CN1696835A - Resin particles and producing method thereof, toner for developing electrostatic latent image and producing method thereof, electrostatic latent image developer as well as image forming method - Google Patents

Abstract

A producing method of resin particles, which comprises at least an emulsification step of emulsifying a composition containing at least a polymerizable monomer and a polymerization step to form droplets of the composition, and a polymerization step of polymerizing the polymerizable monomer in the droplets to synthesize resin particles, wherein the composition is one selected from Composition A, Composition B, or Composition C: (Composition A): a composition containing a vinyl-based monomer, lactone, a vinyl-based monomer polymerization catalyst for polymerizing the vinyl-based monomer, and a lactone polymerization catalyst for polymerizing the lactone (Composition B): a composition containing a polyester resin, lactone, and a lactone catalyst for polymerizing the lact

Description

Resin particle and production method thereof, developing toner for electrostatic latent images and production method thereof, electrostatic latent image developer and formation method

Technical field

The present invention relates to resin particle and production method thereof, developing toner for electrostatic latent images and production method thereof, electrostatic latent image developer and formation method.

Background technology

Make the visible method of image information just be widely used in various fields at present in modes such as for example electrofaxs by electrostatic image.Electrofax is made up of following operation: form electrostatic image by charge step and step of exposure on photoreceptor; The developer that employing comprises toner particle makes this electrostatic image development and makes this image through developing as seen by transfer step and photographic fixing step.

By the way, there is following two types known developer: comprise the two-component developing agent of toner particle and carrier particle and comprise the magnetic color tuner particle or the monocomponent toner of nonmagnetic toner particle.These toner particles are prepared by kneading-comminuting method usually.This kneading-comminuting method comprises fusion and mediates thermoplastic resin and pigment, charge control agent and detackifier (for example wax), after cooling with the product pulverizing that obtains and according to size with the product classification of pulverizing to obtain required toner.Be performance such as the flowability and the spatter property of the toner particle that improves such preparation, inorganic particulate and/or organic filler can be added to the surface of this toner particle in case of necessity.

Usually under the situation of the toner particle that is prepared by kneading-comminuting method, their shape is uncertain and their surface composition is uneven.Although the shape of toner particle and surface composition with the grindability and the condition during the grinding technics of employed material delicate variation take place, be difficult to as desired these aspects are adjusted to required degree.Especially, the material that has high grindability degree in use is prepared by kneading-comminuting method under the situation of toner particle, and the further pulverizing of particle and the change of their shapes take place because of the mechanical forces such as various shearing forces that for example exist in developing machine usually.

The result is, in two-component developing agent, the problem of appearance is that the toner particle of fine gtinding is attached on the surface of carrier (carrier) and has quickened the charged deterioration of developer.Equally, in monocomponent toner, size-grade distribution broadens, and the toner particle of fine gtinding disperses, and is accompanied by the change of shape of toner, development reduction, deterioration in image quality.

Have in use under the situation of toner particle of uncertain shape, the problem of existence is even when adding flow aid, flowability is still not enough.And because for example effect of the mechanical forces such as shearing force between the operating period, the particulate of flow aid moves to the recessed portion of toner particle and is embedded in its inside, and flowability reduces in time simultaneously, and development, transfer printing and spatter property deterioration.

In addition, when such toner is reclaimed by cleaning, and when turning back to developing machine and re-using, the problem of existence is the easy deterioration of picture quality.For preventing these problems, imagination further increases the amount of flow aid.Yet in the case, the problem of generation is that the particle that occurs stain and flow aid on the photoreceptor can disperse.

Simultaneously, if toner particle comprises detackifier such as wax, depend on the combination of detackifier and thermoplastic resin, detackifier may expose on the surface of toner particle.Specifically, if toner particle has adopted elasticity by resin and fragility wax such as poly combination that polymers compositions produces and is difficult to a certain extent pulverize, will there be the tygon of remarkable ratio to expose on the surface of toner particle.Although on the antiseized and photoreceptor of these toner particles in the photographic fixing operation not the aspects such as cleaning of transfer printing toner be favourable, for example mechanical force such as shearing force of developing apparatus inside can make tygon separate from toner particle and move to such as on the parts such as developer roll, photoreceptor and supporting mass.Therefore, since the pollution of these parts, the reliability decrease of developer.

Under such situation, in recent years, the measure as the controlled toner of the preparation shape of particle and surface composition has proposed suspension polymerization (for example, referring to Japanese kokai publication hei 8-44111 communique and the flat 8-286416 communique of Te Kai).This suspension polymerization is in aqueous medium polymerisable monomer to be disperseed with colorant and detackifier and suspend, and makes this monomer polymerization to obtain the method for toner particle.According to this suspension polymerization, can obtain for example to have the toner particle of sandwich construction, wherein, the wax that is used as detackifier is covered by resin glue.

Yet, under the situation of using this suspension polymerization, must regulate particle and make them under suspended state, have appropriate size.For this reason, must acutely and stir this suspending liquid at high speed.Yet generally speaking, the viscosity pole the earth of polymerisable monomer and wax is different, and both compatibilities are relatively poor, and therefore, extremely difficulty is disperseed them equably.Therefore this wax is free shape, and it is extremely low or do not comprise a large amount of toner particles of wax to produce wax content.As a result, between toner particle, it is big that the uneven distribution of composition becomes, and the problem of existence is fully to satisfy the required various performances of toner such as fixation performance and charging property.At present, in suspension polymerization, do not set up the free technology that effectively suppresses detackifier such as wax.

In recent years, improved the more requirement of high image quality, particularly, in coloured image formed, for realizing high precise image, the particle diameter of toner minimized with the tendency of particle diameter homogenising remarkable further.For this reason, must more violent, more speed ground dispersed with stirring liquid.Yet in the case, the problem of existence is not only further to have encouraged the uneven distribution of forming between the toner particle, but also the size-grade distribution of having widened toner, thereby make the homogenising of toner particle diameter become difficult.When use has the toner formation image of wide size-grade distribution, since in the toner size-grade distribution than the existence of fine tuning toner powder, dispersing of the pollution of developer roll, charging roller, charging blade, photoreceptor and supporting mass and toner can become serious, and is difficult to realize simultaneously high image quality and high reliability.

Also the problem of Cun Zaiing is in the system with cleaning function or toner circulation function, and the reliability of this toner with wide size-grade distribution is relatively poor.For realizing high image quality and high reliability simultaneously, must make toner have narrower size-grade distribution, and particle diameter is reduced and homogenising.

For satisfying the demand of high image quality more, the fixation performance of toner is important factor.For obtaining enough fixation performances in the toner, must enlarge the fixing temperature scope.In the art, various kinds of resin or the gel component that generally has a different molecular weight by use prevented the offset that high temperature one side occurs as resin glue in the past, and required to be generally more than or equal to 40 by the molecular weight distribution of weight-average molecular weight (Mw) with respect to ratio (Mw/Mn) expression of number-average molecular weight (Mn) in the toner.

Yet particularly for coloured image, the colour mixture of photographic fixing image, the flatness of imaging surface also have the transparency of image to suffer damage because of the existence of various kinds of resin with different molecular weight or gel component, and the remarkable deterioration of picture quality.Particularly, when photographic fixing image on film, it is very serious that this influence becomes.On the contrary, plant resin when use is single, and the molecular weight maintenance is constant, maybe when use did not comprise the resin of gel component, the colour mixture of photographic fixing image, the flatness of imaging surface or the image transparency did not have problems.Yet specifically, when adding a large amount of detackifier, the viscosity of toner can reduce, and the easier offset that causes high temperature one side.

Particularly, when forming coloured image, when fusing toner on paper or film, the flatness that must improve the toner fixing image is to keep the colour development and the transparency of image.Reason for this reason, general in the past by oil such as the silicone oil with high antistick characteristic is provided to fixing roller in the art, make fixing roller have antistick characteristic and flatness simultaneously with respect to toner.

Yet in the case, the problem of existence is to transfer on paper or the film at oil during the photographic fixing, produces the viscosity on the image.Using under the situation of paper, the problem of existence is because the surface energy of paper reduces because of the existence of oil, so be difficult to writing on the paper that is formed with the photographic fixing image.In addition, using under the situation of film, the problem of existence is because the residual oily transparency deterioration that makes the photographic fixing image on the film.

In the art, the toner that obtains by based on the emulsion polymerization aggegation method (EA method) of free radical monomer quasi-styrene/acrylate copolymer or styrene/methacrylic acid ester copolymer has been proposed.Yet the defective of this toner is the weak strength of photographic fixing image, has the height tack to vestolit, and the image retentivity worsens.For making toner have high photographic fixing image intensity, must set high mean molecular weight on the whole and add bread molecular weight distribution.As a result, the fixing temperature that raise has reduced photographic fixing gloss afterwards, can not obtain high color development.

Be head it off, proposed following method: dissolved polyester resin in organic solvent, it is mixed with colorant, and this potpourri that suspends is with the preparation toner.Yet,, need carry out the influence of solvent recovery, thereby this situation is unsafty with residual solvent in the elimination toner owing to used a large amount of solvents.

In addition, following method has been proposed also: the crystallinity polyester is heated to make it fusion, makes this material in water, form particulate, and with the resin particle that disperses with the dispersed particle aggegation of colorant and wax, combine together with the preparation toner.Yet, in this process, this vibrin must be heated to high temperature, and from the viewpoint to the burden of environment, this method can not be satisfactory.

The multipolymer (for example, speciallyying permit communique No. 2826634 referring to Japan) of ring-type ketene acetal compound and special ethylene base class monomer has been proposed on the other hand.Yet, because the multipolymer of this structure is both biodegradable also photodegradable multipolymer, so it is not suitable for using in developing toner for electrostatic latent images.

In addition, proposed to use the rubber composition (for example, speciallyying permit communique No. 3348471) of specific ring-type ketene acetal referring to Japan.Yet, when adopting this to constitute, can not make toner with toner production process of the present invention.

On the other hand, in recent years,, need to reduce the energy that is used to prepare the energy of toner and is used for printer or duplicating machine on the market from environment being caused the viewpoint of burden.

About preparing the method for toner, in the past method is heat fusing-kneading, grinds and the method for classification from this area, is developed to suspension polymerization and emulsion polymerization aggegation method (EA method).From the viewpoint of energy that is used to prepare, this method develops to the direction that reduces energy.

Yet, be used to prepare the required energy of toner resin and do not obtain enough reductions as yet.

Specifically, when employing can reduce the vibrin of the energy that is used for photographic fixing, compare with the vinyl polymerization resin, the energy that vibrin consumes at present is more.And, we can say that the wastage in bulk or weight energy that is used for resins, toner preparation or photographic fixing does not reach gratifying level as yet.

From this viewpoint, a kind of developing toner for electrostatic latent images has been proposed, it is characterized in that this toner is by making vinyl monomer suspension polymerization obtain (for example, referring to Japanese kokai publication hei 9-269610) in the presence of the ring-opening polymerization polymer of colorant and lactone.Yet, in the method,, added vinyl monomer thereafter again owing to prepared the ring-opening polymerization polymer of lactone, and with the raw material dissolving, thereby be difficult in polyester construction, introduce three-dimensional cross-linked structure.

Also proposed to relate to the production method (for example, referring to Japanese kokai publication hei 9-269610) that makes the lactone multipolymer that lactone and vibrin react in the presence of ring-opening polymerization catalyst.

In the art, when the ring-opening polymerization of lactone, came synthesizing polyester by kation ring-opening polymerization, anionic ring-opening polymerization and coordination anion ring-opening polymerization in the past.

Yet the method is the production method of resin, and when the method is used for toner-production method, this resin must be transformed into even thinner particle.In order to accomplish this point, owing to will use big energy or organic solvent, this will be to causing great burden to environment.

On the other hand, when using the EA method as toner-production method, the resin particle that is less than or equal to 1 μ m is essential, thereby when using common vibrin, maybe when using the resin that proposes by Japanese kokai publication hei 7-149878, must be at high temperature and/or grind resin under high pressure, thereby need to use more energy to grind.In addition, be difficult to make the vibrin structure to present cross-linked structure.Therefore, still can not obtain to have the toner of gratifying fixation performance and retentivity.

Summary of the invention

Design the object of the present invention is to provide the production method of resin particle, this production method can reduce the environmental pressure of producing the resin particle be used for preparing toner, specifically, this method can reduce the use of organic solvent, and the present invention also provides the resin particle that is obtained by this method.

The present invention also provides developing toner for electrostatic latent images and production method, electrostatic latent image developer and formation method, this toner has excellent retentivity and photographic fixing image retentivity, and this toner can suppress the appearance of undesirable peculiar smell during the photographic fixing.

Developing toner for electrostatic latent images and production method thereof, electrostatic latent image developer and formation method have been the present invention further provides, this toner can not cause unevenness or the background portion contamination in the solid fusion, have excellent fixing strength and to the tack of vinyl chloride, and can suppress the appearance of undesirable peculiar smell during the photographic fixing.

A first aspect of the present invention provides a kind of method of producing resin particle, and this method comprises at least: emulsifying step, this emulsifying step make the composition emulsification that comprises polymerisable monomer and polymerization catalyst at least to form the drop of said composition; And polymerization procedure, this polymerization procedure makes described polymerisable monomer polymerization in this drop with the synthetic resin particle, and wherein, described composition is a kind of composition that is selected among composition A, composition B or the composition C:

(composition A): the composition that comprises vinyl monomer, lactone, is used for the vinyl monomer polymerization catalyst of this vinyl monomer of polymerization and is used for the lactone polymerization catalyst of this lactone of polymerization;

(composition B): comprise vibrin, lactone and be used for the composition of the lactone polymerization catalyst of this lactone of polymerization;

(composition C): comprise vinyl monomer, by the ring-type ketene acetal compound of following general formula (1) expression and the composition of radical polymerization initiator:

General formula (1)

(in general formula (1), R represents optionally to comprise the chain or the ring-type aliphatic divalent group of ehter bond, and wherein, described aliphatic group can have substituting group).

A second aspect of the present invention provides with the described resin particle for preparing the method preparation of resin particle of first aspect.

A third aspect of the present invention provides a kind of production method of developing toner for electrostatic latent images, this production method comprises at least: the aggegation step, this aggegation step will wherein have been disperseed the resin particle dispersion liquid of the described resin particle of second aspect, wherein disperseed the colorant dispersion of colorant and wherein disperseed the detackifier dispersion liquid of detackifier to mix, comprise the agglutination particle of resin particle, colorant and detackifier with formation, thereby obtain the agglutination particle dispersion liquid; And fusion steps, that is, the step of described agglutination particle is merged in heating.

A fourth aspect of the present invention provides the developing toner for electrostatic latent images with preparation method's preparation of the described developing toner for electrostatic latent images of the third aspect.

A fifth aspect of the present invention provides a kind of electrostatic latent image developer, and this developer comprises the described developing toner for electrostatic latent images of fourth aspect at least.

A sixth aspect of the present invention provides a kind of formation method, and this method comprises: sub-image forms step,, forms electrostatic latent image on sub-image supporting body surface that is; Development step promptly, is used the developer that is carried in the developer supporting mass, makes the latent electrostatic image developing that forms on described sub-image supporting body surface, to form toner image; Transfer step promptly, is transferred to the toner image that forms on the described sub-image supporting body surface on the surface of transfer printing acceptor; And the photographic fixing step, that is, carry out hot photographic fixing to being transferred to the lip-deep toner image of described transfer printing acceptor, wherein, described developer is the described electrostatic latent image developer in the 5th aspect.

Embodiment

Below explain in detail resin particle of the present invention and production method, developing toner for electrostatic latent images and production method thereof, electrostatic latent image developer and formation method.

＜resin particle and production method thereof (first pattern) 〉

First pattern that the present invention prepares the method for resin particle comprises at least: emulsifying step, promptly, make resin precursor composition emulsification forming the drop of this resin precursor composition, described resin precursor composition comprises vinyl monomer, lactone at least, be used for the vinyl monomer polymerization catalyst of this vinyl monomer of polymerization and be used for the lactone polymerization catalyst of this lactone of polymerization; The lactone polymerization procedure promptly, makes in described in this drop polyisocyanate polyaddition with the synthesizing polyester resin; And the vinyl monomer polymerization procedure, that is, make described vinyl monomer polymerization in this drop with the synthesis of vinyl resinoid.

