirm as relative quantity and the relative quantity of crystallized polyurethane resin of the wax on contiguous toner-particle surface.For said value, be suitable through changing the mean value that measurement point carries out measuring for 4 times the value that obtains.

Being compared by the peak intensity with the peak intensity that derives from said crystallized polyurethane resin and said release agent of FTIR-ATR measurement and the peak intensity that derives from said resin glue can acquisition and crystalline polyester and the uneven distribution relevant index of release agent in the zone that the surface with said toner-particle is close to.When said peak intensity when low, its amount that shows the crystalline polyester that is present in around the toner-particle surface and release agent is low.If said peak intensity ratio is lower than 0.10, the separating power of said toner is not enough.When said peak intensity when high, its amount that shows the crystalline polyester that is present in the peripheral region, toner-particle surface and release agent is big.If said peak intensity ratio is greater than 0.20, the heat-resisting storage stability of the toner that obtains is not enough.When a large amount of release agents was present in the surperficial zone of contiguous toner-particle, the demoulding ability of said toner was improved, but on the other hand, heat-resisting storage stability worsens because said release agent trends towards being deposited on the parts on every side.When a large amount of crystalline polyesters was present in the surperficial zone of contiguous toner-particle, heat-resisting storage stability worsened.The reason of this deterioration is thought as follows.Said crystalline polyester has 0 ℃ or lower glass transition temperature and 100% or lower crystallinity usually, and the crystalline polyester that therefore disperses has the noncrystalline component that has 0 ℃ or lower glass transition temperature.Be present under the situation in the surperficial zone of contiguous toner-particle at the said crystalline polyester with this component, it is not enough that the heat-resisting storage stability of said toner becomes.In order to improve heat-resisting storage stability and to keep separating power, the aforementioned peak intensity that derives from said crystalline resins and release agent that will measure through FTIR-ATR is than being adjusted in the scope that falls into 0.10-0.20.

Embodiment

To said toner more specifically be described through embodiment, but these embodiment should not be construed as restriction scope of the present invention.In addition, in the following description, unless otherwise indicated, " part " expression " mass parts ".

Measure the various character of toner and the molecular weight distribution of crystallized polyurethane resin in an embodiment in the following manner.

< glass transition temperature of toner >

The glass transition temperature of toner is measured through differential scanning calorimeter (DSC) system (DSC-60, Shimadzu Corporation system).

At first, the aluminum sampling receptacle of the 5mg sample of will having packed into places on the holder, subsequently said holder is put into electric furnace.Next, sample is heated to 150 ℃ with 10 ℃/minute the rate of heat addition from 10 ℃, to confirm the glass transition temperature of said toner, i.e. T1.After heating for the first time, sample was left standstill under 150 ℃ 10 minutes, be cooled to 10 ℃ with 10 ℃/minute cooldown rate subsequently, left standstill afterwards 10 minutes.Sample was heated for second time to confirm the glass transition temperature of toner with 10 ℃/minute the rate of heat addition once more, and it is measured as T2.Use the routine analyzer in the said system, calculate the glass transition temperature of said toner by the contact point of the tangent line of the endothermic curve of adjacent glass transition temperature and baseline.

The glass transition temperature Tg 1st that is confirmed by heating for the first time derives from the glass transition temperature as the said crystalline polyester of the resin that in being used to form each resin of toner, has lowest glass transition temperature.

The glass transition temperature of being confirmed by heating for the second time (being the glass transition temperature Tg 2nd behind the said toner heat fusing) does not derive from the material that is used to form said toner, but since in the process of aforementioned manufacturing approach the compatibility of resin and the new characteristic temperature that produces.

< 1/2 flow starting temperature T1/2 of toner >

Measure 1/2 flow starting temperature T1/2 of toner through overhead system flow tester (CFT500 is made by Shimadzu Corporation).

Specifically, 1/2 flow starting temperature T1/2 can be by through making sample fusing and the flow curve that obtains that flows is confirmed, and it is that flow from the fusing flow starting temperature to the fusing stroke variable quantity of end temp becomes 1/2 o'clock temperature.

The reduction of the viscosity of the 1/2 flow starting temperature T1/2 indication resin of toner.

< through the peak intensity ratio that derives from crystallized polyurethane resin and release agent of FTIR-ATR measurement >

The strength ratio (P2850/P828) of the toner through FTIR device (Avatar 370, Thermo Fisher Scientific K.K. system) beasurement base FTIR-ATR.

At first; 3g is put into automatic cuber (Type M No.50BRP-E as the toner of sample; Maekawa Testing Machine Mfg.Co.Ltd.) in, and with the load of 6t compacting 1 minute, thereby preparation has 40mm diameter (thickness: compressing tablet about 2mm).The surface of the toner compressing tablet that obtains through aforementioned FTIR measurement device.The condition that is used to measure is following:

Measuring condition

Measurement range: 4,000 [cm ^-1]-675 [cm ^-1]

The window material that uses: Ge

Gain 4:4.0

Mirror speed: 0.6327

Aperture: 100

Beam splitter: KBr

The peak that derives from wax and crystallized polyurethane resin and obtain (2,850cm ^-1) with derive from the peak (828cm of resin glue ^-1) strength ratio (P2850/P828) confirm as relative quantity and the relative quantity of crystallized polyurethane resin of the wax on contiguous toner-particle surface.For said value, be suitable through changing the mean value that measurement point carries out measuring for 4 times the value that obtains.

