CN1408079A - Toner for electrostatically charged image development - Google Patents
Toner for electrostatically charged image development Download PDFInfo
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- CN1408079A CN1408079A CN00816783A CN00816783A CN1408079A CN 1408079 A CN1408079 A CN 1408079A CN 00816783 A CN00816783 A CN 00816783A CN 00816783 A CN00816783 A CN 00816783A CN 1408079 A CN1408079 A CN 1408079A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
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- G03G9/093—Encapsulated toner particles
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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
Invention field
The present invention relates in pressure fixation type and heat roller fixation type (also being called " pressure hot type " or " pressure heating systems " thereafter), be used for the toner of electrostatic image development.
More particularly, the present invention relates to the single component magnetic type of actual applicable drying, the dry non magnetic type of single component, dry two-component-type, the toning formulation developer of liquid dried type or liquid-type, but the photographic fixing of described developer pressure is on film to be duplicated or other matrix, has sufficient fixing performance (being called " photographic fixing ability " thereafter), toner inefficacy (spent) performance and transparency, so that under less than 100 ℃ low temperature, even energy pressure photographic fixing under the heat roller fixation situation, can form distinct image, and good aspect high speed photographic fixing ability and storage stability, thereby the suitable temperature range (being called " dislocation-free temperature range " thereafter) of (offset) phenomenon of guaranteeing not take place to misplace.
The invention still further relates to can widespread use in duplicating machine, printer, facsimile recorder, color copy machine, color laser copier, color laser printer and high-velocity electrons photograph printer above-mentioned toner.
Background technology
Along with popularizing fast of nearest office automation, in the duplicating machine of electrostatic image development and printer, exist to the demand of the growth of the higher mechanical shock resistance that adapts with high speed printing and to the requirement of high-grade image, in other words, clear, low-temperature fixing ability and good transmittance are applicable to toner.
To these demands of high speed duplicating and high-grade image require to guarantee at low temperatures can practical application necessity and toner-particle intensity and wide dislocation-free temperature range fully.In addition, also expection can realize not having the oil type clone method, and this method does not require sends into oil in fixing roller, thereby can not produce the problem of polluting matrix to be duplicated.
In these cases, the inventor finds and disclose be used to the to develop toner of heat roller fixation type electrostatic image in JP-A-2000-66438 can adapt to above-mentioned requirements, has the polyolefin resin of ring texture as adhesive resin comprising a kind of, and adopt the appropriate combination of polypropylene wax of Tissuemat E, Tissuemat E and the sour modification of fatty acid amide wax, oxidation, so that give various functions.
Yet this toner has limitation aspect reproduction speed and the fixing temperature in heat roller fixation is used.Simultaneously, market requires even higher reproduction speed and because the demand of saves energy is that cause adapts fully with requirement low-temperature fixing recently.
Adding and mixing three kinds or four kinds of color (Y: yellow by electrophotographic method, M: magenta, C: blue-green, B: in the formation of pure color image blueness), the method that shifts on matrix to be duplicated needs unlimited subglobular or toner-particle really spherical and that have the smooth surface situation.
Yet the air blast Ginding process that conventional mechanical grinding method and adaptation high-speed air flow may successfully prepare sphere hardly and have the toner of smooth surface.
In the heat roller fixation system, described heat roller fixation system is used for photographic fixing pure color image on paper to be duplicated, ohp film or other matrix at present and normally, excessive heat must be used for fixing three kinds or four kinds of toners, and silicone oil etc. also will be used for fixing roller, transfer to (so-called " inconsistent phenomenon ") on the hot-rolling to prevent toner.
To the desired performance of toner is many-sided, comprising chargeding performance, photographic fixing ability, burnish resistance, transmission property, storage stability (toner-particle even not coalescent mutually and form the trend of agglomerate after long-time) etc.Yet, satisfy all these requirements unsatisfactorily by the toner that obtains with conventional method of compounding dry mixed.
In order to adapt to above-mentioned various requirement, toner must provide the function of various conflicts.In order to address these problems, the microcapsules toner has been proposed, it has the structure that core (core material) particle that is called " core " is sealed with the shell material (shell matter) that is called " shell ".For example, has well secured ability, but can be used as core because bad storage stability causes tending to producing the adhesive resin of inconsistent phenomenon, and the coating resin with good storage stability and dislocation-free performance can be used as shell material, thereby satisfy the requirement of conflict.