Make the lactone and the vinyl monomer polymerization in lactone polymerization procedure and vinyl monomer polymerization procedure respectively that are included in the described resin precursor composition, thereby form polymkeric substance.Therefore, organic solvent does not remain in the resin particle of the present invention that is prepared by the method for preparing resin particle of the present invention.

By resin precursor composition is put into water, and under high speed, it is stirred, thereby with its emulsification.Owing to lactone and vinyl monomer be respectively in water polymerization form polymkeric substance, therefore can suppress lactone content in the water and vinyl monomer content and make it reach minimum.The result makes the processing of the waste water that produces in the resin particle preparation become easy.

In addition, by using metal trifluoroacetate mesylate described below or enzyme catalyst, can reduce the required temperature of polymerization lactone as the lactone polymerization catalyst.Therefore, can reduce the required preparation energy of preparation resin particle.

Lactone among the present invention represents to contain in the molecule ring compound of ester group.As lactone, use in the time of 50 ℃ lactone as liquid.

Member's number is preferably 4～20 on the ring of this lactone, and further preferred 5～15.

The object lesson of this lactone comprises beta-propiolactone, gamma-butyrolacton, δ-Wu Neizhi, 6-caprolactone, 11-undecane lactone, 12-dodecane lactone and 15-pentadecane lactone.Wherein, preferably 6-caprolactone, 11-undecane lactone, 12-dodecane lactone and 15-pentadecane lactone.

What described resin precursor composition can comprise certain limit can play polyreaction with the monomer that forms vibrin (below be sometimes referred to as the polyesters monomer), as long as this scope can not make deterioration in characteristics of the present invention with lactone.

The example of this polyesters monomer comprises the acid anhydrides and the carboxylate of alcohol and carboxylic acid, carboxylic acid.

As alcohol, can use aliphatic alcohol as needs, as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerine, trimethylolethane, trimethylolpropane and pentaerythrite; And alicyclic alcohol, as 1,4-cyclohexane diol and 1,4 cyclohexane dimethanol.

The example of aromatic dicarboxylic acid comprises terephthalic acid (TPA), m-phthalic acid and phthalic acid.Aromatic dicarboxylic acid ester's example comprises the low mass molecule alcohol ester of such dicarboxylic acid, for example, and dimethyl terephthalate (DMT), diethyl terephthalate and dimethyl isophthalate.

The example of alkyl succinic acid and alkenyl succinic acid, their acid anhydrides and their ester comprises normal-butyl succinic acid, n-butene base succinic acid, isobutyl succinic acid, isobutenyl succinic acid, n-octyl succinic acid, positive ocentyl succinic, dodecyl succinic acid, positive dodecenyl succinic succinic acid, Permethyl 99A base succinic acid, different dodecenyl succinic succinic acid, their acid anhydrides and their lower alkyl esters.

Can be used for ternary of the present invention or ternary above polybasic carboxylic acid, their acid anhydrides and the example of their lower alkyl esters and comprise 1,2,4-benzene tricarbonic acid (trihemellitic acid), 1,2,5-benzene tricarbonic acid, 2,5,7-naphthalene tricarboxylic acids, 1,2,5-hexane tricarboxylic acids, 1,3-dicarboxyl-2-methyl-2-methylene carboxyl propane, four (methylene carboxyl) methane, 1,2,7,8-octane tetrabasic carboxylic acid, 1,3,5-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid, their acid anhydrides and their lower alkyl ester compound.Specifically, preferably 1,2,4-benzene tricarbonic acid, 1,3,5-benzene tricarbonic acid, 1,2,4,5-benzene tertacarbonic acid, their acid anhydrides and their methyl compound and ethyl ester compound.

The example that can be used for the component of the above alcohol of trihydroxy alcohol of the present invention or ternary comprises D-sorbite, 1,2,3,6-hexane tetrol, 1,4-sorbitan, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-penta triol, glycerine, diglycerol, 2-methyl-prop triol, 2-methyl isophthalic acid, 2,4-butantriol, trimethylolethane, trimethylolpropane and 1,3,5-hydroxymethyl benzene.

The example that can be used for diol component of the present invention comprises polyoxyalkylene bisphenol type glycol, and wherein preferably includes polyoxyethylene bisphenol type two pure and mild polyoxypropylene bisphenol type glycol.

These polyesters monomers can use separately, or can use in conjunction with multiple vinyl monomer.

Described vinyl monomer solubilized is by described lactone with the polymerization of the polyesters monomer that uses in case of necessity and synthetic vibrin, and this vinyl monomer is not particularly limited, as long as it is a liquid in the time of 50 ℃.

The example of described vinyl monomer comprises: phenylethylene, as styrene, vinyltoluene and α-Jia Jibenyixi; The ester that contains vinyl is as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, n-butyl acrylate, lauryl acrylate, acrylic acid-2-ethyl caproite, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, lauryl methacrylate and methacrylic acid-2-Octyl Nitrite; Vinyl nitrile is as vinyl cyanide and methacrylonitrile; Vinyl ether is as vinyl methyl ether and vinyl isobutyl ether; And vinyl ketone, as ethenyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone.

As needs, crosslinking chemical arbitrarily can be used with these vinyl monomers.The example of crosslinking chemical comprises: aromatic divinyl compound, as divinylbenzene, divinyl naphthalene and their derivant; The diolefins esters of unsaturated carboxylic acids is as two (methacrylic acid) glycol esters and two (methacrylic acid) binaryglycol ester; Divinyl compound, as N, N-divinyl aniline and divinyl ether; With the compound that contains the vinyl more than 3 or 3.

These crosslinking chemicals can use separately, or by in conjunction with multiple use the in them.With respect to per 100 mass parts vinyl monomers, the ratio with 0～100 mass parts uses described crosslinking chemical usually.

In described resin precursor composition, with respect to described lactone and vinyl monomer and the polyesters monomer that uses in case of necessity and the total amount of crosslinking chemical, lactone content is 5 quality %～90 quality % preferably, further preferably 10 quality %～80 quality %, especially preferably 10 quality %～60 quality %.

When the content of lactone during, will be difficult to this resin precursor composition of emulsification in some cases more than or equal to 90 quality %.When the content of lactone during less than 5 quality %, the fixation performance of the developing toner for electrostatic latent images of the following stated and retentivity will deteriorations in some cases.

Described lactone polymerization catalyst is not particularly limited, as long as the various polyesters monomer polymerizations that it can make lactone and use in case of necessity.For example, can use metal oxide, organometallics and enzyme catalyst.Preferably serve as lewis acidic catalyzer, special preferably with the lewis acid catalyst of rare earth element as the formation element.

Can pass through with about 0.1ppm～10, the ratio of 000ppm adds and serves as lewis acidic organometallics (organo-tin compound or organic titanic compound), halo organometallics (halo organotin), metal trifluoroacetate mesylate or enzyme catalyst as described lactone polymerization catalyst, and be less than or equal to 150 ℃, preferably be less than or equal under 100 ℃ the temperature, preferably under inert atmosphere, make polymerizable raw material and obtain vibrin.

Preferred metal trifluoroacetate mesylate or the enzyme catalyst of using is as the lactone polymerization catalyst.By using the metal trifluoroacetate mesylate, can be at the described lactone of polymerization under the low temperature (being less than or equal to 100 ℃).And, also can carry out polycondensation reaction at low temperatures with other alcohol and carboxylic acid.

By using enzyme catalyst, can be at the described lactone of polymerization under the low temperature (being less than or equal to 100 ℃).

Preferred described be the rare earth metal fluoroform sulphonate of representing by following general formula with rare earth element as the lewis acid catalyst of component:

X(OSO ₂CF ₃) ₃

(wherein X represents rare earth element).

As the rare earth metal fluoroform sulphonate, lanthanide series fluoroform sulphonate preferably.The lanthanide series fluoroform sulphonate be described in detail in " Synthetic Organic Chemistry association will " (Journal ofSynthetic Organic Chemistry, Japan, vol.53, No.5, p44-54).The object lesson of lanthanide series comprises lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu).

Wherein, as the rare earth element fluoroform sulphonate, X (OSO preferably ₂CF ₃) ₃(X is scandium (Sc), yttrium (Y), ytterbium (Yb) or samarium (Sm)).

The example of enzyme catalyst comprises lipase, proteinase and cellulase.Wherein, the example of described lipase comprise derived from Pseudomonas fluorescens (Pseudomonas fluorescens)Lipase, derived from Pseudomonas cepacia (Pseudomonas cepasia)Lipase, derived from Pig pancreas (Porcine pancreas)Lipase, derived from Candida rugosa (Candida rugosa)Lipase, derived from AN (Aspergillus niger)Lipase, derived from the distiller's yeast bacterium ( Rhizopus Delemer)Lipase and derived from Japan's head mold (Rhizopus japonicus)Lipase.

The lactone polymerization catalyst can use separately, and can use multiple catalyzer as required.

When the metal trifluoroacetate mesylate was used as catalyzer, the content of lactone polymerization catalyst was preferably 0.1ppm～10 in the described resin precursor composition, 000ppm, further preferred 0.1ppm～7,000ppm.When using enzyme catalyst, this content is preferably 100ppm～100, and 000ppm is further preferred 1,000ppm～50,000ppm.

Described vinyl monomer polymerization catalyst can be the oil-soluble polymerization initiator that is dissolved in vinyl monomer, its example comprises superoxide, as Methylethyl superoxide, di-tert-butyl peroxide, acetyl peroxide, diisopropylbenzyl superoxide, lauroyl peroxide, benzoyl peroxide, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, di-isopropyl peroxydicarbonate and peroxidating m-phthalic acid di tert butyl carbonate; Azo-compound, as 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azoisobutyronitrile and 1,1 '-azo two (1-cyclohexane nitrile).

Described oil-soluble polymerization initiator uses with the ratio with respect to 0.1～20 mass parts of per 100 mass parts vinyl monomers, preferred 1～10 mass parts usually.

Can be by described resin precursor composition be put into water, and the bowl mill, sand mill or the ball mill that use rotational shear type homogenizer or contain medium carry out emulsification, and make this resin precursor composition emulsification.Thus, can form the drop of this resin precursor composition.

The mean grain size of this drop preferably is less than or equal to 1 μ m, more preferably 0.01 μ m～1 μ m.Be less than or equal to 1 μ m by the mean grain size that makes this drop, can form the resin particle that mean grain size is less than or equal to 1 μ m.

The mean grain size of resin particle of the present invention preferably is less than or equal to 1 μ m, more preferably 0.01 μ m～1 μ m.When mean grain size surpassed 1 μ m, the size-grade distribution of the final developing toner for electrostatic latent images that obtains was widened, and produced free particle, and caused the reduction of Performance And Reliability easily.On the other hand, when mean grain size was in above-mentioned scope, favourable part was not only there is not above-mentioned defective, and can reduce the deviation between the toner, and the dispersion of toner becomes better, and the variation of Performance And Reliability is diminished.For example can use Ku Erte grain count instrument to measure mean grain size.

＜resin particle and production method thereof (second pattern) 〉

Second pattern that the present invention prepares the method for resin particle comprises at least: emulsifying step, promptly, make the step of polyester and resin composition emulsification with the drop that forms this polyester and resin composition, described polyester and resin composition comprises vibrin, lactone and is used for the polymerization catalyst of this lactone of polymerization; And polymerization procedure, that is, make interior polyisocyanate polyaddition in this drop with the step of synthesizing polyester resin particle.

In described polyester and resin composition, described lactone plays the effect of the solvent of this vibrin, and makes in this polyisocyanate polyaddition to form vibrin in polymerization procedure.Therefore, organic solvent can not remain in by the present invention and prepare in the vibrin particle of method preparation of vibrin particle.Hereinafter, in the present invention, will be called the vibrin that polymerization is derived, and abbreviate other vibrin as vibrin derived from the vibrin of interior polyisocyanate polyaddition.

When as the lactone generation polymerization of solvent during, can not cause the air pollution that causes because of the lactone volatilization and the deterioration in the processing environment with the vibrin that forms polymerization and derive.

By polyester and resin composition is put into water, subsequently it is carried out high-speed stirred, thereby with described polyester and resin composition emulsification.Therefore form the vibrin that polymerization is derived owing to polymerization takes place lactone in water, can suppress the content of lactone in the water and make it to reach minimum.The result makes processing become easy by the waste water of the preparation generation of vibrin particle.

The example of vibrin comprises with aliphatic polyester resin and the aromatic polyester resin of two pure and mild dicarboxylic acid as key component.Can use any vibrin, as long as it is the compatible vibrin of kind and lactone.In addition, this vibrin can have linear structure or the cross-linked structure in the scope that does not hinder compatibility.

The weight-average molecular weight of the vibrin that is recorded by GPC (gel permeation chromatography) method is preferably 2,000～50, and 000, further preferred 5,000～30,000.When the weight-average molecular weight of vibrin is 2,000～50,000 o'clock, it was very fast to add thermo-responsive, can be less than or equal to fusion toner under 150 ℃ the heating-up temperature.

The fusing point of this vibrin or softening point are preferably is less than or equal to 150 ℃, further preferably is less than or equal to 120 ℃.When the fusing point or the softening point of vibrin is when being less than or equal to 150 ℃, the energy that is consumed in the time of can being reduced in toner fixing.

In the present invention, lactone is illustrated in the ring compound that contains ester group in the molecule.As described lactone, use in the time of 80 ℃ lactone as liquid.

Member's number is preferably 4～20 on the ring of this lactone, and further preferred 5～15.

The object lesson of this lactone comprises and the identical lactone of the described lactone of first pattern.

With respect to the total amount of lactone and vibrin in the described polyester and resin composition, the content of this lactone is 10 quality %～90 quality %, further preferred 30 quality %～80 quality %.

When the content of lactone during less than 10 quality %, the viscosity of this polyester and resin composition is higher when lactone mixes with vibrin and stirs, and will be difficult to make resin particleization sometimes in subsequent step.When this content surpassed 90 quality %, it had disadvantageous effect to the fixing performance and the chargeding performance of toner in some cases.

What can comprise certain limit in polyester and resin composition can play the monomer of polyreaction with the vibrin that forms polymerization and derive with lactone, as long as do not hinder characteristic of the present invention.

The example of monomer comprises the acid anhydrides or the carboxylate of alcohol and carboxylic acid and carboxylic acid.

As described alcohol, can use aliphatic polyol in case of necessity, as ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerine, trimethylolethane, trimethylolpropane and pentaerythrite; And alicyclic alcohol, as 1,4-cyclohexane diol and 1,4 cyclohexane dimethanol.

The example of aromatic dicarboxylic acid comprises and the identical aromatic dicarboxylic acid of the described aromatic dicarboxylic acid of first pattern.

Alkyl succinic acid and alkenyl succinic acid, their acid anhydrides and the example of their the ester alkyl succinic acid and alkenyl succinic acid, their acid anhydrides and their ester that comprise first pattern description.

Can be used for the above polybasic carboxylic acid of ternary of the present invention or ternary, their acid anhydrides or the example of their lower alkyl esters and comprise the ternary of first pattern description or polybasic carboxylic acid, their acid anhydrides or their lower alkyl esters more than the ternary.

The example that can be used for the above alcohol of ternary of the present invention or ternary comprises the ternary or the above alcohol of ternary of first pattern description.

The example that can be used for diol component of the present invention comprises the diol component of first pattern description.

Other example comprises lactide, as two lactides and glycolide; And carbonyl lactone (carbolactone), as three salicylides, six salicylides, phthalanone and cumarin.

Above-mentioned polymerization catalyst is not particularly limited, as long as the various monomer polymerizations that it can make lactone and use in case of necessity.Can use metal oxide and organometallics, and preferred the use with rare earth element as the lewis acid catalyst or the enzyme catalyst that constitute element.By using these catalyzer, can be at polymerization lactone under the low temperature (being less than or equal to 100 ℃).Also can carry out polycondensation reaction at low temperatures with other alcohol and carboxylic acid.

