CN1408079A - Toner for electrostatically charged image development - Google Patents

Abstract

A toner for developing an electrostatically charged image, which is constituted with a microcapsule toner particle composed of a core and a shell, the core comprising a colorant and a binder resin containing an olefin copolymer having a cyclic structure, said olefin copolymer having a glass transition temperature ranging from -20 °C to less than 60 °C and a number average molecular weight ranging from 100 to 20,000, and the shell comprising a coating resin for the core, and/or a shell comprising a resin for coating the core containing an olefin copolymer having a cyclic structure, said olefin copolymer having a glass transition temperature ranging from 60 °C to 180 °C and a number average molecular weight ranging from 1,000 to 100,000.

Description

Toners for electrostatic image development

field of invention

The present invention relates to a toner for electrostatic image development in a pressure fixing type and a heat roller fixing type (hereinafter also referred to as "pressure heating type" or "pressure heating system").

More specifically, the present invention relates to a practically applicable dry one-component magnetic type, dry one-component non-magnetic type, dry two-component type, liquid dry type or liquid type toner-type developer, so The developer is pressure-fixable to a film or other substrate to be reproduced, has sufficient fixing performance (hereinafter referred to as "fixing power"), toner spent performance and transparency so that at a low temperature of less than 100°C Under pressure, it can be fixed under pressure even in the case of hot roller fixing, can form a clear image, and is excellent in high-speed fixing ability and storage stability, so that it can ensure an appropriate temperature range in which the offset (offset) phenomenon does not occur (hereinafter referred to as for the "no misalignment temperature range").

The present invention also relates to the above toner which can be widely used in copiers, printers, facsimile machines, color copiers, color laser copiers, color laser printers and high-speed electrophotographic printers.

Background technique

With the recent rapid spread of office automation, there is an increasing demand for higher mechanical shock resistance compatible with high-speed printing and a demand for high-grade images in copiers and printers for electrostatic image development, in other words, Clear, low-temperature fixing ability and excellent light transmittance are suitable for the toner.

These demands for high-speed reproduction and high-grade images require securing necessary and sufficient toner particle strength and a wide misalignment-free temperature range for practical use at low temperatures. In addition, it is also expected that an oil-free type of replication method can be realized, which does not require oil to be fed into the fuser roller, so that there is no problem of contamination of the substrate to be replicated.

Under these circumstances, the inventors have found and disclosed in JP-A-2000-66438 that a toner for developing a heat roller fixing type electrostatic image can meet the above-mentioned requirements, which includes a polyolefin resin having a ring structure As the binder resin, an appropriate combination of fatty acid amide wax, oxidized polyethylene wax, polyethylene wax, and acid-modified polypropylene wax is used in order to impart various functions.

However, this toner has limitations in transfer speed and fusing temperature in thermal roll fusing applications. Meanwhile, the market has recently demanded even higher reproduction speeds and adequate compliance with low-temperature fixing due to the demand for power saving.

In the formation of a solid-color image by adding and mixing three or four colors (Y: yellow, M: magenta, C: cyan, B: blue) by electrophotography, a method of transfer to a substrate to be reproduced Toner particles that are infinitely nearly spherical or truly spherical and have a smooth surface condition are desired.

However, conventional mechanical grinding methods and air impact grinding methods adapted to high-speed air flow are almost impossible to successfully prepare spherical toners with smooth surfaces.

In thermal roll fusing systems, which are currently and commonly used to fuse solid color images on paper, OHP film or other substrates to be reproduced, excess heat must be used to fix three or four toners, And silicone oil or the like is also used for the fixing roller to prevent transfer of toner to the heat roller (so-called "misalignment").

Performances required of toners are various, including charging performance, fixing ability, rubbing resistance, conveyability, storage stability (toner particles do not coalesce with each other and form lumps even after a long time) trend), etc. However, toners obtained by dry mixing in conventional compounding methods cannot satisfy all these requirements satisfactorily.

In order to meet the various requirements described above, toners must provide various conflicting functions. In order to solve these problems, microcapsule toners having a structure in which core material (core substance) particles called "core" are encapsulated with shell material (shell substance) called "shell" have been proposed. For example, a binder resin that has good fixing ability but tends to generate dislocation due to poor storage stability can be used as a core material, and a coating resin that has good storage stability and no dislocation properties can be used as a shell material , thus satisfying the conflicting requirements.

Concepts have been proposed regarding this functionally separated type of microcapsule toner. For example, JP-A-9-292735 discloses a film fixing heating type image forming apparatus using a microcapsule toner prepared by a suspension polymerization method. JP-A-59-53856 and JP-A-59-61842 disclose Examples produced by similar methods.

In addition, JP-B-56-13945 proposes a preparation method based on a spray drying method; JP-B-8-16793 proposes a preparation method based on a water droplet phase separation method; and JP-A-3-56970 proposes an in-situ Polymerization process forms the shell and uses a high pressure homogenizer to obtain microcapsules.

In addition to the above-mentioned methods, an interfacial polymerization method, an agglomeration method, a dry capsule method, and the like have also been introduced.

However, these prior art techniques other than the spray drying method use water as a medium, thereby making the drying process troublesome. Therefore, they are insufficient for the preparation of microcapsules in an industrial-scale manner.

In addition, the spray drying method is difficult to obtain uniform particles with the desired average particle size, usually 10 microns or less.

disclosure of invention

An object of the present invention is to provide a microcapsule toner which can be suitably used in a low-temperature heating fixing system or in a pressure fixing system capable of high-speed reproduction, as well as in a hot roller fixing system, which can solve existing problems. The problem of microcapsules in the technology, and it is excellent in storage stability and prevention of dislocation phenomenon.

The inventors have found that the above-mentioned problems can be solved by using two types of olefin polymers, each of which has a ring structure but are different in glass transition temperature and number average molecular weight, and one of which polymerized One is used as a binder resin for the core material, and another resin is used in the shell to coat the core of the microcapsule toner particles.

More specifically, the present invention provides a toner for developing an electrostatic image comprising a microcapsule toner particle composed of a core and a shell, wherein the core includes a colorant and a toner having a ring structure A binder resin of an olefin polymer having a glass transition temperature of from -20°C to less than 60°C and a number average molecular weight of from 100 to 20,000, the shell comprising a coated core resin.

The present invention also provides a toner for developing an electrostatic image, comprising a microcapsule toner particle composed of a core and a shell, wherein the core includes a colorant and a binder resin, and the shell includes A core-coating resin comprising an olefin polymer having a ring structure, the olefin polymer having a glass transition temperature ranging from 60°C to 180°C and a number average molecular weight ranging from 1,000 to 100,000.

