DE60031580T2 - TONER FOR THE DEVELOPMENT OF ELECTROSTATICALLY LOADED IMAGES - Google Patents

Description

TECHNICAL AREA

The The present invention relates to a toner for developing a Electrostatically charged image of the pressure-fixation type and hot roll fixation type (hereinafter also referred to as "print heating type" or "printer heating system").

Especially The present invention relates to a practically applicable developer toner type of magnetic one-component dry type, non-magnetic One-component dry type, two-component dry type, dried liquid type or liquid type, the on a film or other substrates to be grouped by means Pressure can be fixed, sufficient fixation properties (the hereinafter referred to as "fixability"), sufficient properties regarding Consumed toner and has sufficient transparency, too in the case of hot roll fixing a pressure fixation at a low temperature of less than 100 ° C too enable, sharp images and excellent fast fixability and preservative stability which ensures a sufficient temperature range in which no offset phenomena will occur (the hereinafter referred to as "offset-free temperature range").

The The present invention also relates to the above toner, which in copiers, printers, fax machines, color copiers, color laser copiers and printers and fast electrophotographic printers are widely used Can be found.

STATE OF THE ART

in the Course of the recent rapid dissemination of office automation have at electrostatically charged images developing copiers and printers demands for higher resistance across from mechanical shock for the fast printing and high-quality images, in other words sharpness, Fixability at low temperatures and excellent light transmission, for color toner increased.

One such a need for fast copying and high quality images requires the guarantee of required and sufficient toner particle strength and a Wide offset-free temperature range, practical applications at low temperatures. Further, it is expected to realize the oil-free type copying methods, the no oil supply to the fixing roller and therefore no problem of contamination bring the substrates to be copied with it.

Under these circumstances was in its own JP-A-2000-66438 found and described that a toner for developing an electrostatic charged image of hot roll fixing type, the polyolefin resin having a cyclic structure as a binder resin and a suitable combination of fatty acid amide wax, oxidized polyethylene wax, Polyethylene wax and acid modified Propylene wax to confer various functions, the fulfill the above requirements can.

this However, toners are in terms of copy speed and the Fixing temperature in hot roller fixing applications Set limits. Meanwhile, in the market recently higher copy speeds and a sufficient attitude to demands for fixation at low temperature due to the compulsion to save Electricity has been requested.

at the formation of full-color images with the addition and mixing of three or four colors (G: yellow, M: magenta, C: cyan, B: blue) after the electrophotographic process is used for transfer to the copying Substrate requires a toner particle, the possible spherical is and a smooth surface having.

With the conventional one mechanical grinding and air impact milling using a However, high velocity air can hardly be spherical toner with smooth surfaces produce.

In hot roller fixing systems which are currently and generally used for fixing a full color image on paper, OHP film or other substrates to be grouped, an excessive amount of heat must be supplied for fixing a three- or four-color toner, and silicone oil or the like should be supplied to the fixing roller to transfer from the toner to the hot roller (so-called "offset phenomenon") to prevent.

To the diverse ones performance characteristics that requires a toner will belong Charge characteristics, fixability, abrasion resistance, transportability, preservation stability (The tendency of toner particles not to agglomerate with each other and even after a long time no lumps to form), etc. A through Dry mixing in a conventional However, compounding obtained toner can not all of the satisfying such requirements satisfactorily.

to fulfillment Each of the above requirements must have a toner with different contradictory features to be provided. To the solution Such problems are microcapsule toners having a structure in which a core material particle called "core" (Core substance particles) with a shell material (shell substance) called "shell" encapsulated, has been proposed. For example, as a core material a binder resin which has good fixability, but due to poor preservative stability easily leads to offset phenomenon, and as a shell material a coating resin with good preservative stability and offset-free Behavior, thereby meeting the conflicting requirements.

It Ideas have been proposed which are such microcapsule toners with separate functions. For example, in the JP-A-9-292735 discloses a film fixing heating type image forming apparatus described in the one by a suspension polymerization prepared Mikrokapseltoner is used. In JP-A-59-53856 and JP-A-59-61842 are examples produced by the same method described.

In addition, JP-B-56-13945 proposes a manufacturing method based on the spray-drying method; in JP-B-8-16793, a production method based on the water-drop phase separation method is proposed, and JP-A-3-56970 proposes a production method in which the shell layer is produced by an in-situ polymerization method and microparticles are produced by using a high-pressure homogenizer receives. In the US 5,324,616 The preparation of encapsulated toner compositions with methastene polymerization of cyclic olefins is described. Furthermore, encapsulated toner resins having a cyclized rubber-containing outer layer are described (US Pat. US 4,265,994 ). In the EP 0 978 766 A1 Non-encapsulated toner particles comprising polyolefin resins having cyclic structures are described.

Besides are also interfacial polymerization processes, coacervation, dry capsule, etc. have been introduced.

at However, these techniques of the prior art, except in the Spray drying method water used as a medium, which makes the drying process difficult. Therefore were they are unsuitable for the production of microcapsule toners on an industrial scale.

also was it in the spray drying process difficult, uniform particulate materials with the desired average particle diameter, typically 10 μm or less, to obtain.

PRESENTATION OF THE INVENTION

task The present invention provides a microcapsule toner according to claim 1, which is in a low-temperature heat-fixing system or in a pressure fixation system that enables fast copying and in a Heißwalzenfixiersystem adequate can be used, the problems of microcapsules of the state the technique triggers and has excellent preservation stability and offset phenomenon prevention.

The The present invention is based on the finding that the problems described above by using two types of olefin copolymers, respectively have a cyclic structure, but with respect to glass transition temperature and number average molecular weight, with one as a binder resin for the core and the other as a resin in the shell for coating the Kerns (coating resin) of a Mikrokapseltonerteilchens used will be solved can be.

More specifically, the present invention relates to a toner for developing an electrostatic gela image comprising a microcapsule toner particle of a core and a shell, the core comprising a colorant and a binder resin containing an olefin copolymer having a cyclic structure, a glass transition and the shell comprises a coating resin for the core, wherein the coating resin is an olefin copolymer having a cyclic structure, a glass transition temperature, and a temperature range of from -20 ° C to less than 60 ° C and a number average molecular weight in the range of 100 to 20,000 in the range of 60 ° C to less than 180 ° C and a number average molecular weight in the range of 1000 to 100,000.

The The present invention will now be described in more detail.

[A] materials that the Form core of the microcapsule toner particle

Of the Core covered as essential components, a binder resin and a colorant. He contains optionally additives, such as a function-conferring agent Charge control agents and other additives.