< molecular weight distribution of crystallized polyurethane resin >

Under following condition, measure molecular weight distribution through gel permeation chromatography (GPC) measurement mechanism (GPC-8220GPC is made by TOSOH CORPORATION).

Post: TSKgel SuperHZM-H, 15cm, three connection posts (TOSOH CORPORATION)

Temperature: 40 ℃

Solvent: tetrahydrofuran (THF)

Flow velocity: 0.35mL/min

Sample: 0.15% sample of supplying with 0.4mL.

For said The pretreatment; Sample dissolution (is contained stabilizing agent at tetrahydrofuran (THF); Wako Chemical Industries, Ltd. system) in to reach the concentration of 0.15 quality %, then; Filtrator through having 0.2 μ m aperture filters gained solution, and the filtrating of inherent filtration in the future is as sample.Measure through supplying with 100 μ L tetrahydrofuran (THF) sample solutions.For the measurement of the molecular weight distribution of said sample, by the logarithm value of the calibration curve of making from some kinds of monodisperse polystyrene standard models and the molecular weight distribution that concerns calculation sample between the count value.As the polystyrene standard sample that is used to make said calibration curve; Use Showdex STANDARD Std.No.S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0 and the S-0.580 of SHOWA DENKO K.K., and toluene.As detecting device, use refractive index (RI) detecting device.

< synthesizing of crystallized polyurethane resin 1 >

In the 5L that is equipped with nitrogen inlet tube, drainpipe, stirrer and thermopair four neck flasks, add 1, the 10-decanedioic acid (2,320g), 1, the 8-ethohexadiol (2,530g) with quinhydrones (5.0g), reacted 8 hours down at 180 ℃ subsequently.Then, reaction mixture further is heated to 200 ℃, and makes its reaction 4 hours, under 8.3kPa, reacted again 2 hours subsequently, thereby obtain crystallized polyurethane resin 1.

Crystallized polyurethane resin 1 has 70 ℃ endotherm peak temperature (T2-cp) (wherein T2-cp is by the heating Calculation second time in the dsc measurement), 65 ℃ heat absorption shoulder temperature 1 (T2-cs1), 73 ℃ heat absorption shoulder temperature 2 (T2-cs2), 3; 000 number-average molecular weight and 12,000 weight-average molecular weight.

< synthesizing of crystallized polyurethane resin 2 >

In the 5L that is equipped with nitrogen inlet tube, drainpipe, stirrer and thermopair four neck flasks, add hexane diacid (2,320g), 1, the 5-pentanediol (2,880g) with quinhydrones (4.9g), reacted 10 hours down at 180 ℃ subsequently.Then, reaction mixture further is heated to 200 ℃, and makes its reaction 3 hours, under 8.3kPa, reacted again 2 hours subsequently, thereby obtain crystallized polyurethane resin 2.

The crystallized polyurethane resin 2 that obtains has 58 ℃ endotherm peak temperature (T2-cp) (wherein T2-cp is by the heating Calculation second time in the dsc measurement), 40 ℃ heat absorption shoulder temperature 1 (T2-cs1), 65 ℃ heat absorption shoulder temperature 2 (T2-cs2), 2; 500 number-average molecular weight and 12,000 weight-average molecular weight.

< synthesizing of non-crystalline polyester (low molecular weight polycaprolactone ester) 1 >

In the 5L that is equipped with nitrogen inlet tube, drainpipe, stirrer and thermopair four neck flasks, add bisphenol-A epoxy ethane 2mol adduct (229 parts), bisphenol-A epoxy propane 3mol adduct (529 parts), terephthalic acid (TPA) (208 parts), hexane diacid (46 parts) and dibutyl tin oxide (2 parts).Make the reaction 7 hours under 230 ℃, normal pressure of the potpourri that obtains, under the decompression of 10mmHg-15mmHg, reacted 4 hours subsequently.In the reaction mixture that obtains, add 44 parts of trimellitic anhydrides, and make the potpourri that obtains in the reaction 2 hours down of 180 ℃, normal pressure, thus acquisition non-crystalline polyester 1.

Non-crystalline polyester 1 has 2,400 number-average molecular weight, 6,300 weight-average molecular weight, 43 ℃ glass transition temperature (Tg) and the acid number of 28mgKOH/g.

< preparation of intermedium polyester >

In the reaction vessel that is equipped with condenser, stirrer and nitrogen inlet tube; Add 682 parts of bisphenol-A epoxy ethane 2mol adducts, 81 parts of bisphenol-A epoxy propane 2mol adducts, 283 parts of terephthalic acid (TPA)s, 22 parts of trimellitic acids and 2 parts of dibutyl tin oxides; And make the reaction 8 hours under 230 ℃, normal pressure of gained potpourri; Under the decompression of 10mmHg-15mmHg, reacted 5 hours subsequently, thereby obtain intermedium polyester 1.

Intermedium polyester 1 has 2100 number-average molecular weight, 9500 weight-average molecular weight, 55 ℃ glass transition temperature (Tg), the acid number of 0.5mgKOH/g and the hydroxyl value of 51mgKOH/g.

< synthesizing of polyester prepolyer 1 >

In the reaction vessel that is equipped with condenser, stirrer and nitrogen inlet tube, add 1,89 parts of IPDIs of 410 parts of intermedium polyester and 500 parts of ethyl acetate, and the potpourri that obtains was reacted 5 hours down at 100 ℃, thereby obtain prepolymer 1.Prepolymer 1 has 1.53% free isocyanate rate (quality %).