Notion about the microcapsules toner of this function type of separation has been proposed.For example, JP-A-9-292735 discloses film photographic fixing hot type image processing system, and this device uses the microcapsules toner by the suspension polymerization preparation.JP-A-59-53856 and JP-A-59-61842 disclose the embodiment by similar method preparation.
In addition, JP-B-56-13945 has proposed the preparation method based on spray drying process; JP-B-8-16793 has proposed the preparation method based on the water droplet phase disengagement method; Proposed to form shell and use high-pressure homogenizer to obtain the preparation method of microcapsules with JP-A-3-56970 by the in-situ polymerization method.
Except said method, interfacial polymerization method, condensing method, dry capsule method etc. have also been introduced.
Yet these prior aries except spray drying process make water as medium, thereby make the drying process trouble that becomes.Therefore, they are inadequate for preparing microcapsules in the industrial scale mode.
In addition, spray drying process is difficult to obtain required mean grain size, is generally 10 microns or lower single-size.
Disclosure of an invention
An object of the present invention is to provide a kind of microcapsules toner, it can be in the low-temperature heat fusing system or in the pressure fusing system of energy high speed duplicating, and in the heat roller fixation system, use suitably, it can solve the problem of microcapsules of the prior art, and at storage stability with prevent that aspect the inconsistent phenomenon be good.
The inventor finds by using two types olefin polymer to address the above problem, thereby finished the present invention, wherein every kind of olefin polymer all has ring texture, but glass transition temperature is different with number-average molecular weight, the adhesive resin that wherein a kind of polymkeric substance is used as core, the another kind of resin that in shell, is used to be coated with the core of microcapsules toner-particle.
More particularly, the invention provides a kind of toner of 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.
The present invention also provides a kind of toner of 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.
The present invention provides a kind of toner of developing electrostatic image in addition, 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 with ring texture that contains, described olefin polymer has 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, 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.
The present invention is now described in more detail.
[A] forms the material of microcapsules toner-particle core
Core comprises that a kind of adhesive resin and a kind of colorant are as key component.It randomly contains adjuvant and other adjuvant such as function endowing agent, charge control agent.
(1) adhesive resin
The olefin polymer that is used for heat fixer and is used for the following adhesive resin of pressure photographic fixing or has ring texture is as bonding agent, and wherein said bonding agent constitutes the microcapsules toner core with colorant.Compare with the following coating resin that constitutes shell, these resins have lower fusing point or softening point and higher photographic fixing ability.
The example that is used for the adhesive resin of heat fixer comprises styrene polymer such as polystyrene, substituted polystyrene etc.; Styrol copolymer such as copolymer in cinnamic acrylic ester, styrene-methacrylate copolymer, styrene-acrylonitrile copolymer etc.; Acryl resin is as poly-(methyl) acryl resin, poly-(methyl) acrylate resin etc.; Vibrin and epoxy resin.These resins can use separately or two or more are used in combination.
The example that is used for the adhesive resin of pressure photographic fixing comprises plant, animal, mineral and pertroleum wax such as Brazil wax, candelila wax, sheep oil, beeswax, montan wax, paraffin, microcrystalline wax etc.; Advanced higher fatty acid derivative such as polyol ester, for example stearic acid, palmitic acid, oleic acid, lauric acid etc.; With the slaine of higher fatty acid such as calcium stearate, zinc stearate, lead stearate, dolomol etc.; Polyolefin-wax such as Tissuemat E, polypropylene wax etc.; Olefin homo and multipolymer such as ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate copolymer, ethylene-vinyl acetate copolymer, ionomer resin etc.; Styrene resin such as low-molecular-weight polystyrene, Styrene-Butadiene, styrene-acrylonitrile copolymer etc.; Epoxy resin and vibrin.These resins can use separately or two or more are used in combination.
Use energy high speed duplicating and acquisition are clear, the low-temperature fixing system of high-grade image requires the reliable photographic fixing ability applicable to pressure heat fixer (heated pressure photographic fixing) system.Therefore, should select to be suitable for the type and the component of the adhesive resin of fixation method.
In order to provide by widen the dislocation-free performance of the height that dislocation-free temperature range (inconsistent phenomenon does not take place) obtains in this temperature range, preferred following olefin copolymer with ring texture (cyclic olefin copolymer hereinafter referred to as that uses, also be abbreviated as COC) as the adhesive resin of core, substitute the above-mentioned adhesive resin that uses in heat fixer and the pressure photographic fixing.