(1) binder resins

The listed below Binder resins for heat fixing and for pressure fixation or olefin copolymers of cyclic structure are used as a binder resin, which together with a colorant forms the core of the microcapsule toner. These resins have a lower one Melting point or softening point and a higher fixability than the listed below Coating resins that form the shell.

Examples for binder resins for the heat setting are styrenic polymers such as polystyrene, substituted polystyrene, etc .; Styrene copolymers, such as styrene-acrylic acid ester copolymer, styrene-methacrylic ester copolymer, Styrene-acrylonitrile copolymer, etc .; Acrylic acid resins, such as poly (meth) acrylic acid resin, Poly (meth) acrylsäureesterharz etc.; Polyester resins and epoxy resins. These resins can be left alone or used as a combination of two or more resins.

Examples for binder resins for the Pressure fixation are plant, animal, mineral and petroleum waxes, such as Carnauba wax, candelilla wax, lanolin, beeswax, montan wax, Paraffin wax, microcrystalline wax, etc .; higher fatty acid derivatives, such as polyvalent esters Alcohols, e.g. With stearic acid, Palmitic acid, oleic acid, lauric acid, etc., and metal salts of higher fatty acids, z. Calcium stearate, zinc stearate, lead stearate, magnesium stearate etc.; Polyolefin waxes, such as polyethylene wax, polypropylene wax etc.; Olefin homopolymers and copolymers, such as ethylene (meth) acrylic acid copolymer, Ethylene- (meth) acrylate copolymer, Ethylene-vinyl acetate copolymer, Ionomer resin, etc .; Styrene resins, such as low molecular weight polystyrene, Styrene-butadiene copolymer, Styrene-acrylonitrile copolymer, etc .; Epoxy resins and polyester resins. These resins can for themselves used alone or as a combination of two or more resins become.

The Use of a low temperature fixation system to enable fast copying and maintaining a sharp, high quality Picture requires a reliable Fixability for a pressure-heat fixing system (heating-pressure fixing system) suitable is. Therefore, those suitable for fixing procedures should Types and compositions of the binder resins are selected.

to Providing high offset freedom by broadening the offset-free temperature range in which the offset phenomenon is not occurs, it is preferable to use the one described below Olefin copolymer having a cyclic structure (hereinafter cycloolefin copolymer, also abbreviated as COC) as the binder resin of the core material instead of the above-mentioned heating fixation and pressure fixation.

to Providing the core with better fixability than the shell used cycloolefin copolymer, the olefin copolymer has a Glass transition temperature (Tg) in the range of -20 ° C to less as 60 ° C and a number average molecular weight (Mn) in the range of 100 to have 20,000. A Tg of less than -20 ° C will cause high viscoelasticity and make the printed image sticky, whereas Tg is 60 ° C or more because of too big Stiffness provides insufficient fixation. It also puts a Mn of less than 100 does not provide sufficient fixation, whereas an Mn of more than 20,000 makes a resin in a solvent poorly soluble so that it does for the practical use is inappropriate.

Here, the glass transition temperature (Tg) refers to the temperature at the mid-point of the deflection, which shows the transition heat as measured by differential scanning calorimetry (DSC). The number average molecular weight (Mn) is the value measured by gel permeation chromatography (GPC) and is based on calibration with polyethylene or polystyrene standards. More precisely, the number average mole is cular weight of the value obtained by measurement under the following conditions. [Conditions] Used column: JORDI PILLAR 500 × 10 LINEAR Mobile phase: 1,2-dichlorobenzene (135 ° C), flow rate: 0.5 ml / min Detector: differential refractometer

in the The following describes the cyclodefin polymer (COC) in detail.

at the cycloolefin copolymer (COC) is a copolymer from a lower alkene of 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as an α-olefin (or wider noncyclic Olefins), e.g. For example, ethylene, propylene, butylene, etc., and a cyclic and / or polycyclic compound (cyclic olefin (cycloolefin)) having 3 to 17 carbon atoms and preferably 5 to 12 carbon atoms with at least one double bond, such as norbornene, tetracyclododecene, Dicyclopentadiene, cyclohexene, etc., preferably norbornene or tetracyclododecene. Such a copolymer is colorless and transparent and has a high light transmission.

The Production of the COC is carried out by polymerization under Use of a metallocene catalyst system, a Ziegler catalyst system, a catalyst for the metathesis polymerization, d. H. a catalyst for the opening of a Double bond and a ring-opening polymerization reaction.

Examples for the Synthesis of olefin copolymers having the above structure are disclosed in U.S. Pat JP-A-5-339327, JP-A-5-9223, JP-A-6-271628, EP-A-203799, EP-A-407870, EP-A-283164, EP-A-156464 and JP-A-7-253315.

According to the above References may be the cycloolefin copolymer by copolymerization one or more kinds of the above monomers, optionally with one kind of the above non-monomer, in the presence of aluminoxane or other cocatalysts and at least one type of metallocene catalyst, the For example, zirconium or hafnium, at a temperature of -78 to 150 ° C and preferably 20 to 80 ° C and be prepared at a pressure of 0.01 to 64 bar. Other useful polymers are described in EP-A-317262. In consideration also comes a hydrogenated polymer or a copolymer of styrene and dicyclopentadiene.

One Metallocene catalyst becomes soluble upon dissolution in an inert hydrocarbon, such as an aliphatic or aromatic hydrocarbon activated. For example, a metallocene catalyst becomes preactivation dissolved in toluene, whereby in the solvent carried out a reaction becomes.

The important features of the cycloolefin polymer are a softening point, a melting point, viscosity, dielectric properties, offset-free temperature range and Transparency. these can by effectively choosing the monomer / comonomer ratio, i. H. of the relationship the monomer units in the copolymer, the molecular weight, the molecular weight distribution, of a hybrid polymer, mixing and additives.

The molar ratio the noncyclic olefin and the cycloolefin used for the reaction can be entered, depending on the desired cycloolefin copolymer be varied in a wide range and is preferably on 50: 1 to 1:50 and more preferably 20: 1 to 1:20 set.

So becomes for example when using the two components ethylene as a non-cyclic olefin and norbornene as a cyclic olefin for the reaction for the preparation of a cycloolefin copolymer, the glass transition temperature (Tg) of the reaction product is strongly influenced by the ratio of these components. at In general, Tg also increases in norbornene content to. For example, a composition with a norbornene content of 15 mol% or less (ethylene content of 85 mol% or more) Copolymer with a Tg of -20 ° C to 60 ° C. In contrast, a composition with a norbornene content of 15 mol% or more provide a copolymer having a Tg of 60 ° C to 180 ° C. The physical properties, such as the number average molecular weight, are set according to literature methods.

