CN1847988A - Toner for electrostatic image development and process for preparing the same - Google Patents

Abstract

A process for preparing a toner for electrostatic image development, the process comprising the steps of: (S1) mixing an aqueous pigment dispersion and an aqueous resin particle dispersion containing self-dispersible polyester resin particles as a binder resin to prepare a mixture; and (S2) adding a polyvalent metal salt as a flocculant to the mixture while stirring to form aggregates of the pigment bonded to the resin particles, wherein the self-dispersible polyester resin is prepared by reacting a carboxylic acid compound with an alcohol compound inclusive of a polyhydric alcohol, the carboxylic acid compound being one or more of a polycarboxylic acid having three or more carboxyl groups and its anhydride.

Description

Electrostatic image developing toner and manufacture method thereof

Technical field

The present invention relates to be used for electrostatic image developing toner and the manufacture method thereof that electrophotographic image forms device.In addition, the present invention relates to electrostatic charge image developer, adopt the image forming method of this developer, and formed image.

Background technology

Along with the marked improvement of recent business automation equipment, adopt electrophotographic method and duplicating machine, the Printers and Faxes equipment implementing to print have become universal.Electrophotographic image forms device and implements image formation by charged, exposure, development, transfer printing, cleaning and photographic fixing step usually.

In charged step, in the dark place with the surperficial uniform charged of photoreceptor.In step of exposure, original image is projected to charged photoreceptor, thereby on photosensitive surface, forms electrostatic latent image by the electric charge of removing the rayed position.In development step, toner is bonded to the electrostatic latent image that is formed on the photosensitive surface, thereby forms toner image (visual picture).In transfer step, for example paper and sheet material are in contact with one another with being formed at the toner image of photosensitive surface and recording medium, make from a side generation corona discharge of the surface opposite of the recording medium that contacts toner image, to become the electric charge of opposite polarity to be applied to recording medium with toner, thereby the toner image that will be formed at photosensitive surface be transferred to recording medium.In the photographic fixing step, by the heating or the pressurization means with toner image to recording medium.In cleaning, the toner that is not transferred to recording medium and remain on the photosensitive surface is reclaimed.Electrophotographic image forms device and form desired images by above-mentioned steps on recording medium.

Be used for the electrostatic image developing toner that electrophotographic image forms device, its manufacture method can comprise dry method and wet method.The example of dry method can be comminuting method.Comminuting method is with resin, pigment (colorant) and wax fusing and kneads, and by comminutor gained kneaded that product is pulverized and classification, thereby obtains the method for toner, the widespread use in industrial circle of this method.Toner expectation should have small particle diameter forming high-quality image, but its energy and time of pulverizing usefulness of comminuting method increase, and this method is complicated and reduced productive rate thereby its problem that exists cost of products significantly to raise.

Suspension polymerization and emulsion polymerization method can be used as the example of wet method.Suspension polymerization is by in containing the aqueous solvent of pigment the synthetic resin monomer such as vinyl monomer being carried out the method that suspension polymerization obtains toner.

On the other hand, emulsion polymerization method is by the water-borne dispersions of synthetic resin particle is mixed with pigment dispersion in being scattered in organic solvent, form the agglutination particle (agglomerated particles) of synthetic resin particle and pigment, and with this agglutination particle heat fused, thereby the method for acquisition toner.As described later, this method has been used surfactant in the resin particle dispersion of toner preparation with raw material, thereby leaves surfactant in the toner of producing.

Another kind of wet method is to adopt the method for rp-emulsification.The phase transfer emulsification method is by resin that self is water dispersible and pigment dissolved or is scattered in the organic solvent, and be used for adding entry in the neutralizing agent that the group that dissociates to resin neutralizes adding and stir, thereby the resin solution droplet that includes pigment is carried out phase transfer emulsification, thereby obtain the method for toner particle.In addition, the another kind of wet method that obtains toner particle is by with resin dissolves or be scattered in the soluble solvent of resin, gained solution or dispersion are carried out granulation in the aqueous medium that contains inorganic dispersant,, obtain toner particle thus except that desolvating and the gained particle being carried out drying.This method of electrostatic image developing toner, be the material dissolves by will comprising vibrin and pigment or be scattered in the soluble solvent of vibrin, gained solution is carried out granulation in containing the aqueous medium of inorganic dispersant, remove then and desolvate, thereby produce toner.

Above-mentionedly prepare toner by wet method, residual in the gained toner have organic solvent, resin monomer and a surfactant.This type of component can be oozed out from toner when toner being actually used in the development of electrostatic latent image, causes impaired such as the parts of developer roll.In addition, make the charging property (chargeability) of toner become inhomogeneous.Therefore, after producing toner, need the step of from toner, removing organic solvent, monomer and surfactant.But, remove in the step at this, according to the slight fluctuations of pressure, condition of work that temperature and time is relevant, can make the shape of gained toner and charging property trend towards becoming inhomogeneous.Therefore, in order to obtain to have the toner of uniform shapes, needing to regulate condition of work to optimization, is very difficult and will finish this adjusting.In addition, because a large amount of organic solvent, monomer and surfactant that surrounding environment is had heavy burden that use needs the facility that it is handled, this has just caused the cost of toner preparation to increase.In addition, in the forming process of toner, residual in this emulsion polymerization method have a monomer.Thereby the new problem of its appearance is, when carrying out photographic fixing or the like toner being applied heat and pressure, residual monomer can evaporate and discharge stench.

In addition, the toner that obtains by above-mentioned conventional wet method not necessarily all keeps good on all properties of toner, for example use toner and be formed at image color and the picture quality such as the photographic fog of the image on the recording medium, and the dispersibility of the pigment on the recording medium and toner are to the transferring rate of recording medium.

For this reason, as another conventional wet method, Japanese laid-open patent application 10-39545 (document 1) discloses when forming toner particle and has neither adopted any organic solvent also not relate to the method for preparing toner of any polyreaction.In the manufacture method of the method for producing toner and toner of the document 1, the pigment aqueous dispersion is added in the emulsion, add alkaline halide solution in addition, thereby form agglutinator (agglomerates), described pigment aqueous dispersion is by the polyester (sodium sulfonated polyester) that adopts the sodium sulfonation pigment dispersing to be obtained in water, and described emulsion obtains in the water for the polyester with the sodium sulfonation is scattered in.

In addition, Japanese laid-open patent application 2002-131977 (document 2) disclose adopt similarly can self-dispersed resin method for preparing toner, described resin contains hydrophilic ethylenically unsaturated monomers.In the document 2, with the sulfonate sodium of styrene derivative or sulfonic acid potassium salt as hydrophilic ethylenically unsaturated monomers.The method of document 2 is that what to adopt the hydrophilic group contain metal organic sulfonate can be the method that agglutinant (flocculant) is produced toner with the multivalent metal salt from dispersion resin.

In addition, as adopting the patent that can disperse polyester certainly, the example has Japanese laid-open patent application 2004-354411 (document 3) and 2005-140855 (document 4).These two applications disclose the method that adopts vinyl-type resin dispersion and the potpourri that can disperse polyester certainly to prepare toner.These documents disclose the vibrin that can disperse polyester to be preferably not contain the trivalent monomer certainly.It also discloses ionic surfactant as the agglutinant that causes soft aggegation (soft flocculation).

To produce simple and easyly in order making, and to have good toner performance, electrostatic image developing toner should not contain unnecessary component, for example organic solvent or monomer ideally.

Method for preparing toner for document 1, carry out aggegation by polyester that adopts the sodium sulfonation and the pigment that the polyester that is scattered in the sodium sulfonation in the water will be scattered in the water, thereby make method for producing toner and toner, so this method for producing toner and toner manufacture method can be produced and not contain for example method for producing toner and toner of organic solvent and monomer of unnecessary component.But, if only adopt the polyester dispersed color of sodium sulfonation, the dispersibility deficiency of pigment, thereby form the only agglutinator of pigment, toner performance such as colorrendering quality just can not be met, so this method is not suitable for producing the method for producing toner and toner with good toner performance.In addition, by the method for producing toner and toner that this method is produced, its charging property depends on ambient environmental conditions and becomes unstable, and it exists it to use according to environmental baseline and restricted problem estimates that this question attribution is in the sulfonic group as hydrophilic radical.

Similarly, in document 2 disclosed method for preparing toner, although it has kept the dispersibility of pigment, its performance relevant with ambient environmental conditions of the toner of being produced is because above-mentioned same cause, be that hydrophilic radical is a metal organic sulfonate, thereby have similar problem.

In addition, about disclosed toner in document 3 and the document 4, they be to use can self-dispersed polyester and the potpourri of vinyl-type dispersion make.Although used the vinyl-type resin dispersion as mentioned above, toner contains monomer.In addition, owing to the employing surfactant causes soft aggegation, thereby be very difficult to control particle diameter.

Summary of the invention

According to an aspect of the present invention, the manufacture method of electrostatic image developing toner is provided, this method comprises the steps: that (S1) mixes the pigment aqueous dispersion and make potpourri with the resin particle aqueous dispersion, and described resin particle aqueous dispersion contains can disperse the vibrin particle certainly as binder resin; (S2) when stirring, will be added to as the multivalent metal salt of agglutinant in the potpourri, thereby form the agglutinator of the pigment that is bonded to resin particle, wherein said can be from disperseing vibrin to react and making by carboxylic acid compound and alcoholic compound, described alcoholic compound comprises polyvalent alcohol, and described carboxylic acid compound is to have the polybasic carboxylic acid of three or more carboxyls and in the acid anhydrides one or more thereof.

That in the methods of the invention, can disperse certainly that vibrin contains that two or more have different number-average molecular weights can disperse vibrin certainly.

According to a further aspect of the invention, provide the electrostatic image developing toner that makes by said method.

According to a further aspect of the invention, provide the electrostatic charge image developer that contains above-mentioned electrostatic image developing toner and carrier.

According to a further aspect of the invention, provide image forming method, it comprises following steps: form electrostatic latent image on photoreceptor; By the electrostatic charge image developer that adopts claim 16 electrostatic latent image on the photoreceptor is carried out video picture, thereby form toner image; And with toner image transfer printing and photographic fixing to recording medium.

Another aspect of the present invention provides by the formed image of above-mentioned image forming method.

Manufacture method according to electrostatic image developing toner of the present invention, described toner prepares by the following method: but stirring the aqueous solution that contains agglutinant by adding when pigment and self-dispersion type binder resin are mixed in the potpourri that obtains in the water at least, thus but formation comprises the agglutinator that is bonded to self-dispersion type vibrin dispersion of nano-particles pigment at least.Its result can easily produce the toner that does not contain unnecessary component, and described unnecessary component for example is used for the spreading agent of emulsification and dispersion resin, organic solvent and the monomer that constitutes binder resin, and these components are essential in conventional method.In addition, comprising under the conventional method situation that pigment and binder resin is melted and knead, polymkeric substance can be cut off owing to shear stress, thereby make its molecular weight produce fluctuation, thereby the fluctuation of molecular weight distribution and the toner performance that can not obtain expecting sometimes can be owing to blending the time, yet this type of problem can not take place in the present invention.