The present invention further provides a toner for developing an electrostatic image comprising a microcapsule toner particle composed of a core and a shell, wherein the core includes a colorant and a binder having a ring structure. The olefin polymer has a glass transition temperature between -20°C and less than 60°C and a number average molecular weight between 100 and 20,000, and the shell consists of a coated core resin containing rings An olefin polymer with a like structure, the olefin polymer has a glass transition temperature ranging from 60°C to 180°C and a number average molecular weight ranging from 1,000 to 100,000.

The present invention will now be described in more detail.

[A] Materials constituting the core of microcapsule toner particles

The core includes a binder resin and a colorant as main components. It optionally contains additives such as a function-imparting agent, a charge control agent, and other additives.

(1) Binder resin

The following binder resins for heat fixing and for pressure fixing or olefin polymers having a cyclic structure are used as the binder, wherein the binder constitutes the microcapsule toner core together with the colorant. These resins have a lower melting point or softening point and higher fixing ability than the below-described coating resins constituting the shell.

Examples of binder resins for heat fixing include styrene polymers such as polystyrene, substituted polystyrene, etc.; styrene copolymers such as styrene-acrylate copolymer, styrene-methacrylate copolymer substances, styrene-acrylonitrile copolymers, etc.; acrylic resins such as poly(meth)acrylic resins, poly(meth)acrylate resins, etc.; polyester resins and epoxy resins. These resins may be used alone or in combination of two or more.

Examples of the binder resin used for pressure fixing include vegetable, 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 Polyol esters such as stearic acid, palmitic acid, oleic acid, lauric acid, etc.; and metal salts of higher fatty acids such as 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 copolymers, ethylene-(meth)acrylate copolymers, ethylene-vinyl acetate copolymers, ionomers Resins, etc.; styrene resins such as low molecular weight polystyrene, styrene-butadiene copolymers, styrene-acrylonitrile copolymers, etc.; epoxy resins and polyester resins. These resins may be used alone or in combination of two or more.

The use of a low-temperature fixing system capable of high-speed reproduction and obtaining a clear, high-grade image requires reliable fixing ability applicable to a pressure heating fixing (heating pressure fixing) system. Therefore, the type and composition of the binder resin suitable for the fixing method should be selected.

In order to provide a high degree of dislocation-free performance by widening the dislocation-free temperature range in which the dislocation phenomenon does not occur, it is preferable to use the following olefin copolymers having a ring structure (hereinafter referred to as cyclic olefin copolymers, Also abbreviated as COC) as the binder resin of the core material in place of the above-mentioned binder resins used in heat fixing and pressure fixing.

In order to provide a cyclic olefin copolymer for use as a core having higher fusing ability than the shell, the olefin copolymer is required to have a glass transition temperature (Tg) between -20°C to less than 60°C and a glass transition temperature (Tg) between 100 To a number average molecular weight of 20000, a Tg of less than -20°C will result in high viscoelasticity and make printed images sticky, while a Tg of 60°C or higher will provide insufficient fixing ability due to excessive stiffness. Mn less than 100 cannot provide sufficient fixing, while Mn exceeding 20000 will make the resin almost insoluble in solvents, thus being unsuitable for practical use.

The glass transition temperature (Tg) here refers to the median temperature of the displacement shown by the thermal transition measured according to differential scanning calorimetry (DSC). The number average molecular weight (Mn) is a value measured according to gel permeation chromatography (GPC) and corrected on the basis of standard polyethylene or polystyrene. More specifically, the number average molecular weight is obtained by measurement under the following conditions.

[condition]

Column used: JORDI-SAEULE 500×10 LINEAR

Mobile phase: 1,2-dichlorobenzene (135°C),

Flow rate: 0.5ml/min

Detector: Differential refractometer

The cyclic olefin copolymer (COC) is described in detail below.

Cyclic olefin copolymers (COC) are lower olefins with 2-12 carbons, preferably 2-6 carbons, such as α-olefins (or acyclic olefins in a wider sense) such as ethylene, propylene, butene, etc. Cyclic or polycyclic compounds (cyclic (cyclo)alkenes) with at least one double bond of 3-17 carbons, preferably 5-12 carbons, such as norbornene, tetracyclododecene, dicyclopentadiene ene, cyclohexene, etc., preferably a copolymer of norbornene or tetracyclododecene. This copolymer is colorless and transparent with high light transmittance.

COCs are prepared by using metallocene catalyst systems, Ziegler catalyst systems, metathesis polymerization catalysts, ie catalysts for double bond opening and ring opening polymerization reactions.

In 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 synthesis example of an olefin polymer having the above structure is disclosed in A-7-253315.

According to the above-mentioned documents, it can be obtained by heating at a temperature of -78 to 150° C., preferably 20 to 80° C. and a pressure of 0.01 to 64 bar, in the presence of an aluminum alkyl oxide or other catalyst and at least one catalyst of the metallocene type containing, for example, zirconium or hafnium. Cyclic olefin copolymers are prepared by copolymerizing under pressure one or more types of the aforementioned monomers, optionally with one type of the aforementioned acyclic monomers. EP-A-317262 discloses other useful polymers. Hydrogenated polymers or copolymers of styrene and dicyclopentadiene may also be used.

Metallocenes are activated when dissolved in inert hydrocarbons such as aliphatic or aromatic hydrocarbons. For example, metallocene catalysts are preactivated by dissolving in toluene, thereby performing the reaction in the solvent.

Important characteristics of cyclic olefin copolymers are their softening point, melting point, viscosity, dielectric properties, dislocation-free temperature range, and transparency. These characteristics can be tuned by effectively selecting the monomer/comonomer ratio, ie the ratio of monomer units in the copolymer, molecular weight, molecular weight distribution, hybrid polymer, blending and additives.

The molar ratio of acyclic olefin and cyclic olefin introduced into the reaction can be varied within a wide range depending on the target cyclic olefin copolymer, preferably adjusted to 50:1 to 1:50, and particularly preferably 20:1 to 1:20 .

For example, when two components (ethylene as an acyclic olefin and norbornene as a cyclic olefin) are used for the reaction to prepare a cyclic olefin copolymer, the glass transition temperature (Tg) of the reaction product is greatly affected by The proportions of these components used affect. As the norbornene content increases, Tg also tends to increase. For example, a composition having a norbornene content of 15 mol% or less (and an ethylene content of 85 mol% or more) can provide a copolymer having a Tg of -20°C to 60°C. On the other hand, a composition having a norbornene content of 15 mol% or more provides a copolymer having a Tg of 60°C to 180°C. Physical properties such as number average molecular weight are adjusted according to methods known in the literature.