For the cyclic olefin copolymer as core is provided, described core has the photographic fixing ability more senior than shell, require olefin copolymer to have between-20 ℃ to less than 60 ℃ glass transition temperature (Tg) with between 100 to 20000 number-average molecular weight, Tg will cause high viscoelasticity less than-20 ℃ and make the image of printing be clamminess, and 60 ℃ or higher Tg will provide not enough photographic fixing ability owing to excessively harden.Mn can not provide sufficient photographic fixing less than 100, and Mn will make resin be dissolved in solvent hardly above 20000 simultaneously, thereby be unsuitable for practical application.
Glass transition temperature (Tg) is meant the intermediate value temperature according to the shown displacement of the heat deflection of differential scanning calorimetric method (DSC) measurement herein.Number-average molecular weight (Mn) is to measure and be the value of N Reference Alignment with normal polyethylene or polystyrene according to gel permeation chromatography (GPC).More particularly, the measurement by under the following conditions obtains number-average molecular weight.
[condition]
Employed pillar: JORDI-SAEULE 500 * 10 LINEAR
Moving phase: 1,2-dichloro-benzenes (135 ℃),
Flow velocity: 0.5ml/min
Detecting device: differential refractometer
Below describe cyclic olefin copolymer (C0C) in detail.
Cyclic olefin copolymer (COC) is to have 2-12 carbon, the light alkene of preferred 2-6 carbon, as alpha-olefin (or more broadly non-cyclic olefin) for example ethene, propylene, butylene etc. and have 3-17 the carbon that has of at least one two key, the ring-type of preferred 5-12 carbon or polycyclic compund (ring-type (ring) alkene) be as norborene, tetracyclododecane, bicyclopentadiene, cyclohexene etc., preferably the multipolymer of norborene or tetracyclododecane.This multipolymer water white transparency also has high transmittance.
Prepare COC by using metallocene catalyst system, ziegler catalyst system, metathesis polymerization catalyzer promptly to open the catalyzer that two keys and ring-opening polymerization use.
The synthetic example of the olefin polymer with said structure is disclosed 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-7-253315.
According to above-mentioned document, can be by in the presence of oxidation of alkyl aluminium or other catalyzer and at least a metallocene type catalysts that contains zirconium for example or hafnium, at-78 to 150 ℃, the above-mentioned monomer that makes one or more types under preferred 20 to 80 ℃ temperature and 0.01 to 64bar the pressure randomly with one type above-mentioned non-cyclic monomer copolymerization, preparation cyclic olefin copolymer.EP-A-317262 discloses other useful polymkeric substance.Also can use the polymkeric substance or the multipolymer of the hydrogenation of styrene and bicyclopentadiene.
Metallocene is activated in being dissolved in inertia hydro carbons such as aliphatic series or aromatic hydrocarbons the time.For example, metallocene catalyst is dissolved in the toluene and is activated in advance, thereby reacts in solvent.
The key character of cyclic olefin copolymer is its softening point, fusing point, viscosity, dielectric properties, dislocation-free temperature range and transparency.Can be by selecting the ratio of monomers/comonomers effectively, promptly ratio, molecular weight, molecular weight distribution, hybridized polymer, mixing and the adjuvant of monomeric unit regulated these features in the multipolymer.
Introducing the non-cyclic olefin of reaction and the mol ratio of cyclic olefin can change in wide scope with the target cyclic olefin copolymer, preferably is adjusted to 50: 1 to 1: 50 and preferred especially 20: 1 to 1: 20.
For example, when being used for the prepared in reaction cyclic olefin copolymer, the glass transition temperature of reaction product (Tg) is subjected to the scale effect of employed these components widely when two kinds of components (ethene is used as cyclic olefin as non-cyclic olefin and norborene).When norborene content increased, Tg also was tending towards increasing.For example norborene content is that Tg can be provided is-20 ℃ to 60 ℃ multipolymer for the composition of 15mol% or lower (ethylene contents is 85mol% or higher).On the other hand, norborene content is 60 ℃ to 180 ℃ multipolymer for 15mol% or higher composition can provide Tg.Regulate physical property such as number-average molecular weight according to method known in the document.