In addition, the self-dispersion type binder resin that uses two or more to have different number-average molecular weights has improved the toner performance, has particularly improved the storge quality and the fixation performance of toner.

In addition, adopt dispersion pigment to prepare toner, make the pigment dispersion particle diameter in the toner to be controlled at lessly, and can obtain having for example toner of colorrendering quality of good toner performance with good dispersibility.

In addition, because electrostatic image developing toner of the present invention makes by said method, thereby contain such as organic solvent hardly and constitute the unnecessary component of the monomer etc. of binder resin, and this toner has good toner performance.

In addition because electrostatic image developing toner of the present invention contains carboxylic acid as hydrophilic radical, thereby can become toner into hydrophobicity by pickling, and with contain sulfonic vibrin and compare and have more fine environment stability.

Description of drawings

Fig. 1 is the process flow diagram of the manufacture method of demonstration electrostatic image developing toner of the present invention.

Embodiment

The manufacture method of electrostatic image developing toner of the present invention is characterised in that, the characteristic of electrostatic image developing toner manufacture method, this method comprises following steps: (S1) the pigment aqueous dispersion is mixed with the resin particle aqueous dispersion and make potpourri, described resin particle aqueous dispersion contains can disperse the vibrin particle certainly as binder resin; To be added to as the multivalent metal salt of agglutinant in the potpourri when (S2) stirring, thereby form the agglutinator of the pigment that is bonded to resin particle, wherein said can be from disperseing vibrin to react and making by carboxylic acid compound and alcoholic compound, described alcoholic compound comprises polyvalent alcohol, and described carboxylic acid compound is to have the polybasic carboxylic acid of three or more carboxyls and in the acid anhydrides one or more thereof.

That in the methods of the invention, can disperse certainly that vibrin contains preferably that two or more have different number-average molecular weights can disperse vibrin certainly.

Another feature of electrostatic image developing toner manufacture method of the present invention is that above-mentioned self-dispersion type adhesive resin particles is to be made by two or more self-dispersion type binder resins with different number-average molecular weights.

Fig. 1 is for showing the artwork of electrostatic image developing toner manufacture method of the present invention.In the method for preparing toner of the embodiment of the present invention, press potpourri preparation process S1, agglutinator and form that order that step S2, particle form step S3 and washing step S4 implements.

(potpourri preparation process S1)

In potpourri preparation process S1, the pigment that the toner component is for example independently disperseed, self-dispersion type binder resin (hereinafter be sometimes referred to as binder resin or only be called resin) etc. mix with water and make potpourri.Form among the step S2 at agglutinator, the aqueous solution that will contain agglutinant is added in the said mixture, thereby forms the toner of agglutinator form in aqueous medium.In addition, implement particle and form step S3 and washing step S4, thus the toner that obtains having good toner performance.Particularly, form among the step S3 at particle, thereby the aqueous medium that will contain agglutinator heats the agglutinator granulation.In washing step S4, with the washing of the agglutinator after the granulation and dry.

Hereinafter will carry out more detailed description to above steps.

In potpourri preparation process S1, adopt stirring apparatus (emulsifier or diverting device) hereinafter will have the pigment and the binder resin of description to be scattered in the water independently, but thereby make the pigment aqueous dispersion that contains dispersed color respectively and contain the adhesive resin particles aqueous dispersion of self-dispersion type polyester binding resin particle (hereinafter being sometimes referred to as adhesive resin particles), this pigment aqueous dispersion is mixed with the adhesive resin particles aqueous dispersion and stir, thereby make the potpourri that contains the toner component.Preferably, the adhesive resin particles aqueous dispersion is mixed with proper ratio with the pigment aqueous dispersion, but make and contain the binder resin of 80-99.9 weight % and the dispersed color of 0.1-20 weight % in solid substance concentration, adopt stirring apparatus at room temperature to stir 1-5 hour, thereby obtain potpourri.In addition, in this potpourri preparation process S1, wax particulate aqueous dispersion can be mixed with said mixture, described wax particulate aqueous dispersion contains the natural and/or synthetic wax particulate of emulsification in water, and the ratio of wax particulate aqueous dispersion is counted 0.1-20 weight % with solid substance concentration.

(agglutinator forms step S2)

Form among the step S2 at agglutinator, by in the potpourri that contains such as pigment and adhesive resin particles (also containing the wax particulate under some situation), adding the agglutinant of ormal weight (for example 100 weight portion toner components with respect to this potpourri are the 0.5-20 weight portion), thereby form the agglutinator that contains the toner component.Therefore do not contain the unnecessary component outside the toner component in the toner, for example the monomer of organic solvent and formation binder resin.

Step S2 preferably at room temperature implements, and can implement under the temperature conditions that is heated to the glass transition temperature (Tg) near binder resin.At this moment, if self-dispersion type polyester binding resin particle is made by the self-dispersion type binder resin that two or more have different number-average molecular weights, then can be heated near the glass transition temperature (Tg) that has the binder resin of lowest glass transition temperature in described two or more resins.

In addition, in step S2, preferably adopt stirring apparatus by mechanical shear stress potpourri to be stirred, this is owing to can obtain having the agglutinator of the particulate forms of uniform grading and shape easily.

In addition, also can adopt the have low number-average molecular weight binder resin of (hereinafter abbreviating molecular weight sometimes as), and pigment and the formation of wax dispersed particle in case of necessity agglutinator, add resin particle subsequently with high molecular, the resin-bonded that thus will the back adds to before the surface of the agglutinator particle that forms, implement agglutinator with this and form.

Increase this step and given toner with storage stability, this is that the low-molecular-weight resin that is present in the inner casing has then been guaranteed fixation performance (particularly effective to low-temperature fixing) because high molecular weight resin is present in the top layer of the toner of being produced.In addition, can control wittingly the surface nature of toner.For example, in the toner top layer, contain the toner that contains colored pigment (cyan, carmetta and yellow) in toner and the top layer of conductive materials of carbon black etc. and have different charging property, thereby need design developer respectively.Because charged characteristic mainly is subjected to the influence of toner surface texture, thereby prevent that by formation pigment directly is exposed to the layer on surface, can reduce the charging property difference between the pigment.Forming resin bed from the teeth outwards also can estimate to produce the so favourable spinoff of carrier consumption that improvement wax causes.

Form among step S2 at this agglutinator, but hybrid regulatory quantitative the containing adhesive resin particles but do not contain the adhesive resin particles aqueous dispersion of pigment of (the 1-5 weight % of for example used resin total amount).In this case, then in advance the amount of resin in the adhesive resin particles aqueous dispersion to be mixed among the previous potpourri preparation process S1 is reduced ormal weight.In addition,, can add surfactant, also can add NaOH pH is transferred to 8 or higher in order to prevent the aggegation again (reflocculation) between the agglutinator.

(particle forms step S3)

Form among the step S3 at particle, will contain the aqueous medium heating of gained agglutinator and form and have the roughly agglutinator particle of uniform grading and shape.In this case, preferably be heated to the glass transition temperature of binder resin, perhaps using two or more to have the next maximum glass transition temperature that is heated to of binder resin situation of different glass transition temperature, thereby particle diameter is being transferred to 1-20 μ m.Can obtain having the roughly toner particle of uniform grading and shape in this way.

In addition, form among the step S3, can add the adhesive resin particles aqueous dispersion that contains binder resin that is used to control the toner shape in addition, thereby form agglutinator once more at this particle.At this moment, can add surfactant and prevent that the aggegation again of agglutinator and NaOH from transferring to 8 or higher with pH.At this moment, in advance the amount of resin in the adhesive resin particles aqueous dispersion to be mixed among the previous potpourri preparation process S1 is reduced ormal weight.

(washing step S4)

In washing step S4, the potpourri that will contain toner (agglutinator) is cooled to for example room temperature, removes by filter supernatant, and washes isolated toner with water.For washing, preferably adopting conductivity is the water of 20 μ S/cm or lower (preferred 10 μ S/cm or lower), also preferably the toner washing is reduced to 50 μ S/cm or lower until the conductivity of the supernatant of the washings that are used to wash toner.Can be in batches or wash toner continuously with water.Wash the toner purpose with water and be to remove unnecessary component outside the toner component, for example can influence the toner charging property impurity and with the irrelevant unnecessary agglutinant of aggegation, thereby can produce the toner that does not contain unnecessary component easily.In the water wash step process, can add at least once step, thereby can remove impurity more fully with pH6 or lower water washing.Afterwards, the toner of washing is in this way separated from washings after filtration, and can be carried out drying by Minton dryer.In addition, desired adjuvant (for example charged controlling agent, release agent (release agent) and external additive (extrapolating agent)) can be added in the toner of dry back gained.

[toner components description]

(self-dispersion type adhesive resin particles)

In the present invention, the resin that constitutes the self-dispersion type adhesive resin particles is not particularly limited, as long as this resin can be scattered in the water and keep disperse state in water, known resin such as vibrin, vinyl-type copolymer resin, urethane resin and epoxy resin can be used as the example of useful resin, and these resins can use separately or multiple being used in combination.

In addition, can use two or more to have the resin of different number-average molecular weights.At this moment, even single resin also can use in one or more performances various kinds of resin of differing from one another of aspect such as number-average molecular weight, monomer composition for example.In addition, but can use contain 50 weight % or the higher synthetic resin that is selected from least two kinds of resins in illustrative vibrin, vinyl-type copolymer resin, urethane resin and the epoxy resin etc. and contains the heating and melting outside one or more illustration resins that are lower than 50 weight % as the potpourri of surplus as binder resin.At this moment, but each resin to be used is preferably the synthetic resin with compatibility and heating and melting.Binder resin further preferably has hydroxyl in main chain.

About two or more have the binder resin of different number-average molecular weights among the present invention, minimum number-average molecular weight is 2000 or higher, is preferably 2500 or higher, more preferably 3000 or higher.In addition, the number-average molecular weight difference of these resins be set in 1000 or higher scope in situation under, can further improve the toner performance, especially, make toner storge quality and fixation performance become good.If the minimum average molecular weight is 2000 or lower, then storge quality and fixation performance trend towards reducing.

Consider powder flowbility, low-temperature fixing and the secondary colors repeatability of gained toner particle, the binder resin that uses among the present invention is preferably vibrin and vinyl-type copolymer resin, is preferably especially to contain the resin of vibrin as major constituent.In constituting the whole resin of binder resin, the ratio of vibrin is preferably 50 weight % or higher, 80 weight % or higher more preferably, even 90 weight % or higher more preferably.This is in order to improve as the colorrendering quality of toner and the performance function to the adhesive strength of paper etc.Hereinafter vibrin will be described.