By using enzyme catalyst, can be at polymerization lactone under the low temperature (being less than or equal to 100 ℃).

If polymerization can be carried out when being less than or equal to 100 ℃, owing to this polyreaction can be carried out under normal pressure, so can improve the productive capacity of vibrin particle.Preferred described be following rare earth metal fluoroform sulphonate described in first pattern with rare earth element as the lewis acid catalyst that constitutes element:

X(OSO ₂CF ₃) ₃

(wherein X represents rare earth element).

The example of rare earth metal fluoroform sulphonate comprises and the identical rare earth metal fluoroform sulphonate of the described rare earth metal fluoroform sulphonate of first pattern.

The example of enzyme catalyst comprises and the identical enzyme catalyst of the described enzyme catalyst of first pattern.

The example of the emulsification of polyester and resin composition comprises and the identical emulsification of emulsification described in first pattern.

The mean grain size of this drop preferably is less than or equal to 1 μ m, further 0.01 μ m～1 μ m preferably.Be less than or equal to 1 μ m by the mean grain size that makes this drop, can form the vibrin particle that mean grain size is less than or equal to 1 μ m.

Be less than or equal to 100 ℃ by these drops are heated to, be included in the lactone polymerization reaction take place in the drop, thereby form the vibrin particle.Preferably under inert atmosphere, heat described drop.

The mean grain size of vibrin particle of the present invention preferably is less than or equal to 1 μ m, more preferably 0.01 μ m～1 μ m.When mean grain size surpassed 1 μ m, the size-grade distribution of the final developing toner for electrostatic latent images that obtains was widened, and produced free particle, and caused the reduction of Performance And Reliability easily.On the other hand, when mean grain size was in above-mentioned scope, favourable part was not only there is not above-mentioned defective, and can reduce the deviation between the toner, and the dispersion of toner becomes better, and the variation of Performance And Reliability is diminished.For example can use Ku Erte grain count instrument to measure mean grain size.

In the production method of vibrin particle of the present invention, the solvent as the dissolved polyester resin is used has used lactone.Lactone can form the vibrin that polymerization is derived through heating.Therefore, vibrin particle of the present invention does not comprise residual solvent.

＜resin particle and production method thereof (three-mode) 〉

The three-mode for preparing the method for resin particle of the present invention comprises at least: emulsifying step, promptly, make the step of resin precursor composition emulsification with the drop that forms this resin precursor composition, described resin precursor composition comprises vinyl monomer, by the ring-type ketene acetal compound and the radical polymerization initiator of following general formula (1) expression; And polymerization procedure, that is, make vinyl monomer in this drop and ring-type ketene acetal compound polymerization step with the synthesis of vinyl analog copolymer.

General formula (1)

In general formula (1), R represents optionally to comprise the chain or the ring-type aliphatic divalent group of ehter bond.This aliphatic group can have substituting group.

Make the vinyl monomer that is included in the resin precursor composition and ring-type ketene acetal compound in polymerization procedure polymerization to form polymkeric substance.Therefore, organic solvent can not remain in the resin particle of the present invention that is prepared by resin particle production method of the present invention.

By this resin precursor composition is put into water, subsequently it is carried out high-speed stirred and with its emulsification.Form polymkeric substance owing to polymerization takes place for vinyl monomer and ring-type ketene acetal compound in water, therefore can suppress the content of vinyl monomer and ring-type ketene acetal compound in the water and make it to reach minimum.The result makes the waste water that generates in the process resin particle preparation become easy.

Described vinyl monomer is not particularly limited, as long as it is a liquid in the time of 100 ℃.

The molecular weight of this vinyl monomer is preferably 50～500, and further preferred 70～300.When the molecular weight of vinyl monomer in particular 70～250 time, the glass transition temperature of the resin that is obtained by the reaction of it and ring-type ketene acetal can be 40 ℃～150 ℃.

The example of this vinyl monomer comprises and the identical vinyl monomer of the described vinyl monomer of first pattern.

Crosslinking chemical arbitrarily can be used with described vinyl monomer in case of necessity.The example of crosslinking chemical comprises and the identical crosslinking chemical of the described crosslinking chemical of first pattern.

Chain or the ring-type aliphatic divalent group of representing optionally to comprise ehter bond by the R in the ring-type ketene acetal of general formula (1) expression.

This aliphatic group can contain substituting group.The number of carbon is not particularly limited in the aliphatic group, but normally 1～22, and preferably 1～12, be more preferably 1～8.

When aliphatic group comprised ehter bond, the number that is included in the ehter bond in this aliphatic group was not particularly limited, but can be one or more.The object lesson that comprises the aliphatic group of ehter bond comprises polyoxymethylene, polyoxyethylene, polyoxypropylene and polyoxy butylene.

Aliphatic group can contain substituting group; and described substituent example comprises various substituting groups, as alkyl, aryl, aralkyl, alkoxy, aryloxy group, aralkoxy, acyl group, acyloxy, hydroxyl, sulfydryl, carboxyl, alkoxy carbonyl, ketone group, amino, halogen.

The example that is used for ring-type ketene acetal of the present invention comprises 2-methylene-1,3,6-three butyl oxide links, 2-methylene-1,3-dioxolanes, 2-methylene-1,3-dioxane, 2-methylene-1,3-dioxepin, 2-methylene-4-phenyl-1,3-dioxolanes, 4,7-dimethyl-2-methylene-1,3-dioxepin, 5,6-benzo-2-methylene-1,3-dioxepin, 4-n-hexyl-2-methylene-1,3-dioxolanes, the positive decyl of 4--2-methylene-1,3-dioxolanes and 4,5-diformazan ester group-1, the 3-dioxolanes.

The example that is used for radical polymerization initiator of the present invention comprises the ultraviolet radical polymerization initiator that uses following initiating agent: superoxide, as Methylethyl superoxide, di-tert-butyl peroxide, acetyl peroxide, diisopropylbenzyl superoxide, lauroyl superoxide, benzoyl peroxide, tert-butyl hydroperoxide-2 ethyl hexanoic acid ester, di-isopropyl peroxydicarbonate and peroxidating m-phthalic acid di tert butyl carbonate; Azo-compound, as 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azoisobutyronitrile and 1,1 '-azo two (1-cyclohexane nitrile); Aromatic ketone is as benzophenone, Michler's keton, xanthone, thioxanthones, 2-clopenthixal ketone and 2-EAQ; Acetophenones is as acetophenone, trichloroacetophenone, 2-hydroxy-2-methyl ethyl phenyl ketone, 2-hydroxy-2-methyl-4 '-isopropyl ethyl phenyl ketone, benzoin isobutyl ether and 2,2-diethoxy acetophenone; And the visible light radical polymerization initiator that uses α-diketone/amine initiating agent, described α-diketone/amine initiating agent is norcamphor quinone/methacrylic acid-N for example, N-dimethyl aminoethyl ester and camphorquinone/methacrylic acid-N, N-dimethyl aminoethyl ester.

With respect to the total amount of the vinyl monomer and the ring-type ketene acetal compound of per 100 mass parts, described radical polymerization initiator uses with the ratio of 0.1～20 mass parts, preferred 1～10 mass parts usually.

The content of ring-type ketene acetal compound 5 quality %～90 quality % preferably in this resin precursor composition, further preferably 7 quality %-80 quality %, especially preferably 10 quality %～70 quality %.When the content of ring-type ketene acetal compound during more than or equal to 90 quality %, be difficult in some cases to control by the variation in the environment of developing toner for electrostatic latent images described later cause charged.When the content of ring-type ketene acetal compound during less than 5 quality %, the fixing performance of developing toner for electrostatic latent images described later, retentivity and the anti-vinyl chloride performance of adhering to can worsen in some cases.

Owing to by the free radical ring-opening polymerization of ring-type ketene acetal compound ester bond is introduced main chain backbone, thereby intermolecular hydrogen bond is enhanced, therefore the photographic fixing image intensity of developing toner for electrostatic latent images described later is enhanced.And because there is a large amount of ester groups, so can prevent that vinyl chloride from adhering to.

＜developing toner for electrostatic latent images and production method thereof 〉

The production method of developing toner for electrostatic latent images of the present invention comprises at least: the aggegation step, promptly, to wherein disperse the resin particle dispersion liquid of resin particle of the present invention, wherein disperse the colorant dispersion of colorant and wherein disperseed the detackifier dispersion liquid of detackifier to mix, comprise the agglutination particle of resin particle, colorant and detackifier with formation, thereby obtain the agglutination particle dispersion liquid; And fusion steps, i.e. the step of described agglutination particle is merged in heating.

In case of necessity, the method for preparing developing toner for electrostatic latent images of the present invention also can comprise other steps.For example, after described aggegation step and before described fusion steps, this method can preferably include following steps: will wherein disperse the particle dispersion liquid of particulate to join in the described agglutination particle dispersion liquid, and with its mixing so that make described particulate be attached to described agglutination particle, adhere to particle (hereinafter being referred to as " attachment steps ") thereby form.

Below, in the present invention, abbreviate developing toner for electrostatic latent images as toner or toner particle.

Described aggegation step is a step as described below: in the dispersion liquid that obtains by hybrid resin particle dispersion, colorant dispersion and detackifier dispersion liquid, make described resin particle, colorant and detackifier aggegation to form agglutination particle, make the agglutination particle dispersion liquid thus.

In the present invention, as resin particle, can use at least two kinds of resin particles with different molecular weight.In the described at least two kinds resin particles with different molecular weight, the weight-average molecular weight (Mw) with resin particle of maximum molecular weight is preferably 100,000～1,500,000, more preferably 100,000～1,200,000, especially preferably 150,000～1,000,000.

In the present invention, weight-average molecular weight (Mw) as resin particle with maximum molecular weight, preferred quantitative range is as lower limit, and with any lower limit of above-mentioned numerical range or the value of the weight-average molecular weight (Mw) among higher limit or the embodiment described later numerical range as the upper limit with any lower limit of above-mentioned quantitative range or weight-average molecular weight (Mw) numerical value among higher limit or the embodiment described later.

When the weight-average molecular weight (Mw) of the resin particle with maximum molecular weight was in above-mentioned numerical range, favourable part had been to obtain the required transparency.On the one hand, when the weight-average molecular weight (Mw) of the resin particle with maximum molecular weight surpasses at 1,500,000 o'clock, will be difficult to obtain the flatness of photographic fixing image.On the other hand, when the weight-average molecular weight (Mw) of the resin particle with maximum molecular weight is lower than at 100,000 o'clock, because therefore the reduction of viscosity can not suppress the high temperature photographic fixing time causes offset easily.

In the aggegation step, make the resin particle, colorant and the detackifier aggegation that disperse in above-mentioned resin particle dispersion liquid, colorant dispersion and the detackifier dispersion liquid of mutual mixing to form agglutination particle.

Described agglutination particle is formed by inhomogeneous aggegation (heteroaggregation), and can form by for example following mode: make in advance desire add the dispersion liquid of another kind of dispersion liquid therein and the dispersion liquid that will add in the polarity of the ionic surface active agent that comprises and the balance of quantity be offset, add ionic surface active agent with polarity and the quantity that compensates this balanced deflection then.

In attachment steps, described agglutination particle is a coatingparticles, described agglutination particle is scattered in the agglutination particle dispersion liquid, has added and sneaks into the surface that particulate in the particle dispersion liquid of agglutination particle dispersion liquid is attached to described coatingparticles equably, adheres to particle thereby form.This adheres to particle and is formed by inhomogeneous aggegation, and form by for example following mode: make in advance desire add the dispersion liquid of another kind of dispersion liquid therein and the dispersion liquid that will add in the polarity of the ionic surface active agent that comprises and the balance of quantity be offset, add ionic surface active agent with polarity and the quantity that compensates this balanced deflection then.

In fusion steps, make the resin fusion in the agglutination particle, and resin particle, colorant and detackifier are merged to form developing toner for electrostatic latent images.When implementing attachment steps, in fusion steps, make the resin fusion of adhering in the particle, and merge to form developing toner for electrostatic latent images.

At least be dispersed with colorant in the described colorant dispersion.

The example of described colorant comprises various pigment, as carbon black, chrome yellow, Hansa yellow, benzidine yellow, flavanthrone (threne yellow), quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, C lake red CAN'T (Watchung red), permanent red, bright fuchsin 3B, bright fuchsin 6B, Du Pont (Dupont) oil red, pyrazolone red, lithol red, rhodamine B lake, lake red C, rose-red, aniline blue, ultramarine, calco oil blue, methylene chloride indigo plant, phthalocyanine blue, phthalocyanine green and oxalic acid peacock green; Various dyestuffs are as acridine series, xanthine series, azo series, benzoquinones series, azine series, anthraquinone series, dioxazine series, thiazine series, azomethine series, indigo series, thioindigo series, phthalocyanine series, nigrosine series, polymethine series, triphenylmethane series, diphenylmethane series, thiazine series, thiazole series and xanthene series.These colorants can use separately, maybe can be used in combination they two or more.

The mean grain size of this colorant preferably is less than or equal to 1 μ m, further preferably is less than or equal to 0.5 μ m, preferred especially 0.01 μ m～0.5 μ m.When mean grain size surpassed 1 μ m, the size-grade distribution of the final developing toner for electrostatic latent images that obtains was widened, and produced free particle, and caused the reduction of Performance And Reliability easily.On the other hand, when mean grain size was in above-mentioned scope, favourable part was not only there is not above-mentioned defective, and can reduce the deviation between the toner, the dispersion of toner is become better, and the variation of Performance And Reliability is diminished.

In addition, when mean grain size is when being less than or equal to 0.5 μ m, favourable part is colour development, color rendition and OHP (elevated projecting) the transmittance excellence of the toner particle that obtains.Can measure mean grain size by for example Microtrack.

Described detackifier dispersion liquid is the dispersion liquid that has disperseed detackifier at least.In the present invention, detackifier comprises at least a by the ester that constitutes one of at least in the following material: carbon number is that 12～30 higher alcohol and carbon number are 12～30 higher fatty acid.Because such ester has suitable polarity, and compare with for example polyolefin except that ester, such ester has compatibility fabulous and resin resin particle, when at least a such ester is used as detackifier, can effectively suppress the appearance of free detackifier in the aggegation step or in the fusion steps described later.

Generally speaking, preferred detackifier is the detackifier with the compatibility difference of the resin glue of toner particle.When use had the detackifier of this compatibility, this resin had reduced the viscosity of toner when the high temperature photographic fixing by this detackifier plasticizing, is easy to generate offset.The dispersal unit of the detackifier that comprises in anti-adhesion effects and the toner particle is relevant, and generally speaking, when dispersal unit was big, anti-adhesion effects was more remarkable.

Under the situation of using the method for preparing developing toner for electrostatic latent images of the present invention, because toner particle is to obtain by aggegation step different with normal kneading step or fusion steps, the mechanical stress that therefore gives detackifier in aggegation step or fusion steps will be much smaller than the mechanical stress that gives detackifier in normal kneading step.Therefore, in the method for preparing developing toner for electrostatic latent images of the present invention,, all can controlling packet be contained in the dispersal unit of the detackifier in the toner particle no matter the compatibility between detackifier and the resin how.As a result, in the toner that is obtained by the method for preparing developing toner for electrostatic latent images of the present invention, even the detackifier that comprises in this toner is when having compatibility with the resin of resin particle, and this detackifier still can show enough anti-adhesion effects.

It is that 12～30 higher alcohol and/or carbon number are the ester that 12～30 higher fatty acid constitutes by carbon number that this detackifier comprises at least a, and when acid constituents be that carbon number is when being 12～30 higher fatty acid, as alkoxide component, except that monohydroxy alcohol such as methyl alcohol, ethanol, propyl alcohol and butanols, also preferred: glycol, as ethylene glycol and propylene glycol and their polymer; Triol is as glycerine and polymer thereof; Polyvalent alcohol is as pentaerythrite, sorbitan and cholesterol.When these alkoxide components were polyvalent alcohol, described higher fatty acid can be single replacement or polysubstituted.