The composition of employed olefin copolymer with ring texture is as follows among the present invention:
The adhesive composition that is used for core preferably is made up of with 95: 5 to 5: 95 weight ratio the cyclic olefin polymer of unmodified cyclic olefin polymer and sour modification.
Unmodified cyclic olefin polymer has 100-20000, the number-average molecular weight (Mn of preferred 1000-10000; Measure according to the tygon base value of standard by GPC, identical therewith thereafter), its weight-average molecular weight (Mw) is 200-40000, preferably 6000-30000, and glass transition temperature (Tg) is-20 ℃ and arrives less than 60 ℃ preferred 40 ℃ to 59 ℃.
Simultaneously, the cyclic olefin polymer of sour modification has 100-20000, the number-average molecular weight (Mn) of preferred 1000-10000, its weight-average molecular weight (Mw) is 300-80000, preferably 3000-40000, and glass transition temperature (Tg) is-20 ℃ and arrives less than 60 ℃ preferred 40 ℃ to 59 ℃.
In order to ensure desired photographic fixing ability with widen the dislocation-free temperature range of practical application, above-mentioned cyclic olefin copolymer preferably includes a kind of low-molecular-weight polymkeric substance or low viscous polymer moieties (A) and a kind of high molecular weight polymers or full-bodied polymer moieties (B), and its physical property is as described below.
More particularly, olefin copolymer of the present invention can be the potpourri of polymkeric substance (A) and polymkeric substance (B); Maybe can have unimodal molecular weight distribution, and a kind of polymer moieties has less than 7500 number-average molecular weight and a kind of polymer moieties and has 7500 or higher number-average molecular weight; The molecular weight distribution that maybe can have two or more peaks wherein has less than 7500 number-average molecular weight with corresponding to the polymer moieties at other peak corresponding to the polymer moieties at least a peak and has 7500 or higher number-average molecular weight.
The composition of aforementioned olefin copolymer all plays the effect of widening the dislocation temperature range at low temperature and high temperature both sides, thereby improves the ability of toner fixing and improve fixing performance in high speed duplicating under low temperature and low pressure.
Polymkeric substance or polymer moieties (A) (being called " component (A) " thereafter) have
Less than 7500, preferred 1000 to less than 7500 and more preferably 2000 to less than 7500 number-average molecular weight (by GPC (gel permeation chromatography) is that benchmark is measured with the normal polyethylene, identical therewith thereafter);
Less than 15000, preferred 1000 arrive the weight-average molecular weight that arrive less than 15000 less than 15000 and more preferably 4000;
Limiting viscosity (i.v. less than 0.25dl/g; Down solve homogeneously in limiting viscosity in the 100ml naphthalane when the 1.0g polymkeric substance at 135 ℃); With
Preferably less than 70 ℃ glass transition temperature.
Polymkeric substance or polymer moieties (B) (being called " component (B) " thereafter) have
7500 or higher, preferred 7500 to 50000 number-average molecular weight;
15000 or higher, preferred 15000 to 50000 weight-average molecular weight;
0.25dl/g or higher limiting viscosity (i.v.).
In addition, the content of component (B) is less than 50wt%, preferred 5-35wt% (all adhesive resins).
Component (B) provides a kind of toner-particle with structural viscosity that improving misplaces prevents effect and adhere on paper to be duplicated, film or other matrix.Yet, when the content of component (B) is 50wt% or when higher, the even rapid variation of mixed performance, thus damage the performance of toner.In other words, be difficult to form high quality graphic or picture rich in detail with high fixing strength and good thermal response property, or mechanical lapping performance step-down, make to be difficult to prepare toner with the particle diameter that requires.
By the way, polymkeric substance as used herein or polymer moieties are meant the polymer moieties of cyclic olefin copolymer; Wherein olefin polymer is made up of various components with different number-average molecular weights etc., polymkeric substance or polymer moieties are meant each polymers compositions before mixing, and polymkeric substance or polymer moieties are meant by GPC or other suitable means and separate the polymer moieties that final synthetic product obtains simultaneously.When polymer moieties is single disperses or during near single the dispersion, 7500 number-average molecular weight (Mn) is corresponding to about 15000 weight-average molecular weight (Mw).
The low viscosity component of olefin copolymer (A) works to widening the dislocation-free temperature range in low temperature one side, and high viscosity component (B) works to widening the dislocation-free temperature range in high temperature one side.Therefore, Mn be 20000 or higher high viscosity component (B) to widen the dislocation-free temperature range in high temperature one side more effective requiredly.