The vibrin that is used for adhesive resin particles can obtain by the polycondensation reaction of acid constituents and alkoxide component, preferably by adopting polyfunctional carboxylic acids as acid constituents and the vibrin that adopts polyvalent alcohol to obtain as alkoxide component.

The example of above-mentioned polyfunctional carboxylic acids has aromatic dicarboxylic acid such as terephthalic acid (TPA), m-phthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2, the 6-naphthalenedicarboxylic acid, anthracene dipropionic acid, anthracene dioctyl phthalate, diphenic acid, sulfo group terephthalic acid (TPA), 5-sulfoisophthalic acid, the 4-sulfosalicylic phthalate, 4-sulfo group naphthalene-2,7-dioctyl phthalate, 5 (4-sulfophenoxy) m-phthalic acid, with and slaine and ammonium salt; Aromatic hydroxycarboxylic acids is P-hydroxybenzoic acid and right-(hydroxyl-oxethyl) benzoic acid for example; Aliphatic dicarboxylic acid is succinic acid, hexane diacid, azelaic acid for example, decanedioic acid and tetracosandioic acid (dodecanedicarboxylic acid); The unsaturated polyfunctional carboxylic acids of aliphatic series is fumaric acid, maleic acid, itaconic acid and mesaconic acid for example; The unsaturated polyfunctional carboxylic acids of aromatics is the benzene diacrylate for example; The alicyclic dicarboxylic acid is hexahydrophthalic acid and tetrahydrophthalic acid for example; And three-or higher polyfunctional carboxylic acids for example trimellitic acid, trimesic acid and pyromellitic acid and/or its acid anhydrides, above-mentioned substance can use separately or multiple being used in combination.

In the present invention, above-mentioned acid constituents can be contain monocarboxylic those.This monocarboxylic acid is preferably the one dollar aromatic carboxylic acid.One dollar aromatic carboxylic acid's example has benzoic acid, chlorobenzoic acid, bromobenzoic acid, P-hydroxybenzoic acid, naphthoic acid, anthroic acid, 4-methyl benzoic acid, 3-methyl benzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, their lower alkyl esters, sulfosalicylic acid mono-ammonium, sulfosalicylic acid list sodium salt, cyclohexyl amino carbonyl benzoic acid, dodecyl amino carbonyl benzoic acid, p t butylbenzoic acid and t-butyl naphthalin formic acid.

In above-mentioned acid constituents, the content of polyfunctional carboxylic acids is 70 moles of % or higher, is preferably 80 moles of % or higher, 90 moles of % or higher more preferably, and preferred aromatics polyfunctional carboxylic acids is as polyfunctional carboxylic acids.Further, preferably contain terephthalic acid (TPA) and m-phthalic acid as the aromatics polyfunctional carboxylic acids, the content of terephthalic acid (TPA) is preferably 40-95 mole % in the acid constituents, 60-95 mole % more preferably, even 70-90 mole % more preferably.The content of m-phthalic acid is preferably 5-60 mole % in the acid constituents.Further, the total content of terephthalic acid (TPA) and m-phthalic acid is preferably 80 moles of % or higher in the acid constituents, more preferably 90 moles of % or higher.In the present invention, especially preferably contain from three-or higher polyfunctional carboxylic acids for example pyromellitic acid acid anhydride, cyclohexane-1 of trimellitic acid, trimesic acid and pyromellitic acid and acid anhydrides thereof for example, 2,3,4-tetrabasic carboxylic acid-3, one or more that select in 4-dianhydride, the ethylene glycol bis dehydration trimellitate (ethylene glycolbisanhydrotrimellitate) are as polyfunctional carboxylic acids, and its content is preferably 0.5-8 mole % in acid constituents, be preferably 0.5-20 mole % especially.When containing monocarboxylic acid in the acid constituents, this monocarboxylic acid content is preferably 2-25 mole %, more preferably 5-20 mole %.Its reason is to keep the dispersed certainly of vibrin.

In the present invention, above-mentioned examples of polyhydric alcohols can be aliphatic polyol, cycloaliphatic polyol and aromatic polyol.The example of aliphatic polyol has aliphatic diol for example ethylene glycol, propylene glycol, 1, ammediol, 2,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diglycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polyglycol, polypropylene glycol and polytetramethylene glycol; Three pure and mild tetrols are trimethylolethane, trimethylolpropane, glycerine and pentaerythrite for example.The example of alicyclic polyol has 1, the ethylene oxide adduct of 4-cyclohexane diol, 1,4 cyclohexane dimethanol, spiral shell glycol (spiroglycol), hydrogenated bisphenol A, hydrogenated bisphenol A and propylene oxide adduct, three cyclododecane glycol (tricyclododecanediol) and three cyclododecane dimethanols (tricyclododecanedimethanol).The example of aromatic polyol has terephthalyl alcohol (p-xylene glycol), isophthalic alcohol, phthalyl alcohol, 1,4-penylene glycol (1,4-phenylene glycol), 1, the ethylene oxide adduct and the propylene oxide adduct of the ethylene oxide adduct of 4-penylene glycol, bisphenol-A, bisphenol-A.In addition, the example of polyester polyol has the lactone type polyester polyol that the ring-opening polymerization by lactone such as 6-caprolactone obtains.

In the present invention, as alkoxide component, described polyvalent alcohol can contain monohydroxy alcohol.The example of monohydroxy alcohol has aliphatic alcohol, aromatic alcohol and alicyclic alcohol.

In constituting the alkoxide component of vibrin of the present invention, the content of polyvalent alcohol is 50 moles of % or higher, preferred 70 moles of % or higher, 80 moles of % or higher more preferably, even 90 moles of % or higher more preferably.Preferably contain aliphatic diol and/or alicyclic diol as polyvalent alcohol.The preferred embodiment of aliphatic diol has ethylene glycol, propylene glycol and 2,3-butylene glycol.Wherein more preferably ethylene glycol and propylene glycol.The preferred embodiment of alicyclic diol has three cyclododecane dimethanols, cyclohexane diol and cyclohexanedimethanol.Especially, in the present invention, the content of ethylene glycol and/or propylene glycol is 50 moles of % or higher in the alkoxide component, 60 moles of % or higher more preferably, even 70 moles of % or higher more preferably.

As mentioned above, the vibrin that constitutes adhesive resin particles be by two-or higher polyfunctional carboxylic acids and two-or higher polyvalent alcohol obtain through polycondensation reaction as raw material, its purpose is to expand the molecular weight distribution of vibrin rather than in order to make resin gelization.The gelation of resin makes that resin is difficult to take out from polyplant, thereby can obviously reduce throughput rate.The vibrin that uses among the present invention in fact can gelation, more particularly, the component concentration that is insoluble to chloroform of this vibrin is no more than 0.5 weight %, preferably is not higher than 0.25 weight %, and the acid number of vibrin is 40mgKOH/g or lower, preferred 30mgKOH/g or lower.

In the present invention, the glass transition temperature (or softening point) of the vibrin of formation adhesive resin particles is preferably 40-80 ℃ (80-150 ℃), more preferably 45-80 ℃ (85-150 ℃), even more preferably 50-75 ℃ (80-145 ℃).Be lower than respectively at glass transition temperature and softening temperature under the situation of 40 ℃ and 80 ℃, the toner that is obtained by the vibrin particle trends towards causing adhesion (blocking), produces the problem of storage stability.On the other hand, if glass transition temperature is above 80 ℃, then toner trends towards producing offset (off-set), particularly undertaken by overlapping colors under the situation of color printing, this problem trends towards more obvious, and if softening point surpasses 150 ℃, then the toner that is obtained by the vibrin particle has problems on fixation performance, need simultaneously fixing roller is heated to high temperature, thereby the material used of fixing roller and the backing material of offset medium just are restricted.

Hydrophilic radical contained in the binder resin main chain is preferably ionic group, wherein special preferred anionic group.Particularly, the preferred embodiment of hydrophilic radical has the ammonium salt and the slaine of carboxyl, sulfonic group, phosphate, phosphonate group, phosphinic acids base, these groups, wherein more preferably carboxy acid alkali's slaine and ammonium carboxylate salt.Under the situation of vibrin, when introducing carboxy acid alkali's slaine and ammonium carboxylate salt, can be introduced into by the method that comprises following steps: for example trimellitic acid and/or its acid anhydrides append to carboxyl in polymer ends and/or the strand illustrative polyfunctional carboxylic acids thus on the polyester last stage reaction is introduced in reaction system, and with in ammonia or the NaOH etc. and carboxylic acid and/or acid anhydrides, thereby be translated into carboxylic acid.Ionic group provides water dispersible for vibrin, and when polyester was made in polymerization, the anti-lotus sun particle that contains the monomer of ionic group was preferably monovalent cation.Having carboxylate, to make the advantage that the self-dispersion type vibrin of hydrophilic radical has be it to be become hydrophobicity by the washing methods of implementing thereafter.

The method that obtains to have the particle of the mean grain size of regulation and size distribution from the self-dispersion type binder resin that has ionic group will be described below.Under the situation of vibrin, the vibrin that contains ionic group has water dispersible.The water-based differential prose style free from parallelism (aqueous micro-dispersion) that can contain the vibrin of ionic group by the known method manufacturing.For example, the existing vibrin and the water-soluble organic compounds that will contain ionic group is heated to 50-200 ℃ respectively, and it is mixed, and adds the manufacture method of entry then in potpourri.

Also have another kind of by will containing ionic group vibrin and the potpourri of water-soluble organic compounds (for example as the cationic compound of anti-lotus) add in the entry, with the gained potpourri 40-120 ℃ of heating, thus described resin and compound are disperseed, make the method for an above-mentioned water-based differential prose style free from parallelism with this.

In addition, also have another kind to be added in the potpourri of water and water-soluble organic compounds, at 40-100 ℃ the gained potpourri is heated, and stir described potpourri, make the method for an above-mentioned water-based differential prose style free from parallelism with this by the vibrin that will contain ionic group.

The example that can be used as above-mentioned water-soluble organic compounds has such as ethanol, butanols, isopropyl alcohol, ethyl cellosolve, butyl cellosolve, dioxane, tetrahydrofuran, acetone and methyl ethyl ketone equal solvent.

The mean grain size of the adhesive resin particles of the water-based differential prose style free from parallelism of vibrin etc. is 0.2 μ m or littler, preferred 0.01-0.15 μ m, more preferably 0.01-0.1 μ m.If the mean grain size of adhesive resin particles is greater than 0.2 μ m, then the particle of aggegation becomes big, so that may be difficult to it is controlled at suitably the toner-sized of expectation.