The composition of the olefin copolymer with ring structure used in the present invention is as follows:

The adhesive composition for the core preferably consists of an unmodified cyclic olefin polymer and an acid-modified cyclic olefin polymer in a weight ratio of 95:5 to 5:95.

The unmodified cyclic olefin polymer has a number-average molecular weight (Mn; measured by GPC based on a standard polyvinyl value, and the same thereafter) of 100-20000, preferably 1000-10000, and its weight-average molecular weight (Mw ) is 200-40000, preferably 6000-30000, and the glass transition temperature (Tg) is -20°C to less than 60°C, preferably 40°C to 59°C.

Meanwhile, the acid-modified cyclic olefin polymer has a number average molecular weight (Mn) of 100-20000, preferably 1000-10000, a weight average molecular weight (Mw) of 300-80000, preferably 3000-40000, and a glass transition temperature (Tg) is -20°C to less than 60°C, preferably 40°C to 59°C.

In order to secure the required fixing ability and broaden the misalignment-free temperature range for practical use, the above-mentioned cyclic olefin copolymer preferably comprises a low-molecular-weight polymer or a low-viscosity polymer part (A) and a high-molecular-weight polymer or a high viscosity polymer fraction (B) whose physical properties are described below.

More specifically, the olefin copolymer of the present invention may be a mixture of polymer (A) and polymer (B); or may have a monomodal molecular weight distribution, and one polymer fraction has a number average molecular weight of less than 7500 and A polymer fraction has a number average molecular weight of 7500 or higher; or may have a molecular weight distribution of two or more peaks, wherein the polymer fraction corresponding to at least one peak has a number average molecular weight of less than 7500 and corresponds to The polymer portion of the other peak has a number average molecular weight of 7500 or higher.

The foregoing olefin copolymer composition acts to broaden the dislocation temperature range at both low and high temperatures, thereby improving toner fixability in high-speed copying and improving fixability at low and low pressures.

The polymer or polymer part (A) (hereinafter referred to as "component (A)") has

A number average molecular weight of less than 7500, preferably 1000 to less than 7500, and more preferably 2000 to less than 7500 (measured by GPC (gel permeation chromatography) based on standard polyethylene, and the same thereafter);

A weight average molecular weight of less than 15000, preferably 1000 to less than 15000, and more preferably 4000 to less than 15000;

an intrinsic viscosity (i.v.; intrinsic viscosity when 1.0 g of polymer is homogeneously dissolved in 100 ml of decalin at 135° C.) of less than 0.25 dl/g; and

A glass transition temperature of less than 70°C is preferred.

The polymer or polymer part (B) (hereinafter referred to as "component (B)") has

Number average molecular weight of 7500 or higher, preferably 7500 to 50000;

A weight average molecular weight of 15000 or higher, preferably 15000 to 50000;

Intrinsic viscosity (i.v.) of 0.25dl/g or higher.

Furthermore, the content of component (B) is less than 50% by weight, preferably 5-35% by weight (all binder resins).

Component (B) provides a toner particle having a structural viscosity that enhances the dislocation preventing effect and adhesion on paper, film or other substrates to be reproduced. However, when the content of the component (B) is 50% by weight or more, uniform mixing performance is sharply deteriorated, thereby impairing the performance of the toner. In other words, it is difficult to form a high-quality image or a clear image with high fixing strength and excellent thermal response performance, or mechanical grinding performance becomes low, making it difficult to prepare a toner having a desired particle diameter.

By the way, the polymer or polymer part used here means the polymer part of the cyclic olefin copolymer; wherein the olefin polymer is composed of various components having different number average molecular weights etc., the polymer or the polymer part is Refers to each polymer component before mixing, while the polymer or polymer part refers to the polymer part obtained by separating the final synthesized product by GPC or other suitable means. A number average molecular weight (Mn) of 7500 corresponds to a weight average molecular weight (Mw) of about 15000 when the polymer fraction is monodisperse or nearly monodisperse.

The low-viscosity component (A) of the olefin copolymer contributes to widening the dislocation-free temperature range on the low-temperature side, and the high-viscosity component (B) contributes to widening the dislocation-free temperature range on the high-temperature side. Therefore, it is more effective to widen the dislocation-free temperature range on the high-temperature side as required for the high-viscosity component (B) whose Mn is 20000 or higher.

The components (A) and (B) are contained in an amount of 0.5 parts by weight or more, preferably 5-100 parts by weight, based on the total amount of the binder resin being defined as 100 parts by weight. Less than 0.5 parts by weight of each of the two components will not provide a wide dislocation-free temperature range suitable for practical use.

The high-viscosity (high molecular weight) and low-viscosity (low molecular weight) olefin copolymers having a ring structure have the number average molecular weight (Mn), weight average molecular weight (Mw) and intrinsic viscosity (i.v.) as described above, so that Mw/ The molecular weight distribution characterized by Mn has a dispersity as low as 1-2.5, ie is monodisperse or close to monodisperse. This makes it possible to prepare a toner having high thermal response and high fixing strength, thereby enabling fixing of the toner at low temperature and low pressure. This also contributes to the storage stability of the toner, toner failure performance, uniformity of charge distribution, and electrical stability through constant charge and discharge efficiency. Monodispersity or substantially monodispersity is particularly preferred for low-viscosity polymers or polymer parts, since such toners have excellent so-called thermal response properties such as exhibiting instant melting and solidification and the like.

Olefin copolymers are also colorless and transparent and have high light transmittance. Therefore the olefin polymer can be sufficiently applied to the color toner. For example, it has been proved that excellent transparency can be obtained even when adding an azo pigment "PermanentRubin F6B" (manufactured by Clariant Co.), followed by sufficient kneading, and then producing a sheet by a press. Furthermore, measurements by the DSC method (Differential Scanning Calorimetry) have shown that olefin copolymers have an extremely low heat of fusion. Therefore, a significant reduction in energy consumed for toner fixing can be expected.

Furthermore, by introducing carboxyl groups into the olefin copolymer, compatibility with other resins can be improved and the dispersibility of pigments in toner can be improved. The introduction of the carboxyl group makes it possible to improve the adhesion and fixability of the toner on paper, film or other reproduction media.

For the introduction of carboxyl groups, a two-step reaction method is advantageously used in which an olefin copolymer having a ring structure is first prepared and then carboxyl groups are introduced.

At least two methods for introducing a carboxyl group can be given.

In one approach, methyl or other alkyl groups at the end of the copolymer chains are oxidized to carboxyl groups by molten air oxidation. However, in the case of producing an olefin polymer using a metallocene catalyst, it is difficult to introduce many carboxyl groups by this method since this polymer has only a small amount of side chains.