< synthesizing of noncrystalline polyester resin 2 >

Heat with two dry neck flasks in add starting material and as the dibutyl tin oxide of catalyzer; Said starting material comprise 780 molar part polyoxypropylenes (2; 2)-2,2-two (4-hydroxyphenyl) propane, 18 molar part polyoxyethylene (2,2)-2; 2-two (4-hydroxyphenyl) propane, 47 molar part terephthalic acid (TPA)s, 24 molar part fumaric acid and the positive dodecene base of 24 molar part succinic acid, and to introduce in the flask nitrogen to keep internal atmosphere be inert atmosphere.Potpourri in the flask heats, and under 230 ℃, carries out copolycondensation 12 hours subsequently.Afterwards, the pressure with internal atmosphere under 230 ℃ reduces gradually, thereby obtains noncrystalline polyester resin 2.Noncrystalline polyester resin 2 has 6,700 number-average molecular weight, 17,400 weight-average molecular weight, 61 ℃ glass transition temperature (Tg) and the acid number of 14mgKOH/g.

< preparation of non-crystalline polyester solution 1 >

In the canister of 2L, add 125 parts of noncrystalline polyester resin 2 and 75 parts of ethyl acetate; And with mixture heated to 65 ℃ with dissolving noncrystalline polyester resin 2; The solution that in ice-water bath, obtains subsequently with the speed quenching of 27 ℃/min, thus non-crystalline polyester solution 1 obtained.

< preparation of non-crystalline polyester solution 2 >

In the canister of 2L, add 100 parts of noncrystalline polyester resin 2 and 100 parts of ethyl acetate; And with mixture heated to 65 ℃ with dissolving noncrystalline polyester resin 2; The solution that in ice-water bath, obtains subsequently with the speed quenching of 27 ℃/min, thus non-crystalline polyester solution 2 obtained.

< preparation of non-crystalline polyester solution 3 >

In the canister of 2L, add 75 parts of noncrystalline polyester resin 2 and 125 parts of ethyl acetate; And with mixture heated to 65 ℃ with dissolving noncrystalline polyester resin 2; The solution that in ice-water bath, obtains subsequently with the speed quenching of 27 ℃/min, thus non-crystalline polyester solution 3 obtained.

< synthesizing of ketimide >

In the reaction vessel that is equipped with stirring rod and thermometer, add 170 parts of IPDs and 75 parts of methyl ethyl ketones, and the potpourri that obtains was reacted 5 hours down at 50 ℃, thereby obtain ketimine compound 1.

The amine value of ketimine compound 1 is 418.

< synthesizing of masterbatch (MB) >

Use Henschel mixer (Mitsui Mining Co., the product of Ltd), water (1200 parts), carbon black (Printex 35, the product of Degussa) [DBP oil absorption=42mL/100mg, pH=9.5] (540 parts) and vibrin (1200 parts) are mixed.Use two roller mills under 150 ℃, the gained potpourri to be mediated 30 minutes, carry out rolling, cooling then, and use comminutor to pulverize, thereby obtain masterbatch 1.

< synthesizing of dispersing agent for wax >

In the autoclave retort that is equipped with thermometer and stirrer; Add 600 parts of xylene and 300 parts of low molecular weight polyethylene (SANWAX LEL-400; Sanyo Chemical Industries, the Ltd. system, softening point is 128 ℃); And tygon fully is dissolved in the xylene, introduce nitrogen subsequently to purge the internal atmosphere of retort.Under 175 ℃; With 3 hours with styrene (2; 310 parts), the mixed solution of vinyl cyanide (270 parts), butyl acrylate (150 parts), di-tert-butyl peroxide six hydrogen terephthalate (78 parts) and xylene (455 parts) dropwise joins in this retort; Thereby carry out polymerization, kept identical temperature subsequently 30 minutes.Afterwards, from potpourri, remove and desolvate, thereby obtain dispersing agent for wax.

< preparation of oil phase (pigment-wax dispersion 1) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 77 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 1.

Starting material solution 1 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 1.This pigment-wax dispersion 1 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 2) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 77 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 1.

Starting material solution 1 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 5 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 2.This pigment-wax dispersion 2 has the average particulate diameter of 0.35 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 3) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 71 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 2.

Starting material solution 2 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 3.

This pigment-wax dispersion 3 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 4) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 66 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 3.

Starting material solution 3 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 4.This pigment-wax dispersion 4 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 5) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 55 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 4.

Starting material solution 4 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 5.This pigment-wax dispersion 5 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 6) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 359 parts of non-crystalline polyesters, synthesizes above 77 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 966 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 5.

Starting material solution 5 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 60 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 6.This pigment-wax dispersion 6 has the average particulate diameter of 0.5 μ m and 52% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 7) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 359 parts of non-crystalline polyesters, synthesizes above 66 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 966 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 6.

Starting material solution 6 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 7.This pigment-wax dispersion 7 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 8) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 359 parts of non-crystalline polyesters, synthesizes above 55 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 966 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 7.

Starting material solution 7 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 60 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 8.This pigment-wax dispersion 8 has the average particulate diameter of 0.5 μ m and 48% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 9) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 33 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 8.