It is that 12～30 higher alcohol and carbon number are the ester that 12～30 higher fatty acid constitutes that the preferred example of detackifier comprises by carbon number, as stearic acid stearyl ester, palmitic acid palm ester, docosanoic acid docosyl ester and montanic acid stearyl ester; By carbon number is the higher fatty acid of 12-30 and the ester that low-grade monobasic alcohol constitutes, as butyl stearate, docosanoic acid isobutyl ester, montanic acid propyl ester and oleic acid-2-Octyl Nitrite; By carbon number is the ester that 12～30 higher fatty acid and polyvalent alcohol constitute, as montanic acid ethylene glycol ester, diglycol stearate, glycerin monostearate, single docosane acid glyceride, tripalmitin, single docosanoic acid pentaerythritol ester, dilinoleic acid pentaerythritol ester, three pentaerythritol oleates and pentaerythritol tetrastearate; By carbon number is the ester that 12～30 higher fatty acid and polyvalent alcohol polymer constitute, as single docosanoic acid binaryglycol ester, two docosanoic acid binaryglycol ester, monostearate dipropylene glycol ester, distearyl acid two glyceride, four glycerol stearates, six (docosanoic acid), four glyceride and ten stearic acid, ten glyceride; By carbon number is the ester that 12～30 higher fatty acid and polyvalent alcohol monomer or polymer (optionally comprising short chain functional group) constitute, as glycerine monoacylphosphine monostearate, the single linoleate of glycerine monoacylphosphine and two glycerine monoacylphosphine distearates; The sorbitan high-grade aliphatic ester is as monostearate sorbitan ester, two docosanoic acid anhydro sorbitol sugar ester and three oleic acid Isosorbide Dinitrates; The cholesterol high-grade aliphatic ester is as stearic acid cholesteryl ester, oleic acid cholesteryl ester and linoleic acid cholesteryl ester.

In the present invention, in these detackifiers, the detackifier that is used for aftermentioned embodiment is particularly preferred.These detackifiers can use separately, maybe can be used in combination two or more.

As the fusing point of detackifier, the viewpoint from the retentivity of toner preferably is greater than or equal to 30 ℃, is more preferably and is greater than or equal to 40 ℃, especially preferably is greater than or equal to 50 ℃.Consider fusing point, can determine to be that 12～30 higher alcohol and/or carbon number are the carbon number of the alkoxide component in the ester that constitutes of 12～30 higher fatty acid and/or the carbon number of acid constituents by carbon number suitably as detackifier.When the carbon number of the carbon number of alkoxide component and/or acid constituents less than 12 the time, the fusing point of detackifier is beyond above-mentioned preferred value scope in some cases.When carbon number surpasses 30,, can be increased in detackifier free in aggegation step or the fusion steps in some cases because the polarity of detackifier becomes too little.Either way not preferred.

Under the temperature conditions in aggegation step or fusion steps, detackifier must have less solubleness in water.Reason for this reason, HLB (hydrophilic radical/hydrophobic group balance) preferably smaller or equal to 7, is more preferably smaller or equal to 5, especially preferably smaller or equal to 3.When HLB surpasses 7, since detackifier the aggegation step or the fusing step in soluble in water, the problem that is easy to generate is to reduce the content of detackifier in the toner, can not obtain required toner performance, detackifier remains in the waste water that toner preparation back produces easily, thereby makes the wastewater treatment trouble that becomes.

The content of detackifier is preferably 0.5 quality %～50 quality % in the toner, 1 quality %～40 quality % more preferably, preferred especially 1 quality %～30 quality %.When content during less than 0.5 quality %, antistick characteristic deficiency, and cause so-called offset easily, wherein this toner is attached on the fixing roller when the high temperature photographic fixing.When this content surpassed 50 quality %, toner became fragile, and toner particle is developed the agitation grinding in the machine easily.Either way not preferred.

The mean grain size of detackifier preferably is less than or equal to 1 μ m, more preferably 0.01 μ m～1 μ m.When mean grain size surpassed 1 μ m, the size-grade distribution of the final developing toner for electrostatic latent images that obtains was widened, and produced free particle, caused the reduction of Performance And Reliability easily.On the other hand, when mean grain size was in above-mentioned scope, favourable part was not only there is not above-mentioned defective, and can reduce the deviation between the toner, the dispersion of toner is become better, and the variation of Performance And Reliability is diminished.For example can using, Microtrack measures described mean grain size.

The combination of the resin of resin particle, colorant and detackifier is not particularly limited, but can suitably freely select according to purpose.

In the present invention, according to purpose, other component (particle) can be disperseed, as antiseized component (except that above-mentioned detackifier), internal additives, charge control agent, inorganic powder, organic dust, lubricant and lapping compound in any dispersion liquid in resin particle dispersion liquid, colorant dispersion and the detackifier dispersion liquid.In the case, other component (particle) can be dispersed in any dispersion liquid in resin particle dispersion liquid, colorant dispersion and the detackifier dispersion liquid, maybe can will wherein disperse the dispersion liquid of other component (particle) to sneak into the mixed solution that obtains by hybrid resin particle dispersion, colorant dispersion and detackifier dispersion liquid.

Except that above-mentioned detackifier, the example of described detackifier comprises low-molecular-weight polyolefin, as tygon, polypropylene and polybutylene; Silicone with softening point softening when being heated; Fatty acid amide is as oleamide, mustard acid amides, castor-oil plant acid amides and stearmide; Vegetable wax is as Brazil wax, rice bran wax, candelila wax, Japan tallow and jojoba oil; Animal wax is as beeswax; Mineral/pertroleum wax, the wax (Fisher-Tropsch wax) that obtains in synthetic as montan wax, ceresine, ceresin, paraffin, microcrystalline wax and Fischer-Tropsch; And the modified product of these waxes.

With respect to the amount of above-mentioned detackifier, the content of these detackifiers is generally and is less than or equal to 100 quality % in the toner, preferably is less than or equal to 70 quality %, is more preferably less than or equals 50 quality %.When content surpasses 100 quality %, the quantitative change of free antiseized component gets too big, the aggegation of overslaugh detackifier easily, can not obtain effect, in addition, be difficult to separate and remove the detackifier component that is free on toner corresponding to addition, on the other hand, increased the free antiseized component that enters waste water, and made the wastewater treatment trouble that becomes, so be not preferred.

When these waxes disperse to enter for example aqueous medium of water with for example polyelectrolyte of ionic surface active agent, polymer acid and polymeric alkali, be heated fusing point or higher, and when using the homogenizer to apply strong shearing force or pressure release type dispersion machine to handle, easily they are prepared into particulate smaller or equal to 1 μ m.

The example of internal additives comprises magnetisable material, and this magnetisable material comprises metal and alloy, as ferrite, magnetic iron ore, reduced iron, cobalt, nickel and manganese and the compound that comprises these metals.

The example of charge control agent comprises quaternary ammonium compound; The nigrosine compound; The dyestuff that contains the complex of aluminium, iron, chromium etc.; With triphenylmethane pigment.In the present invention, from be controlled at aggegation, when merging to the viewpoint of the influential ionic strength of stability and from reducing the viewpoint of contaminated waste water, this charge control agent preferably has the low solubility in water.

The example of inorganic particulate comprises all inorganic particulates that are used as the external additive on the toner surface usually, as silicon dioxide, aluminium oxide, titania, lime carbonate, magnesium carbonate, calcium phosphate and cerium oxide.

The example of organic filler comprises all organic fillers that are used as the external additive on the toner surface usually, as vinyl-based resin, vibrin and silicones.These inorganic particulates and organic filler can be used as flow aid, cleaning additive etc.

The example of lubricant comprises fatty acid amide, as ethylenebisstearamide and oleamide; And fatty acid metal salts, as zinc stearate and calcium stearate.

The example of lapping compound comprises above-mentioned silicon dioxide, aluminium oxide and cerium oxide.

The mean grain size of other component is preferably and is less than or equal to 1 μ m, more preferably 0.01 μ m～1 μ m.When mean grain size surpassed 1 μ m, the size-grade distribution of the final developing toner for electrostatic latent images that obtains was widened, and produced free particle, caused the reduction of Performance And Reliability easily.On the other hand, when mean grain size was in above-mentioned scope, favourable part was not only there is not above-mentioned defective, and can reduce the deviation between the toner, the dispersion of toner is become better, and the variation of Performance And Reliability is diminished.For example can using, Microtrack measures described mean grain size.

The example of the dispersion medium in resin particle dispersion liquid, colorant dispersion and the detackifier dispersion liquid comprises aqueous medium.The example of aqueous medium comprises water, as distilled water and ion exchange water; And alcohols.These materials can use separately, maybe can be used in combination wherein two or more.

In the present invention, preferred above-mentioned aqueous medium comprises surfactant.

The example of this surfactant comprises: anionic surfactant, as sulfuric acid, sulfonate, phosphate ester salt and soap; Cationic surfactant is as amine salt and quaternary ammonium salt; And nonionic surfactant, as polyethylene glycol type, alkylphenol/ethylene oxide adduct and polyvalent alcohol.In these surfactants, anionic surfactant and cationic surfactant are preferred.Nonionic surfactant preferably is used in combination with anionic surfactant or cationic surfactant.These surfactants can use separately or exercise usefulness with being combined into of two or more in them.

Examples of anionic surfactants comprises soap, as potassium laurate, sodium oleate and castor-oil plant grease sodium; Sulfuric ester is as sulfuric acid monooctyl ester, lauryl sulfate, lauryl ether sulfuric ester and nonylplenyl ether sulfuric ester; Sulfonate is as lauryl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate, naphthalene sulfonate formalin condensation product, single octyl group sulfosuccinate, dioctyl sulfosuccinate, lauramide sulfonate and oleamide sulfonate; Phosphate is as lauryl phosphate, p isopropylbenzoic acid ester, nonylplenyl ether phosphate; Sulfosuccinate, for example, as dialkyl sulfosuccinates, lauryl disodium sulfosuccinate and the lauryl polyoxyethylene disodium sulfosuccinate of dioctyl sodium sulphosuccinate.

The object lesson of above-mentioned cationic surfactant comprises amine salt, the amino propylamine of example hydrochloric acid lauryl amine, hydrochloric acid stearylamine, acetate oleyl amine, acetate stearylamine and acetate stearyl; And quaternary ammonium salt, as lauryl trimethyl ammonium chloride, dilauryl alkyl dimethyl ammonium chloride, distearyl ammonium chloride, VARISOFT TA100, lauryl dihydroxy ethyl ammonio methacrylate, oil base double focusing oxygen ethene ammonio methacrylate, lauroyl aminopropyl dimethyl ethyl QAE quaternary aminoethyl sulfate, lauroyl aminopropyl dimethyl hydroxyethyl ammonium perchlorate, alkyl benzene alkyl dimethyl ammonium chloride and alkyl trimethyl ammonium chloride.

The example of nonionic surfactant comprises alkyl ether, as polyoxyethylene Octyl Ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether and polyoxyethylene oleyl ether; Alkyl phenyl ether is as NONIN HS 240 and polyoxyethylene nonylplenyl ether; Arrcostab is as polyoxyethylene laurate, Myrj 45 and polyoxyethylene oleate; Alkyl amine is as polyoxyethylene lauryl amino ethers, polyoxyethylene stearyl base amino ethers, polyoxyethylene oil base amino ethers, polyoxyethylene soybean amino ethers and polyoxyethylene tallow amino ethers; Alkylamide is as polyoxyethylene lauramide, polyoxyethylene stearyl acid amides and polyoxyethylene oleamide; Plant ether is as Emulsifier EL-60 ether, polyoxyethylene rape seed oil ether; Alkanolamide is as lauric acid diethyl amide, Stearic acid diethanolamine salt and oleic acid diethyl amide; Sorbitan ester ether is as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monoleate.

When hybrid resin particle dispersion, colorant dispersion and detackifier dispersion liquid, the content of colorant can be for being less than or equal to 50 quality %, preferred about 2 quality %～40 quality %.The content of detackifier can be for being less than or equal to 50 quality %, preferred about 2 quality %-40 quality %.In addition, described other components contents can be not hinder the degree of the object of the invention, generally is indivisible, and specifically, this content is about 0.01 quality %～5 quality %, preferred about 0.5 quality %～2 quality %.

The production method of other resin particle dispersion liquid that can use with resin particle of the present invention is not particularly limited, but can adopt the method for suitably selecting according to purpose.For example, this dispersion liquid can be by being prepared as follows: when the resin in the resin particle is the homopolymer of vinyl monomer (the ester class, ethene nitrile, ethene ethers and the ethene ketone that for example have vinyl) or multipolymer (vinyl-based resin), can make this vinyl monomer in ionic surface active agent, carry out emulsion polymerization or seeding polymerization, thus the dispersion liquid that the resin particle of the homopolymer of preparation therein ethylene base class monomer or multipolymer (vinyl-based resin) disperses in ionic surface active agent.

When the resin in the resin particle is during except that the homopolymer of described vinyl monomer or the resin the multipolymer, if this resin of dissolving in the oil-based solvent that solubleness is lower in water, can be by this resin of dissolving in this oil-based solvent, this solution is added entry with ionic surface active agent and polyelectrolyte, for example using, the dispersion machine of homogenizer carries out microparticulate, and heat or reduce pressure, thereby make dispersion liquid with this oil-based solvent that volatilizees.

Can prepare colorant dispersion by the toner that for example in aqueous medium such as surfactant, is scattered here and there.The detackifier dispersion liquid disperses with macromolecule electrolyte such as ionic surface active agent, polymer acid and for example polymeric alkalis detackifier in water.This material is heated to fusing point or higher temperature, makes the detackifier micronize by using homogenizer or pressure release type dispersion machine to apply strong shearing force simultaneously, can prepare described detackifier dispersion liquid thus.Can prepare the dispersion liquid that is dispersed with other component (particle) by in the aqueous medium of for example surfactant, disperseing above-mentioned other component.

When respectively at resin particle dispersion liquid, the resin particle that disperses in colorant dispersion and the detackifier dispersion liquid, colorant and detackifier are the composite particles that has comprised resin particle component in addition, when having comprised the composite particle of colorant component in addition and having comprised the composite particle of detackifier component in addition, can prepare the dispersion liquid that disperses these composite particles by for example following mode: for example, they can be prepared by following mode: each component of dissolving and dispersion composite particle in solvent, as mentioned above it is disperseed in water with suitable spreading agent, and heat or reduce pressure and desolvate to remove, thereby make the dispersion liquid of composite particle, perhaps carry out mechanical shearing or electricity and be adsorbed onto on the surface of the latex that forms by emulsion polymerization or seeding polymerization, make the dispersion liquid of composite particle thus to be fixed to the upper.These methods have effectively suppressed removing of colorant, or have effectively improved the dependence of the charging property of developing toner for electrostatic latent images to colorant.

Diverting device is not particularly limited, but its example comprises known dispersing apparatus itself, as rotational shear type homogenizer and the bowl mill, sand mill and the ball mill that contain medium.

Described agglutination particle can prepare by for example following mode: the ionic surface active agent (1) that polarity is opposite with above-mentioned ionic surface active agent; Or add and mixed the aqueous medium (2) of this material; Or second dispersion liquid (in resin particle dispersion liquid, colorant dispersion and the detackifier dispersion liquid at least a) (3) that has comprised described aqueous medium sneaks into first dispersion liquid that comprises aqueous medium (in resin particle dispersion liquid, colorant dispersion and the detackifier dispersion liquid at least a), adds in the aqueous medium of described first dispersion liquid and mixed above-mentioned ionic surface active agent.When using stirring apparatus to stir this mixed solution, resin particle aggegation in dispersion liquid has formed agglutination particle by resin particle under the effect of ionic surface active agent, thus, makes the agglutination particle dispersion liquid.

Stirring apparatus is not particularly limited, but can suitably be selected from known mixing plant according to purpose.Mix under the temperature of the glass transition point of the resin that preferably in mixed solution, comprises.When under this temperature conditions, carrying out described mixing, can under stable status, carry out aggegation.