Another method is to use tert-butanol peroxide or other peroxides as initiators to graft-polymerize maleic anhydride, acrylic acid or methacrylic acid onto olefin polymers with a ring structure in order to obtain 1-5 wt%, A method with a graft ratio of 3-5% by weight (relative to the weight ratio of the olefin polymer) is preferred.

A graft ratio of less than 1 wt% is insufficient for the purpose of improving compatibility and the like. On the other hand, a graft ratio exceeding 5 wt% will increase the intermolecular crosslinking in the olefin polymer, thereby increasing the molecular weight. This makes the kneading and grinding properties unsuitable for practical use. Additionally, a severe yellow tint develops and loss of clarity occurs. Therefore, this polymer is not suitable for color toners requiring colorless transparency.

In the same manner, introducing a hydroxyl group or an amino group by a known method can improve the compatibility with other resins and the degree of dispersion of the pigment in the toner.

In addition, a crosslinked structure may be introduced into the olefin polymer to improve the fixing performance of the toner.

One method of introducing a crosslinked structure is to combine acyclic olefins and cyclic olefins with cyclopentadiene, cyclohexadiene, norbornene, tetracyclododecene, butadiene in the synthesis of the above-mentioned olefin polymers. Or other diene monomer ternary polymerization.

As a result of this process, olefinic polymers have terminal groups exhibiting activity, even in the absence of crosslinkers. Known chemical reactions such as oxidation or epoxidation or addition of crosslinking agents to form crosslinked structures lead to functionalization of olefin polymers.

Another method is to add a metal such as zinc, copper or calcium to an olefin polymer having a ring structure in which a carboxyl group is introduced, and then mix and melt the mixture with a screw to disperse the metal in the form of fine particles in the olefin polymer, Thus forming an ionomer with a cross-linked structure. With regard to the art of such ionomers themselves, for example US4693941 discloses terpolymers of carboxyl-containing ethylene in the form of partially or fully neutralized divalent metal salts in an attempt to obtain toughness.

JP-A-6-500348 reports a polyester molded product containing an unsaturated carboxylic acid ionomer (the ionomer is prepared for the same purpose), wherein about 20-80% of the carboxyl groups are made of zinc, cobalt , Nickel, Aluminum or Copper(II) neutralization.

A cyclic olefin polymer to which 5-95 wt% of an acid-modified olefin polymer having a carboxyl group-introduced ring structure may be added may be used as a core material. This will be an effective way to ensure the fusing ability and misalignment-free temperature range.

(2) Colorant

Carbon black, diazo yellow, phthalocyanine blue, quinacridone, carmine 6B, monoazo red, perylene, or other colorants used in conventional monochrome or color copier toners can be incorporated into the core as a coloring agent.

(3) Function imparting agent

Various types of paraffins can be used as function-imparting agents for widening the dislocation-free temperature range and improving dislocation-free performance. At least one wax selected from the following can be used as the function-imparting agent: polar waxes such as amide waxes, carnauba waxes, higher fatty acids and esters thereof, metal soaps of higher fatty acids, partially saponified higher fatty acid esters and higher fatty acid alcohols; and non-polar waxes such as polyolefin waxes and paraffin waxes.

Among various waxes, fatty acid amide waxes, oxidized polyethylene waxes, and acid-modified polypropylene waxes are preferable from the viewpoint of realizing a wide dislocation-free temperature range.

In order to broaden the above-mentioned dislocation-free temperature range of the toner and improve toner performance, it is preferable to use the wax in the following manner.

That is, it is preferable to use two or more types of waxes having different melting points (peak temperatures in differential scanning calorimetry (DSC) measurement) in the range of 80 to 140° C. in combination. If the melting point is less than 80° C., blocking tends to occur due to low melting point substances. Meanwhile, since the function-imparting agent is required to be completely melted at a melting temperature higher than the softening point of the binder resin, the upper limit of the wax is limited by the softening point (about 135-140° C.) of the olefin polymer having a ring structure and is preferably 140° C. , the olefin polymer is the main component in the binder resin.

More specifically, two or more types of waxes selected from fatty acid amide waxes and hydrocarbon waxes described below are used.

(i) Waxes with polar groups

Waxes with polar groups include various fatty acid amide waxes, such as eicosanoic acid monoamide (melting point: 110°C), behenic acid (melting point: 115°C), N,N'-dioleyl decanoic acid acid amide (melting point: 115°C), N,N'-dioleyl adipamide (melting point: 119°C) and N,N'-distearyl isophthalic acid amide (melting point: 129°C); oxidation Olefin waxes such as oxidized polyethylene wax (melting point: 116°C); acid-modified polyolefin waxes such as acid-modified polypropylene wax (melting point: 138°C) and carnauba wax (melting point: about 80°C).

(ii) Non-polar waxes (waxes without polar groups)

Non-polar waxes include olefin waxes (they are hydrocarbon waxes), such as polyethylene wax (melting point: 130°C), polypropylene wax (melting point: 120-150°C), paraffin wax (melting point: about 60 to 80°C), sazole Wax (solidification point: about 98°C) and microcrystalline wax (melting point: 80-100°C).

Silicone oil having release properties can be used in combination with the above-mentioned wax as a function-imparting agent for preventing the dislocation phenomenon as long as it does not adversely affect the effect of the present invention.

(4) Charge control agent

Nigrosine dyes, fatty acid-modified nigrosine dyes, metallized nigrosine dyes, metallized fatty acid-modified nigrosine dyes, chromium of 3,5-di-tert-butylsalicylic acid can be incorporated into the core material complexes, quaternary ammonium salts, triphenylmethane dyes, azochromium complexes and other known charge control agents.

(5) Other additives

In addition to the aforementioned toner components, flow agents such as colloidal silica (including fumed silica), alumina or titanium oxide, and fatty acid-containing metal salts such as stearic acid may be incorporated in the core material if necessary. Lubricants of barium, calcium stearate or barium laurate as long as it does not adversely affect the effects of the present invention.

(6) Amount of components to be incorporated

The amounts of components incorporated into the core material of the present invention are similar to those in the case of toners used in developing copiers and printers for electrostatic images, and are shown in Table 1.

Table 1: General composition of toner (unit: wt %) binder resin Colorant charge control agent function imparting agent magnetic powder solvent dry two-component toner 50-100 0-20 0-10 0-20 - - Dry non-magnetic one-component toner 50-100 0-20 0-10 0-20 - - Dry magnetic one-component toner 0-100 0-20 0-10 0-20 0-60 - dry polymerized toner 50-100 0-20 0-10 0-20 - - liquid dry toner 15-50 0-10 0-5 0-10 - 50-70 liquid toner 15-50 0-10 0-5 0-10 - 50-70

[B] Materials constituting the shell material of microcapsule toner particles

The shell material includes a coating resin as a main component and arbitrary additives such as a function-imparting agent or a charge control agent and the like. The coating resin used in the shell also has fixing ability, thereby acting as a binder similar to the aforementioned resin used in the core.