(pigment)

In the present invention, can use known pigment, any pigment is for example blue, brown, cyan, green, purple, carmetta, redness and yellow uitramarine all can use, and also can use its potpourri.Particularly, described pigment can comprise anthraquinone type pigment, phthalocyanine blue type pigment, phthalocyanine green type pigment, diazonium-type pigment, Monoazo type pigment, pyranthrone type pigment, perylene type pigment, heterocyclic yellows (heterocyclic yellow), quinoline a word used for translation ketone, indigo type pigment and thioindigo type pigment.The example of anthraquinone type pigment can be pigment red 43, and paratonere 194 (perylene ketone are red, perinone red), pigment red 21 6 (the bromination pyranthrone is red) and paratonere 226 (pyranthrone is red).The example of phthalocyanine blue type pigment has copper phthalocyanine blue and its derivant, pigment blue 15.The example of perylene type pigment have pigment red 123 (vermilion, Vermilion), pigment red 149 (scarlet), paratonere 179 (aubergine, maroon), paratonere 190 (red), pigment violet, paratonere 189 (Huang Tiaohong, yellow shade red) and paratonere 224.The example of heterocyclic yellows type pigment has pigment yellow 117 and pigment yellow 13 8.The example of quinoline a word used for translation ketone type pigment has pigment orange 48, pigment orange 49, pigment red 122, paratonere 192, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209, pigment violet 19 and pigment violet 42.The example of thioindigo type pigment has pigment Red 86, pigment Red 87, pigment Red 88, paratonere 181, paratonere 198, pigment violet 36 and pigment red 38.The carbon black that makes by the whole bag of tricks can be used as black pigment.

Above-mentioned pigment can be scattered in the water by the spreading agent such as surfactant.At this moment, spreading agent is preferably anionic surfactant and non-ionic surfactant, more preferably anionic surfactant.The use of spreading agent makes pigment be scattered in easily in the water, makes that the dispersing of pigments particle diameter is little in the toner, and makes and can produce the toner with good toner performance.In addition, can remove unnecessary spreading agent by washing step.

Can be used alone pigment, maybe two or more pigment combinations can be used.In addition, two or more pigment combinations use following, the pigment of the identical colour system of use capable of being combined also can be used in combination the pigment of the color of multiple systems.In the present invention, can select the content of pigment according to required toner performance in wide scope, with respect to the binder resin of 100 weight %, the content of pigment is preferably 0.1-20 weight %, more preferably 0.1-15 weight %.If pigment content is lower than 0.1 weight %, then the image color of formed image is difficult to uprise, if pigment content surpasses 20 weight %, then is difficult to guarantee the dispersiveness of pigment in formed image.

(wax particulate)

In the present invention, the wax particulate can be added as one of toner component.Can be with known wax as described particulate, for example natural wax such as Brazil wax and rice bran wax (rice wax); Synthetic wax such as polypropylene wax, Tissuemat E and Fischer-Tropsch (Fischer-Tropsch) wax; Coal wax (coalwax) is montan wax for example; Alcohol type wax; And ester type wax.Can be used alone wax, and two or more wax can be used in combination.In potpourri preparation process S1 the wax particulate is mixed in the potpourri, preferably add in the potpourri the wax particulate aqueous dispersion of making by mixing in water and emulsifying wax in advance or by the wax (eneapsulatedwax) sealed of gained being sealed on the wax surface with resin this moment.Its reason is, seals wax if add, and does not then form in the toner manufacture process of resin bed in toner surface, and wax can not be exposed to toner surface, thereby can improve the consumption of wax to carrier.For the situation that comprises wax in the toner component, wax content is preferably the 0.5-20 weight % of binder resin weight, more preferably 1-10 weight %.

(adjuvant)

In the present invention, except that above-mentioned toner component, the adjuvant of appropriate amount can be in toner, added as required usually, for example charged controlling agent and release agent can be after washing step, in the toner of drying, added.

In addition, known external additive (extrapolating agent) can be added, with the surface of improvement toner particle after washing step in the toner of drying.Can be with known external additive as this external additive, for example can the illustration silica and the be scattered in water of titanium dioxide etc. in inorganic particulate.The mean grain size of these inorganic particulates is 1 μ m or littler, is preferably 0.01-0.8 μ m, and one or more inorganic particulates can be used in combination.In addition, silicones (silicone resin) can be added in the external additive with improved surface.With respect to the toner particle of 100 weight portions, the addition of external additive is preferably the 1-10 weight portion.

The mean grain size that the toner that obtains by the invention described above method has is preferably 10 μ m or littler, 2-9 μ m more preferably, even 3-8 μ m more preferably.If mean grain size surpasses 10 μ m, then relevant with method for preparing toner size distribution broadens and charging property disperses to broaden, and causes image abnormity thus.

Toner by the invention described above method gained can be used for one-pack type developer or two-component developer.For the situation that toner is used for the one-pack type developer, do not use carrier (carrier) and only use toner, use with blade and hairbrush, make frictional electrification by the developer sleeve pipe, toner is adhered to and be transferred on the sleeve pipe, carry out image with this and form.

On the other hand, the situation for toner being used for two-component developer then is used in combination toner with carrier.Can be with known carrier as this carrier, for example carrier of being made by single-element such as iron, copper, zinc, nickel, cobalt, manganese, magnesium and chromium, and complex ferrite also has surface coated that the carrier core particle of coating material is arranged.Can be with known coating material as this coating material, for example color lake, silica micro mist and the alumina micro mist of teflon, a chlorotrifluoroethylene polymer, polyvinylidene fluoride, silicones, vibrin, di-tert-butyl salicylic acid metallic compound, styrene type resin, acryl resin, polyprotonic acid (polyacid), Pioloform, polyvinyl acetal (polyvinyl-ral), nigrosine, amino acrylates resin, basic-dyeable fibre, basic-dyeable fibre preferably can be selected it suitably according to the toner component.Coating material can use separately, maybe two or more can be used in combination.The mean grain size of carrier is preferably 10-100 μ m, more preferably 20-80 μ m.

[to the explanation of agglutinant]

Known agglutinant used agglutinant in the step can be formed as agglutinator in the method for preparing toner of the present invention, for example, ion polarity electrolyte substance opposite and organic compound can be used with pigment.As mentioned above, because binder resin and pigment preferably have ionic group and/or ionogen on its surface, thereby described agglutinant is preferably the multivalent metal salt that can form ionic link with this type of binder resin and pigment.In addition, the magnesium sulphate and the aluminium sulphate that easily are dissolved in the water are gone by washing easily, thereby are preferred.Wherein particularly preferably be magnesium sulphate.Its reason is, because the ion valence of magnesium salts is a divalence, thereby under the situation used as agglutinant, the situation that has the aluminium salt of trivalent with employing is compared its aggegation speed mitigation, and magnesium salts is optimum for the control particle diameter.Also can adopt the organic type agglutinant as agglutinant, for example dimethyl aminoethyl (2, the 2-dihydroxymethyl) propionic ester.

The consumption of agglutinant is the 0.5-20 weight portion, is preferably the 0.5-18 weight portion, more preferably the 1.0-18 weight portion.If the consumption of agglutinant is lower than 0.5 weight portion, then aggegation does not take place and make and can not carry out granulation, if its consumption is higher than 20 weight portions, then produces detrimental effect and make agglutinator excessive.

[to the explanation of water]

In the method for preparing toner of the present invention, used water preferably has 20 μ S/cm or lower conductivity in the washing step.Such water can by known method for example the combination of acticarbon method, ion exchange process, the way of distillation and hyperfiltration and multiple said method obtain.With regard to preventing aggegation again, the temperature of water preferably is equal to or less than the lowest glass transition temperature of binder resin during washing.

[explanation of stirring apparatus]

Agglutinator at method for preparing toner of the present invention forms in the step, preferably adopts stirring apparatus that potpourri is stirred.Can adopt known emulsifier unit and diverting device as stirring apparatus, preferred device be can be in batches or receive toner component and aqueous medium continuously, have heater means (heating means), by under heating condition, the toner component mixed the toner that can produce the adhesive resin particles form that contains pigment and can be in batches or give off the device of toner continuously with aqueous medium.In addition, emulsifier unit and diverting device preferably can apply shearing force to the potpourri of toner and aqueous medium, can easily the agglutinator that forms be formed the particle with uniform grading and shape because this makes.In addition, emulsifier unit and diverting device preferably have in mixer means (stirring means) and the rotary means at least either party, thereby can stir or rotating condition under mix toner and aqueous medium.Emulsifier unit and diverting device preferably have the mixer that is used to mix toner and aqueous medium, and the adiabatic means used of container.

Particularly, the example that can be used as emulsifier unit and diverting device has for example ULTRA TURRAX (trade name of batch-type emulsifier unit, by IKA Japan Co., Ltd. make), POLYTRONHOMOGENIZER (trade name is made by Kinematica), TKAUTOHOMO-MIXER (trade name, by Tokushu Kika Kogyo Co., Ltd. make) and MAX BLEND (trade name, by Sumitomo Heavy Industries, Ltd. makes); The continuous type emulsifier unit is EBARA MILDER (trade name for example, make by Ebara Corp.), (trade name is by Tokushu Kika Kogyo Co. for TK PIPELINE HOMO-MIXER, Ltd. make), TK HOMOMIC LINE LOW (trade name, by Tokushu Kika Kogyo Co., Ltd. makes), FILMIX (trade name, by Tokushu Kika Kogyo Co., Ltd. makes), COLLOID MILL (trade name, by Shinko Pantec Co., Ltd. make), (trade name is by Mitsui-Miike Kakoki Co. for SLASHER, Ltd. make), TRIGONAL WETFINE PULVERIZER (trade name, by Mitsui-Miike Kakoki Co., Ltd. makes), CAVITRON (trade name, by EUROTEC, LTD. makes) and FINE FLOW MILL (trade name is by Pacific Machinery ﹠amp; Engineering Co., Ltd. makes); CLEAMIX (trade name, by M.Technique Co., Ltd. makes) and FILMIX (trade name, by Tokushu Kika Kogyo Co., Ltd. makes).

Embodiment

Describe the present invention in detail with reference to embodiment and comparative example below, but the present invention is not subjected to any restriction of these embodiments.Can be under the situation that does not depart from the spirit and scope of the invention concrete process conditions and structure be changed and replace.The acid number of self-dispersion type polyester, glass transition temperature and number-average molecular weight are measured by the following method.

[acid number]

Measure acid number according to JIS K 0070.

[glass transition temperature]

Adopt differential scanning calorimeter (DSC210, make by Seiko Instruments Inc.) sample is heated to 200 ℃, sample is cooled to 0 ℃ with the cooldown rate of 10 ℃/min from 200 ℃, and with the rate of heat addition of 10 ℃/min heated sample once more, measure peak figure (peak chart) with this, the extended line that glass transition temperature is defined as the following baseline of maximum peak temperature and demonstration temperature from the rising part at peak to the intersection point of the positive tangent of the maximum inclination the peak maximum.

[number-average molecular weight]

Distribute by following gel permeation chromatography (GPC) determining molecular weight, and calculate number-average molecular weight by the survey molecular weight.

Determinator: CO-8010 (making) by Tosoh Corp..