Adopting under the situation of (1) or (2), formed following agglutination particle, that wherein disperses in first dispersion liquid is selected from least a material generation aggegation in resin particle, colorant and the detackifier.Under the situation that adopts (3), formed following agglutination particle, wherein in second dispersion liquid, disperse be selected from least a material in resin particle, colorant and the detackifier and in first dispersion liquid, disperse be selected from least a material generation aggegation in resin particle, colorant and the detackifier.

When forming agglutination particle, the preferred polarity of the ionic surface active agent that comprises in desire polarity of adding the ionic surface active agent that comprises in the dispersion liquid of another kind of dispersion liquid and the dispersion liquid that is added that makes in advance is opposite, and making the balanced polarities skew, the skew to this balance compensates then.That is, the ionic surface active agent in the solution that preferably adds being included in joins desire and adds in the ionic surface active agent that the solution of another kind of solution comprises, to compensate the skew of this balance.

Usually, depend on the kind or the polarity of resin, colorant and the detackifier of resin particle, be difficult to carry out aggegation sometimes, the particle of certain material can dissociate when aggegation, thereby can not obtain required toner composition sometimes.Specifically, have little polarity, and it is poor especially with the compatibility of the resin of resin particle, thereby it tends to significantly dissociate when aggegation owing to be usually used in the polyolefins detackifier of toner such as tygon and polypropylene.When increasing the amount of free detackifier, the problem that produces is the various performance degradations that not only make toner intrinsic, and free detackifier can be from the developing machine overflow when developing, thereby pollute the inside of developing machine, and free detackifier can be damaged or take place coalescent because of the mechanical stress in the developing machine, and goes up film forming in developing sleeve (sleeve).

Yet, when forming agglutination particle as mentioned above, can not cause such problem.For example, favourable part is even the resin in the resin particle has identical polarity chron with colorant, has the surfactant of opposite polarity by adding, can easily be formed the particle of even aggegation by resin particle and colorant.

The mean grain size of the agglutination particle that forms in this aggegation step is not particularly limited, and makes this mean grain size be approximately the mean grain size of required developing toner for electrostatic latent images but control it usually.Can be easy to control by the condition of for example suitably setting or change temperature and mixed/stirred.By above-mentioned aggegation step, form the approximately agglutination particle identical of mean grain size, and make the agglutination particle dispersion liquid that has wherein disperseed agglutination particle with the mean grain size of developing toner for electrostatic latent images.The content of agglutination particle is generally and is less than or equal to 40 quality % in this agglutination particle dispersion liquid.In the present invention, this agglutination particle is called " coatingparticles " in some cases.

Can implement attachment steps in case of necessity, this attachment steps is as follows: will disperse the particle dispersion liquid of particulate to join the agglutination particle dispersion liquid, and mix them so that particulate is attached to agglutination particle, and adhere to particle thereby form.

The example of particulate comprises resin particle from resin particle, from the colorant particles of colorant, from the detackifier particulate of detackifier with from the particulate of other component (particle), they were above being described.The example of particle dispersion liquid comprise the resin dispersion liquid that wherein disperseed resin particle, wherein disperseed the colorant dispersion of colorant, wherein disperseed the detackifier dispersion liquid of detackifier and wherein disperseed the dispersion liquid of other component (particle), they were above being described.These particle dispersion liquids can use separately, maybe can be used in combination in them two or more.

Particle is adhered to formation in the surface that is attached to agglutination particle when particulates such as for example resin particles equably, and in fusion steps described later heating and fusion this when adhering to particle, comprise at agglutination particle under the situation of colorant or detackifier, because their surface covers (forming shell) by particle matter, can prevent effectively that these detackifiers from exposing from toner particle.

In this attachment steps, when in preparation used for static latent image developing multi-color toner, using resin particle, owing on the surface of agglutination particle, form the resin particle layer, the colorant that comprises in the agglutination particle is minimized the influence of charged behavior, and make charged characteristic be difficult to produce difference with the difference of colorant kind.When the resin of selecting to have high glass-transition temperature during, can prepare the developing toner for electrostatic latent images that has hot retentivity and fixation performance and antistatic property excellence simultaneously as the resin in the resin particle.In this attachment steps, when interpolation has disperseed after for example the detackifier of wax mixes as the detackifier particle dispersion liquid of particulate and with it, add the resin or the inorganic powder that have disperseed to have high rigidity and mix, can on the outermost surface of toner particle, form the shell of forming by resin with high rigidity or inorganic powder as the particle dispersion liquid of particulate and with it.In the case, can make wax when photographic fixing, bring into play effect effectively, suppress again exposing of wax simultaneously as detackifier.By above process, for example, the surface of toner particle can be covered by resin, or can be covered by charged controlling agent, and colorant and detackifier may reside in the position near the surface of toner particle.

The mean grain size of this particulate is preferably and is less than or equal to 1 μ m, more preferably 0.01 μ m～1 μ m.When mean grain size surpassed 1 μ m, the size-grade distribution of the final developing toner for electrostatic latent images that obtains was widened, and produced free particle, and caused the reduction of Performance And Reliability easily.On the other hand, when mean grain size was in above-mentioned scope, favourable part was not only there is not above-mentioned defective, and can form the layer structure of being made up of particulate.For example can using, Microtrack measures described mean grain size.

The volume of particulate depends on the volume fraction of the developing toner for electrostatic latent images of gained, and be preferably the developing toner for electrostatic latent images that is less than or equal to gained volume 50%.When the volume of particulate surpass gained developing toner for electrostatic latent images volume 50% the time, this particulate can not adhere to or aggegation to agglutination particle, but form the new agglutination particle of forming by particulate, the composition distribution of the developing toner for electrostatic latent images of gained and the variation in the size-grade distribution will become significantly, can not obtain required performance in some cases.

In particle dispersion liquid, can disperse a kind of particulate in these particulates with the preparation particle dispersion liquid separately, maybe two or more particulates can be used in combination, and their are disperseed with the preparation particle dispersion liquid.Under one situation of back, the particulate combination that be used in combination is not particularly limited, but can suitably select according to purpose.

The example of the dispersion medium in the particle dispersion liquid comprises above-mentioned aqueous medium.In the present invention, preferably at least a above-mentioned surfactant is joined in the aqueous medium, and with its mixing.

The content of particulate is generally 5 quality %～60 quality % in the particle dispersion liquid, is preferably 10 quality %～40 quality %.When this content is beyond the above-mentioned scope, can not control fully in some cases from the inside of developing toner for electrostatic latent images to the structure and the composition on surface.

Described particle dispersion liquid be by for example in the aqueous medium that has added ionic surface active agent distribution of at least one particulate and it is mixed prepare.Perhaps, described particle dispersion liquid can prepare by the surface that is made particulate absorption by mechanical shearing or electric mode or be affixed to by the latex of emulsion polymerization or seeding polymerization preparation.

In this attachment steps, by adding agglutination particle dispersion liquid that particle dispersion liquid prepares in the aggegation step and they being mixed, particle is adhered to formation in the surface that makes particulate be attached to agglutination particle.Because this particulate is equivalent to newly add particle for agglutination particle, thereby this particulate is called as " additional particles " in the present invention sometimes.

The method of described adding and mixing is not particularly limited, but for example can slowly carry out continuously, maybe can be divided into repeatedly and carries out step by step.So, by adding and mixing described particulate (additional particles), can suppress the generation of particulate, and can make the size-grade distribution of the developing toner for electrostatic latent images of gained become narrower.In addition, can progressively change from the electrostatic latent image developing toner surface of gained, and can easily control the structure of developing toner for electrostatic latent images to the composition and the physical property of inside.

In addition, select to be used for the resin of resin particle and resin particle by following mode: make the glass transition point of the resin that the outside of toner particle exists be higher than the glass transition point of the inner resin that exists of this toner particle, can guarantee the flowability and the bin stability of toner and can make it under lower temperature, demonstrate excellent fixing performance.

Equally, the molecular weight of the resin by increasing the high molecular side can increase the elasticity under the molten condition, thereby prevents the offset to hot-rolling.This measure is unusual effective method not implementing under the situation of oil coating.

In addition, the molecular weight of selecting the outside resin (being the resin in the particulate) that exists of toner is so that its molecular weight less than the resin (being the resin in the agglutination particle) of toner inside existence, owing to strengthened the flatness on surface of the toner particle of gained, improve mobile and transfer printing performance easily.When agglutination particle is not when only being formed by a kind of resin particle, promptly, when by two or more resin particles of aggegation when obtaining agglutination particle, the molecular weight of the inner resin (being the resin in the agglutination particle) that exists of toner refers to the mean value of the molecular weight of all resins that comprise in the agglutination particle.

If the molecular weight difference of the molecular weight of the outside resin that exists of toner and the inner resin that exists of toner is very big, then may reduce the kernel of the toner particle that is obtained and the clinging power between the coating.In the case, if in developing apparatus, mix with carrier particle and it is applied mechanical stress, may destroy toner particle by the agitation of toner particle or with it.Therefore, when making resin particle be attached to agglutination particle, can adopt the process that comprises following operation: at first make resin particle be attached to agglutination particle, afterwards selected resin particle is attached to agglutination particle, the molecular weight of last resin particle and/or glass transition point are between the molecular weight and/or glass transition point of the molecular weight of the outside resin that exists of toner particle and/or glass transition point and the inner resin that exists of toner particle.

When being divided into repeatedly and adding step by step and mixing, favourable part is progressively stacked particulate layer on the surface of agglutination particle, can form structural change or composition gradient to the outside from the inside of developing toner for electrostatic latent images particle, physical property can be changed, and the skin hardness of particle can be improved.In addition, when in fusion steps, merging, can keep size-grade distribution, and can suppress its variation, simultaneously, will need not to add surfactant and acid or the alkali that is used to strengthen the stability when merging, maybe their addition can be reduced to minimum, thus escapable cost and improve quality.

It is as follows to make particulate be attached to the condition of agglutination particle: promptly, temperature is to be lower than the temperature that equals the glass transition point of the resin in the resin particle in the aggegation step, and preferably is similar to room temperature.When heating under being lower than the temperature that equals glass transition point, agglutination particle and particulate adhere to easily, and the result makes particle-stabilisedization of adhering to of formation easily.Because the processing time depends on temperature, thus this time can not unconditionally determine, but be generally about 5 minutes～2 hours.When adhering to, the dispersion liquid that comprises agglutination particle and particulate is left standstill, maybe can adopt mixer to carry out gentle stirring.The latter's favourable part is the particle that easy formation is evenly adhered to.

In the present invention, this attachment steps can be carried out one or many.In the former case, on the surface of agglutination particle, only form layer of particles (additional particles) layer, and under one situation of back, when two or more particle dispersion liquids of preparation, be included in a plurality of layers of the particulate (additional particles) in these particle dispersion liquids by stacked formation.Under one situation of back, can obtain to have the developing toner for electrostatic latent images of complexity and accurate hierarchy, its favourable part is and can provides required function to developing toner for electrostatic latent images.

When attachment steps is carried out repeatedly, the particulate (additional particles) that at first is attached to the particulate (additional particles) of agglutination particle (coatingparticles) and next or adheres to later on can be any combination, and can suitably select according to the function of developing toner for electrostatic latent images.

When attachment steps is carried out repeatedly, preferably, add and during hybrid fine particles each, in the aggegation step with the temperature of the glass transition point of being less than or equal to the resin in the resin particle, heating comprises the dispersion liquid of particulate and agglutination particle, and this heating-up temperature that more preferably raises gradually.By carrying out such operation, favourable part is to make adheres to particle-stabilisedization, and can suppress the appearance of free particle.

By above-mentioned attachment steps, formed the following particle that adheres to, this adheres in the particle, and described particulate is attached to the agglutination particle for preparing in the aggegation step.When attachment steps is carried out repeatedly, adhere to particle below having formed, this adheres in the particle, and described particulate repeatedly is attached to the agglutination particle for preparing in the aggegation step.Therefore, be attached to agglutination particle, can freely design and prepare developing toner for electrostatic latent images with desired properties by the particulate that in attachment steps, makes suitable selection.Because adhering to colorant distribution in the particle, these finally become colorant distribution in the toner particle, therefore along with described colorant distribution of adhering in the particle becomes meticulousr or more even, the colour development of the developing toner for electrostatic latent images of gained can improve.

Fusion steps is that agglutination particle (adhering to when promptly carrying out attachment steps particle) is heated and merges to form the step of toner particle.

The temperature of described heating can be the degradation temperature of the glass transition temperature of the resin that comprises from agglutination particle (adhering to when promptly carrying out attachment steps particle) to this resin.Therefore, heating-up temperature is different and different with the kind of the resin of resin particle (with particulate), therefore can not unconditionally determine, but generally be the glass transition temperature to 180 ℃ of the resin from be included in agglutination particle (adhering to when promptly being included in the attachment steps of the resin the agglutination particle particle).By suitably selecting heating-up temperature, can be from the amorphous shape of controlling the toner particle of gained to spherical ground arbitrarily.Can heat by known firing equipment or the device of use itself.

Time of fusion short when heating-up temperature is high is just much of that, then must be long-time when heating-up temperature is low.That is because time of fusion depends on heating-up temperature, so it can not unconditionally determine, but generally be 30 minutes～10 hours.In the present invention, can clean under proper condition and the dry developing toner for electrostatic latent images that after fusion steps is finished, obtains.Can under drying condition, add inorganic powder, as silicon dioxide, aluminium oxide, titania and lime carbonate by applying shearing force; Or resin particle, as vinyl-based resin, vibrin and silicones.These inorganic powders or resin particle are as external additive, as flow aid or cleaning additive.

In the present invention, preferably merge particle with speed cooling described later after the above-mentioned fusion in this fusion steps.Reason is as follows: promptly, known to comprise at least a be that 12～30 higher alcohol and/or carbon number are that the detackifier of the ester that constitutes of 12～30 higher fatty acid has polytropism by carbon number.For example, E.S.Lutton is at J.Am.Oil Chem.Soc., report in 27,276 (1950) to have multiple homogeneity crystal formation, and they has different fusing points respectively.

Usually, for controlling the fusing point of these a plurality of polymorphic things, prevailing is to heat-treat.The result of the research of this heat-treat condition is find by the speed cooling of the toner particle after will merging with 1～50 ℃/min, even identical detackifier also can show high-melting-point.Even owing to use identical detackifier also can therefore can make the retentivity of toner become better by the raise fusing point of this detackifier of described cooling.In the present invention, the speed of described cooling is 1～50 ℃/min preferably, is more preferably 5～50 ℃/min, especially preferably 10～50 ℃/min.Even when speed surpasses 50 ℃/min, also seen similar effect, but disadvantage is to enlarge the scale of cooling with facility.On the other hand, when speed during less than 1 ℃/min, disadvantage be to be difficult to the to raise fusing point of detackifier.

By above-mentioned fusion steps agglutination particle (coatingparticles) is merged, when carrying out attachment steps, be attached under the state on agglutination particle surface at particulate (additional particles) and the particle that adheres to for preparing in the attachment steps merged, thereby make developing toner for electrostatic latent images by above-mentioned fusion steps.

In the preparation method of developing toner for electrostatic latent images of the present invention, owing to during the preparation of toner particle, do not cause the generation of fine powder, therefore favourable part is to remove the fine powder of generation when pulverizing or the raw material dispersion liquid in the suspension polymerization in kneading-breaking method, and can simplify step.In addition, because by agglutinator being merged form toner particle and described agglutinator is aggegation under the state that has at least evenly disperseed resin particle, colorant and detackifier, therefore can control the composition of this developing toner for electrostatic latent images equably.When having the resin particle of different molecular weight, can easily control the molecular weight distribution of developing toner for electrostatic latent images by at least two kinds of attachment steps uses.In addition, can optionally exist in the inside of toner particle, therefore can reduce the amount of the detackifier on the surfaces of toner particles owing to as detackifier, have the material of high hydrophobicity.

When carrying out attachment steps, the developing toner for electrostatic latent images of the present invention that is obtained by the said method of preparation developing toner for electrostatic latent images of the present invention has following structure: wherein, under the situation of carrying out attachment steps, described agglutination particle is a coatingparticles, and is formed with particulate (additional particles) overlayer on the surface of this coatingparticles.The number of this particulate (additional particles) layer can be one deck or two-layer or multilayer.Generally speaking, to prepare the enforcement number of times of the attachment steps in the said method of developing toner for electrostatic latent images identical for Ceng number and the present invention.