(1) Coating resin

A resin for fixing or an olefin polymer having a cyclic structure described below is used as the coating resin constituting the shell of the microcapsule toner particles.

Compared with the binder resin of the core material, the coating resin has a higher melting point or softening point, and thus has better storage stability.

Examples of coating resins for fixing include styrene, substituted styrene and derivatives thereof, (meth)acrylic acid, (meth)acrylate esters, maleic anhydride, maleic anhydride esters and derivatives thereof, maleic anhydride Amides, 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 homopolymers and copolymers of olefin monomers such as ethylene, propylene, etc., condensation polymers such as polyester, epoxy resin, polycarbonate, polyamide, polyurethane, polyurea, rosin, modified rosin , phenol resin, melamine resin, polyphenylene ether and terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin and petroleum resin, and this resin may be used alone or in combination of two or more types.

In order to prevent a dislocation phenomenon in which toner is transferred to a heat roller, and in order to further improve storage stability, an olefin polymer having a cyclic structure described below is preferably used as the coating resin of the shell material.

An unmodified olefin having a ring structure is preferably used as the coating resin for the shell material. Since the storage stability of the toner can be sufficiently ensured as long as the glass transition temperature of the polymer used is 60° C. or higher, the polymer having a cyclic structure and having a Tg of 60° C. or higher can be used in all amounts. Acid-modified olefin polymers are used instead.

This unmodified olefin polymer having a ring structure has a number average molecular weight (Mn) between 1000-100000, preferably 2000 to 50000, and has a weight average molecular weight (Mw) between 2000-200000, preferably 4000-100000. ), and a glass transition temperature (Tg) between 60°C-180°C, preferably 60°C-80°C.

Meanwhile, the above-mentioned acid-modified olefin polymer has a number average molecular weight (Mn) between 1000-100000, preferably 2000 to 50000, has a weight average molecular weight (Mw) between 3000-300000, preferably 6000-200000, and A glass transition temperature (Tg) between 60°C and 180°C, preferably between 60°C and 80°C.

If the glass transition temperature of the above-mentioned olefin polymer is less than 60°C, there are many problems in the storage stability of toner particles, and if the glass transition temperature exceeds 180°C, the melting point rises and the fixing ability tends to be poor . In addition, if the number average molecular weight of the above-mentioned olefin polymer is less than 1,000, sufficient fixing strength cannot be obtained, and if the number average molecular weight exceeds 100,000, it is difficult to secure the required stability in a solvent.

The modified substance, the crosslinked substance, and the above-mentioned olefin polymer having a cyclic structure have the same characteristics as the above-mentioned olefin polymer having a cyclic structure used in the core material except for the glass transition temperature and number average molecular weight. are the same as those of , and their descriptions are omitted here.

(2) Function imparting agent

In order to broaden the dislocation-free temperature range and further improve the dislocation-free performance of the toner particle surface, the same function-imparting agents (wax, silicone oil) used in the above-mentioned core material may also be incorporated into the shell material. The preferred forms and the like of the above-mentioned applications can also be applied to the function-imparting agent to be incorporated into the shell material.

(3) Charge control agent

The same charge control agents used in the core material described above can be incorporated into the shell material.

(4) Additives for external use

The surface of the shell material of the toner particles may be coated with desired external additives.

Examples of additives for external use include flow agents such as colloidal silica (including fumed silica), alumina, titanium oxide, etc., and lubricants containing fatty acid metal salts such as barium stearate, calcium stearate, or barium laurate, etc. agents, and such external additives may be used alone or in combination of two or more types. Preferably these additives are hydrophobic.

The external additive is used in an amount of 0.01-10, preferably 0.05-5 parts by weight per 100 parts by weight of toner particles.

If the shell material is coated by an external additive, a solution containing the external additive is applied to the surface of the particle or the external additive is adhered to the surface of the particle by other methods.

(5) Amount of components to be blended

The amounts of the above components in the shell material are shown in the table above, except for the colorant to be incorporated.

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

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

According to the present invention, there are the following three modes of combinations of resins for the core material and the shell material.

(a) Core material: Olefin polymer with ring structure (-20℃≤Tg<60℃, 100≤Mn≤20000)

Shell material: Coating resin for fixing

(b) Core material: binder resin for heat fixing and binder resin for pressure fixing

Shell material: Olefin polymer with ring structure (60℃≤Tg≤180℃, 1000≤Mn≤100000)

(c) Core material: Olefin polymer with ring structure (-20℃≤Tg<60℃, 100≤Mn≤20000)

Shell material: Olefin polymer with ring structure (60℃≤Tg≤180℃, 1000≤Mn≤100000)

As examples given in the above-mentioned fixing resins [A](1) and [B](1), an olefin having a ring structure is incorporated in at least one shell material or a core material and various crystalline and amorphous are mixed As a result, the resins (which are compatible with olefin polymers) can exhibit transparency, low-temperature fixing ability, mechanical shock resistance and other characteristics of olefin polymers with a ring structure (which are important for toner performance). of).

In the mode (c), an olefin polymer having a ring structure is used in both the shell material and the core material, and the above characteristics are fully exhibited as the performance of the toner.

The most preferred form of toner particles is an olefin polymer having a ring structure with a glass transition temperature (Tg) of 40-59°C, a number average molecular weight (Mn) of 1000-10000 and a polydispersity An ethylene-norbornene copolymer having (weight average molecular weight (Mw)/number average molecular weight (Mn)) of 10 or less and a copolymerization molar ratio of ethylene to norbornene of 85/15 to 95/5 is used as the core Binder resins for materials, and olefin polymers having a ring structure that are soluble in methyl ethyl ketone (MEK), have a glass transition temperature (Tg) between 60-80°C, and have a number-average molecular weight (Mn) between Ethylene-norbornene copolymers with a polydispersity (Mw/Mn) between 2000-50000 and a polydispersity (Mw/Mn) between 4-10 and a copolymerization molar ratio of ethylene to norbornene of 75/25 to 85/15 are used as shell materials Coating resin.

Microcapsule toner particles are preferably prepared by a reprecipitation method. More specifically, it is a solvent reprecipitation method of causing the shell material to precipitate around the core material by dropping a good solvent solution with a poor solvent solution of the coating resin of the shell material with dissolved therein. Binder resins and colorants.

Microcapsule toner particles can also be produced according to the phase separation method shown in, for example, JP-B-08-16793 and JP-B2-2631019.