Analytical column: GMHLX+G3000HXL (making) by Tosoh Corp..

Sample concentration: 0.5g/100mL tetrahydrofuran

Eluant, eluent: tetrahydrofuran (40 ℃)

Eluant, eluent flow velocity: 1ml/min

Standard model: monodispersed polystyrene

[copolymer polyester resin synthetic that is used for the self-dispersion type adhesive resin particles]

(copolymer polyester resin 1)

Dimethyl terephthalate (DMT) with 137 weight portions, the dimethyl isophthalate of 55 weight portions, the ethylene glycol of 68 weight portions, the bisphenol-A epoxy ethane adduct (mean molecular weight 350) of 175 weight portions and 0.1 weight portion join in the autoclave that is equipped with thermometer and stirrer as four titanium butoxide (tetrabutoxytitanate) of catalyzer, and 150-220 ℃ of heating 180 minutes, carry out ester exchange reaction, be heated to 240 ℃ subsequently, then, pressure in the reaction system is progressively reduced, after 30 minutes, reduce to 10mmHg, and make reaction proceed 70 minutes.Afterwards, replace gas in the autoclave, and pressure is transferred to atmospheric pressure with nitrogen.Temperature is remained on 200 ℃ and add the trimellitic anhydride of 2 weight portions, reaction was carried out 70 minutes, obtain copolymer polyester resin 1.

Measure the acid number of gained copolymer polyester resin 1, measured value is 15KOHmg.

(copolymer polyester resin 2)

At first, with 1 of 38 weight portions, 5-naphthalenedicarboxylic acid methyl esters, 96 weight portion dimethyl terephthalate (DMT), 58 weight portion dimethyl isophthalate, 136 weight portion ethylene glycol and 0.1 weight portion join in the autoclave that is equipped with thermometer and stirrer as four titanium butoxide of catalyzer, and, carry out ester exchange reaction 150-220 ℃ of heating 180 minutes.Reaction mixture is heated to 240 ℃ subsequently, the pressure in the reaction system is progressively reduced, after 30 minutes, reduce to 10mmHg, and make reaction proceed 70 minutes.Afterwards, replace gas in the autoclave, and pressure is transferred to atmospheric pressure with nitrogen.Temperature is remained on 200 ℃ and add the trimellitic anhydride of 10 weight portions, reaction was carried out 70 minutes, obtain copolymer polyester resin 2.

Measure the acid number of gained copolymer polyester resin 2, measured value is 14KOHmg.

(copolymer polyester resin 3)

The dimethyl terephthalate (DMT) of 112 weight portions, the dimethyl isophthalate of 76 weight portions, dimethyl isophthalate-5-sodium sulfonate, 96 weight portion ethylene glycol, 50 weight portion propylene glycol and 0.1 weight portion, four titanium butoxide of 6 weight portions are joined in the autoclave that is equipped with thermometer and stirrer, and, carry out ester exchange reaction 180-230 ℃ of heating 120 minutes.Reaction system is heated to 250 ℃ subsequently, then the pressure in the reaction system is transferred to 1-10mmHg, and make reaction proceed 60 minutes, thereby obtain copolymer polyester resin 3.

Measure the acid number of gained copolymer polyester resin 3, measured value is 0.1KOHmg.

(copolymer polyester resin 4)

With 199 weight portion terephthalic acid (TPA)s, 465 weight portion m-phthalic acids, 468 weight portions 2,2-dimethyl-1, ammediol, 156 weight portions 1,5-pentanediol and 0.41 weight portion join in the reaction vessel that is equipped with stirrer, condenser and thermometer as four titanium butoxide of catalyzer, through 4 hours it is heated to 230 ℃ from 160 ℃, carries out esterification.Pressure in the reaction system is progressively reduced, in 20 minutes, reduces to 5mmHg, under the vacuum below the 0.3mmHg in 260 ℃ of polycondensation reactions of further carrying out 40 minutes.Flow down at nitrogen, reaction system is cooled to 220 ℃, and add 23 parts by weight of trimelitic acid anhydrides and 16 weight portion ethylene glycol bis dehydration trimellitate, further carry out 30 minutes reaction, obtain copolymer polyester resin 4.

Measure the acid number of gained copolymer polyester resin 4, measured value is 22mgKOH/g.

(copolymer polyester resin 5)

96 weight portion dimethyl terephthalate (DMT), 96 weight portion dimethyl isophthalate, 72 weight portion ethylene glycol, 103 weight portion neopentyl glycols and 0.1 weight portion, four titanium butoxide are joined in the autoclave that is equipped with thermometer and stirrer, and, carry out ester exchange reaction 150-220 ℃ of heating 180 minutes.Reaction system is heated to 240 ℃ subsequently, the pressure in the reaction system is progressively reduced, after 30 minutes, transfer to 10mmHg, and make reaction proceed 60 minutes.Afterwards, with the gas in the nitrogen replacement autoclave, thereby the pressure in the autoclave is transferred to atmospheric pressure.The trimellitic anhydride that adds 4 weight portions when temperature is remained on 200 ℃ carried out reaction 60 minutes, obtained copolymer polyester resin 5.Measure the acid number of gained copolymer polyester resin 5, measured value is 25KOHmg.

(copolymer polyester resin 6)

With 49.8 weight portion terephthalic acid (TPA)s, 116.2 weight portion m-phthalic acids, 58.5 weight portion 2-methyl isophthalic acids, ammediol, 51.1 weight portions 1, four titanium butoxide of 4-cyclohexanedimethanol and 0.1 weight portion join in 4 mouthfuls of autoclaves of the 3L that is equipped with thermometer and stirrer, progressively be heated to 235 ℃ through 4 hours, carry out esterification.The initial stage polymerization of reducing pressure subsequently, and temperature is risen to 250 ℃ simultaneously and carry out polymerization.When reaching target molecular weight, under blanket of nitrogen, reaction system progressively is cooled to 220 ℃.Add the ethylene glycol bis dehydration trimellitate of 2 weight portions and the trimellitic anhydride of 1.8 weight portions then successively, and under blanket of nitrogen in 200-230 ℃ with reaction system continuous stirring 1 hour, obtain copolymer polyester resin 6.Measure the acid number of gained copolymer polyester resin 6, measured value is 23KOHmg.

Glass transition temperature and the number-average molecular weight of gained copolymer polyester resin 1-6 are as shown in table 1.Glass transition temperature is measured by DSC (differential scanning calorimetry), and number-average molecular weight is measured by GPC (gel permeation chromatography).

[table 1]

	Glass transition temperature (℃)	Number-average molecular weight
			Copolymer polyester resin 1	64	7800
Copolymer polyester resin 2	65	3500
			Copolymer polyester resin 3	58	3100
Copolymer polyester resin 4	60	5800
			Copolymer polyester resin 5	58	2100
Copolymer polyester resin 6	39	1900

[a copolymer polyester resin water differential prose style free from parallelism 1]

Butanols, the methyl ethyl ketone of 12 weight portions and the isopropyl alcohol of 20 weight portions of above-mentioned copolymer polyester resin 1,48 weight portions of 100 weight portions are added in the removable flask of four-hole (separable flask) of the 10L that is equipped with thermometer, condenser and stirring vane, and in 70 ℃ of stirring and dissolving.In addition, the 1N ammonia spirit that adds 270 weight portions with the acid number equivalence of multipolymer vibrin 1, gained solution is remained on 70 ℃ and stirred 30 minutes, subsequently, in agitating solution, add the water of 70 ℃ of 300 weight portions, obtain the water differential prose style free from parallelism of copolymer polyester resin 1.A gained water differential prose style free from parallelism is joined distillation with in the flask, and under 70 ℃ of temperature, reduce pressure in the flask, thereby remove organic solvent by vacuum pump.At last, regulate solid matter, obtain solid substance concentration and be a desolvated copolymer polyester resin water differential prose style free from parallelism 1 of 30% with deionized water.The mean grain size of this copolymer polyester resin water differential prose style free from parallelism 1 is 0.095 μ m.Volume average particle size be to adopt laser diffraction and scattering type distribution of particles determinator (MICROTRACK UPA-EX150, by Nikkiso CO., Ltd. makes) to measure.

[a copolymer polyester resin water differential prose style free from parallelism 2]

Except that adopting copolymer polyester 2, obtain a copolymer polyester resin water differential prose style free from parallelism 2 in the mode identical with an above-mentioned copolymer polyester resin water differential prose style free from parallelism 1.The mean grain size of this copolymer polyester resin water differential prose style free from parallelism is 0.080 μ m.

[a copolymer polyester resin water differential prose style free from parallelism 3]

Except that adopting copolymer polyester 3, obtain a copolymer polyester resin water differential prose style free from parallelism 3 in the mode identical with an above-mentioned copolymer polyester resin water differential prose style free from parallelism 1.The mean grain size of this copolymer polyester resin water differential prose style free from parallelism is 0.2 μ m.

[a copolymer polyester resin water differential prose style free from parallelism 4]

Except that adopting copolymer polyester 4, obtain a copolymer polyester resin water differential prose style free from parallelism 4 in the mode identical with an above-mentioned copolymer polyester resin water differential prose style free from parallelism 1.The mean grain size of this copolymer polyester resin water differential prose style free from parallelism is 0.073 μ m.

[a copolymer polyester resin water differential prose style free from parallelism 5]

Except that adopting copolymer polyester 5, obtain a copolymer polyester resin water differential prose style free from parallelism 5 in the mode identical with an above-mentioned copolymer polyester resin water differential prose style free from parallelism 1.The mean grain size of this copolymer polyester resin water differential prose style free from parallelism is 0.043 μ m.

[a copolymer polyester resin water differential prose style free from parallelism 6]

Except that adopting copolymer polyester 6, obtain a copolymer polyester resin water differential prose style free from parallelism 6 in the mode identical with an above-mentioned copolymer polyester resin water differential prose style free from parallelism 1.The mean grain size of this copolymer polyester resin water differential prose style free from parallelism is 0.037 μ m.

[preparation of dispersed color]

(pigment aqueous dispersion 1)

Adopt the zirconia pearl of diameter phi 0.5mm, by planetary ball mill (by FritschCo., Ltd. make) with 50 weight portion green pigments (Eupolen Blue 69-1501, by BASFCO., Ltd. make), 5 weight portion anionic surfactant (Neogen R, by Dai-IchiKogyo Seiyaku Co., Ltd. make) and 223 weight portion ion-exchange aqueous dispersions 40 minutes, then dispersion is joined homogenizer (PT3000, make by Polytron Devices Inc.) in and stirring at room 20 minutes with pigment dispersing, pass through ultrasonic homogenizer in addition (by NipponSeiki Co., Ltd. make) carry out 20 minutes dispersion, obtain the blue pigment aqueous dispersion 1 of mean grain size 0.10 μ m.