The in the present invention used olefin copolymer with cyclic Structure is as follows together.

The Binder resin for the core preferably consists of an unmodified cycloolefin polymer and an acid modified Cycloolefin polymer in a weight ratio of 95: 5 to 5:95.

The Unmodified cycloolefin polymer has a number average molecular weight (Mn, measured as a value based on polyethylene standards by means of GPC, the same applies hereinafter) from 100 to 20,000 and preferably 1000 to 10,000, a weight average molecular weight (Mw) of 200 to 40,000 and preferably 6000 to 30,000 and a glass transition temperature (Tg) from -20 ° C to less as 60 ° C and preferably 40 ° C up to 59 ° C.

meanwhile has the acid modified Cycloolefin polymer has a number average molecular weight (Mn) of 100 to 20,000 and preferably 1,000 to 10,000, a weight average Molecular weight (Mw) of 300 to 80,000 and preferably 3,000 to 40000 and a glass transition temperature (Tg) from -20 ° C to less than 60 ° C and preferably 40 ° C up to 59 ° C.

to warranty the required fixability and broadening the offset-free Temperature range for the practical use includes the above cycloolefin copolymer is preferably a low molecular weight Polymer or a low molecular weight polymer fraction (A) with lower viscosity and a high molecular weight polymer or a high molecular weight polymer fraction (B) high viscosity, the physical properties of which will be described below.

in the individual, the inventive olefin copolymer a mixture of polymer (A) and polymer (B) or a single Peak in a molecular weight distribution with a polymer fraction having a number average molecular weight of less than 7500 and a polymer fraction having a number average molecular weight of 7500 or more, or two or more peaks in one Have molecular weight distribution in which the at least one Peak corresponding polymer fraction a number average molecular weight less than 7500 and corresponding to the other peaks Polymer fraction has a number average molecular weight of 7500 or has more.

The The above composition of the olefin copolymer serves to broaden the offset-free temperature range on both the high-temperature side as well as on the low temperature side, causing the toner fixability with fast copying as well as the fixing properties at low Temperatures and low pressures is improved.

The polymer or polymer fraction (A) (hereinafter "component (A)") has a number-average molecular weight (measured on the basis of polyethylene standards by GPC (gel permeation chromatography), hereinafter, is less than 7500, preferably 1000 to less than 7500 and more preferably 2000 to less than 7500;
a weight average molecular weight of less than 15,000, preferably 1,000 to less than 15,000, and more preferably 4,000 to less than 15,000;
an intrinsic viscosity (IV, the intrinsic viscosity at 135 ° C with uniform dissolution of 1.0 g of the polymer in 100 ml of decalin) of less than 0.25 dl / g; and
a glass transition temperature (Tg) of preferably less than 70 ° C.

The polymer or polymer fraction (B) (hereinafter "component (B)")
a number average molecular weight of 7500 or more, and preferably 7500 to 50,000;
a weight average molecular weight of 15,000 or more, and preferably 15,000 to 500,000 and
an intrinsic viscosity (IV) of 0.25 dl / g or more.

Further amounts the content of component (B) to less than 50 wt .-% and preferably 5 to 35 wt .-%, based on the total binder resin.

The Component (B) provides a toner particle having the intrinsic viscosity for improvement the offset-preventing effect and adhesion to paper, foil or ready for other substrates to be copied. At a content of component (B) of 50% by weight or more, however, the uniformity deteriorates Kneading dramatically, which affects the performance of the toner. In other words, it is difficult to get a high quality picture or a sharp image with high fixation strength and outstanding heat response to form, or the properties of mechanical grinding bad, resulting in the production of a toner with the required particle diameter makes difficult.

Incidentally, the polymer or polymer fraction used herein refers to Po lymerfraktionen the cycloolefin copolymer; when the olefin polymer consists of a mixture of different components of different number average molecular weight, etc., the polymer or polymer fraction refers to each of the polymer components before mixing, while the polymer or polymer fraction refers to that by separation of the final synthesis product by GPC or relates to polymer fractions obtained by other suitable means. When the polymer fraction is monodisperse or approximately monodisperse, a number average molecular weight (Mn) of 7500 corresponds approximately to a weight average molecular weight (Mw) of 15,000.

While the low-viscosity component (A) of the olefin copolymer for broadening the offset-free temperature range on the low-temperature side contributes wears the high-viscosity component (B) for broadening the offset-free temperature range on the high temperature side at. Therefore, a high viscosity component (B) with a Mn of 20,000 or more desired to be offset-free Temperature range on the high-temperature side to broaden more efficient.

Of the Content of components (A) and (B) should be 0.5 part by weight or more and preferably 5 to 100 parts by weight, based in each case on the total amount of the binder resin defined as 100 parts by weight is, amount. Less than 0.5 part by weight of each of the two components will not provide a wide offset-free temperature range, which is practical Use is suitable to deliver.

The high-viscosity (high molecular weight) and low-viscosity (low molecular weight) Olefin copolymers with cyclic structure have the number average Molecular weights (Mn), weight average molecular weights (Mw) and intrinsic viscosity (I.V.) according to the above Data and thus a specified by Mw / Mn degree of dispersion of Molecular weight distribution of only 1-2.5, are monodisperse or nearly monodisperse. this makes possible the production of a toner with high heat response and high fixation strength, what the fixation of toner at low temperatures and low To press allows. This also contributes for preservation stability of the toner, the properties related to spent toner, the Uniformity of charge distribution and electrical stability constant charge / discharge efficiency at. In particular, that is low-viscosity polymer or the low-viscosity polymer fraction monodisperse or largely monodisperse, since the toner is then excellent so-called heat response, like instant melting and solidification, etc.

The Olefin copolymer is also colorless, transparent and very translucent. Therefore For example, the olefin polymer can be sufficiently applied to color toners. For example, it was confirmed that too upon addition of the azo pigment "Permanent Ruby F6B "(made from Clariant Co.) followed by sufficient kneading and subsequent preparation of fabrics on a press machine excellent transparency is obtained. In addition, measurements have after The DSC method (differential calorimetry method) showed that the olefin copolymer an extremely low heat of fusion having. Thus, a considerable Reduction of for the toner fixation consumed consumed energy.