In developing toner for electrostatic latent images of the present invention, by the molecular weight distribution of ratio (Mw/Mn) expression of the weight-average molecular weight (Mw) of using gel permeation chromatography to record and number-average molecular weight (Mn) preferably 4～30, be more preferably 4～20, especially preferably 5～15.When the molecular weight distribution of being expressed by described ratio (Mw/Mn) surpasses 30, the transparency of photographic fixing image, flatness and colour mixture deficiency.Especially, when this developing toner for electrostatic latent images develops or during photographic fixing, the image that is shown by transmittance becomes unclear dark image, or become projected image impermeable and that not have development on film.When molecular weight distribution less than 4 the time, the viscosity of toner significantly descends when the high temperature photographic fixing, and easily offset takes place.On the other hand, when the molecular weight distribution of being expressed by ratio (Mw/Mn) is in above-mentioned numerical range, not only the transparency of photographic fixing image, flatness and colour mixture are enough, and the viscosity that can prevent this developing toner for electrostatic latent images when the high temperature photographic fixing descends, and can effectively suppress the generation of offset.

The various performances of developing toner for electrostatic latent images of the present invention such as charging property, development, transfer printing, fixation performance and spatter property excellence, particularly, the flatness in the image, the transparency, colour mixture and colour development excellence.In addition, owing to play consistently and keep various performances and be not subjected to the influence of environmental baseline so reliability height.

Prepare developing toner for electrostatic latent images of the present invention owing to prepared the method for developing toner for electrostatic latent images by the present invention, with different by the toner of kneading-breaking method preparation, the mean grain size of toner of the present invention is little, its narrow particle size distribution.

In the size-grade distribution of developing toner for electrostatic latent images of the present invention, as its index, use the D16 or the D84 of cumulative distribution, can simply use volume GSD (volume GSD=(volume D84/ volume D16) ^0.5) or quantity GSD (quantity GSD=(quantity D 84/ quantity D 16) ^0.5).As volume GSD,, be more preferably smaller or equal to 1.27 preferably smaller or equal to 1.3.When volume GSD surpassed 1.30, development worsened in time under the certain situation that selectivity is developed.The mean grain size of developing toner for electrostatic latent images is 2 μ m～9 μ m preferably, are more preferably 3 μ m～8 μ m.When mean grain size during less than 2 μ m, it is not enough that chargeding performance becomes easily, can reduce development in some cases.When mean grain size surpasses 9 μ m, can reduce the resolution of image in some cases.

Owing to use resin particle of the present invention to prepare developing toner for electrostatic latent images of the present invention, do not comprise residual solvent in this toner.As a result, developing toner for electrostatic latent images of the present invention can improve the stability of the retentivity and the photographic fixing image of toner, in addition, and the generation of the unhappy peculiar smell of deriving by residual solvent in the time of can also being suppressed at toner fixing.

The carried charge of developing toner for electrostatic latent images of the present invention is preferably 10 μ C/g～40 μ C/g, more preferably 15 μ C/g～35 μ C/g.When carried charge during less than 10 μ C/g, background takes place easily stain, when carried charge surpassed 40 μ C/g, the reduction of image color took place easily.This developing toner for electrostatic latent images is more preferably 0.7～1.3 at the ratio of the carried charge in summer and carried charge in the winter time preferably 0.5～1.5.When ratio was beyond above-mentioned preferable range, toner was strong to the dependence of environment, and the stability of chargeding performance lacks, and this is not preferred actually in some cases.

＜electrostatic latent image developer 〉

Electrostatic latent image developer of the present invention comprises developing toner for electrostatic latent images of the present invention at least.Except electrostatic latent image developer of the present invention comprised developing toner for electrostatic latent images of the present invention, electrostatic latent image developer of the present invention did not have special restriction, can adopt suitable component to form according to purpose.When independent use developing toner for electrostatic latent images of the present invention, electrostatic latent image developer of the present invention is prepared as the single component electrostatic latent image developer, maybe when described toner is used in combination with carrier, electrostatic latent image developer of the present invention is prepared as the bi-component electrostatic latent image developer.

This carrier is not particularly limited, but example comprises known carrier itself.For example, can use known carrier, as the carrier of describing among Japanese kokai publication sho 62-39879 and the clear 56-11461 of Te Kai that is coated with resin.

The object lesson of carrier comprises the following carrier that is coated with resin.That is, the example of the interior nuclear particle of carrier comprises the molded article of common iron powder, ferrite and magnetic iron ore, and its mean grain size is about 20 μ m～200 μ m.The covering of nuclear particle comprises styrene resin with the example of resin in being used to cover, for example styrene, to resins such as chlorostyrene and α-Jia Jibenyixi; Alpha-methylene fatty acid monocarboxylic acid resin is as methyl acrylate, ethyl acrylate, acrylic acid n-propyl, lauryl acrylate, acrylic acid-2-ethyl caproite, methyl methacrylate, n propyl methacrylate, lauryl methacrylate and methacrylic acid-resins such as 2-Octyl Nitrite; Nitrogenous acrylic resin is as the dimethylaminoethyl methacrylate resin; The vinyl nitrile resinoid is as resins such as vinyl cyanide and methacrylonitriles; The vinylpyridine resinoid is as resins such as 2-vinylpyridine, 4-vinylpridines; The vinyl ether resinoid is as resins such as vinyl methyl ether and vinyl isobutyl ethers; The vinyl ketone resin is as resins such as ethenyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketones; Polyolefin resin is as resins such as ethene and propylene; Silicone resin is as resins such as methylsiloxane and methyl phenyl siloxanes; The multipolymer of vinyl-based fluorochemical monomer such as vinylidene, tetrafluoroethene and hexafluoroethylene; The polyester, epoxy resin, urethane resin, polyamide, celluosic resin and the polyether resin that comprise bis-phenol or glycol.

These resins can use separately, maybe can be used in combination in them two or more.With respect to carrier, the amount that covers with resin is about 0.1～10 mass parts, preferably 0.5～3.0 mass parts.For preparing this carrier, can use hot type kneader, hot type Henschel (Henschel) mixer and UM mixer, or can use the rolling bed of hot type fluidisation (rollingbed) and hot type kiln according to covering with the amount of resin.

The mixture ratio of developing toner for electrostatic latent images of the present invention and carrier is not particularly limited in electrostatic latent image developer of the present invention, but can suitably select according to purpose.

＜formation method 〉

Formation method of the present invention comprises: sub-image forms step,, forms the step of electrostatic latent image on sub-image supporting body surface that is; Development step promptly, makes the latent electrostatic image developing that forms on the described sub-image supporting body surface, to form the step of toner image; Transfer step promptly, is transferred to the toner image that forms on the described sub-image supporting body surface step on transfer printing acceptor surface; And the photographic fixing step, that is, and to being transferred to the step that the lip-deep toner image of described transfer printing acceptor carries out hot photographic fixing, and with electrostatic latent image developer of the present invention as above-mentioned developer.

Each above-mentioned step itself is a general step, and it is described in for example Japanese kokai publication sho 56-40868 and the clear 49-91231 of Te Kai.Formation method of the present invention can be undertaken by known imaging device itself such as duplicating machine and facsimile recorder.

It is the step that forms electrostatic latent image on sub-image supporting body surface that sub-image forms step.Development step is to make described latent electrostatic image developing to form the step of toner image with the developer layer on the developer supporting mass.This developer layer is not particularly limited, as long as it comprises electrostatic latent image developer of the present invention, described developer comprises developing toner for electrostatic latent images of the present invention.Transfer step is the step that described toner image is transferred to transfer printing acceptor surface.In addition, adopt the photographic fixing machine to carry out hot photographic fixing, and form final toner image (photographic fixing step) being transferred to the lip-deep toner image of described transfer printing acceptor.When adopting the photographic fixing machine to carry out hot photographic fixing, the supply of the fixing member in photographic fixing machine detackifier is to prevent offset usually.

Preferred formation method of the present invention further comprises cleaning that the lip-deep remaining toner of described sub-image supporting body is reclaimed and the circulation step that the remaining toner that reclaims in the described cleaning is transported to the developer supporting mass after described transfer step.This cleaning is to remove the step that remains in the lip-deep electrostatic latent image developer of sub-image supporting body.This circulation step is a step of the remaining toner that reclaims in the described cleaning being transferred to the developer layer of developer supporting mass.

Can comprise the formation method of this form of this circulation step by using imaging device such as toner circulation system type duplicating machine and facsimile recorder.Perhaps, this also can be applied to omit cleaning and reclaim the circulation system of the mode of toner when developing.

[embodiment]

Followingly be further explained in detail the present invention, but the present invention never is subjected to the restriction of these embodiment according to embodiment.Below, " part " expression mass parts.

Use Ku Erte grain count instrument (trade name: the TA2 type, make by Coulter) the measurement of electrostatic image development mean grain size of toner.Use laser diffraction type particle size distribution measurement equipment (trade name: LA-700 makes manufacturing by the hole field) to measure the mean grain size of resin particle, colorant and detackifier.

In addition, by using the Docu Centre Color500CP transformation apparatus of making by company of Fuji-Xerox to form image, and by visual inspection the picture quality (unevenness of solid image-region) during in the starting stage with at the 50000th paper and background are stain, assess electrostatic latent image developer with this.Evaluation criteria is as follows.

The evaluation criteria of picture quality (unevenness of solid image-region)

A: when by the solid section of visual inspection photographic fixing image, can not pick out gloss part and non-gloss part (part), or they are uniformly, and do not have sense of discomfort between partly at gloss part and non-gloss with low gloss.

C: obviously, the differentiation in different regions of gloss part and non-gloss part is remarkable, and has sense of discomfort.The evaluation criteria that background is stain

A: can not pick out toner with naked eyes and adhere to.

C: the toner contamination is remarkable as can be known with naked eyes, and has sense of discomfort with respect to the paper look.

The Docu Centre Color500CP transformation apparatus of being made by company of Fuji-Xerox is the equipment that can implement formation method of the present invention.

The assessment result of gained is summarized in table 1 in embodiment and the Comparative Examples.

[embodiment 1]

The preparation of＜resin particle dispersion liquid (1) 〉

200 parts of γ-decalactones

2 parts of trifluoromethanesulfonic acid scandiums

100 parts of styrene

100 parts of butyl acrylates

4 parts in acrylic acid

10 parts of AIBN (azoisobutyronitrile)

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in following solution, in this solution, 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), this material of emulsification is so that mean grain size is 1 μ m or littler, and carries out 15 hours lactone ring opening polymerization under 50 temperature of reaction.Then, carried out the simultaneously slow mixed material of nitrogen replacement 10 minutes, adopt oil bath under agitation to heat this flask and become 70 ℃, continued emulsion polymerization after this manner 7 hours, thereby make resin particle dispersion liquid (1) up to content.

[embodiment 2]

The preparation of＜resin particle dispersion liquid (2) 〉

200 parts of pentadecanolides

50 parts in lipase (derived from pseudomonas (Pseudomonas genus) biosome)

100 parts of styrene

100 parts of butyl acrylates

4 parts in acrylic acid

10 parts of AIBN (azoisobutyronitrile)

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in following solution, in this solution, 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), this material of emulsification is so that mean grain size is 1 μ m or littler, and carries out lactone ring opening polymerization 50 hours under 50 ℃ temperature of reaction.Then, carry out nitrogen replacement, simultaneously slow mixed material 10 hours adopts oil bath under agitation to heat this flask and becomes 70 ℃ up to content, continues emulsion polymerization after this manner 7 hours, thereby makes resin particle dispersion liquid (2).

[embodiment 3]

The preparation of＜resin particle dispersion liquid (3) 〉

200 parts of pentadecanolides

1,2,5 parts of 4-benzene tricarbonic acids

2 parts of trifluoromethanesulfonic acid scandiums

100 parts of styrene

100 parts of butyl acrylates

4 parts in acrylic acid

10 parts of AIBN (azoisobutyronitrile)

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in solution, in this solution, 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), this material of emulsification is so that mean grain size is 1 μ m or littler, and carries out lactone ring opening polymerization 15 hours under 50 ℃ temperature of reaction.Then, carry out nitrogen replacement, simultaneously slow mixed material 10 hours adopts oil bath under agitation to heat this flask and becomes 70 ℃ up to content, continues emulsion polymerization after this manner 7 hours, thereby makes resin particle dispersion liquid (3).

[Comparative Examples 1]

The preparation of＜comparative resin particle dispersion (1) 〉

200 parts of pentadecanolides

10 parts of organotin catalysts

Above component is put into flask, and reaction 10 hours under 100 ℃ temperature of reaction, mix simultaneously and stir raw material with synthetic resin.

Then, in this flask, mix:

100 parts of styrene

100 parts of butyl acrylates

4 parts in acrylic acid

100 parts of AIBN (azoisobutyronitrile)

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in following solution, this solution is by add 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)) obtain, adopt rotor stator type homogenizer (trade name: Ultratalax is made by IKA) this material of emulsification to make that mean grain size is 1 μ m or littler.Then, carry out nitrogen replacement, simultaneously slow mixed material 10 minutes adopts oil bath under agitation to heat this flask and becomes 70 ℃ up to content, continues emulsion polymerization after this manner 7 hours, thereby makes comparative resin particle dispersion (1).

[embodiment 4]

The preparation of＜developing toner for electrostatic latent images (1) 〉

The preparation of-colorant dispersion (1)-

Phthalocyanine color (trade name: PV FAST BLUE, by refining big day (strain) make) 60 parts

2 parts of anionic surfactants (trade name: Ionet D-2 changes into (strain) by Sanyo and makes)

300 parts of ion exchange waters

With above component mix, dissolving and use homogenizer (trade name: Ultratalax T50, make) to disperse by IKA, with preparation colorant dispersion (1), wherein disperseed to have the colorant (phthalocyanine color) of the mean grain size of 160nm.

The preparation of-detackifier dispersion liquid (1)-

100 parts of the docosane acid esters of pentaerythrite

(trade name: Rikestar EW-861, HLB=3.2, by Riken Vitamin Co.,

Ltd. make)

6 parts of anionic surfactants

(trade name: Neogen SC, make by the first industrial pharmacy (strain))

1000 parts of ion exchange waters

Above component is heated to 90 ℃, use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and adopt pressure release type homogenizer to do to suspend and handle with preparation detackifier dispersion liquid (1), wherein having disperseed mean grain size is the detackifier (the docosane acid esters of pentaerythrite) of 330nm.

The preparation of-agglutination particle (aggegation step)-

(1) 240 part of resin particle dispersion liquid

(1) 40 part of colorant dispersion

(1) 100 part of detackifier dispersion liquid

2 parts of cationic surfactants

(trade name: Sanizol B50, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and in hot oil bath, be heated to 47 ℃.Make flask after 47 ℃ keep 30 minutes, adopt this material of observation by light microscope, through having confirmed to form the agglutination particle that mean grain size is about 5.1 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (1) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and it was kept 1 hour at 48 ℃.Adopt this material of observation by light microscope, through having confirmed to form the particle that adheres to that mean grain size is about 5.5 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 6 portions of anionic surfactants (trade name: Neogen SC, make) to this material, and this material is heated to 94 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain).With reaction product speed cooling with 10 ℃/min after, with its filtration, adopt ion exchange water fully wash, and use vacuum dryer drying to obtain developing toner for electrostatic latent images (1) thereafter.

The mean grain size of the developing toner for electrostatic latent images of gained (1) is 5.7 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (1) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the developing toner for electrostatic latent images (1) of this material to obtain to add through the outside.

The preparation of＜electrostatic latent image developer (1) 〉

(by Powder-Tech Co., Ltd. makes with 100 parts of ferrite particles; Mean grain size 50 μ m) and 1 part of methacrylate resin (by Mitsubishi Rayon Co., Ltd. makes; Molecular weight 95000) puts into the pressure-type kneader with 500 parts of toluene, mixed material is 15 minutes at normal temperatures, temperature is elevated to 70 ℃, simultaneously under reduced pressure mix them, distill out toluene, with this material cooling, use 105 μ m screen fractionation to obtain ferrite carrier (being coated with the carrier of resin).The developing toner for electrostatic latent images (1) that mixes this ferrite carrier and add through the outside is the bi-component electrostatic latent image developer (1) of 7 quality % with the preparation toner concentration.Use electrostatic latent image developer (1) to carry out imaging as stated above, and the evaluate image quality.