Starting material solution 8 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 9.This pigment-wax dispersion 9 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of oil phase (pigment-wax dispersion 10) >

In the container that is equipped with stirring rod and thermometer; The dispersing agent for wax that adds 1,110 parts of Brazil waxs of 378 parts of non-crystalline polyesters, synthesizes above 110 parts, 22 parts of charge control agents (CCA) are (based on salicylic metal complex; ORIENT CHEMICAL INDUSTRIES CO., the E-84 of LTD system) and 947 parts of ethyl acetate, under agitation with the mixture heated to 80 that obtains ℃; And with temperature remain on 80 ℃ following 5 hours, be cooled to 30 ℃ with 1 hour afterwards.Subsequently, in this container, add 500 parts of masterbatch 1 and 500 parts of ethyl acetate, and mixed the potpourri that obtains 1 hour, thus acquisition starting material solution 9.

Starting material solution 9 (1324 parts) is poured in the independent container; And with ball mill (ULTRA VISCOMILL; AIMEX Co., the product of Ltd.) disperse black carbon and wax under following condition: liquid feeding speed is 1kg/ hour, and the dish peripheral speed is 6m/s; 0.5mm zirconium oxide bead is filled to 80 volume %, and carries out 3 times.Next, to the 65 quality % ethyl acetate solutions (1042.3 parts) that wherein add non-crystalline polyester 1, and under these conditions through ball mill once, thereby obtain pigment-wax dispersion 10.

This pigment-wax dispersion 10 has the average particulate diameter of 0.5 μ m and 50% solid content (130 ℃, 30 minutes).

< preparation of crystalline polyester dispersion liquid 1 >

In the 2L canister, add 100g crystallized polyurethane resin 1 and 400g ethyl acetate, ℃ with dissolving crystallized vibrin 1, the speed with 27 ℃/minute makes the solution quenching in ice-water bath subsequently with this mixture heated to 75.To wherein adding 500mL beaded glass (diameter of 3mm), and through the batch-type sand mill (Kanpe Hapio Co. Ltd.) carries out 10 hours pulverizing, thereby obtains crystalline polyester dispersion liquid 1.

< preparation of crystalline polyester dispersion liquid 2 >

In the 2L canister, add 100g crystallized polyurethane resin 2 and 400g ethyl acetate, ℃ with dissolving crystallized vibrin 2, the speed with 27 ℃/minute makes the solution quenching in ice-water bath subsequently with this mixture heated to 75.To wherein adding 500mL beaded glass (diameter of 3mm), and through the batch-type sand mill (Kanpe Hapio Co. Ltd.) carries out 10 hours pulverizing, thereby obtains crystalline polyester dispersion liquid 2.

< synthesizing of organic granular emulsion >

Sodium salt (the ELEMINOL RS-30 that in the reaction vessel that is equipped with stirring rod and thermometer, adds the sulfuric ester of 683 parts of water, 11 parts of methacrylic acid-ethylene oxide adducts; Sanyo Chemical Industries; Ltd. system), 138 parts of styrene, 138 parts of methacrylic acids and 1 part of ammonium persulfate; And under 400rpm, stirred the gained potpourri 15 minutes, thereby obtain white emulsion.Heat this white emulsion, become 75 ℃, and make its reaction 5 hours until internal temperature.To the ammonium persulfate aqueous solution that wherein adds 30 part 1%; Wore out 5 hours down at 75 ℃ subsequently, thereby obtain particle dispersion 1 (aqueous dispersion of vinylite (multipolymer of the sodium salt of the sulfuric ester of styrene/methacrylic acid/methacrylic acid ethylene oxide adduct)).

(Horiba Ltd.) measure, and it is 0.14 μ m to the equal particle diameter of the body of particle dispersion 1 through LA-920.The part of particle dispersion 1 is dry with the separation resin component.

< preparation of water >

With water (990 parts), particle dispersion 1 (83 parts), 48.5% the dodecyl diphenyl ether sodium disulfonate WS (ELEMINOL MON-7; The product of Sanyo Chemical Industries Ltd.) (37 parts) and ethyl acetate (90 parts) mix and stir to obtain opaque and white liquid, and it is as water 1.

< emulsification and removal of solvents 1 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 1,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 1 of emulsification.

The slurry 1 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 1 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 1.

< emulsification and removal of solvents 2 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 1,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 1 of emulsification.

The slurry 1 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 1 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 20 hours down, thereby obtain dispersed paste 2.

< emulsification and removal of solvents 3 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 2 of 1,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 2 of emulsification.

The slurry 2 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 2 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 3.

< emulsification and removal of solvents 4 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 2 of 1,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 2 of emulsification.

The slurry 2 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 2 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 20 hours down, thereby obtain dispersed paste 4.

< emulsification and removal of solvents 5 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 2,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 3 of emulsification.

The slurry 3 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 3 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 5.

< emulsification and removal of solvents 6 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 3,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 4 of emulsification.

The slurry 4 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 4 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 6.

< emulsification and removal of solvents 7 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 4,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 5 of emulsification.

The slurry 5 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 5 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 7.

< emulsification and removal of solvents 8 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 5,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 6 of emulsification.

The slurry 6 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 6 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 8.

< emulsification and removal of solvents 9 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 6,109.4 parts of non-crystalline polyester solution of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 7 of emulsification.

The slurry 7 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 7 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 9.