In addition, can one by introduction of carboxyl groups in the olefin copolymer compatibility improve with other resins and the dispersing properties of Improve pigment in the toner. The introduction of carboxyl groups allows one Improve the adhesion of toner to paper, foil or other Copy medium and the fixability.

to introduction of carboxyl groups is advantageously used a two-step Reaction process, in which first the olefin copolymer with produces cyclic structure and then introduces carboxyl groups.

to introduction of carboxyl groups at least two procedures are given.

at a method is a methyl group or other alkyl group on End of the copolymer by the process of air oxidation in the Melt oxidized and converted into a carboxyl group. In the case of one using a metallocene catalyst prepared olefin polymer However, it is difficult to many carboxyl groups by this method introduce, because such a polymer has only a few branches.

at Another method uses t-butanol peroxide or a other peroxide as initiator for the graft polymerization of maleic anhydride, acrylic acid or methacrylic acid to the olefin polymer having a cyclic structure to obtain a graft ratio from 1 to 5 wt .-%, preferably 3 to 5 wt .-%, based on the Weight of the olefin polymer.

One graft less than 1% by weight is to achieve the improvement of Compatibility and such inadequate. On the other hand, a graft ratio of more than 5 wt% of the intermolecular crosslinking in the olefin polymer and thus increases the molecular weight. As a result, the kneading and milling properties for the practical use unsuitable. Furthermore, a serious occurs yellowing and loss of transparency. The polymer is thus for one Color toner, which requires colorlessness and transparency, unsuitable.

On the same way can compatibility with other resins and the dispersion of the pigments in the toner by introducing a Hydroxyl group or an amino group according to a known method be improved.

In addition, can a networked structure to improve toner fixation into the olefin polymer.

One Procedure for introduction a crosslinked structure is the terpolymerization of the non-cyclic olefin and the cycloolefin with cyclopentadiene, cyclohexadiene, norbornadiene, Tetracyclododecadiene, butadiene or other diene monomer the synthesis of the above-described olefin polymer.

in the As a result of this process, the olefin copolymer also has no crosslinking agent showing an activity End group on. A known chemical reaction, such as oxidation or Epoxidation, or the addition of a crosslinker to form a networked structure leads to the functioning of the olefin polymer.

at another method involves adding the cyclic olefin polymer Structure and introduced therein Carboxyl groups with a metal such as zinc, copper or calcium, and then mix and melt the mixture with a snail for dispersing the metal in the form of fine particles in the Olefin polymer, giving an ionomer of crosslinked structure. In terms of For example, a technology itself becomes such an ionomer in US-4,693,941 a terpolymer of ethylene with carboxyl groups disclosed in an attempt to achieve toughness after partial or complete Neutralization takes the form of a salt of a divalent metal can accept.

In JP-A-6-500348 describes a polyester resin molded body which is one for the same Purpose to produce tes ionomer of an unsaturated carboxylic acid, wherein approximately 20 to 80% of the carboxylic acid groups neutralized with zinc, cobalt, nickel, aluminum or copper (II) are.

One Cycloolefin polymer containing an acid-modified Olefin polymer having a cyclic structure with introduced carboxyl group in one Amount of 5 to 95% by weight may be added as the core material be used. This is an effective means of ensuring the fixability and the offset-free temperature range.

(2) colorants

When Colorants can Carbon black, diazo yellow, Phthalocyanine blue, quinacridone, carmine 6B, monoazorot, perylene or others for conventional Monochrome or color copier toner used colorants in the core material be incorporated.

(3) End of function medium

When function-providing means for broadening the offset-free Temperature range and to improve the offset freedom can be different Types of waxes are used. As a function-conferring agent Can be at least one type of wax that is under polar waxing, like Amide wax, carnauba wax, higher fatty acids and their esters, metal soaps higher fatty acids, partially saponified higher Fettsäureestern and higher Fatty alcohols, and nonpolar waxes, such as polyolefin waxes and paraffin wax, selected is to be used.

From the various waxes are fatty acid amide waxes, oxidized polyethylene waxes and acid modified Polypropylene waxes from the standpoint of achieving a broad offset-free Temperature range preferred.

For widening the above-described offset-free temperature range of the toner and improving the performance of the toner, the wax is preferably used as described below Fashion used.

It namely, will preferably two or more types of waxes with different Melting points (the peak temperature at differential calorimetric Measurements (DSC measurements)) in the range of 80-140 ° C in combination. At a melting point of less than 80 ° C occurs easily blocking due of low-melting substances. As a feature-giving Means at the softening point of the binder resin Kneading temperature completely must melt the upper limit of the wax through the softening point (about 135 to 140 ° C) of the Olefin polymer having a cyclic structure which is the main component of the binder resin is limited and preferably 140 ° C.

in the individual can two or more types of waxes growing under the fatty acid amides listed below and hydrocarbon waxes are selected.

(i) waxes with polar groups

waxes with polar groups are u. a. various fatty acid amide waxes, for example, arachidic acid monoamide (Melting point: 110 ° C), Behensäuremonoamid (Melting point: 115 ° C), N, N'-dioleylsebacic acid amide (Melting point: 115 ° C), N, N'-dioleyladipic acid amide (Melting point: 119 ° C) and N, N'-distearylisophthalic acid amide (Melting point: 129 ° C); oxidized olefin waxes, for example oxidized polyethylene wax (Melting point: 116 ° C); acid-modified Polyolefin waxes, for example, acid-modified polypropylene wax (Melting point: 138 ° C); and carnauba wax (melting point: about 80 ° C).

(ii) nonpolar waxes (waxes without polar groups)

nonpolar Waxes are u. a. Olefin waxes which are hydrocarbon waxes For example, polyethylene wax (melting point: 130 ° C), polypropylene wax (Melting point: 120 to 150 ° C), Paraffin wax (melting point: about 60 to 80 ° C), Sazol wax (Solidification point: about 98 ° C) and microcrystalline Wax (melting point: 80 to 100 ° C).

When function providing agent for preventing the offset phenomenon can in combination with a wax mentioned above, a silicone oil with mold release properties used as long as it has the effect of the present invention not adversely affected.

(4) Charge control agent

In the core material can Nigrosine dyes, fatty acid modified Nigrosine dyes, metallized nigrosine dyes, metallized fatty acid-modified Nigrosine dyes, chromium complexes of 3,5-di-t-butyl-salicylic acid, quaternary ammonium salts, Triphenylmethane dyes, azo chromic complexes and other known charge control agents be incorporated.