[embodiment 5]

The preparation of＜developing toner for electrostatic latent images (2) 〉

The preparation of-agglutination particle (aggegation step)-

(2) 250 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 130 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Kotamine 24P, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and in hot oil bath, be heated to 48 ℃.After 48 ℃ keep 30 minutes, adopt this material of observation by light microscope, through having confirmed to form the agglutination particle that mean grain size is about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (2) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 51 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.3 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 90 ℃ continues simultaneously to stir, kept 5 hours by the first industrial pharmacy (strain)., reaction product with the speed of 40 ℃/min be cooled to room temperature after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (2) thereafter.

The mean grain size of the developing toner for electrostatic latent images of gained (2) is 5.6 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (2) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the developing toner for electrostatic latent images (2) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation electrostatic latent image developer (2), difference is to have used the developing toner for electrostatic latent images (2) that adds through the outside.Use electrostatic latent image developer (2) to carry out imaging as stated above, and the evaluate image quality.

[embodiment 6]

The preparation of＜developing toner for electrostatic latent images (3) 〉

The preparation of-agglutination particle (aggegation step)-

(3) 250 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 130 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Kotamine 24P, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, in hot oil bath, be heated to 48 ℃.After 48 ℃ keep 30 minutes down, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (3) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 51 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.3 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 90 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain).Thereafter, reaction product is cooled to room temperature with the speed of 40 ℃/min after, reaction product is filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (3).

The mean grain size of the developing toner for electrostatic latent images (3) that obtains is 5.3 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (3) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the developing toner for electrostatic latent images (3) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation electrostatic latent image developer (3), difference is to have used the developing toner for electrostatic latent images (3) that adds through the outside.Use electrostatic latent image developer (3) to carry out imaging as stated above, and the evaluate image quality.

[Comparative Examples 2]

The preparation of＜contrast developing toner for electrostatic latent images (1) 〉

The preparation of-agglutination particle (aggegation step)-

(1) 250 part of comparative resin particle dispersion

(1) 40 part of colorant dispersion

(1) 40 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Sanizol B50, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and in hot oil bath, be heated to 49 ℃.After 49 ℃ keep 20 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 70 parts of comparative resin particle dispersions (1) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 50 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.4 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 97 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain).Thereafter, reaction product is cooled to room temperature with the speed of 20 ℃/min after, reaction product is filtered, adopt ion exchange water fully to wash, and use vacuum dryer 40 ℃ of dryings 10 hours to obtain contrast developing toner for electrostatic latent images (1).

The mean grain size of the contrast developing toner for electrostatic latent images (1) that obtains is 5.7 μ m.With a cataloid (trade name: R972, make by Aerosil) join the contrast developing toner for electrostatic latent images (1) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the contrast developing toner for electrostatic latent images (1) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation contrast electrostatic latent image developer (1), difference is to have used the contrast developing toner for electrostatic latent images (1) that adds through the outside.Use contrast electrostatic latent image developer (1) to carry out imaging as stated above, and the evaluate image quality.

[table 1]

	Image quality measure (unevenness of solid image-region)		Background is stain
					Initially (the 10th paper)	The 50000th paper	Initially (the 10th paper)	The 50000th paper
	Developing toner for electrostatic latent images (1) (embodiment 4)	??a	??a	??a					??a
Developing toner for electrostatic latent images (2) (embodiment 5)					??a	??a	??a	??a
	Developing toner for electrostatic latent images (3) (embodiment 6)	??a	??a	??a					??a
Contrast developing toner for electrostatic latent images (1) (Comparative Examples 2)					??c	??c	??a	??c

According to the result shown in the table 1, following content is conspicuous.That is, compare with contrast electrostatic latent image developer (1), electrostatic latent image developer (1)～(3) are less in the unevenness of solid image-region, excellent in uniformity, and be difficult to produce vaporific fuzzy (fog) in the picture quality.In addition, the stability of picture quality is also better.

In following embodiment, use gel permeation chromatography (trade name: HLC-8120 GPC, make) to measure the resin in the vibrin particle and the molecular weight and the molecular weight distribution of the resin in the developing toner for electrostatic latent images by Tosoh Corporation.

Under the heating rate of 3 ℃/min, the resin in use differential scanning calorimeter (trade name: DSC-50 is made by Shimadzu Seisakusho Ltd.) the measurement vibrin particle and the glass transition point of the resin in the developing toner for electrostatic latent images.

In addition, form image by the Docu Centre Color500CP transformation apparatus that uses company of Fuji-Xerox to make, and the background of the image that obtains by visual inspection initial pictures quality with when the 50000th paper stains, and carries out the assessment of electrostatic latent image developer with this.Evaluation criteria is as follows:

A:, can not pick out toner and adhere to through visual inspection.

B: through visual inspection, it is obvious slightly to find that toner stains, and has sense of discomfort hardly with respect to the paper look.

C:, find that toner stains significantly, exists sense of discomfort with respect to the paper look through visual inspection.

Carry out the net assessment of electrostatic latent image developer.Evaluation criteria is as follows:

A: synthesizing polyester resin particle at low temperatures, the contamination at image background place does not exist, or not remarkable.

C: synthesizing polyester resin particle at low temperatures.

The assessment result that obtains in embodiment and Comparative Examples is summarized in table 2.

[embodiment 7]

The preparation of＜resin particle dispersion liquid (4) 〉

The preparation of-vibrin (1)-

789.0 parts of decanedioic acid

310.5 parts of ethylene glycol

199.7 parts of 5-sodium sulfo isophthalates

40.7 parts of fumaric acid

2.0 parts of dibutyl tins

Above component (by making with the pure medicine of light (strain)) is mixed in flask, under reduced pressure be heated to 240 ℃ carrying out dehydrating condensation 6 hours, thereby obtain vibrin (1).

The preparation of-vibrin particle (1)-

(1) 60 part in vibrin

40 parts of γ-decalactones

2 parts of trifluoromethanesulfonic acid scandiums

Above component (except that vibrin (1) by with the pure medicine of light (strain) make) is mixed and dissolving, use Ultratalax (making) with this material forced emulsification and be scattered in following solution in flask by IKA Japan, in this solution, 4 parts of nonionic surfactant (trade name: Nonipol 85 in 250 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 5 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), adopt nanometer mixer (nanomizer thereafter, by Yoshida Kikai Co., Ltd. manufacturing) this suspending liquid is regulated in emulsification, make that mean grain size is 1 μ m or littler, under 50 ℃ temperature of reaction, carry out lactone ring opening polymerization 15 hours, and obtained wherein to have disperseed the resin particle dispersion liquid (4) of vibrin particle (1).

[embodiment 8]

The preparation of＜resin particle dispersion liquid (5) 〉

The preparation of-vibrin (2)-

(1) 50 part in vibrin

50 parts of pentadecanolides

20 parts in lipase

(derived from pseudomonas (Pseudomonas genus) biosome)

The same with the manufacturing of vibrin particle dispersion (1) among the embodiment 1, mix above component and obtained wherein to disperse the resin particle dispersion liquid (5) of vibrin particle (2).

[embodiment 9]

The preparation of＜resin particle dispersion liquid (6) 〉

The preparation of-vibrin (3)-

(1) 50 part in vibrin

1,2,1 part of 4-benzene tricarbonic acid

50 parts of pentadecanolides

2 parts of trifluoromethanesulfonic acid scandiums

Above component (except that vibrin (1) by with the pure medicine of light (strain) make) is mixed and dissolving, use Ultratalax (making) in flask, this material to be scattered in the following solution by IKA Japan, in this solution, 4 parts of nonionic surfactant (trade name: Nonipol 85 in 250 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 5 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), adopt the nanometer mixer (by Yoshida KikaiCo., Ltd. make) this material of emulsification, make that mean grain size is 1 μ m or littler, and under 60 ℃ temperature of reaction, carried out lactone ring opening polymerization 12 hours.Obtain wherein to have disperseed the resin particle dispersion liquid (6) of vibrin particle (3).

[Comparative Examples 3]

The preparation of＜comparative resin particle dispersion (2) 〉

The preparation of-contrast vibrin particle (1)-

(1) 50 part in vibrin

50 parts of pentadecanolides

0.5 part of organotin catalysts

Above component is put into flask, when mixing and stirring raw material, it was reacted 3 hours under 160 ℃ temperature of reaction, cooling is with synthetic resin.

Then, using mechanical crusher is 20 μ m with this resin particleization to mean grain size.Be difficult to micronize to 1 μ m or littler.Reason for this reason, then, this material is scattered in following solution, in this solution, 2 parts of nonionic surfactant (trade name: Nonipol 85 in 200 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 1 part of anionic surfactant (trade name: Neogen SC, make by the first industrial pharmacy (strain)), under the pressure of heating (160 ℃) condition, use nanometer mixer heating system that mean grain size is adjusted to 1 μ m or littler, to obtain wherein to have disperseed the comparative resin particle dispersion (2) of contrast vibrin particle (1) at 130MPa.

[embodiment 10]

The preparation of＜developing toner for electrostatic latent images (4) 〉

The preparation of-agglutination particle (aggegation step)-

(4) 240 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 100 part of detackifier dispersion liquid

2 parts of cationic surfactants

(trade name: Sanizol B50, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, in hot oil bath, be heated to 47 ℃.After 47 ℃ keep 30 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.1 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (4) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 48 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.5 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 6 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 94 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., with the speed of 10 ℃/min reaction product cooled off after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (4) thereafter.

The mean grain size of the developing toner for electrostatic latent images (4) that obtains is 5.7 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (4) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the developing toner for electrostatic latent images (4) of this material to obtain to add through the outside.

The preparation of＜electrostatic latent image developer (4) 〉

With 100 parts of ferrite particles (by Powder-Tech Co., Ltd. make, mean grain size 50 μ m) and 1 part of methacrylate resin (by Mitsubishi Ryon Co., Ltd. make molecular weight 95000) put into the pressure-type kneader with 500 parts of toluene, mixed material is 15 minutes at normal temperatures, temperature is elevated to 70 ℃ of whiles mixed material under reduced pressure, distill out toluene,, use 105 μ m screen fractionation to obtain ferrite carrier (being coated with the carrier of resin) with this material cooling.The developing toner for electrostatic latent images (4) that mixes this ferrite carrier and add through the outside is the bi-component electrostatic latent image developer (4) of 7 quality % with the preparation toner concentration.Use electrostatic latent image developer (4) to carry out imaging as stated above, and the evaluate image quality.

[embodiment 11]

The preparation of＜developing toner for electrostatic latent images (5) 〉

The preparation of-agglutination particle (aggegation step)-

(5) 250 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 130 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Kotamine 24P, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, in hot oil bath, be heated to 48 ℃.After 48 ℃ keep 30 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (5) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 51 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.3 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 90 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., speed with 40 ℃/min with reaction product be cooled to room temperature after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (5) thereafter.

The mean grain size of the developing toner for electrostatic latent images (5) that obtains is 5.6 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (5) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the developing toner for electrostatic latent images (5) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation electrostatic latent image developer (5), difference is to have used the developing toner for electrostatic latent images (5) that adds through the outside.Use electrostatic latent image developer (5) to carry out imaging as stated above, and the evaluate image quality.

[embodiment 12]

The preparation of＜developing toner for electrostatic latent images (6) 〉

The preparation of-agglutination particle (aggegation step)-

(6) 250 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 130 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Kotamine 24P, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, in hot oil bath, be heated to 48 ℃.After 48 ℃ keep 30 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (6) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 51 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.3 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 90 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., speed with 40 ℃/min with reaction product be cooled to room temperature after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (6) thereafter.

The mean grain size of the developing toner for electrostatic latent images (6) that obtains is 5.3 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (6) of 100 parts of gained from the outside, adopt the Henschel mixer to mix the developing toner for electrostatic latent images (6) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation electrostatic latent image developer (6), difference is to have used the developing toner for electrostatic latent images (6) that adds through the outside.Use electrostatic latent image developer (6) to carry out imaging as stated above, and the evaluate image quality.

[Comparative Examples 4]

The preparation of＜contrast developing toner for electrostatic latent images (2) 〉

The preparation of-agglutination particle (aggegation step)-

(2) 250 parts of comparative resin particle dispersions

(1) 40 part of colorant dispersion

(1) 40 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Sanizol B50, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, in hot oil bath, be heated to 49 ℃.After 49 ℃ keep 20 minutes down, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 70 parts of comparative resin particle dispersions (2) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 50 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.4 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 97 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., after the speed with 20 ℃/min is cooled to room temperature with reaction product, reaction product is filtered, adopts ion exchange water fully to wash thereafter, and use vacuum dryer 40 ℃ of dryings 10 hours to obtain contrast developing toner for electrostatic latent images (2).

The mean grain size of the contrast developing toner for electrostatic latent images (2) that obtains is 5.7 μ m.With a cataloid (trade name: R972, make by Aerosil) join the contrast developing toner for electrostatic latent images (2) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the contrast developing toner for electrostatic latent images (2) of this material to obtain to add through the outside.

According to as embodiment 4 described same way as, prepare contrast electrostatic latent image developer (2), difference is to have used the contrast developing toner for electrostatic latent images (2) that adds through the outside.Use contrast electrostatic latent image developer (2) to carry out imaging as stated above, and the evaluate image quality.

[table 2]

	The synthesis temperature of vibrin particle		Background is stain		Net assessment
						Temperature (℃)	Energy consumption ( *1)	Initially (the 10th paper)	The 50000th paper
	Developing toner for electrostatic latent images (4) (embodiment 10)	??50	??a	??a	??a						??a
Developing toner for electrostatic latent images (5) (embodiment 11)						??50	??a	??a	??a	??a
	Developing toner for electrostatic latent images (6) (embodiment 12)	??60	??a	??a	??a						??a
Contrast developing toner for electrostatic latent images (2) (Comparative Examples 4)						??160	??c	??b	??c( *2)	??c

^*1: this energy consumption is to compare by the synthesis temperature (150 ℃-200 ℃) of the vibrin particle when using tin oxide catalysts to obtain.Situation less than 70% is " a ", and 70% the situation of being equal to or greater than is " c ".

^*2:, can reckon with that sex change meeting that particle surface takes place because of being heated causes the deterioration of charging property according to the difference of the heated particulate condition of resin.

According to result displayed in the table 2, following content is conspicuous: promptly, compare with contrast electrostatic latent image developer (2), electrostatic latent image developer (4)～(6) have less particle manufacturing process, and the necessary heating-up temperature of synthetic resin is lower.Excellent in uniformity in the picture quality, and be difficult to produce vaporific blur (fog).In addition, the stability of picture quality is also better.

In following embodiment, by using the Docu CentreColor500CP transformation apparatus of making by company of Fuji-Xerox to form image, and by visual inspection the picture quality (unevenness of solid image-region) during in the starting stage with at the 50000th paper, carry out the assessment of electrostatic latent image developer with this.Evaluation criteria is as follows:

The evaluation criteria of picture quality (unevenness of solid image-region)

A: when by the solid section of visual inspection photographic fixing image, can not pick out gloss part and non-gloss part (part), or they are uniformly, and do not have sense of discomfort between partly at gloss part and non-gloss with low gloss.

C: obviously, the area differentiation of gloss part and non-gloss part is remarkable, and has sense of discomfort.The evaluation criteria that background is stain

A: can not pick out toner by naked eyes and adhere to.

C: through visual inspection, it is significant that toner stains, and has sense of discomfort with respect to the paper look.

Carry out the assessment of folding line fixing strength by following method: use the Docu Centre Color500CP transformation apparatus of making by company of Fuji-Xerox to prepare the solid sample of not photographic fixing.Regulate solid sample and make that the quality of toner per unit area is 0.7mg/cm in the solid sample ²～0.8mg/cm ²The paper that uses is ecolor081 A4 paper (by the Office Supply Co. of Fuji-Xerox, Ltd. makes).