(1) Method of preparation by reprecipitation method (solvent reprecipitation method)

At a temperature of 25-30°C, 16-20wt% olefin polymer with a ring structure and 1-2wt% function-imparting agent constituting the core material are added and dissolved in a 76-80wt% solvent (a mixture of toluene and cyclohexane) solvent, etc.), a solution (solution A) is prepared by dispersing 1 to 2 wt % of the colorant using a ball mill or the like.

On the other hand, a solution (Solution B) was prepared by dissolving 1.8-2.2 wt% of an olefin polymer having a ring structure constituting the shell material and 0.015-0.025 wt% of a charge control agent in 98 wt% of MEK or other solvent.

In the next step, solution A is dripped into high-speed stirred solution B from a nozzle with multiple 20-30 micron diameter pores to obtain a precipitate, which is then passed through 2 micron, 0.5 micron and 0.2 micron multi-step filtration device for separation from the solvent. In the latter step, particles were formed by removing residual solvent using a high-temperature vacuum dryer.

This results in a substantially spherical shape with a mean diameter of 4-10 microns and a particle size distribution of 2-12 microns (corresponding to 3σ, where σ=standard deviation), and a shell material thickness of 0.2-0.5 microns (based on passing solvent gravimetric measurement of separation method) of microcapsule toner particles.

Hydrophobic silica is then added externally as a developer.

(2) The method prepared by the gas phase separation method

An olefin polymer having a cyclic structure, an olefin polymer having a cyclic structure modified with an acid, a wax, a colorant, and a charge control agent are melt-kneaded. In hot water, after microdispersing hydrophilic silica as a protective colloid under high-speed stirring, solidification is carried out by rapid cooling with a large amount of water, the silica is then dissolved and removed by an aqueous alkaline solution, and by water/methanol The core material particles are obtained by rinsing, and then filtered.

Independently dissolve the olefin polymer having a ring structure, wax and charge control agent in a ketone solvent, preferably MEK, disperse a predetermined amount of the above-mentioned core material particles with a homomixer, add a predetermined amount of acetic acid, and then cool in deep Next, water is added dropwise at a predetermined rate to re-precipitate the shell material onto the surface of the core particle.

Then, rinsed with a mixed solution of water and methanol, filtered and dried to obtain microcapsule toner particles.

Hydrophobic silica is then added externally as a developer.

From the comparison of the above two preparation methods, it can be seen that the reprecipitation method is more suitable for industrial production, because it uses a low-cost general-purpose solvent, and it is easier to dry due to the difference in the hidden heat of the solvent and water, And mutual coalescence of toner particles becomes less.

Best Mode for Carrying Out the Invention

Although the present invention has been described in more detail by way of Examples and Comparative Examples, these Examples and Comparative Examples do not limit the effective scope of the present invention at all.

Dry one-component toners and dry two-component toners were prepared as follows.

Examples 1-4 are examples of preparing microcapsules by reprecipitation method and Example 5 is an example of preparing microcapsules by phase separation method.

Example 1

Prepare solution A (core material)

17 wt% of "Topas T-936" manufactured by Ticona GmbH and having a glass transition temperature (Tg) of 49°C and a number average molecular weight (Mn) of 2000 was used as an olefin polymer having a ring structure, and 1 wt% was produced by Ticona "Topas AG-07" manufactured by GmbH and having a glass transition temperature (Tg) of 58°C and a number average molecular weight (Mn) of 3700 was used as an acid-modified olefin polymer having a ring structure, 0.5% by weight "BNT22H" manufactured by Nippon Seika and 0.5% by weight of "Ceridust 3715" (trade name) manufactured by Clariant were used as function-imparting agents, and these components were gradually added to and dissolved at 30°C and a stirring speed of 200 rpm In a mixed solvent of 80 wt% toluene and cyclohexane (weight ratio 50:50).

Then, beads (stainless steel powder manufactured by Ashizawa, particle diameter: 500 µm) were added to the above solution, and 1 wt% of a black colorant ("Carbon Black MA-7" manufactured by Mitsubishi Chemical) was gradually added and dispersed with a stirring speed of 500 rpm , to obtain solution A.

Preparation of solution B (shell material)

2% by weight of "Topas AG-09" manufactured by Ticona and having a glass transition temperature (Tg) of 67°C and a number average molecular weight (Mn) of 4600 was used as an olefin polymer having a ring structure, and it was mixed with 0.02 % by weight of a charge control agent ("Copy Charge NX" (trade name); manufactured by Clariant) was dissolved together in about 98% by weight of methyl ethyl ketone to obtain a solution B.

Granulation process

The above-mentioned solution A was dropped into the high-speed stirred solution B from a nozzle having a plurality of 30-micrometer-diameter holes to form particles.

Regarding the dropping rate, in the case of producing granules in a tank with a volume of 500 liters, gradually add 100 liters of solution A to 200 liters of solution in 20 minutes by dripping from 100 pores at a rate of 5 liters/minute In B, a precipitate was obtained.

The stirring speed of the fixed solution B was 2000 rpm, and the stirring was continued for 10 minutes after the dropwise addition of the solution A was completed. The precipitate is then separated from the solvent by passing through multi-stage filters of 2 micron, 0.5 micron and 0.2 micron. Then, the residual solvent is removed by using a high-temperature vacuum drier to form microcapsule toner particles.

The average diameter of the obtained toner particles was about 6 microns and all the particles were distributed in the particle size range of 2-12 microns. The process was found to be good in terms of yield due to the size separation of the coarse particles and the fact that very fine particles are not required.

Observation by a scanning microscope confirmed that the particles were substantially spherical, and the thickness of the shell material was calculated to be 0.2-0.5 microns by measuring the following weights according to the solvent separation method.

Regarding the yield of the toner, the yield after drying was 21.7 kg (yield: 92%), relative to 100 liters (about 85.6 kg, in which the core polymer included 17.1 kg) of Solution A and 200 liters (about 162 kg, in which Shell material polymer comprised 6.5 kg) Solution B (23.6 kg total solids).

The toner yields obtained by a conventional mechanical grinding method and an air impingement flow method (which uses high-speed air flow) are about 80% and about 75%, respectively, in which ultrafine particles of 1 micron or less are formed. It was thus found that the yield of toner can be significantly improved by the above method.

The average particle diameter of the toner particles is measured according to a laser diffraction scattering type particle diameter distribution measuring device ("LA-700" manufactured by Horiba Seisakusho). The particle size distribution was also measured by the same device, and it was found that particles with a size of 4-10 microns accounted for 95% by volume and 75% by number.

To measure the thickness of the shell material, 10 g of toner particles were weighed and placed in 1 liter of methyl ethyl ketone. After the shell material was dissolved by heating to 50°C and stirring for 20 minutes, the solvent was removed by hot filtration and the residual weight was measured to calculate The thickness of the shell material.