(5) Other additives

Next the above Toner components can optionally, a flow agent, such as colloidal silica, into the core material (including fumed silica), alumina or titania, and a fatty acid metal salt, such as barium stearate, calcium stearate or barium laurate, comprehensive Lubricants are incorporated as long as they have the effect of the present Do not adversely affect the invention.

(6) Amount of work to be done components

The Quantities of the core material according to the invention similar components to be incorporated those in the case of the toner for electrostatically charged images developing copiers and printers and are listed in Table 1.

[B] Materials that the Form shell material of the microcapsule toner particles

The Shell material includes a coating resin as an essential component and optional Additives, such as a function-providing agent, a charge control agent or similar. The coating resins used in the shell are also fixable and thus have a similar effect to those listed above Kern used resins as binder resins.

(1) Coating resin

One A resin for fixing or an olefin polymer having a cyclic structure according to the following Description is used as a coating resin, which is the shell forms the microcapsule toner particles.

in the As compared with the binder resin of the core material, the coating resin has a higher melting point or softening point and thus a better preservation stability.

Examples for coating resins for the Fixation are homopolymers and copolymers of styrene, substituted Styrenes and derivatives thereof, (meth) acrylic acid, (meth) acrylic esters, Maleic anhydride, maleic anhydride esters and derivatives thereof, maleic anhydride amide, nitrogen-containing vinyl compounds such as vinylpyridine, N-vinylimidazole etc., vinyl monomers such as vinyl acetal, vinyl chloride, acrylonitrile, Vinyl acetate, etc .; Vinylidene monomers, such as vinylidene chloride, vinylidene fluoride etc., and olefin monomers such as ethylene, propylene, etc., polycondensates, such as polyesters, epoxy resins, polycarbonates, polyamides, polyurethanes, Polyureas, rosin, modified rosin, phenolic resins, Melamine resins, polyphenylene oxides and terpene resins, fatty hydrocarbon resins, Fatty cyclohydrocarbons and petroleum resins, and such Resin can for used alone or as a combination of two or more resins become.

to Prevention of the offset phenomenon, in which the toner is transferred to the heating roller, and to the other Improvement of preservative stability is called coating resin of the shell material, the olefin polymer described below used with cyclic structure.

There the preservation stability the toner sufficiently ensured is as long as the glass transition temperature (Tg) of the polymer used 60 ° C or more, the entire amount can be replaced by an acid-modified olefin polymer having a cyclic structure whose Tg is 60 ° C or more replaced become.

One such unmodified olefin polymer having a cyclic structure has a number average molecular weight (Mn) in the range of 1000 to 100,000 and preferably from 2,000 to 50,000, a weight average Molecular weight (Mw) in the range of 2000 to 200,000 and preferably 4000 to 100000 and a glass transition temperature (Tg) in the range of 60 ° C up to 180 ° C and preferably 60 ° C up to 80 ° C.

meanwhile has the above mentioned acid-modified Olefin polymer has a number average molecular weight (Mn) in the range from 1000 to 100000 and preferably 2000 to 50,000, a weight average Molecular weight (Mw) in the range of 3000 to 300,000 and preferably 6000 to 200000 and a glass transition temperature (Tg) in the range of 60 ° C up to 180 ° C and preferably 60 ° C up to 80 ° C.

If the glass transition temperature of the above-described olefin polymer is less than 60 ° C there are many problems with the preservative stability of the toner particles, and when the glass transition temperature is over 180 ° C the melting point increases, and fixability is generally poor. Besides that is at a number average molecular weight of the above-described Olefin polymer of less than 1000 does not have sufficient fixation strength available, whereas at a number average molecular weight of more than 100000 the required solubility in the solvent difficult to ensure is.

The modified substances, the cross-linked substances and the different ones Properties besides the glass transition temperature and the number average molecular weight of the above-described Cyclic structure olefin polymers are the same as those above olefin polymer having a cyclic structure used in the core material described so that their description is unnecessary.

(2) End of function medium

To broaden the offset-free temperature range and to further improve the offset-free nature of the toner particle surface, the same function-conferring agents (wax, silicone oil) may be used used in the core material described above may also be incorporated into the shell material. The preferred uses, etc. described above may also be applied to the function-imparting agents to be incorporated into the shell material.

(3) Charge Control Agent

In the shell material can the same charge control agents as in the core material described above be incorporated.

(4) External additives

The surface the shell material of the toner particles may, if necessary, with an external Be coated additive.

Examples for external Additives are superplasticizers, such as colloidal silica (including pyrogenic Silica), alumina or titania, etc., and a fatty acid metal salt, such as barium stearate, calcium stearate, barium laurate, etc., comprehensive Lubricant, and such an external additive can be on its own or used as a combination of two or more species. Preferably, these additives are hydrophobic.

The Use amount of external additive is 0.01 to 10 parts by weight and preferably 0.05 to 5 parts by weight based on 100 parts by weight Toner particles.

If coating the shell material with an external additive, to bring a solution containing the external additive the surface the particle or brings the external additive to other methods sticking to the surface of the particles.

(5) Amount of work to be done components

The Quantities of those listed above Components in the shell material are with the exception of the incorporated Colorant listed in Table 1 above.

[C] microcapsule toner particles

The Microcapsule toner particles have a capsule-like or so-called core-shell structure, in which the core material is coated with the shell material.

The mean particle size (diameter) of a whole particle preferably 3 to 10 μm, and the thickness of the outer shell {[(Outer diameter the capsule) - (diameter of the core material)] × 1/2} is preferably 0.1 to 0.5 μm.

• (a) Kernmaterial: Olefinpolymer mit cyclischer Struktur (–20°C s Tg < 60°C, 100 s Mn s 20000) Schalenmaterial: Beschichtungsharz zur Fixierung
• (b) Kernmaterial: Bindemittelharz zur Wärmefixierung und Bindemittelharz zur Druckfixierung Schalenmaterial: Olefinpolymer mit cyclischer Struktur (60°C s Tg s 180°C, 1000 s Mn s 100000)
• (c) Kernmaterial: Olefinpolymer mit cyclischer Struktur (–20°C s Tg < 60°C, 100 s Mn s 20000) Schalenmaterial: Olefinpolymer mit cyclischer Struktur (60°C s Tg s 180°C, 1000 s Mn s 100000)

In view of the following three resin combination possibilities for the core material and the shell material possibility (c) describes encapsulated toner particles according to the present invention.