< emulsification and removal of solvents 10 >

In container, add 2,73.9 parts of crystalline polyester dispersion liquids 1 of 7,109.4 parts of non-crystalline polyester solution of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 8 of emulsification.

The slurry 8 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 8 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 10.

< emulsification and removal of solvents 11 >

In container, add 3,73.9 parts of crystalline polyester dispersion liquids 1 of 8,109.4 parts of non-crystalline polyester solution of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 9 of emulsification.

The slurry 9 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 9 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 11.

< emulsification and removal of solvents 12 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 1,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 1 of emulsification.

The slurry 1 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 1 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 30 hours down, thereby obtain dispersed paste 12.

< emulsification and removal of solvents 13 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 2 of 1,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 10 of emulsification.

The slurry 10 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 10 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 2 hours down, thereby obtain dispersed paste 13.

< emulsification and removal of solvents 14 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 5,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 9 of emulsification.

The slurry 9 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 9 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 30 hours down, thereby obtain dispersed paste 14.

< emulsification and removal of solvents 15 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 2 of 5,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 11 of emulsification.

The slurry 11 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 11 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 2 hours down, thereby obtain dispersed paste 15.

< emulsification and removal of solvents 16 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 9,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 12 of emulsification.

The slurry 12 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 12 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 30 hours down, thereby obtain dispersed paste 16.

< emulsification and removal of solvents 17 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 2 of 9,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 13 of emulsification.

The slurry 13 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 13 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 2 hours down, thereby obtain dispersed paste 17.

< emulsification and removal of solvents 18 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 10,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 14 of emulsification.

The slurry 14 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 14 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 30 hours down, thereby obtain dispersed paste 18.

< emulsification and removal of solvents 19 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 2 of 10,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 15 of emulsification.

The slurry 15 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 15 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 2 hours down, thereby obtain dispersed paste 19.

< emulsification and removal of solvents 20 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 9,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 12 of emulsification.

The slurry 12 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 12 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 20.

< emulsification and removal of solvents 21 >

In container, add 1,73.9 parts of crystalline polyester dispersion liquids 1 of 10,109.4 parts of prepolymers of 664 parts of pigment-wax dispersions and 4.6 parts of ketimine compounds 1; And mixed the potpourri obtain 1 minute with 5000rpm through TK homo-mixer (Tokushu Kika Kogyo Co., the product of Ltd.).Afterwards, 1,200 part of water 1 is added said container, and pass through the TK homo-mixer with 13,000rpm mixes the potpourri that obtains 20 minutes, thereby obtains the slurry 14 of emulsification.

The slurry 14 that in the container that is equipped with stirrer and thermometer, adds emulsification, and under 30 ℃, from the slurry 14 of emulsification, removed and desolvate with 8 hours, subsequently 45 ℃ aging 10 hours down, thereby obtain dispersed paste 21.

(embodiment 1)

< washing and dry >

After under reduced pressure 100 parts of dispersed pastes 1 being filtered, gains are carried out twice of a series of following processing (1)-(4), thereby make filter cake 1:

(1) in filter cake, adds ion exchange water (100 parts), use TK homo-mixer (carrying out 10 minutes) to mix subsequently, filter then with 12000rpm;

(2) in the filter cake that in (1), obtains, add 10% sodium hydrate aqueous solution (100 parts), use TK homo-mixer (carrying out 30 minutes) to mix subsequently, under reduced pressure filter then with 12000rpm;

(3) in the filter cake that in (2), obtains, add 10 quality % hydrochloric acid (100 parts), use TK homo-mixer (carrying out 10 minutes) to mix subsequently, filter then with 12000rpm; And

(4) in the filter cake that in (3), obtains, add ion exchange water (300 parts), use TK homo-mixer (carrying out 10 minutes) to mix subsequently, filter then with 12000rpm.

Use the air circulation exsiccator under 45 ℃ with filter cake 1 dry 48 hours, making it then is the sieve of 75 μ m through mesh size, thus preparation toner 1.

(embodiment 2)

With with embodiment 1 in identical mode obtain the toner 2 of embodiment 2, condition is to substitute dispersed pastes 1 with dispersed paste 2.

(embodiment 3)

With with embodiment 1 in identical mode obtain the toner 3 of embodiment 3, condition is to substitute dispersed pastes 1 with dispersed paste 3.

(embodiment 4)

With with embodiment 1 in identical mode obtain the toner 4 of embodiment 4, condition is to substitute dispersed pastes 1 with dispersed paste 4.

(embodiment 5)

With with embodiment 1 in identical mode obtain the toner 5 of embodiment 5, condition is to substitute dispersed pastes 1 with dispersed paste 5.

(embodiment 6)

With with embodiment 1 in identical mode obtain the toner 6 of embodiment 6, condition is to substitute dispersed pastes 1 with dispersed paste 6.

(embodiment 7)

With with embodiment 1 in identical mode obtain the toner 7 of embodiment 7, condition is to substitute dispersed pastes 1 with dispersed paste 7.

(embodiment 8)

With with embodiment 1 in identical mode obtain the toner 8 of embodiment 8, condition is to substitute dispersed pastes 1 with dispersed paste 8.

(embodiment 9)

With with embodiment 1 in identical mode obtain the toner 9 of embodiment 9, condition is to substitute dispersed pastes 1 with dispersed paste 9.

(embodiment 10)

With with embodiment 1 in identical mode obtain the toner 10 of embodiment 10, condition is to substitute dispersed pastes 1 with dispersed paste 10.