Example 2

Microcapsule toner particles were obtained in the same manner as in Example 1 except that the yellow colorant "Yellow HG (trade name)" manufactured by Clariant was used as the colorant.

Example 3

Microcapsule toner particles were obtained in the same manner as in Example 1 except that a magenta colorant "Pink EO2 (trade name)" manufactured by Clariant was used as the colorant.

Example 4

Microcapsule toner particles were obtained in the same manner as in Example 1 except that the cyan colorant "Blue BO2G (trade name)" manufactured by Clariant was used as the colorant.

Example 5

Referring to JP-B1-8-16793 and JP-B2-2631019, microcapsule toner particles are produced by the phase separation method as follows.

Preparation of core particles

85 wt% of "Topas T-936" manufactured by Ticona was used as an olefin polymer having a ring structure, and 5 wt% of "Topas AG-07" manufactured by Ticona was used as an acid-modified olefin polymer having a ring structure , a mixed powder of 2 wt% behenic acid amide wax ("BNT22H" (trade name) manufactured by Nippon Seika) and 2 wt% oxidized and non-oxidized polyethylene wax ("Ceridust 3715" (trade name manufactured by Clariant) )) was used as a function-imparting agent, and these components were melt-kneaded at 120°C with a kneader ("Reomix 600" manufactured by Haake) and 5 wt% of a black colorant ("CarbonBlack MA-7" manufactured by Mitsubishi Chemical) and 1 wt% of a charge control agent ("Copy ChargeNX" (trade name) manufactured by Clariant), and the resulting mixture was transferred to a stainless steel container equipped with a heater and kept at 130°C.

Separately, water was placed in a homomixer (manufactured by Tokushu Kika) and heated to and maintained at about 95°C. Then 0.4 wt% of colloidal silica ("HDK N-30" manufactured by Wacker Chemie) was added and sufficiently dispersed by stirring.

The rotation speed of the homomixer was fixed at 8500 rpm, and about 15 parts by weight (phr) of the above molten mixture was added to the dispersion medium of hot water, followed by continuous stirring for about 15 minutes to form microparticles.

Then, the dispersion was poured on previously prepared ice (twice as much ice as the dispersion) to rapidly cool and solidify the microparticles. Then add the amount of sodium hydroxide equal to the amount of neutralized colloidal silicon dioxide to the dispersion, and stir with a propeller stirrer for 24 hours at room temperature to dissolve the colloidal silicon dioxide, and separate the alkaline solution and the solid.

Then the slurry was rinsed with water/methanol solution (50/50wt%), filtered every two times, and dried with a hot air drier fixed at 40° C. to obtain core material particles.

The volume average particle diameter of these particles was about 8 micrometers (measured by "LA-700" manufactured by Horiba Seisakusho).

Preparation of shell material solution

Using 95 parts by weight of the above-mentioned "Topas AG-09" as an olefin polymer having a ring structure, 2 parts by weight of behenic acid amide wax ("BNT22H" (trade name) manufactured by Nippon Seika), and 2 wt% of oxidized and non-oxidized polyethylene wax mixed powder ("Ceridust 3715" (trade name) manufactured by Clariant) was used as a function-imparting agent, and 1 part by weight of a charge control agent ("Copy Charge NX" (trade name) manufactured by Clariant) ) and 2400 parts by weight of methyl ethyl ketone to prepare a shell material solution for encapsulation.

A homogeneous mixer was equipped with a reactor with a 20-liter volume jacket, and 7.6 kg of the above solution was added to the reactor, and after cooling to -25° C. under stirring, 120 g of acetic acid was added and stirred for 5 minutes.

Then add 2.0kg of the above-mentioned core material particles into the reactor, and after fully dispersed with a homomixer, add cold water at 0-5°C at a dropping rate of 10g/min. The dropping rate was gradually increased to 100 g/min in the last step, and about 3 kg of water was finally added. The time required for this process is about 2 hours.

Then, the capsule solution was separated by a centrifugal filter and the capsule particles separated by filtration were rinsed twice with water/methanol (50/50 wt%), separated by filtration and dried at 40°C.

The volume average particle diameter of the capsule particles is about 8.5 microns, which is significantly larger than the core particles and the diameter becomes larger due to encapsulation.

Substantially similar shell material thicknesses (0.2-0.3 microns) were calculated from the weights measured by the solvent separation method described above.

0.5 parts by weight of hydrophobic colloidal silica was added externally to the microcapsules thus obtained as a developer.

Comparative Example 1

The toner is a commercially available toner prepared by an air impact grinding method (jet mill method), more specifically, a toner for copiers "FT-5520" manufactured by Ricoh, using the toner And performance evaluation was carried out using the copier described above.

Comparative Example 2

The toner is a commercially available toner prepared by a mechanical grinding method, more specifically a toner manufactured by QMS for the printer "Magicolor 2CX", using this toner and using the above-mentioned copier manufactured by Ricoh " FT-5520" for performance evaluation.

By using the microcapsule toners obtained in Examples 1 to 4 and the commercially available toners of Comparative Examples 1 and 2, actual reproduction was performed with the copier "FT-5520" manufactured. The results are shown in Table 2.

(a) Effect of antispent toner

A true replication experiment was carried out on high quality paper using the toner samples of each Example and Comparative Example. Copying was carried out until the toner component adhered to the developing sleeve and the photoconductor reached the allowable limit, and the paper copied to the paper at that point was used for comparison.

(b) transfer performance

The efficiency of transfer from the photoconductor to high quality paper was measured, based on the amount of toner recovered after replication on 10,000 sheets of paper, which was the substrate to be replicated.

(c) Fixing ability

Use various toners to form images on high-quality paper, place a piece of unprinted paper of the same quality on top of the printed paper and wipe the printed image with a rubbing resistance tester to make it under the action of external force Transfer to unprinted paper.

The image fixing speed was fixed at 150 mm/sec and the fixing temperature was fixed at 150°C.

The conditions of the abrasion resistance test were fixed at 20 reciprocating movements under a load of 2 lbs (about 907 g). After wiping, the initial image density before wiping (A), the density transferred to the unprinted paper (B) and the density of the non-image area of the paper (C) were measured using a Macbeth-type reflection densitometer, and The transfer speed was determined by the following formula [(B-C)/A×100(%)]. The lower limit of the fixing temperature and the lower limit of the fixing pressure at a transfer speed of 60% or more were measured and compared.