Component (A) and content (B) are respectively 0.5 weight portion or higher, preferred 5-100 weight portion, and being defined as 100 weight portions with the total amount of adhesive resin is benchmark.In two kinds of components each can not provide the wide dislocation-free temperature range that is suitable for practical application less than 0.5 weight portion.
High viscosity (high molecular) and low viscosity (low-molecular-weight) olefin copolymer with ring texture have aforesaid number-average molecular weight (Mn), weight-average molecular weight (Mw) and limiting viscosity (i.v.), thereby the dispersion degree of the molecular weight distribution that characterizes with Mw/Mn is low to moderate 1-2.5, promptly is single disperse or near monodispersed.This makes and may prepare the toner with high heat response and high fixing strength, thus can be under low temperature and low pressure fusing toner.By constant charging and discharging efficiency, this also works to the homogeneity and the electrical stability of the storage stability of toner, toner failure performance, CHARGE DISTRIBUTION.Concerning low viscosity polymer or polymer moieties, especially preferably have single dispersion degree or have single dispersion degree basically, this is because like this toner has good so-called thermal response property, as showing fusing and curing etc. at once.
Olefin copolymer also is water white and has high transmittance.Therefore olefin polymer can be applied on the color toner fully.For example proved even, then fully mediated, can obtain good transparency when making sheet material by pressing machine then when adding AZO pigments " PermanentRubin F6B " (Clariant Co. manufacturing).In addition, the measurement by DSC method (differential scanning calorimetric method) has shown that olefin copolymer has extremely low melting heat.Therefore, can expect the obvious reduction of the energy that toner fixing consumed.
In addition, by in olefin copolymer, introducing carboxyl, can improve with the compatibility of other resin and also can improve dispersing of pigments performance in the toner.The introducing of carboxyl makes may improve adhesion and the photographic fixing ability of toner on paper, film or other replicating medium.
In order to introduce carboxyl, advantageously use two-step reaction method, wherein at first prepare olefin copolymer with ring texture, introduce carboxyl then.
Can provide at least two kinds of methods of introducing carboxyl.
In one approach, by the fusion air oxidation process methyl or other alkyl of the multipolymer end of the chain is oxidized to carboxyl.Yet, under the situation of using the metallocene catalysts olefin polymer, because this polymkeric substance only has a small amount of side chain and causes being difficult to introducing many carboxyls by this method.
Other method is that tertbutanol peroxide or other superoxide are used as initiating agent, make maleic anhydride, acrylic or methacrylic acid graft polymerization to olefin polymer with ring texture, so that obtain 1-5wt%, the method for the graft ratio of preferred 3-5wt% (with respect to the weight ratio of olefin polymer).
Graft ratio less than 1wt% is not enough to reach purposes such as improvement compatibility.On the other hand, the graft ratio that surpasses 5wt% will increase the intermolecular cross-linking in the olefin polymer, thus the increase molecular weight.This makes kneading and nonferromagnetic substance be unsuitable for practical application.In addition, can produce serious yellow and lose transparency.Therefore, this polymkeric substance is unsuitable for requiring water white color toner.
According to identical mode, introduce hydroxyl or the amino compatibility and the dispersing of pigments degree that can improve in the toner with other resin by known method.
In addition, can in olefin polymer, introduce cross-linked structure to improve the fixing performance of toner.
A kind of method of introducing cross-linked structure is to make non-cyclic olefin and cyclic olefin and cyclopentadiene, cyclohexadiene, norborene, tetracyclododecane, butadiene or other diolefinic monomer binary polymerization in synthetic above-mentioned olefin polymer.
The result of this method is, olefin polymer even do not having under the situation of crosslinking chemical has and shows active end group.The known chemical reaction of formation cross-linked structure is as oxidation or epoxidation or add the functionalization that crosslinking chemical causes olefin polymer.
Other method is to add metal such as zinc, copper or calcium in the olefin polymer with ring texture of introducing carboxyl therein, then with screw mixes and fusion mixture, metal is dispersed in the olefin polymer with thin particle form, thereby forms ionomer with cross-linked structure.About the technology of this ionomer itself, for example US4693941 discloses the ter-polymers of carboxylic ethene, and it exists with the form of divalent metal salt of partially or completely neutralization, and purpose is in order to attempt to obtain toughness.