(embodiment 11)

With with embodiment 1 in identical mode obtain the toner 11 of embodiment 11, condition is to substitute dispersed pastes 1 with dispersed paste 11.

(Comparative Examples 1)

With with embodiment 1 in identical mode obtain the toner 12 of Comparative Examples 1, condition is to substitute dispersed pastes 1 with dispersed paste 12.

(Comparative Examples 2)

With with embodiment 1 in identical mode obtain the toner 13 of Comparative Examples 2, condition is to substitute dispersed pastes 1 with dispersed paste 13.

(Comparative Examples 3)

With with embodiment 1 in identical mode obtain the toner 14 of Comparative Examples 3, condition is to substitute dispersed pastes 1 with dispersed paste 14.

(Comparative Examples 4)

With with embodiment 1 in identical mode obtain the toner 15 of Comparative Examples 4, condition is to substitute dispersed pastes 1 with dispersed paste 15.

(Comparative Examples 5)

With with embodiment 1 in identical mode obtain the toner 16 of Comparative Examples 5, condition is to substitute dispersed pastes 1 with dispersed paste 16.

(Comparative Examples 6)

With with embodiment 1 in identical mode obtain the toner 17 of Comparative Examples 6, condition is to substitute dispersed pastes 1 with dispersed paste 17.

(Comparative Examples 7)

With with embodiment 1 in identical mode obtain the toner 18 of Comparative Examples 7, condition is to substitute dispersed pastes 1 with dispersed paste 18.

(Comparative Examples 8)

With with embodiment 1 in identical mode obtain the toner 19 of Comparative Examples 8, condition is to substitute dispersed pastes 1 with dispersed paste 19.

(Comparative Examples 9)

With with embodiment 1 in identical mode obtain the toner 20 of Comparative Examples 9, condition is to substitute dispersed pastes 1 with dispersed paste 20.

(Comparative Examples 10)

With with embodiment 1 in identical mode obtain the toner 21 of Comparative Examples 10, condition is to substitute dispersed pastes 1 with dispersed paste 21.

< external additive processing >

Through Henschel mixer, will mix with 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titania with each toner (100 parts) that aforementioned manner obtains.Measure the physical property of each toner.The result is presented in the table 1.

< manufacturing of developer >

To be used to prepare developer through the copper-Zn ferrite carrier (95 quality %) of external additive toner of handling (5 quality %) and the average particulate diameter that applies through organic siliconresin with 40 μ m.

< image formation >

The image forming apparatus (imagio Neo 450, Ricoh Company Limited system) that can print 45 pages of A4-size paper through per minute prints continuously, and estimates in the following manner.

< heat-resisting storage stability >

Toner is stored 8 hours down at 50 ℃, sieved two minutes with 42 mesh subsequently.Remain in the amount (toner residual rate) of the toner on the sieve with respect to the total amount measurement of toner, and the result is based on the standards evaluation.Notice that the heat-resisting storage stability of toner is good more, the toner residual rate is low more.

[evaluation criterion]

A: the toner residual rate is lower than 10%

B: the toner residual rate is 10% or higher, but is lower than 30%

C: the toner residual rate is 30% or higher

< low-temperature fixing ability and heat-resisting anti-seal property >

To adopt TEFLON (registered trademark) roller partly to retrofit to make the duplicating machine of remodeling as the photographic fixing of the duplicating machine (MF 2200, Ricoh Company, Ltd. system) of fixing roller.The duplicating machine that the developer and the 6200 type paper (Ricoh Company, the product of Ltd.) of top manufacturing are put into remodeling prints test.

Specifically, when changing fixing temperature, confirm cold anti-Yin Wendu (minimum fixing temperature) and hot anti-Yin Wendu (the highest fixing temperature).

The appreciation condition of minimum fixing temperature is set as follows: the linear velocity of paper feeding: 120mm/s-150mm/sec, surface pressing: 1.2kgf/cm ²And roll-gap width: 3mm.

The appreciation condition of high fixing temperature is set as follows: the linear velocity of paper feeding: 50mm/s, surface pressing: 2.0kgf/cm ²And roll-gap width: 4.5mm.

Notice that the minimum fixing temperature of conventional low-temperature fixing toner is about 140 ℃.

Minimum fixing temperature is lower than 120 ℃ situation and is chosen as " A "; Minimum fixing temperature is 120 ℃ or higher but be lower than 130 ℃ situation and be chosen as " B "; Minimum fixing temperature is 130 ℃ or higher but be lower than 140 ℃ situation and be chosen as " C ", and minimum fixing temperature is 140 ℃ or higher but be lower than 150 ℃ situation and be chosen as " D ".

For the evaluation of high fixing temperature, the highest fixing temperature is that 190 ℃ or higher situation are chosen as " A ", and the highest fixing temperature is 170 ℃ or higher but be lower than 190 ℃ situation and be chosen as " B ", and the highest fixing temperature is lower than 170 ℃ situation and is chosen as " C ".

< release property in the fixing >

Use retrofit device printed images on paper of the image forming apparatus (imagio MP7500, Ricoh Company Limited system) that fixation unit retrofited, make the deposition constant (0.85mg/cm that on each paper, becomes ²), thereby when changing fixing temperature, measure the required power of the demoulding.