The mean grain size of this pigment aqueous dispersion l and following described pigment aqueous dispersion 2-5 is by Nikkiso Co., and the MICROTRACK UPA-ST150 that Ltd. makes measures.

(pigment aqueous dispersion 2)

Adopt the zirconia pearl of diameter phi 0.5mm, by planetary ball mill (by FritschCo., Ltd. make) with 50 weight portion magenta pigments 1 (Eupolen Red 47-9001, by BASF CO., Ltd. make), 5 weight portion anionic surfactant (Neogen R, by Dai-Ichi Kogyo Seiyaku Co., Ltd. make) and 223 weight portion ion-exchange aqueous dispersions 40 minutes, then dispersion is joined homogenizer (PT3000, make by Polytron Devices Inc.) in and stirring at room 20 minutes with pigment dispersing, carry out 20 minutes dispersion in addition by ultrasonic homogenizer, obtain the red pigment aqueous dispersion 2 of mean grain size 0.09 μ m.

(pigment aqueous dispersion 3)

Adopt the zirconia pearl of diameter phi 0.5mm, by planetary ball mill (by FritschCo., Ltd. make) with 50 weight portion yellow uitramarines (Eupolen Yellow 09-6101, by BASFCO., Ltd. make), 5 weight portion anionic surfactant (Neogen R, by Dai-IchiKogyo Seiyaku Co., Ltd. make) and 223 weight portion ion-exchange aqueous dispersions 40 minutes, then dispersion is joined homogenizer (PT3000, make by Polytron Devices Inc.) in and stirring at room 20 minutes with pigment dispersing, carry out 20 minutes dispersion in addition by ultrasonic homogenizer, obtain the yellow uitramarine aqueous dispersion 3 of mean grain size 0.08 μ m.

(pigment aqueous dispersion 4)

Adopt the zirconia pearl of diameter phi 0.5mm, by planetary ball mill (by FritschCo., Ltd. make) with 50 weight portion carbon black (MOGUL L, make by Cabot Corp.), 5 weight portion non-ionic surfactant (Nonipol, by Sanyo Chemical Industries, Ltd. make) and 223 weight portion ion-exchange aqueous dispersions 40 minutes, then dispersion is joined homogenizer (PT3000, make by Polytron Devices Inc.) in and stirring at room 20 minutes with pigment dispersing, obtain the black pigment aqueous dispersion 4 of mean grain size 0.13 μ m.

(pigment aqueous dispersion 5)

Adopt the zirconia pearl of diameter phi 0.5mm, by planetary ball mill (by FritschCo., Ltd. make) with 50 weight portion magenta pigments 2 (Eupolen Red 47-9001, by BASF CO., Ltd. make), 5 weight portion cationic surfactant (Sanisol B50, make by Kao Corp.) and 223 weight portion ion-exchange aqueous dispersions 40 minutes, then dispersion is joined homogenizer (PT3000, make by Polytron Devices Inc.) in and stirring at room 20 minutes with pigment dispersing, carry out 20 minutes dispersion in addition by ultrasonic homogenizer, obtain the red pigment aqueous dispersion 5 of mean grain size 0.09 μ m.

[preparation of wax particulate aqueous dispersion]

With 50 weight portion paraffin (HNP10,72 ℃ of fusing points, by Nippon Seiro Co., Ltd. make), the anionic surfactant of 5 weight portions (Neogen R, by Dai-Ichi KogyoSeiyaku Co., Ltd. make) and 161 weight portion ion exchange waters join in the stainless steel beaker that is equipped with chuck, in the time of 95 ℃ of heating, pass through homogenizer (PT3000, make by PolytronDevices Inc.) disperseed 30 minutes, be transferred to pressure discharge type homogenizer then (by Nippon Seiki Co., Ltd. make) and 90 ℃ of stirrings 20 minutes, obtaining mean grain size was the wax particulate aqueous dispersion of 0.4 μ m.The mean grain size of the dispersed color of wax particulate is measured by MICROTRACK UPA-ST150 (by Nikkiso Co., Ltd. makes).

Embodiment 1

(potpourri preparation process)

Separately with the ratio shown in the table 2, will contain the above-mentioned pigment aqueous dispersion 2 of decentralized pigment fuchsin, an above-mentioned vibrin water differential prose style free from parallelism 1 (shown in the table 2 85% of 90 weight portions) and wax particulate aqueous dispersion and mix and obtain potpourri with solid substance concentration (weight portion) expression.At this moment, water transfers to 10% with total solid material concentration.

(agglutinator formation step)

When by Max Blend stirring apparatus the gained potpourri being stirred with 1500rpm, the magnesium chloride brine that drips 270 weight portions, 1 weight % then, stirs potpourri 1 hour as agglutinant.In aqueous medium, form the toner agglutinator thus.Add a remaining vibrin water differential prose style free from parallelism 1 (90 weight portions shown in the table 2 all the other 15%) then, and drip the magnesium chloride brine of 30 weight portions, 1 weight %, afterwards potpourri was stirred 1 hour.In aqueous medium, further form the toner agglutinator thus.

(particle formation step)

The aqueous medium that will contain the agglutinator that forms in agglutinator forms step is heated to 75 ℃, and further continuous stirring 30 minutes, and further stirs 20 minutes at 94 ℃, makes the particle diameter of agglutinator and shape even.At this moment,, pH is transferred to 10, and add the sodium n-alkylbenzenesulfonate of 1 weight portion in order to prevent aggegation again.

(washing step)

Subsequently, the supernatant that will contain the aqueous medium of agglutinator is removed, and washes agglutinator with water three times (supernatant is changed three times), then transfers to 2 HCl solution washing with pH, further washes with water three times.Carry out drying with the filtration of gained agglutinator and by Minton dryer, obtain the carmetta toner.

The water that is used to wash is that conductivity is the water of 0.5 μ S/cm, adopts ultrapure water preparation facilities (Ultra Pure Water System CPW-102 is made by ADVANTEC) to be made by tap water.The pH of water and conductivity are measured by La comme tester (EC-PHCON 10, made by IUCHISEIEIDO).

Embodiment 2

Make outside the potpourri by a pigment aqueous dispersion 1 that contains decentralized pigment green grass or young crops and a vibrin water differential prose style free from parallelism 2 divided by the ratio shown in the table 2 with solid substance concentration (weight portion) expression, make toner in the mode identical, obtain the cyan toner of embodiment 2 with embodiment 1.

Embodiment 3

Make outside the potpourri by a pigment aqueous dispersion 3 that contains the decentralized pigment yellow and a vibrin water differential prose style free from parallelism 3 divided by the ratio shown in the table 2 with solid substance concentration (weight portion) expression, make toner in the mode identical, obtain the Yellow toner of embodiment 3 with embodiment 1.

Embodiment 4

Make outside the potpourri by a pigment aqueous dispersion 4 that contains the decentralized pigment black and a vibrin water differential prose style free from parallelism 2 divided by the ratio shown in the table 2 with solid substance concentration (weight portion) expression, make toner in the mode identical, obtain the black toner of embodiment 4 with embodiment 1.

Embodiment 5

Make potpourri with the ratio shown in the table 2 by a pigment aqueous dispersion 4 that contains the decentralized pigment black and a vibrin water differential prose style free from parallelism 2 with solid substance concentration (weight portion) expression.By mixing at twice the embodiment 4 of twice of aggegation respectively, made the toner same herein, with the black toner of embodiment 4 with the disposable mixing of the vibrin of predetermined weight part rather than as vibrin.In other words, after this do not carry out the aggegation step and make toner.

Comparative example 1

Make outside the potpourri by a pigment aqueous dispersion 4 that contains the decentralized pigment black and a vibrin water differential prose style free from parallelism 3 divided by the ratio shown in the table 2 with solid substance concentration (weight portion) expression, make toner in the mode identical, obtain the black toner of comparative example 1 with embodiment 1.

Comparative example 2

Make potpourri divided by the ratio shown in the table 2 by a pigment aqueous dispersion 4 that contains the decentralized pigment black and a vibrin water differential prose style free from parallelism 2 with solid substance concentration (weight portion) expression, and used agglutinant among the embodiment 1 is become outside the Sanisol B50 (being made by Kao Corp.) (zephiran), make toner in the same manner, obtain the black toner of comparative example 2.

Comparative example 3

Make agglutinator in the mode identical with embodiment 1.Make the carmetta toner in the mode identical with embodiment 1, difference is to use the step of the HCl solution washing of pH2, but the step of carrying out thereafter is all identical with embodiment 1.

[table 2]

		Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Comparative example 1	Comparative example 2	Comparative example 3
										The self-dispersion type binder resin	Polyester 1	90		90					90
Polyester 2		90		87	87		87
									Polyester 3							87
Pigment	Blue or green		5
									Fuchsin	5							5
	Yellow			5
									Black				8	8	8	8
	Wax		5	5	5	5	5	5										5	5

[preparation of toner]

Is the 0.7 weight portion silica particle of 20nm by add (the outside interpolation) in the toner of embodiment 1-5 and comparative example 1 and 2 gained with the average primary particle diameter that silane coupling agent has carried out hydrophobic treatments, obtains toner of all kinds.

[preparation of developer]

To contain each toner 70g of the embodiment 1-5 of described external additive and comparative example 1 and 2 by the V-arrangement mixer and mix, make developer with ferrite carrier 1400g with resin coating.

[evaluation method]

According to following evaluation method, the every evaluation that the toner of embodiment 1-5 is averaged particle diameter, variable coefficient, average roundness, image color, photographic fog (fogging), pigment-dispersing and transferring rate with and overall merit, the result is as shown in table 3.In table 3, each evaluation of symbol zero expression is very good, symbol * expression practical application difficulty.

(mean grain size and variable coefficient)

Adopt Coulter Multicizer II (making) to measure mean grain size and variable coefficient, and on the basis of variable coefficient, estimate according to following standard by Coulter Inc..The population of surveying is 50000 countings, and the aperture is 100 μ m.The unit of mean grain size is μ m in the table 3.

Zero: variable coefficient is 40 or lower

*: variable coefficient is less than 40

(average roundness)

Adopt flow model particle image analyzer (FPIA-2000, by Toa Iyo Denshi Co., Ltd. makes) to measure the average roundness of toner particle.Average roundness is by the following expression definition relevant with the particle projects images of flow model particle image analyzer detection, and its value is 1 or lower.Average roundness=(having the girth of the circle of identical table area)/(girth of projects images) with projects images

(image color)

Optical concentration (optical density) by spectrophotometric tintmeter (X-Rite 938, and by Nippon Lithograph, Inc. makes) mensuration image passes through following standard evaluation image color according to this optical concentration.Each evaluation map similarly is that (AR-C 150 by using above-mentioned each developer and digital panchromatic duplicating machine, make by Sharp Corp.) the transformation developing apparatus, simultaneously the adhesion amount of toner particle on panchromatic printing dedicated paper (PP106A4C is made by Sharp Corp.) is controlled at 0.6mg/cm ²Print, and adopt outside fixing device to make.