JP-A-6-500348 has reported a kind of unsaturated carboxylic acid ionomer polyester molding product of (preparing this ionomer for identical purpose) that contains, and wherein the carboxyl of about 20-80% neutralizes with zinc, cobalt, nickel, aluminium or copper (II).
Cyclic olefin polymer can be used as core, wherein can add the olefin polymer that 5-95wt% has the sour modification of the ring texture of introducing carboxyl in described cyclic olefin polymer.This will be an effective means of guaranteeing photographic fixing ability and dislocation-free temperature range.
(2) colorant
Employed carbon black, diazonium Huang, phthalocyanine blue, quinacridone, carmine 6B, monoazo Hong, perylene or other colorant can be incorporated in the core as colorant in conventional monochrome or the color copy machine toner.
(3) function endowing agent
Various types of paraffin can be used as the function endowing agent, are used to widen the dislocation-free temperature range and improve the dislocation-free performance.At least aly be selected from following wax and can be used as the function endowing agent: the metallic soap of polar waxes such as amide waxe, Brazil wax, higher fatty acid and ester thereof, higher fatty acid, partly-hydrolysed high-grade aliphatic ester and higher fatty acid alcohol; And nonpolar wax such as polyolefin-wax and paraffin.
In the middle of various waxes, consider the polypropylene wax of preferred fatty acid amide waxe, oxidized polyethlene wax and sour modification from the angle that realizes wide dislocation-free temperature range.
For above-mentioned dislocation-free temperature range and the improvement toner performance of widening toner, preferably use wax in the following manner.
That is to say that preferred compositions is used the wax of two or more types, described wax has the different melting points (peak temperature in differential scanning calorimetric (DSC) is measured) in 80-140 ℃ of scope.If fusing point less than 80 ℃, then causes being tending towards sticking together owing to low melting point.Simultaneously, owing to require function endowing agent fusing fully under the melt temperature that is higher than the adhesive resin softening point, the upper limit of wax is subjected to having the restriction of olefin polymer softening point (about 135-140 ℃) of ring texture and preferred 140 ℃, and described olefin polymer is the key component in the adhesive resin.
More particularly, use the following wax that is selected from two or more types of fatty acid amide wax and hydrocarbon wax.
(i) has the wax of polar group
Wax with polar group comprises various fatty acid amide wax, for example arachic acid monoamides (fusing point: 110 ℃), docosanoic acid (fusing point: 115 ℃), N, N '-two oil base decanedioic acid acid amides (fusing point: 115 ℃), N, N '-two oil base hexane diacid acid amides (fusing point: 119 ℃) and N, N '-distearyl m-phthalic acid acid amides (fusing point: 129 ℃); The oxyalkylene chloroflo is oxidized polyethlene wax (fusing point: 116 ℃) for example; The polyolefin-wax of acid modification is polypropylene wax of sour modification (fusing point: 138 ℃) and Brazil wax (fusing point: about 80 ℃) for example.
(ii) nonpolar wax (wax that does not have polar group)
Nonpolar wax comprises alkene wax (they are hydrocarbon waxs), for example Tissuemat E (fusing point: 130 ℃), polypropylene wax (fusing point: 120-150 ℃), paraffin (fusing point: about 60 to 80 ℃), sazole wax (set. pt.: about 98 ℃) and microcrystalline wax (fusing point: 80-100 ℃).
Silicone oil with stripping feature can combine with above-mentioned wax as the function endowing agent that prevents inconsistent phenomenon, as long as its not negative effect effect of the present invention.
(4) charge control agent
Can in core, mix aniline black byestuffs, fatty acid modified aniline black byestuffs, metallized aniline black byestuffs, metallized fatty acid modified aniline black byestuffs, 3, the chromium complex of 5-di-tert-butyl salicylic acid, quaternary ammonium salt, triphenhlmethane dye, azo chromium complex and other known charge control agent.
(5) other adjuvant
Except aforementioned toner component, optionally can in core, mix the lubricant of flowable such as colloidal silica (comprising fumed silica), aluminium oxide or titanium dioxide and fatty acids slaine such as barium stearate, calcium stearate or barium laurate, as long as its not negative effect effect of the present invention.