As shown in fig. 1, the measurement mechanism of the separating force of the fixing roller side after fusing nip provides measuring disengaging pawl 102 as being used to measure just.Knockout press is measured with the power that is wound on fixing roller 101 paper 103 on every side as passing fusing nip 105.

Because the paper 103 that passes fusing nip is carried bearing under the situation that is used to be wound on the power around the fixing roller, so this paper is carried under the situation of pushing probe claws 102.The load cell 104 of the edge of the pressing force in this process through being arranged on disengaging pawl reads, and confirms as separating force (gf).

Because separating force becomes maximal value under specific fixing temperature; Therefore change fixing temperature; And definite separating force becomes separating force under the peaked fixing temperature as separating resistibility (separation resistance), and based on following standard evaluation release property.

[evaluation criterion]

A: little separation resistibility

B: big separation resistibility

C: can not separate

The evaluation result of embodiment 1-11 and Comparative Examples 1-10 is presented in the table 1.

Table 1

Find by result displayed in the table 1, in embodiment 1-11, obtained to have excellent heat-resisting storage stability, the highest fixing temperature, low-temperature fixing ability and the toner that separates resistibility.On the other hand, the toner of Comparative Examples 1-10 has relatively poor result in heat-resisting storage stability, the highest fixing temperature, low-temperature fixing ability with aspect separating resistibility.

Comparing embodiment 1 and embodiment 2, and embodiment 3 and embodiment 4 find that the difference aspect the aging duration removal of solvents after becomes the factor of 1/2 flow starting temperature T1/2 of change toner.

Comparing embodiment 1 and 2 and embodiment 3 and 4; The variation of discovery aspect the amount of the amount of prepolymer 1 and ketimine compound 1 become change toner among the DSC the first time heated glass transition temperature Tg1st and toner among the DSC the second time heated glass transition temperature Tg2nd factor.

Comparing embodiment 1 and embodiment 5 are found to become the factor of separating resistibility that changes in the difference that is used to prepare aspect the condition of pigment-wax dispersion.

Comparing embodiment 6, embodiment 7 and embodiment 8 find that the difference of amount (part) aspect of dispersing agent for wax becomes the factor that changes the peak intensity of toner among the FTIR-ATR.

Comparing embodiment 1 and embodiment 9, the existence of finding prepolymer become the factor of high fixing temperature of change.

Comparing embodiment 9, embodiment 10 and embodiment 11; The difference of finding the solid content aspect of non-crystalline polyester 2 has caused the difference aspect the peak intensity of toner in FTIR-ATR, and this helps heat-resisting storage stability, the low-temperature fixing ability of toner and separates resistibility.

As above-described; In this embodiment; The toner that is used for developing electrostatic image obtains through following: oil phase is dispersed in the water-bearing media that wherein there is particle dispersants obtaining the dispersion liquid of emulsification, wherein said oil phase passes to the major general and contains the resin glue of crystallized polyurethane resin and noncrystalline resin, colorant and release agent dissolving or be dispersed in the organic solvent and prepare; And remove said organic solvent.Said toner has 45 ℃-65 ℃ glass transition temperature Tg 1st and 25 ℃-35 ℃ glass transition temperature Tg 2nd, wherein Tg1st be toner among the DSC the first time heated glass transition temperature and Tg2nd be that toner is for the heated glass transition temperature second time among the DSC; Said toner has 120 ℃-135 ℃ 1/2 flow starting temperature T1/2; And said toner has the peak intensity ratio of 0.10-0.20, and wherein said peak intensity is than the ratio that is FTIR-ATR peak intensity of measuring that derives from crystallized polyurethane resin and release agent and the peak intensity that derives from resin glue.Therefore, can obtain to have the toner of excellent low-temperature fixing ability, heat-resisting storage stability and separating power.

According to this embodiment; Resin glue contains binder resin precursor; Said binder resin precursor is the modified polyester resin that uses as noncrystalline resin; And can with said binder resin precursor chain extension or crosslinked compound dissolution in oil phase, and make binder resin precursor in the dispersion liquid of emulsification, carry out cross-linking reaction and/or chain extending reaction.As a result, can crystalline polyester be introduced in the noncrystalline resin.

According to this embodiment, through forming the toner that crystalline polyester can obtain to satisfy aforesaid properties with C4-C12 saturated dicarboxylic acid and C4-C12 saturated diols.

According to the present invention, like gpc measurement, the number-average molecular weight Mn of crystalline polyester be 500 or the ratio of littler molecule be 0%-2.0% and Mn be 1000 or the ratio of littler molecule be 0%-4.0%.About the molecular weight of crystalline polyester, have sharp-pointed molecular weight distribution and low-molecular-weight crystalline polyester and have excellent low-temperature fixing ability, and the crystalline polyester that has a low-molecular-weight molecule of its vast scale has not enough heat-resisting storage stability.Therefore, the crystalline polyester that has the molecular weight distribution in aforementioned range can be realized low-temperature fixing ability and heat-resisting storage stability.

According to this embodiment, oil phase contains the spreading agent that is useful on the dispersiveness of improving crystallized polyurethane resin and release agent (wax).As a result, can obtain desirable crystallized polyurethane resin to resin glue and wax dispersiveness to resin glue, and the amount of the crystalline polyester in the zone on the contiguous toner-particle of may command surface and the amount of wax.Therefore, can obtain to satisfy the toner of aforesaid properties.