Zero: optical concentration is 1.2 or higher

*: optical concentration is lower than 1.2

(photographic fog)

By following evaluation photographic fog.Situation for black toner, then use leucometer (Z-∑ 90 COLOR MEASURING SYSTEM in advance, by Nippon Denshoku Kogyo Co., Ltd. manufacturing) colored printing dedicated paper (the PP106A4C of mensuration A4 size, make by Sharp Corp.) whiteness, and measured value is defined as the first measured value W1.Then, obtain comprising diameter 55mm 3 copies of the drawing of circle in vain, measure the whiteness of the white portion of copy, and measured value is defined as the second measured value W2 by duplicating.Calculate photographic fog concentration W (%) by following formula, and on the basis of the photographic fog concentration that calculates according to following standard evaluation photographic fog.

W＝{100×(W1-W2)/W1}

Zero: photographic fog concentration W is 2.0% or lower

*: photographic fog concentration W is higher than 2.0%

(environmental evaluation)

In environmental baseline ((a) 5 ℃ of temperature and 10% humidity; (b) 35 ℃ and 80% humidity) under add in the existing shadow groove respectively above-mentioned each developer of ormal weight and store overnight, with the rotational speed rotation identical 2 minutes with above-mentioned image processing system, measure the carried charge of toner, based on the relative ratios of the carried charge under (b) high temperature and the high humidity, estimate according to following standard to the carried charge under (a) low temperature and the low humidity condition.

Zero: rate of change is 60% or higher

*: rate of change is higher than 60%

(transferring rate)

Transferring rate (%) calculates according to following formula by measure duplicating remaining toner particle weight Md on toner particle weight Mp on the paper that the regulation chart is arranged and the photoreceptor.And according to following standard evaluation transferring rate (%).

T＝{Mp/(Md+Mp)×100}

Zero: transferring rate T (%) is 90% or higher

*: transferring rate T (%) is lower than 90%

[table 3]

	A	B		C	D		E		F		G		H
														Embodiment 1	6.5	28	○	0.97	1.3	○	0.9	○	76	○	94	○	○
Embodiment 2	7.3	29	○	0.97	1.2	○	0.8	○	74	○	95	○	○
														Embodiment 3	6.9	26	○	0.97	1.3	○	0.8	○	77	○	94	○	○
Embodiment 4	7.1	29	○	0.97	1.9	○	0.9	○	75	○	93	○	○
														Embodiment 5	7.3	28	○	0.97	1.8	○	0.9	○	76	○	92	○	○
Comparative example 1	7.1	29	○	0.97	1.8	○	1.1	○	55	×	90	○	×
														Comparative example 2	25	50	×	0.88	-	×	-	×	-	×	-	×	×
Comparative example 3	6.5	28	○	0.97	1.3	○	0.9	○	45	×	94	○	×

A: mean grain size B: variable coefficient C: average roundness D: image color

E: photographic fog F: environmental evaluation G: transferring rate H: comprehensive evaluation

Can know from table 3 and to find out, can be manufactured on size distribution, image color, photographic fog, all good toner of environmental evaluation and transferring rate aspect by the present invention (embodiment 1-5).

In addition, based on embodiment 4 and 5 more as can be known, the toner that has resin bed on the particle surface is showing stable slightly aspect the toner charging property of environmental correclation.

In addition, based on embodiment 4 and comparative example 1 more as can be known, at carboxylic acid type self-dispersion type polyester with contain between the sulfonic self-dispersion type polyester toner that adopts carboxylic acid polyester to make, it is better aspect environmental characteristics.

In addition, based on embodiment 4 and comparative example 2 more as can be known, adopt multivalent metal salt can more stably make toner as agglutinant.

In addition, can find out based on the comparison of embodiment 1 and comparative example 3, owing in washing step, do not wash with pH6 or lower water, so environmental characteristics becomes unstable.

Embodiment 6

(potpourri preparation process)

With the ratio shown in the table 4 with solid substance concentration (weight portion) expression will contain the above-mentioned pigment aqueous dispersion 1 of pigment green grass or young crops, the above-mentioned vibrin water differential prose style free from parallelism 1 that made by said method (weight shown in the table 4 85%) and a vibrin water differential prose style free from parallelism 4 and wax microparticle dispersion mix, thereby obtain potpourri.At this moment, water transfers to 10% with total solid material concentration.

(agglutinator formation step)

When the gained potpourri being stirred with 500rpm by Max Blend stirring apparatus, drip 1 weight % magnesium chloride brine, 270 weight portions as agglutinant, after this potpourri was stirred 1 hour.In aqueous medium, form the toner agglutinator thus.Then, a remaining vibrin water differential prose style free from parallelism 1 (residue 15% of weight shown in the table 4) is added, and drip 1 weight % magnesium chloride brine, 30 weight portions, afterwards potpourri was stirred 1 hour.In aqueous medium, further form agglutinator thus.

(particle formation step)

To form the aqueous medium that contains agglutinator that forms in the step at agglutinator and be heated to 75 ℃, further continuous stirring is 30 minutes, and further stirs 20 minutes at 94 ℃, makes the particle diameter of agglutinator and shape even.At this moment,, pH is transferred to 10, and add the sodium n-alkylbenzenesulfonate of 1 weight portion in order to prevent aggegation again.

(washing step)

Subsequently, the supernatant of aqueous medium that will contain the agglutinator of precipitation is removed, and washes agglutinator with water three times (supernatant is changed three times), then transfers to 2 HCl solution washing with pH, further washes with water three times.Carry out drying with the filtration of gained agglutinator and by Minton dryer, obtain the carmetta toner.

The water that is used to wash is that conductivity is the water of 0.5 μ S/cm, adopts ultrapure water preparation facilities (Ultra Pure Water System CPW-102 is made by ADVANTEC) to be made by tap water.The pH of water and conductivity are measured by La comme tester (EC-PHCON 10, made by IUCHISEIEIDO).

Embodiment 7

Above-mentioned pigment aqueous dispersion 2, a vibrin water differential prose style free from parallelism 1, a vibrin water differential prose style free from parallelism 2 and the wax microparticle dispersion that will contain pigment fuchsin 1 with the ratio with solid substance concentration (weight portion) expression shown in the table 4 mix, thereby obtain potpourri, in with embodiment 6 identical mode make toner, obtain the carmetta toner of embodiment 7 thereafter.The consumption of a vibrin water differential prose style free from parallelism 1 in the potpourri preparation process is 85 weight % of total amount shown in the table 4, and the consumption that the agglutinator subsequently forms in the step is 15 weight % of total amount shown in the table 4.

Embodiment 8

Above-mentioned pigment aqueous dispersion 3, a vibrin water differential prose style free from parallelism 1, a vibrin water differential prose style free from parallelism 5 and the wax microparticle dispersion that will contain pigment yellow with the ratio separately with solid substance concentration (weight portion) expression shown in the table 4 mix, thereby obtain potpourri, in with embodiment 6 identical mode make toner, obtain the Yellow toner of embodiment 8 thereafter.The consumption of a vibrin water differential prose style free from parallelism 1 in the potpourri preparation process is 85 weight % of total amount shown in the table 4, and the consumption that the agglutinator subsequently forms in the step is 15 weight % of total amount shown in the table 4.

Embodiment 9

Above-mentioned pigment aqueous dispersion 4, a vibrin water differential prose style free from parallelism 1, a vibrin water differential prose style free from parallelism 4 and the wax microparticle dispersion that will contain pigment black with the ratio with solid substance concentration (weight portion) expression shown in the table 4 mix, thereby obtain potpourri, in with embodiment 6 identical mode make toner, thereby obtain the black toner of embodiment 9 thereafter.The consumption of a vibrin water differential prose style free from parallelism 1 in the potpourri preparation process is 85 weight % of total amount shown in the table 4, and the consumption that the agglutinator subsequently forms in the step is 15 weight % of total amount shown in the table 4.

Embodiment 10

Above-mentioned pigment aqueous dispersion 1, a vibrin water differential prose style free from parallelism 2, a vibrin water differential prose style free from parallelism 5 and the wax microparticle dispersion that will contain pigment green grass or young crops with the ratio with solid substance concentration (weight portion) expression shown in the table 4 mix, thereby obtain potpourri, in with embodiment 6 identical mode make toner, obtain the cyan toner of embodiment 10 thereafter.The consumption of a vibrin water differential prose style free from parallelism 2 in the potpourri preparation process is 85 weight % of total amount shown in the table 4, and the consumption that the agglutinator subsequently forms in the step is 15 weight % of total amount shown in the table 4.

Embodiment 11

Above-mentioned pigment aqueous dispersion 4, a vibrin water differential prose style free from parallelism 4 and the wax microparticle dispersion that will contain pigment black with the ratio with solid substance concentration (weight portion) expression shown in the table 4 mix, thereby obtain potpourri.In the mode identical with embodiment 6, agglutinant is added in the potpourri and forms agglutinator, add a vibrin water differential prose style free from parallelism 1 thereafter, and further add agglutinant, thereby obtain toner.Obtain the black toner of embodiment 11 in this way.The consumption of a vibrin water differential prose style free from parallelism 4 is the whole amounts shown in the table 4 in the potpourri preparation process, and the consumption that the agglutinator subsequently forms a vibrin water differential prose style free from parallelism 1 in the step is the whole amounts shown in the table 4.On inner casing, form the coating of a vibrin water differential prose style free from parallelism 4 thus, and on shell, form the coating of a vibrin water differential prose style free from parallelism 1.

Comparative example 4

To contain pigment fuchsin 2 and use cationic surfactant (Sanisol B50 with the ratio shown in the table 4 with solid substance concentration (weight portion) expression, make by Kao Corp.) the pigment aqueous dispersion 5 that disperses, mix as the vibrin water differential prose style free from parallelism 1 of self-dispersion type binder resin and a vibrin water differential prose style free from parallelism 4 and wax microparticle dispersion, thus obtain potpourri.At this moment, when vibrin being mixed with pigment dispersion and during continuous stirring, viscosity being increased thereby formed agglutinator.Therefore, the agglutinator that does not carry out thereafter forms step.

Comparative example 5

With the ratio shown in the table 4 with solid substance concentration (weight portion) expression will contain pigment green grass or young crops pigment aqueous dispersion 1, mix as the vibrin water differential prose style free from parallelism 1 of self-dispersion type binder resin and a vibrin water differential prose style free from parallelism 6 and wax microparticle dispersion, thereby obtain potpourri, make toner in the mode identical afterwards, thereby obtain the cyan toner of comparative example 5 with embodiment 6.The consumption of a vibrin water differential prose style free from parallelism 1 in the potpourri preparation process is 85 weight % of total amount shown in the table 4, and the consumption that the agglutinator subsequently forms in the step is 15 weight % of total amount shown in the table 4.