• (a) Core material: Olefin polymer having cyclic structure (-20 ° C. s Tg <60 ° C., 100 s Mn s 20000) Shell material: Coating resin for fixation
• (b) Core material: Binder resin for heat fixing and binder resin for pressure fixing Shell material: Olefin polymer having a cyclic structure (60 ° C. s Tg s 180 ° C., 1000 s Mn s 100000)
• (c) Core material: Olefin polymer having a cyclic structure (-20 ° C. s Tg <60 ° C., 100 s Mn s 20000) Shell material: Olefin polymer having a cyclic structure (60 ° C. s Tg s 180 ° C., 1000 s Mn s 100000)

In Sequence of the incorporation of an olefin with cyclic structure in the shell material and / or the core material in combination with the various crystalline and non-crystalline resins that as examples of the above-described fixing resins [A] (1) and [B] (1) listed and can be relatively compatible with the olefin polymer, the Transparency, the low-temperature fixability, the resistance across from mechanical impact and other properties of the olefin polymer with cyclic structure, which in terms of performance of the toner are important to be exhibited.

With The possibility (c) in the olefin polymers of cyclic structure in both the shell material as well as being used in the core material become the above-mentioned properties in full measure Toner performance shown.

All Particularly preferred is a form of toner particles in which the the following olefin polymer having a cyclic structure, namely Ethylene-norbornene-Co polymer having a glass transition temperature (Tg) in the Range from 40 to 59 ° C, a number average molecular weight (Mn) in the range of 1000 to 10000 and a polydispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of 10 or less and a copolymerization molar ratio of Ethylene to norbornene from 85/15 to 95/5 as the binder resin of Core material is used and wherein the following olefin polymer with cyclic structure, namely an ethylene-norbornene copolymer, which is soluble in methyl ethyl ketone (MEK) is, a glass transition temperature (Tg) in the range of 60 to 80 ° C, a number average molecular weight (Mn) in the range of 2,000 to 50,000 and polydispersity (Mw / Mn) in the range of 4 to 10 and in which the copolymerization molar ratio of Ethylene to norbornene is 75/25 to 85/15, as the coating resin of Shell material is used.

The Microcapsule toner particles are preferably after the reprecipitation process produced. Specifically, this is the solvent reprecipitation process, where a solution the binder resin and the colorant in a good solvent in a solution the coating resin of the shell material in a bad solvent is dropped, with the shell material around the core material around fails.

microcapsular can also according to the phase separation method as described, for example, in JP-B-08-16793 and JP-B2-2631019 specified.

(1) Manufacturing process after the reprecipitation process (Lösungsmittelumfällungsverfahren)

To Add and release from 16 to 20% by weight of the olefin polymer having a cyclic structure, which constitutes the core material, and 1 to 2% by weight of a function imparting agent By means of from 76 to 80% by weight of solvent (mixed solvent from toluene and cyclohexane, etc.) at a temperature of 25 to 30 ° C 1 to 2% by weight of colorant using a ball mill, etc. dispersed, giving a solution (Solution A) results.

on the other hand is solved by from 1.8 to 2.2% by weight of the olefin polymer having a cyclic structure, which forms the shell material and 0.015 to 0.025 wt .-% of a Charge control agent in 98 wt .-% MEK or another solvent a solution (Solution B).

in the next Step becomes solution A from a nozzle with numerous openings with a diameter of 20 to 30 microns with rapid stirring in solution B dripped, which gives a precipitate, which then passes through a multi-stage filter (2 microns, 0.5 microns and 0.2 microns) out and by the solvent is separated. In the last stage, by removing the residual solvent formed with a high-temperature vacuum dryer particles.

So are obtained microcapsule toner particles which are largely spherical, a mean diameter of 4 to 10 microns and a particle size distribution from 2 to 12 μm (corresponding to 3σ, where σ = Standard deviation) and in which the thickness of the shell material 0.2 to 0.5 μm is (based on weight measurements after the solvent extraction procedure).

Then externally hydrophobic silica is added as a developer.

(2) manufacturing process after the phase separation process

One Olefin polymer having a cyclic structure, an acid-modified olefin polymer with cyclic structure, a wax, a colorant and a charge control agent are kneaded in the melt. After microdispersion of hydrophilic Silica as a protective colloid with rapid stirring in hot Water is released by rapid cooling with a big one Amount of water solidifies. Then the silica with a basic dissolved and removed aqueous solution and the core material particles are washed by water / methanol and subsequent filtration.

Separately are an olefin polymer having a cyclic structure, a wax and a charge control agent in a ketone solvent, preferably MEK, solved, a predetermined amount of the above core material particles is with a homomixer is dispersed, a predetermined amount of acetic acid added, and then under freezing water with a predetermined Rate dropped to the shell material back on the surface of the To precipitate nuclear material particles.

After that comes with a mixed solution rinsed with water and methanol, filtered and dried to give microcapsule toner particles.

Then externally hydrophobic silica is added as a developer.

Out a comparison of the above-described two production methods it follows that the reprecipitation for the technical production is more appropriate than a cheap one All-purpose solvent used and the drying is due to the difference of the latent heat of the solvent and the water is carried out more easily and it is less mutual Agglomeration of the toner particles are.

BEST EMBODIMENT THE INVENTION

The The present invention will now be described by way of examples and comparative examples described in more detail, however, the effective scope of the present invention restrict in any way.

One-component dry toner and two-component dry toner were prepared as described below.

The Examples 1 to 4 are examples of the preparation of microcapsule toner after the repositioning process, and Example 5 is an example of the preparation of microcapsule toner after the phase separation process.

example 1

Preparation of solution A (nuclear material)

When Olefin polymer having a cyclic structure was 17 wt% "Topaz T-936 "from Ticona GmbH with a glass transition temperature (Tg) of 49 ° C and a number average molecular weight (Mn) of 2000, as acid-modified Olefin polymer having a cyclic structure was 1 wt% "Topaz AG-07 "from Ticona GmbH with a glass transition temperature (Tg) of 58 ° C and a number average molecular weight (Mn) of 3700, as a function giving agent, 0.5% by weight of "BNT22H" from Nippon Seika and 0.5% by weight "Ceridust 3715 "(trade name) used by Clariant, and these components were gradually to 80% by weight of a mixed solvent from toluene and cyclohexane (weight ratio: 50:50) at one temperature of 30 ° C and a stirring speed of 200 rpm and dissolved therein.

Then became the above solution with beads (stainless steel powder from Ashizawa, particle diameter: 500 μm) and 1 wt .-% of a black colorant ("Carbon Black MA-7 "from Mitsubishi Chemical) was added gradually and with a Stirring speed of 500 rpm, giving solution A revealed.