According to this embodiment, the developer with excellent low-temperature fixing ability, heat-resisting storage stability and separating power can be provided through in developer, containing aforementioned toner.

Embodiment of the present invention is following:

< 1>toner, contain:

The resin glue that contains crystalline resins and noncrystalline resin;

Colorant; With

Release agent,

Wherein said toner have 120 ℃-135 ℃ 1/2 flow starting temperature T1/2 and

Wherein the peak intensity ratio with FTIR-ATR peak intensity of measuring that derives from said crystalline resins and said release agent and the peak intensity that derives from said resin glue is 0.10-0.20.

< 2>toner of basis < 1 >; Wherein said toner has 45 ℃-65 ℃ glass transition temperature Tg 1st and 25 ℃-35 ℃ glass transition temperature Tg 2nd; Wherein said glass transition temperature Tg 1st is the glass transition temperature by the toner that heating the is confirmed first time among the DSC, and glass transition temperature Tg 2nd is the glass transition temperature by the toner that heating the is confirmed second time among the DSC.

< 3>according to each toner in < 1>or < 2 >, wherein said crystalline resins be crystallized polyurethane resin and

Wherein obtain said toner through containing following method:

Oil phase is dispersed in the water-bearing media that comprises particle dispersants forming the dispersion liquid of emulsification, resin glue, colorant and the release agent dissolving or be dispersed in organic solvent of wherein said oil phase through will containing said crystallized polyurethane resin and said noncrystalline resin prepares; With

From the dispersion liquid of emulsification, remove said organic solvent.

< 4>according to the toner of < 3 >, wherein said noncrystalline resin be the binder resin precursor that forms by modified polyester resin and

Wherein said method further contains: can with said binder resin precursor chain extension or crosslinked compound dissolution in oil phase and make said binder resin precursor in the dispersion liquid of emulsification, carry out cross-linking reaction, or chain extending reaction, or these two kinds of reactions.

< 5>each toner in basis < 1 >-< 4 >, wherein said crystalline resins is by C4-C12 saturated dicarboxylic acid and the synthetic crystallized polyurethane resin of C4-C12 saturated diols.

< 6>each toner in basis < 1 >-< 5 >; The number-average molecular weight of wherein said crystalline resins be 500 or the ratio of littler molecule be 0%-2.0%; And number-average molecular weight be 1000 or the ratio of littler molecule be 0%-4.0%, wherein said number-average molecular weight is with gpc measurement.

< 7>each toner in basis < 3 >-< 6 >, wherein said oil phase further contains the spreading agent of the dispersiveness that can improve crystallized polyurethane resin and release agent.

< 8>developer, contain:

< 1 >-< 7>the said toner of each definition in.

Claims (8)

1. toner comprises:

The resin glue that contains crystalline resins and noncrystalline resin;

Colorant; With

Release agent,

Wherein said toner have 120 ℃-135 ℃ 1/2 flow starting temperature T1/2 and

Wherein the peak intensity ratio with FTIR-ATR peak intensity of measuring that derives from said crystalline resins and said release agent and the peak intensity that derives from said resin glue is 0.10-0.20.

2. according to the toner of claim 1; Wherein said toner has 45 ℃-65 ℃ glass transition temperature Tg 1st and 25 ℃-35 ℃ glass transition temperature Tg 2nd; Wherein said glass transition temperature Tg 1st is the glass transition temperature by the definite said toner of heating for the first time among the DSC, and glass transition temperature Tg 2nd is by the glass transition temperature that heats the said toner of confirming among the DSC for the second time.

3. according to the toner of claim 1, wherein said crystalline resins be crystallized polyurethane resin and

Wherein said toner is to obtain through the method that contains the following step:

Oil phase is dispersed in the water-bearing media that comprises particle dispersants forming the dispersion liquid of emulsification, resin glue, colorant and the release agent dissolving or be dispersed in organic solvent of wherein said oil phase through will containing said crystallized polyurethane resin and said noncrystalline resin prepares; With

From the dispersion liquid of said emulsification, remove said organic solvent.

4. according to the toner of claim 3, wherein said noncrystalline resin be the binder resin precursor that forms of the vibrin by modification and

Wherein said method further contains: can with said binder resin precursor chain extension or crosslinked compound dissolution in said oil phase and make said binder resin precursor in the dispersion liquid of said emulsification, carry out cross-linking reaction or chain extending reaction or this two kinds of reactions.

5. according to the toner of claim 1, wherein said crystalline resins is by C4-C12 saturated dicarboxylic acid and the synthetic crystallized polyurethane resin of C4-C12 saturated diols.

6. according to the toner of claim 1; The number-average molecular weight of wherein said crystalline resins be 500 or the ratio of littler molecule be 0%-2.0%; And number-average molecular weight be 1000 or the ratio of littler molecule be 0%-4.0%, wherein said number-average molecular weight is with gpc measurement.

7. according to the toner of claim 3, wherein said oil phase further contains the spreading agent of the dispersiveness that can improve said crystallized polyurethane resin and said release agent.

8. developer comprises:

Toner, said toner contains:

The resin glue that contains crystalline resins and noncrystalline resin;

Colorant; With

Release agent,

Wherein said toner have 120 ℃-135 ℃ 1/2 flow starting temperature T1/2 and

Wherein the peak intensity ratio with FTIR-ATR peak intensity of measuring that derives from said crystalline resins and said release agent and the peak intensity that derives from said resin glue is 0.10-0.20.

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