Comparative example 6

Generate agglutinator in the mode identical with embodiment 6.Make cyan toner in the mode identical with embodiment 6, difference is not carry out the step with the HCl solution washing of pH2 in washing step thereafter, but step is thereafter all carried out in the mode identical with embodiment 6.

Comparative example 7

To mix respectively as a vibrin water differential prose style free from parallelism 1 and the vibrin water differential prose style free from parallelism 3 of self-dispersion type binder resin with the ratio shown in the table 4 with solid substance concentration (weight portion) expression, and 88 weight % of gained potpourri are mixed with pigment aqueous dispersion 1 that contains pigment green grass or young crops and wax microparticle dispersion, thereby formation agglutinator, after this residue 12 weight % with the potpourri of a vibrin water differential prose style free from parallelism 1 and a vibrin water differential prose style free from parallelism 3 add, add agglutinant in the mode identical once more, obtain the cyan toner of comparative example 7 with embodiment 6.

Comparative example 8

The Sanisol B50 (zephiran) that makes divided by Kao Corp. replaces outside the agglutinant, in the mode identical with embodiment 6, adopt as shown in table 4 with solid substance concentration (weight portion) expression make toner by each component, obtain the carmetta toner of comparative example 8.

Comparative example 9

Pigment aqueous dispersion 1, a vibrin water differential prose style free from parallelism 6 and the wax microparticle dispersion that will contain pigment green grass or young crops with the ratio with solid substance concentration (weight portion) expression shown in the table 4 mix, thereby obtain potpourri.Form agglutinator thereby in potpourri, add agglutinant, add a vibrin water differential prose style free from parallelism 5 thereafter, add agglutinant afterwards once more, obtain toner in the mode identical with embodiment 6.Make the cyan toner of comparative example 9 in this way.The consumption of a vibrin water differential prose style free from parallelism 6 in the potpourri preparation process is the whole amounts shown in the table 4, and the consumption of polyester 5 in agglutinator formation step subsequently is the whole amounts shown in the table 4.Thus, form the coating of vibrin 6 on the inner casing, and on shell, form the coating of vibrin 5.

In embodiment 6-11 and comparative example 4-9, for a specific a kind of vibrin water differential prose style free from parallelism, in the potpourri preparation process, use 85 weight % of total amount as shown in table 4, and form the 15 weight % that use total amount as shown in table 4 in the step at agglutinator subsequently, in addition, also can in above-mentioned two steps, use the potpourri of two or three a vibrin water differential prose style free from parallelism respectively.

Table 4

Solid matter (weight %)

		Embodiment 6	Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Comparative example 4	Comparative example 5	Comparative example 6	Comparative example 7	Comparative example 8	Comparative example 9
														The self-dispersion type binder resin	Polyester 1	15	15	15	15		15	15	15	15	15	15
Polyester 4	75			72		72	75		75
													Polyester 2			75			15						75
Polyester 5			75		75							15
													Polyester 6									75				75
Polyester 3										75
													Pigment		Blue or green	5				5			5	5	5		5
Fuchsin 1		5									5
														Yellow			5
Black				8		8
														Fuchsin 2							5
Wax		5	5	5	5	5	5	5	5	5	5	5															5

[preparation of toner]

Is silica particle 0.7 weight portion of 20nm by add (the outside interpolation) in the toner of embodiment 6-11 and comparative example 4-9 gained with the average primary particle diameter that silane coupling agent has carried out hydrophobic treatments, thereby obtains toner of all kinds.

[preparation of developer]

With the V-arrangement mixer the above-mentioned toner 70g of external additive that contains is mixed with ferrite carrier 1400g with resin coating, thereby make developer.

[evaluation method]

Toner to embodiment 6-11 and comparative example 4-9, with above-mentioned mean grain size, variable coefficient, average roundness, image color, photographic fog and the environmental characteristics similarly estimated, and according to following evaluation method is carried out fixation performance and storability each is estimated, the result is as shown in table 5.In table 5, each evaluation of symbol zero expression is very good, symbol * expression practical application difficulty.

(fixation performance)

Fixation performance is estimated by the following method: adopt outside fixing device each toner to be had in duplicating on the paper of regulation chart and carry out photographic fixing, mensuration is stain the temperature of (coldoff-set) to the temperature range the temperature that the contamination of deep fat China ink takes place from generation cold oil China ink, and estimates on the basis of non-offset (non-off-set) temperature range.

Zero: non-offset zone is 40 ℃ or higher

*: non-offset zone is less than 40 ℃

(storability)

Be performed as follows the storability evaluation: each toner 5g that in the 50mL sample bottle, weighs, rap (tapped), in 50 ℃ of hyperthermal baths, store 24 hours then.Stored sample is taken out and naturally cool to room temperature, rap once more, and the aggegation degree that detects by an unaided eye, under the loose rapidly situation that returns back to original state of toner particle, its storability is evaluated as zero, under the situation that aggegation takes place, then be evaluated as *.

[table 5]

	A	B		C	D		E		I		J	F		H
															Embodiment 6	6.5	28	○	0.97	1.3	○	0.9	○	50	○	○	72	○	○
Embodiment 7	7.3	29	○	0.97	1.2	○	0.8	○	50	○	○	74	○	○
															Embodiment 8	6.9	26	○	0.97	1.3	○	0.8	○	50	○	○	71	○	○
Embodiment 9	7.1	29	○	0.97	1.9	○	0.9	○	50	○	○	76	○	○
															Embodiment 10	6.6	28	○	0.97	1.3	○	0.9	○	50	○	○	73	○	○
Embodiment 11	6.4	29	○	0.97	1.9	○	0.9	○	55	○	○	75	○	○
															Comparative example 4	25	50	×	0.88	-	×	-	×	-	×	-	×	-	×
Comparative example 5	7.2	28	○	0.97	1.2	○	0.9	○	35	×	×	75	○	×
															Comparative example 6	6.5	28	○	0.97	1.3	○	0.9	○	50	○	○	45	×	×
Comparative example 7	6.5	28	○	0.97	1.3	○	0.9	○	50	○	○	40	×	×
															Comparative example 8	55	80	×	-	-	×	-	×	-	×	-	×	-	×
Comparative example 9	7.1	28	○	0.97	1.3	○	0.9	○	30	×	○	71	○	×

A: mean grain size B: variable coefficient C: average roundness D: image color

E: photographic fog I: fixation performance J: storability H: comprehensive evaluation

Can find out obviously that from table 5 toner (embodiment 6-11) that is made by the inventive method has good toner performance, for example size distribution, image color, photographic fog and fixation performance, and fixation performance, storability and environmental characteristics.In addition, based between embodiment 9 and 11 more as can be known, its fixation performance of toner of the embodiment 11 that is applied by high molecular weight resin more has improvement slightly.On the other hand, toner for comparative example 4, owing to cationic surfactant is used as pigment dispersing agent, thereby in the potpourri of a pigment aqueous dispersion before adding agglutinant and a vibrin water differential prose style free from parallelism aggegation takes place, produce the excessive toner of mean grain size.Therefore, there is no need to measure its average roundness, image color, photographic fog and fixation performance.In addition, adopt number-average molecular weight be 2000 or the situation of the comparative example 5 of lower vibrin under, then produce the problem of fixation performance and storability.Do not carry out pH in the comparative example 6 and be 6 or lower washing step, thereby environmental characteristics becomes unstable.Similarly, contain sulfonic vibrin owing to having adopted in the comparative example 7, thereby environmental stability becomes unstable.Under the situation of comparative example 8, owing to do not have slaine to be used to agglutinant, thereby can not control the particle diameter of the particle that is generated, thus generate macroparticle, therefore do not carry out other evaluation.In embodiment 10 and comparative example 9, adopt molecular weight be 2000 or higher resin carried out encapsulatedly, under the situation of comparative example 9, the molecular weight differences of the resin of its use is 1000 or lower, finds that non-offset zone is narrow and the toner performance is inferior.

Claims (18)

1. the manufacture method of electrostatic image developing toner, this method comprises following steps:

(S1) the pigment aqueous dispersion is mixed the preparation potpourri with the resin particle aqueous dispersion that can disperse the vibrin particle certainly that contains as binder resin; With

To be added to as the multivalent metal salt of agglutinant in the potpourri when (S2) stirring, form the agglutinator of the pigment that is bonded to resin particle,

Wherein said can be from disperseing vibrin to react and make by carboxylic acid compound and alcoholic compound, described alcoholic compound comprises polyvalent alcohol, described carboxylic acid compound is to have the polybasic carboxylic acid of three or more carboxyls and in the acid anhydrides one or more thereof.

According to the process of claim 1 wherein described can disperse certainly that vibrin contains that two or more have different number-average molecular weights can disperse vibrin certainly.

3. according to the method for claim 2, wherein said two or more can to disperse the minimum average molecular weight of vibrin certainly be 2000 or higher, and the number-average molecular weight difference of these resins is 1000 or higher.

4. according to the process of claim 1 wherein that described step (S2) further comprises: when stirring, will contain the resin particle aqueous dispersion that can disperse the vibrin particle certainly and mix with the potpourri that contains agglutinator.

5. according to claim 1,2 and 3 each methods, the mean grain size of wherein said toner is 10 μ m or littler.

6. according to claim 1,2 and 3 each methods, the mean grain size of wherein said resin particle is 0.2 μ m or littler.

7. according to the process of claim 1 wherein that described multivalent metal salt is magnesium salts or aluminium salt.

8. according to the method for claim 1, it further is included in the step that step (S2) washes agglutinator and dry agglutinator afterwards with water.

9. method according to Claim 8, wherein said washing step comprise with pH be 6 or lower water agglutinator is washed one or many.

10. according to the process of claim 1 wherein that described pigment aqueous dispersion contains spreading agent, this spreading agent one of comprises in anionic surfactant and the non-ionic surfactant at least.

11. according to the method for claim 1, it further is included in step (S2) and heats particle diameter and the uniform step of shape that the potpourri that contains agglutinator makes agglutinator afterwards.

12. according to the process of claim 1 wherein that described step (S1) further comprises: blended wax particulate aqueous dispersion, described wax particulate aqueous dispersion contain and one of are useful in the natural and synthetic wax particulate that combines with resin particle at least.

13. in described step (S2), when stirring, agglutinant is mixed with potpourri by mechanical shear stress according to the process of claim 1 wherein.

14. the electrostatic image developing toner of making by claim 1,2 and 3 each methods.

15. according to the toner of claim 14, it further comprises one or more mean grain sizes that adhere to surfaces of toner particles is 1 μ m or littler inorganic particulate.

16. electrostatic charge image developer contains the toner and the carrier of claim 14.

17. image forming method comprises following steps:

On photoreceptor, form electrostatic latent image;

Adopt the electrostatic charge image developer of claim 16 that the electrostatic latent image on the photoreceptor is developed, thereby form toner image; With

With toner image transfer printing and photographic fixing to recording medium.

18. the image that forms by the image forming method of claim 17.

Images