Preparation of solution B (shell material)

When Olefin polymer having a cyclic structure was 2 wt% "Topaz AG-09 "from Ticona with a glass transition temperature (Tg) of 67 ° C and a number average molecular weight (Mn) of 4600 which together with 0.02% by weight of a charge control agent ("Copy Charge NX "(trade name) by Clariant) in about 98 wt .-% of methyl ethyl ketone dissolved what solution was B revealed.

granulation

The solution described above A got out of a nozzle with numerous openings with a diameter of 30 microns with rapid stirring in solution B dropped, with particles formed.

What As far as the rate of addition is concerned, in the case of the particles be made in a boiler with a volume of 500 liters, 100 liters solution A gradually from 100 openings at a rate of 5 liters / min over a period of 20 minutes in 200 liters of solution B dripped, giving a Precipitation resulted.

The stirring rate of solution B was set to 2000 rpm, and after completion of the dropwise addition of solution A, stirring was continued for 10 minutes. Thereafter, the precipitate was passed through a multi-stage filter (2 .mu.m, 0.5 .mu.m and 0.2 .mu.m) and thereby separated from the solvent, whereupon the Residual solvent was removed by means of a high temperature vacuum dryer, giving microcapsule toner particles.

Of the average diameter of the obtained toner particles was about 6 μm, and all Particles were in a particle size classification from 2 to Distributed 12 microns. As a size separation coarse particles and very fine particles are not required This process proved to be excellent in terms of productivity.

scanning microscope Observations confirmed that the Particles largely spherical and the thickness of the shell material was as shown below weight measurements determined by the solvent separation method and was 0.2 to 0.5 μm.

Regarding the toner yield was 21.7 kg after drying (92% yield) based on 100 liters (about 85.6 kg, of which the core material 17.1 kg) solution A and 200 liters (approx 162 kg, of which the shell material polymer was 6.5 kg) solution B (total solids content 23.6 kg).

The Toner yield using the conventional Method of mechanical grinding and air-blast air flow method using a high velocity airflow was about 80% and approximately 75%, whereby ultramicrogels having a size of 1 μm or less are formed. It has thus been found that the Toner yield significantly improved by the method described above becomes.

Of the average particle diameter of the toner particles was with a particle size distribution measuring apparatus of the laser diffraction scattering type ("LA-700" by Horiba Seisakusho) certainly. The particle size distribution was also on the same device determined, which showed that particles with a particle diameter of 4 to 10 microns on a volume basis 95% and on Number base made up 75%.

For the measurement of the thickness of the shell material, 10 g of the toner particles were weighed and in 1 liter of methyl ethyl ketone, and after dissolution of the Shell material by heating to 50 ° C and stirring for 20 minutes was the solvent by hot filtration removed and the residual weight determined by the thickness of the shell material to calculate.

Example 2

microcapsular were obtained in analogy to Example 1 except that as the colorant the yellow colorant "Yellow HG "(trade name) used by Clariant.

Example 3

microcapsular were obtained in analogy to Example 1 except that as the colorant the magenta colorant "Pink E02 "(trade name) used by Clariant.

Example 4

microcapsular were obtained in analogy to Example 1 except that as the colorant the cyan colorant "Blue B02G "(trade name) used by Clariant.

Example 5

microcapsular were as described below by the phase separation method according to JP-B1-8-16793 and JP-B2-2631019 produced.

manufacturing of nuclear material particles

Ticona's 85% by weight "Topas T-936" was used as the olefin polymer having a cyclic structure, and 5% by weight of "Topas AG-07" from Ticona was used as the acid-modified olefin polymer having a cyclic structure; 2% by weight were used as function-conferring agents. a behenic acid amide wax ("BNT22H" (trade name) of Nippon Seika) and 2% by weight of a mixed powder of oxidized and unoxidized polyethylene wax ("Ceridust 3715" (tradename) of Clariant), and these components together with 5% by weight of a black colorant (Carbon Black MA-7 "from Mitsubishi Chemical) and 1 wt% of a charge control agent (" Copy Charge NX "(tradename) from Clariant) in the melt with a kneader (" Rheomix 600 "from Haake) 15 Kneaded at 120 ° C, after which the resulting mixture was transferred to a stainless steel container with a heater and kept at 130 ° C.

Separately Water was given to a homomixer (by Tokushu Kika) and at about 95 ° C heated and kept at this temperature. Then, 0.4% by weight of colloidal Silica ("HDK N-30 "from Wacker Chemistry) was added and stirred sufficiently dispersed.

The Rotational speed of the homomixer was set at 8500 rpm, and about 15 parts by weight (phr) of the melt mixture described above to the dispersing medium from hot Water, after which stirring was continued for about 15 minutes, with microparticles forming.

After that was the dispersion on previously prepared ice (the double the amount of dispersion) poured to make the microparticles fast cool and solidify. Then one of the lots became neutralization of colloidal silica equivalent Amount of sodium hydroxide is added to the dispersion, after which Solve the colloidal silica with a propeller mixer 24 hours stirred at room temperature was and the basic solution and the solids were separated by means of a centrifugal filter.

Then became the slurry with a water / methanol solution (50/50 % By weight), each filtered twice and with a set at 40 ° C hot air dryer dried, which gave the core material particles.

Of the volume average particle diameter of these particles was about 8 μm (measured with "LA-700" by Horiba Seisakusho).

manufacturing of shell material solution

A Shell material solution for encapsulation was used with 95 parts by weight of the above-mentioned "Topaz AG-09 "as an olefin polymer with cyclic structure, 2 parts by weight of a behenic acid amide wax ("BNT22H" (trade name) of Nippon Seika) and 2 parts by weight of a mixed powder of oxidized and non-oxidized polyethylene wax ("Ceridust 3715" (trade name) of Clariant) as function-conferring means, 1 part by weight of one Charge Control Agent ("Copy Charge NX "(trade name) from Clariant) and 2400 parts by weight of methyl ethyl ketone.

A Double-jacket reaction tank with a volume of 20 liters was equipped with a homomixer, after which 7.6 kg of the above-described solution is added to the reaction tank and after cooling to -25 ° C while stirring with 120 g of acetic acid were added, after which it was stirred for 5 minutes.

Then 2.0 kg of the above-described core material particles were in the Added reaction tank and after sufficient dispersion with a Homomixer was cold water with a temperature of 0 to 5 ° C with a Dropping rate of 10 g / minute added dropwise. The dripping speed was gradually increased to 100 g / minute in the last stage, and after all were about 3 kg of water added. The one for this needed Time was about 2 hours.