(d) Sharpness of the image

The image clarity of each toner was compared, and the grade, fine line resolution and OHP light transmittance were evaluated as follows.

grade

Using samples manufactured by Dataquest Co., grades were evaluated by 0-16 gray scale steps.

fine line resolution

Using the sample manufactured by Dataquest, thin line resolving power was evaluated by a thin line pattern of 0-600 dpi.

OHP transmittance

An image was formed on an OHP film for PPC manufactured by Fuji Xerox, the light transmittance at the image area (A) and the non-image portion (B) was measured, and the light transmittance was characterized by A/B x 100%.

(e) Storage stability

After storing the toner prepared by each method at 60° C. and 50% RH (relative humidity) for 8 hours, the toner was passed through a 100-mesh sieve for a fixed period of time, and the sieve was divided by the amount of the sample used. The values obtained for residues are expressed in %. Coalescence of toner particles during storage will make this value even higher. The agglomeration is mainly caused by a substance having a melting point of 50° C. or lower contained in the toner composition. The symbol "o" indicates sieve residue of 0.5% or less and "x" indicates sieve residue of more than 0.5%.

Table 2 evaluation item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Anti-failure toner effect 50,000 50,000 50,000 50,000 50,000 20,000 20,000 Transfer performance of photoconductor (%) 99.8 99.8 99.8 99.8 99.8 95 99 Fixing capacity pressure lower limit (kg/cm ² ) 20 20 20 20 20 400 300 Fixing ability temperature lower limit (℃) 100 100 100 100 100 140 130 Image clarity level 16 16 16 16 16 8 8 Image Definition Fine Line Resolution (dpi) 600 600 600 600 600 300 300 Image clarity OHP transmittance (%) 95 95 95 95 95 90 92 storage stability ○ ○ ○ ○ ○ x x

Industrial Applicability

The toner for developing the electrostatic image of the present invention is a microcapsule toner particle composed of a core and a shell. In addition, an olefin polymer having a cyclic structure having a relatively low glass transition temperature and a relatively low average molecular weight is used as a binder resin in a core material, and/or has a relatively high glass transition temperature and a relatively high Olefin polymers with a number average molecular weight having a ring structure are used as coating resins in shell materials.

Therefore, the toner can be used in pressure heating fixing type copying equipment, and it has good storage stability, can produce high-level clear images and it is excellent in anti-fading toner effect, transfer ability, fixing ability and non-displacement performance excellent.

Furthermore, the toner of the present invention is excellent in exhibiting sufficient fixing ability even in a low-temperature heating type copying apparatus.

Furthermore, even in the case of using a heat roller fixing type apparatus, the use of the toner of the present invention can easily achieve a significant reduction in the amount of heating heat, thereby contributing to the manufacture of energy-saving copying apparatus.

Furthermore, by incorporating a function-imparting agent for mold release into the shell material, it becomes unnecessary to apply oil such as silicone oil or wax to the surface of the heating roller.

Claims (14)

1. toner that is used for developing electrostatic image, comprising a kind of microcapsules toner-particle of forming by core and shell, its SMIS comprises a kind of colorant and a kind of adhesive resin that contains the olefin polymer with ring texture, described olefin polymer have between-20 ℃ to less than 60 ℃ glass transition temperature with between 100 to 20000 number-average molecular weight, and shell comprises a kind of resin that is coated with cloth wick.

2. the toner that is used for developing electrostatic image of a claim 1, wherein coating resin is selected from one of the following at least: the homopolymer and the multipolymer of styrene and derivant thereof, (methyl) acrylic acid, maleic anhydride and derivant, vinyl monomer such as nitrogenous vinyl compound, vinyl acetal, vinyl chloride and vinyl acetate, vinylidene monomer and olefinic monomer; Condensation polymer such as polyester, epoxy resin, polycarbonate, polyamide, polyurethane, polyureas, rosin, modified rosin; Terpene resin, fat hydrocarbon resin, alicyclic hydrocarbon resin.

3. toner that is used for developing electrostatic image, comprising a kind of microcapsules toner-particle of forming by core and shell, its SMIS comprises a kind of colorant and a kind of adhesive resin, and shell comprises a kind of resin that is coated with cloth wick, this resin contains the olefin polymer with ring texture, and described olefin polymer has between 60 ℃ to 180 ℃ glass transition temperature with between 1000 to 100000 number-average molecular weight.

4. the toner that is used for developing electrostatic image of a claim 3, wherein adhesive resin is made up of the adhesive resin that is used for hot photographic fixing of at least a type and the adhesive resin that is used for the pressure photographic fixing of at least a type, multipolymer, acryl resin, vibrin and epoxy resin and the described adhesive resin that is used for the pressure photographic fixing that the wherein said adhesive resin that is used for hot photographic fixing is selected from styrene polymer, styrene monomer and (methyl) acrylate are selected from wax, olefin polymer, styrene resin, epoxy resin and vibrin.

5. the toner that is used for developing electrostatic image of a claim 1, the coating resin that wherein contains the olefin copolymer with ring texture is as shell material, the glass transition temperature of described olefin copolymer between 60 ℃ to 180 ℃ and number-average molecular weight between 1000 to 100000.

6. the toner that is used for developing electrostatic image of a claim 1 is wherein with the olefin copolymer with ring texture that contains of acrylic acid or maleic anhydride modified formation core.

7. the toner that is used for developing electrostatic image of a claim 1 wherein mixes wax in the coating resin of adhesive resin that constitutes core and/or formation shell material.

8. the toner that is used for developing electrostatic image of a claim 3 wherein mixes wax in the coating resin of adhesive resin that constitutes core and/or formation shell material.

9. the toner that is used for developing electrostatic image of a claim 7, wherein wax be selected from that fatty acid amide is cured, oxidized polyethlene wax and at least a with in the polypropylene wax of sour modification.

10. the toner that is used for developing electrostatic image of a claim 8, wherein wax be selected from that fatty acid amide is cured, oxidized polyethlene wax and at least a with in the polypropylene wax of sour modification.

11. the toner that is used for developing electrostatic image of a claim 1 wherein externally adds fine silica powder or it is applied to the surface of microcapsules toner-particle.

12. the toner that is used for developing electrostatic image of a claim 3 wherein externally adds fine silica powder or it is applied to the surface of microcapsules toner-particle.

13. the toner that is used for developing electrostatic image of a claim 1, wherein prepare the microcapsules toner-particle by intermediate processing again, this method comprises that the good solvent solution that will be dispersed with the adhesive resin of colorant splashes in the poor solvent solution of coating resin, makes shell material precipitate around core.

14. the toner that is used for developing electrostatic image of a claim 3, wherein prepare the microcapsules toner-particle by intermediate processing again, this method comprises that the good solvent solution that will be dispersed with the adhesive resin of colorant splashes in the poor solvent solution of coating resin, makes shell material precipitate around core.