As fixation method, take out the fixing member of this transformation apparatus, individually by the controlled photographic fixing platform of test method preparation temperature, and use this parts.Regulate fixing conditions and make that the gloss (light) of the image after the photographic fixing is 30% (75～70 degree measurements/3GM-260TYPE: made by color institute system in the village), and the image of acquisition photographic fixing.

After the photographic fixing sample that will obtain is converted into half, be that the roller (profile 600mm is made by brass) of about 500g rolls on this folding position with weight, by the rag folding line of wiping photographic fixing image gently, the miss status of observation image.

Assess by sensory evaluation according to following standard.

A: form folding line, but do not have the miss status of image, or disappearance is arranged slightly.

B: see the small folding line of white, image section ground disappearance.

C: white banded folding line is remarkable, half of discovery image or disappearance over half.

Carry out the assessment that vinyl chloride adheres to by following method: by flexible vinyl chloride film (DOP plastifier: 30% additive) cover the photographic fixing sample that preparation is used for the assessment of folding line fixing strength, per unit area loads the weight of 300g, and it was left standstill 10 hours 70% humidity, 40 ℃ in calibration cell., sample through cover taken out, it was at room temperature left standstill 1 hour thereafter.

Then, peel off this vinyl chloride film, according to the miss status of following criterion evaluation image.

A: image is disappearance not.

C: there is disappearance in image.

The Docu Centre Color500CP transformation apparatus of being made by company of Fuji-Xerox is the equipment that can implement formation method of the present invention.

[embodiment 13]

The preparation of＜resin particle dispersion liquid (7) 〉

2-methylene-1,200 parts of 3-dioxepin

200 parts of butyl acrylates

20 parts in acrylic acid

10 parts of AIBN (azoisobutyronitrile)

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in following solution, in this solution, 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), this dispersion liquid of emulsification makes that mean grain size is 1 μ m, carry out nitrogen replacement, and under 70 ℃ temperature of reaction, make its polymerase 17 hour, thereby make resin particle dispersion liquid (7).

[embodiment 14]

The preparation of＜resin particle dispersion liquid (8) 〉

2-methylene-1,200 parts of 3-dioxolanes

200 parts of styrene

50 parts of butyl acrylates

10 parts in acrylic acid

10 parts of AIBN

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in following solution, in this solution, 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), this dispersion liquid of emulsification makes that mean grain size is 1 μ m, carried out the simultaneously slow mixed material of nitrogen replacement 10 minutes, in oil bath, content is heated to the inside of 70 ℃ of while stirred flask, continue emulsion polymerization after this manner 7 hours, thereby make resin particle dispersion liquid (8).

[embodiment 15]

The preparation of＜resin particle dispersion liquid (9) 〉

2-methylene-1,100 parts of 3-dioxepin

250 parts of styrene

30 parts of n-butyl acrylates

8 parts in acrylic acid

24 parts of dodecyl mercaptans

4 parts of carbon tetrabromides

Above component is mixed and dissolving, in flask, this material is scattered in following solution, in this solution, in the 550g ion exchange water, dissolved 6g nonionic surfactant (trade name: Nonipol 400, changing into (strain) by Sanyo makes) and anionic surfactant (trade name: NeogenSC, make by the first industrial pharmacy (strain)), this material of emulsification, when slowly being mixed 10 minutes, raw material adds the 50g ion exchange water that has dissolved the 4g ammonium persulfate therein, carry out nitrogen replacement, adopt oil bath that it is heated, continued emulsion polymerization after this manner 7 hours, thereby make resin particle dispersion liquid (9).

[Comparative Examples 5]

The preparation of＜comparative resin particle dispersion (3) 〉

100 parts of styrene

100 parts of butyl acrylates

4 parts in acrylic acid

10 parts of AIBN

Above component (by making with the pure medicine of light (strain)) is mixed and dissolving, in flask, this material is scattered in following solution, in this solution, 8 parts of nonionic surfactant (trade name: Nonipol 85 in 582 parts of ion exchange waters, have been dissolved, changing into (strain) by Sanyo makes) and 10 parts of anionic surfactant (trade names: Neogen SC, make by the first industrial pharmacy (strain)), adopt rotor stator type homogenizer (trade name: Ultratalax is made by IKA) this material of emulsification so that mean grain size is 1 μ m or littler.Thereafter, carry out nitrogen replacement, simultaneously slow composite material 10 minutes is heated to 70 ℃ of inside of stirred flask simultaneously with content in oil bath, continued emulsion polymerization after this manner 7 hours, thereby make comparative resin particle dispersion (3).

[embodiment 16]

The preparation of＜developing toner for electrostatic latent images (7) 〉

The preparation of-agglutination particle (aggegation step)-

(7) 240 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 100 part of detackifier dispersion liquid

2 parts of cationic surfactants

(trade name: Sanizol B50, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and in hot oil bath, be heated to 47 ℃.After 47 ℃ keep 30 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.1 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (7) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 48 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.5 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 6 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 94 ℃ continues simultaneously to stir, kept 5 hours by the first industrial pharmacy (strain)., with reaction product speed cooling with 10 ℃/min after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (7) thereafter.

The mean grain size of the developing toner for electrostatic latent images (7) that obtains is 5.7 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (7) of 100 parts of gained from the outside, adopt the Henschel mixer to mix the developing toner for electrostatic latent images (7) of this material to obtain to add through the outside.

The preparation of＜electrostatic latent image developer (7) 〉

100 parts of ferrite particles (are made by Powder-Tech; Mean grain size 50 μ m) and 1 part of methacrylate resin (by Mitsubishi Rayon Co., Ltd. makes; Molecular weight 95000) puts into the pressure-type kneader with 500 parts of toluene, mixed material is 15 minutes at normal temperatures, with temperature be elevated to 70 ℃ of whiles under reduced pressure mixed material to distill out toluene, with this material cooling, use 105 μ m screen fractionation to make ferrite carrier (being coated with the carrier of resin).The developing toner for electrostatic latent images (7) that mixes this ferrite carrier and add through the outside is the bi-component electrostatic latent image developer (7) of 7 quality % with the preparation toner concentration.Use electrostatic latent image developer (7) to carry out imaging as stated above, and the evaluate image quality.

[embodiment 17]

The preparation of＜developing toner for electrostatic latent images (8) 〉

The preparation of-agglutination particle (aggegation step)-

(8) 250 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 130 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Kotamine 24P, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and in hot oil bath, be heated to 48 ℃.After 48 ℃ keep 30 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (8) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 51 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.3 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 90 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., speed with 40 ℃/min with reaction product be cooled to room temperature after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (8) thereafter.

The mean grain size of the developing toner for electrostatic latent images (8) that obtains is 5.6 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (8) of 100 parts of gained from the outside, adopt the Henschel mixer to mix the developing toner for electrostatic latent images (8) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation electrostatic latent image developer (8), difference is to have used the developing toner for electrostatic latent images (8) that adds through the outside.Use electrostatic latent image developer (8) to carry out imaging as stated above, and the evaluate image quality.

[embodiment 18]

The preparation of＜developing toner for electrostatic latent images (9) 〉

The preparation of-agglutination particle (aggegation step)-

(9) 250 parts of resin particle dispersion liquids

(1) 40 part of colorant dispersion

(1) 130 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Kotamine 24P, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, in hot oil bath, be heated to 48 ℃.After 48 ℃ keep 30 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 50 parts of resin particle dispersion liquids (9) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 51 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the particle that adheres to of about 5.3 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 90 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., speed with 40 ℃/min with reaction product be cooled to room temperature after, reaction product filtered, adopt ion exchange water fully to wash, and use the vacuum dryer drying to obtain developing toner for electrostatic latent images (9) thereafter.

The mean grain size of the developing toner for electrostatic latent images (9) that obtains is 5.3 μ m.With a cataloid (trade name: R972, make by Aerosil) join the developing toner for electrostatic latent images (9) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the developing toner for electrostatic latent images (9) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation electrostatic latent image developer (9), difference is to have used the developing toner for electrostatic latent images (9) that adds through the outside.Use electrostatic latent image developer (9) to carry out imaging as stated above, and the evaluate image quality.

[Comparative Examples 6]

The preparation of＜contrast developing toner for electrostatic latent images (3) 〉

The preparation of-agglutination particle (aggegation step)-

(3) 250 parts of comparative resin particle dispersions

(1) 40 part of colorant dispersion

(1) 40 part of detackifier dispersion liquid

5 parts of cationic surfactants

(trade name: Sanizol B50, make by KAO. Corp. SA)

300 parts of ion exchange waters

Above component is put into round stainless steel flask, the use homogenizer (trade name: Ultratalax T50, make by IKA) disperse, and in hot oil bath, be heated to 49 ℃.After 49 ℃ keep 20 minutes, adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.0 μ m.

-adhere to the preparation (attachment steps) of particle-

In this agglutination particle dispersion liquid, slowly add 70 parts of comparative resin particle dispersions (3) as the resin particle dispersion liquid, the temperature of rising hot oil bath, and 50 ℃ of maintenances 1 hour.Adopt this material of observation by light microscope, through confirming that having formed mean grain size is the agglutination particle of about 5.4 μ m.

-adhere to the fusion (fusion steps) of particle-

Add 7 portions of anionic surfactants (trade name: Neogen SC, make) to this material, this material is heated to 97 ℃ continues simultaneously to stir, and kept 5 hours by the first industrial pharmacy (strain)., after the speed with 20 ℃/min is cooled to room temperature with reaction product, reaction product is filtered, adopts ion exchange water fully to wash thereafter, and use vacuum dryer 40 ℃ of dryings 10 hours to obtain contrast developing toner for electrostatic latent images (3).

The mean grain size of the contrast developing toner for electrostatic latent images (3) that obtains is 5.7 μ m.With a cataloid (trade name: R972, make by Aerosil) join the contrast developing toner for electrostatic latent images (3) of 100 parts of gained from the outside, and adopt the Henschel mixer to mix the contrast developing toner for electrostatic latent images (3) of this material to obtain to add through the outside.

According to embodiment 4 described same way as, preparation contrast electrostatic latent image developer (3), difference is to have used the contrast developing toner for electrostatic latent images (3) that adds through the outside.Use contrast electrostatic latent image developer (3) to carry out imaging as stated above, and the evaluate image quality.

[table 3]

	Image quality measure (unevenness of solid image-region)		Background is stain		Fixing strength	The vinyl chloride tack
							Initially (the 10th paper)	The 50000th paper	Initially (the 10th paper)	The 50000th paper
	Developing toner for electrostatic latent images (7) (embodiment 16)	??a	??a	??a							??a	??a	??a
Developing toner for electrostatic latent images (8) (embodiment 17)					??a	??a	??a	??a	??a	??a
	Developing toner for electrostatic latent images (9) (embodiment 18)	??a	??a	??a							??a	??a	??a
Contrast developing toner for electrostatic latent images (3) (Comparative Examples 6)					??c	??c	??a	??c	??c	??c

According to the result shown in the table 3, following content is conspicuous.That is, compare with contrast electrostatic latent image developer (3), the unevenness of the solid image-region of electrostatic latent image developer (7)～(9) is less, excellent in uniformity, and be difficult to produce vaporific fuzzy in the picture quality.In addition, their stable image quality and anti-vinyl chloride tack are also better.

Claims (19)

1. method of producing resin particle, this method comprises:

Emulsifying step, this emulsifying step make the composition emulsification that comprises polymerisable monomer and polymerization catalyst at least with the drop that forms said composition and

Polymerization procedure, this polymerization procedure make described polymerisable monomer polymerization in this drop with the synthetic resin particle,

Wherein, described composition is a kind of composition that is selected among composition A, composition B or the composition C:

Composition A: the composition that comprises vinyl monomer, lactone, is used for the vinyl monomer polymerization catalyst of this vinyl monomer of polymerization and is used for the lactone polymerization catalyst of this lactone of polymerization;

Composition B: comprise vibrin, lactone and be used for the composition of the lactone polymerization catalyst of this lactone of polymerization;

Composition C: comprise vinyl monomer, by the ring-type ketene acetal compound of following general formula (1) expression and the composition of radical polymerization initiator, described general formula (1) is:

General formula (1)

In general formula (1), R represents optionally to comprise the chain or the ring-type aliphatic divalent group of ehter bond, and this aliphatic group optionally contains substituting group).

2. the method for claim 1, wherein described composition is composition A, and described polymerization procedure comprises at least: make in described in the drop of composition A polyisocyanate polyaddition with the lactone polymerization procedure of synthesizing polyester resin; And make vinyl monomer polymerization in this drop with the resinoid vinyl monomer polymerization procedure of synthesis of vinyl.

3. method as claimed in claim 2, wherein, described vinyl monomer is an esters of unsaturated carboxylic acids.

4. the method for claim 1, wherein described composition is composition A or composition B, and described lactone polymerization catalyst is as the lewis acid catalyst that constitutes element with rare earth element.

5. method as claimed in claim 4 wherein, is the rare earth metal fluoroform sulphonate of being represented by following general formula with rare earth element as the described lewis acid catalyst that constitutes element:

X(OSO ₂CF ₃) ₃

Wherein, X represents rare earth element.

6. the method for claim 1, wherein described composition is composition A or composition B, and described lactone polymerization catalyst is an enzyme catalyst.

7. the method for claim 1, wherein described composition is composition B, and described polymerization procedure makes interior polyisocyanate polyaddition in the drop of composition B to form vibrin.

8. the method for claim 1, wherein described composition is composition C, and described polymerization procedure makes vinyl monomer in the drop of composition C and ring-type ketene acetal compound polymerization with the synthesis of vinyl analog copolymer.

9. resin particle, this resin particle is by the method production of claim 1.

10. resin particle as claimed in claim 9, wherein, the mean grain size of this resin particle is to be less than or equal to 1 μ m.

11. the production method of a developing toner for electrostatic latent images, this method comprises:

The aggegation step, this aggegation step will wherein have been disperseed the resin particle dispersion liquid of the described resin particle of claim 9, wherein disperseed the colorant dispersion of colorant and wherein disperseed the detackifier dispersion liquid of detackifier to mix, the agglutination particle that comprises resin particle, colorant and detackifier with formation, thereby obtain the agglutination particle dispersion liquid, and

Fusion steps, that is, the step of described agglutination particle is merged in heating.

12. method as claimed in claim 11, wherein, after described aggegation step and before described fusion steps, described method further comprises following attachment steps: the particle dispersion liquid that has wherein disperseed particulate is added in the described agglutination particle dispersion liquid, they are mixed, and make described particulate be attached to described agglutination particle, adhere to particle thereby form.

13. method as claimed in claim 12, wherein, described interpolation and mixing are divided into repeatedly to be carried out step by step.

14. method as claimed in claim 11, wherein, described method further comprises cooling step after this fusion steps.

15. method as claimed in claim 11, wherein, described detackifier comprises at least a material in the following material: carbon number is that 12～30 higher alcohol and carbon number are 12～30 higher fatty acid.

16. a developing toner for electrostatic latent images, this toner is by the described method preparation of claim 11.

17. an electrostatic latent image developer, this developer comprise the described developing toner for electrostatic latent images of claim 16 at least.

18. a formation method, this method comprises:

Sub-image forms step,, forms the step of electrostatic latent image on sub-image supporting body surface that is;

Development step promptly, is used the developer that is bearing in the developer supporting mass, makes the latent electrostatic image developing that forms on described sub-image supporting body surface, to form the step of toner image;

Transfer step promptly, is transferred to the lip-deep step of transfer printing acceptor with the toner image that forms on the described sub-image supporting body surface; And

The photographic fixing step, that is, to being transferred to the step that the lip-deep toner image of described transfer printing acceptor carries out hot photographic fixing, wherein, described developer is the described electrostatic latent image developer of claim 17.

19. formation method as claimed in claim 18, wherein, described method further comprises after described transfer step: cleaning that the lip-deep remaining toner of described sub-image supporting body is reclaimed and the circulation step that the remaining toner that reclaims in the described cleaning is transported to the developer supporting mass.