After that became the encapsulation solution separated by means of a centrifugal filter, and the filtered off Capsule particles were washed twice with water / methanol (50/50 wt%) rinsed, filtered off and at 40 ° C dried.

Of the volume average particle diameter of the capsule particles was about 8.5 μm and was thus clearly bigger than the diameter of the core material particles, the diameter was due Enlarged by encapsulation.

By Weight measurements according to the solvent separation method described above a largely equal shell material thickness (0.2 to 0.3 microns) is calculated.

To The microcapsule toner thus obtained was externally 0.5 parts by weight hydrophobic colloidal silica as a developer.

Comparative Example 1

It became after the Luftprallmahlverfahren (Strahlmahlverfahren) manufactured commercially available Toner and more specifically a toner used for the copier "FT-5520" by Ricoh, and with the above mentioned Copiers became performance evaluations carried out.

Comparative Example 2

It was prepared by the method of mechanical grinding commercially available Toner and more specifically the toner for the printer "Magicolor 2CX "(trade name) used by QMS, and with the copier "FT-5520" from Rico were performance evaluations carried out.

With the copier "FT-5520" were used the microcapsule toner obtained in Examples 1 to 4 described above and the commercially available Toner according to the comparative examples 1 and 2 copies made. The results are shown in Table 2.

(a) protective effect against spent toner

Under Use of the toner samples of the respective examples and comparative examples Copy tests were performed on high quality paper. It Copies were made until the toner components on the developer roller sticking and the photoconductor reached the allowable limit, and there were comparisons with the number of sheets of paper that had been copied to this point.

(b) transfer properties

The Transmission efficiency from the photoconductor on high quality paper, which is the The substrate to be copied was based on that after copying on 10000 leaves recovered Amount of toner determined.

(c) fixability

Under Use of each toner were made on high quality paper pictures, an unprinted paper of the same quality was placed over the printed paper and the printed image was rubbed with a friction tester to force it to transfer to the unprinted paper.

The Fixation rate for The imaging was set to 150 mm / second and the fixing temperature was at 150 ° C set.

When Conditions for The rub test was 20 double strokes under a load of 2 pounds (about 907 g). To the rubbing was the initial image density before rubbing (A), the Density of transmission on unprinted paper (B) and the density of a non-image area of the Paper (C) measured with a Macbeth reflection densitometer, after which the transmission rate using the formula [(B-C) / A × 100 (%)] was determined. Lower fixation temperature and lower fixation pressure, at the or a transfer rate of 60% or more was measured and compared.

(d) image sharpness

The definition each toner was compared, and the gradation, resolution of thin lines and OHP light transmission were as follows certainly.

gradation

The Gradation was reduced to gray scale steps from 0 to 16 Use of image samples evaluated by Dataquest Co.

Resolution of thin lines

The Resolution for thin lines became thinner with a pattern Lines from 0 to 600 dpi using image samples from Dataquest evaluated.

OHP transparency

On an OHP film for Fuji Xerox PPC made a picture showing the light transmission in an image area (A) and a non-image area (B) were measured and the permeability as A / B × 100 (%) was specified.

(e) preservation stability

To Preservation of the toner produced by each procedure over a Period of 8 hours at 60 ° C and 50% RH (relative humidity), the toner became over period passed through a 100-mesh sieve and dividing by dividing the sieve residue the percentage value obtained by the amount of sample used. By agglomeration of toner particles during preservation is this value increases. The agglomeration is mainly by the substances having a lower melting point of 50 ° C or less caused contained in the toner composition. The Symbol "O" gives a sieve residue 0.5% or less and "X" represents a residue of more than 0.5%.

commercial applicability

at the toner according to the invention It is the development of an electrostatic charged image a microcapsule toner particle of a core and a shell. Further, an olefin polymer having a cyclic structure which is a relatively low glass transition temperature and having a relatively low average molecular weight, as Binder resin used in the core material and / or an olefin polymer with a cyclic structure that has a relatively high glass transition temperature and has a relatively high number average molecular weight, used as a coating resin in the shell material.

consequently is the toner on photocopiers of pressure-fixing type and has good preservative stability high-quality sharp pictures and has an excellent protective effect against spent toner, excellent transferability, excellent Fixability and excellent offset freedom.

Of further comprises the toner according to the invention also excellent in low temperature heating type copying machines sufficient fixability.

In addition, the Use of the toner according to the invention also with devices of the heat roller fixing type the easy achievement of a significant reduction in heat energy and allows thus contributions to the energy savings of photocopiers.

Besides that is because of the incorporation of a function-imparting agent for mold release, like a silicone oil or wax, in the shell material does not supply oil to the hot roll surface necessary.

Claims (7)

Toner for developing an electrostatically charged Image showing a microcapsule toner particle consisting of a core and a Shell covers, the core being a colorant and a binder resin containing an olefin copolymer with cyclic structure, a glass transition temperature in the range from -20 ° C to less as 60 ° C and a number average molecular weight in the range of 100 to 20,000 contains comprises and the shell comprises a coating resin for the core, wherein the coating resin is an olefin copolymer having a cyclic structure, a glass transition temperature in the range of 60 ° C to less than 180 ° C and a number average molecular weight in the range of 1000 to Contains 100,000. Toner for developing an electrostatically charged Image according to claim 1, wherein the binder resin for the core an unmodified cocoloolefin polymer and an acid modified Cycloolefin polymer having a carboxyl group in a weight ratio of 95: 5 to 5:95 contains. Toner for developing an electrostatically charged Image according to claim 1, wherein the olefin copolymer is cyclic Structure, which forms the core material, by acrylic acid or maleic anhydride is modified. Toner for developing an electrostatically charged The image of claim 1, wherein the binder resin which is the core material forms, and / or the coating resin, which is the shell material forms, wax is incorporated. Toner for developing an electrostatically charged Image according to claim 4, wherein the wax comprises at least one wax the group consisting of fatty acid amide waxes and oxidized polyethylene waxes. Toner for developing an electrostatically charged An image according to claim 1, wherein silica micropowder is added externally or on the surface of the microcapsule toner particle is applied. Toner for developing an electrostatically charged Image according to one of the claims 1 to 6, wherein the microcapsule toner particles after a reprecipitation process is prepared, wherein a solution of the binder resin in a good solvent, in which a colorant is dispersed, in a solution of the coating resin in a bad solvent drips, thereby depositing the shell material around the core material becomes.