(6) consumption of component to be mixed
Be incorporated into amounts of components in the core of the present invention and be similar to the development duplicating machine that is used in electrostatic image and under the toner situation in the printer those, and as shown in table 1.
Table 1: the general composition (unit: wt%) of toner
| Adhesive resin | Colorant | Charge control agent | The function endowing agent | Magnaglo | Solvent | |
| Two dry component toners | 50-100 | ?0-20 | ?0-10 | ?0-20 | ?- | - |
| Dry non-magnetic monocomponent toner | 50-100 | ?0-20 | ?0-10 | ?0-20 | ?- | - |
| Dry magnetic mono-component toner | 0-100 | ?0-20 | ?0-10 | ?0-20 | ?0-60 | - |
| Dry polymerization toner | 50-100 | ?0-20 | ?0-10 | ?0-20 | ?- | - |
| The toner of liquid dried | 15-50 | ?0-10 | ?0-5 | ?0-10 | ?- | 50-70 |
| Liquid toner | 15-50 | ?0-10 | ?0-5 | ?0-10 | ?- | 50-70 |
[B] constitutes the material of the shell material of microcapsules toner-particle
Shell material comprises as the coating resin of principal ingredient and adjuvant such as function endowing agent or charge control agent etc. arbitrarily.The coating resin that uses in shell also has the photographic fixing ability, thereby as bonding agent, described bonding agent is similar to the aforementioned resin of using in core.
(1) coating resin
Resin that photographic fixing is used or following coating resin with olefin polymer of ring texture as formation microcapsules toner-particle shell.
Compare with the adhesive resin of core, coating resin has high melt point or softening point, and has better storage stability thus.
The example of the coating resin that photographic fixing is used comprises styrene, substituted styrene and derivant thereof, (methyl) acrylic acid, (methyl) acrylate, maleic anhydride, maleic anhydride ester and derivant thereof, the maleic anhydride acid amides, nitrogenous vinyl compound such as vinylpyridine, N-vinyl imidazole etc., vinyl monomer such as vinyl acetal, vinyl chloride, vinyl cyanide, vinyl acetate etc., vinylidene monomer such as vinylidene chloride, vinylidene etc. and olefinic monomer such as ethene, the homopolymer of propylene etc. and multipolymer, condensation polymer such as polyester, epoxy resin, polycarbonate, polyamide, polyurethane, polyureas, rosin, modified rosin, phenol resin, melamine resin, polyphenylene oxide and terpene resin, the fat hydrocarbon resin, alicyclic hydrocarbon resin and petroleum resin, and can use this resin separately or with the use that combines of two or more types.
In order to prevent that toner wherein from transferring to the inconsistent phenomenon on the hot-rolling, and in order further to improve storage stability, following olefin polymer with ring texture is preferably used as the coating resin of shell material.
Unmodified alkene with ring texture is preferably used as the coating resin of shell material.Owing to as long as the glass transition temperature of employed polymkeric substance is 60 ℃ or higher, just can guarantee the storage stability of toner fully, so all consumptions can be 60 ℃ or higher have ring texture and substitute with the olefin polymer of sour modification with Tg.
This unmodified olefin polymer with ring texture has between 1000-100000, preferred 2000 to 50000 number-average molecular weight (Mn), have between 2000-200000, the weight-average molecular weight (Mw) of preferred 4000-100000, with between 60 ℃-180 ℃, preferred 60 ℃-80 ℃ glass transition temperature (Tg).
Simultaneously, the olefin polymer of the sour modification of above-mentioned usefulness has between 1000-100000, preferred 2000 to 50000 number-average molecular weight (Mn), have between 3000-300000, the weight-average molecular weight (Mw) of preferred 6000-200000, with between 60 ℃-180 ℃, preferred 60 ℃-80 ℃ glass transition temperature (Tg).
If, will there be many problems less than 60 ℃ in the glass transition temperature of above-mentioned olefin polymer on the storage stability of toner-particle and if glass transition temperature surpasses 180 ℃, then fusing point rising and photographic fixing ability are tending towards variation.In addition, if the number-average molecular weight of above-mentioned olefin polymer less than 1000, then can not obtain sufficient fixing strength, and, then be difficult to guarantee desired stability in solvent if number-average molecular weight surpasses 100000.
Those of the material of modification, crosslinked material and above-mentioned olefin polymer with ring texture various features except glass transition temperature and number-average molecular weight and the above-mentioned olefin polymer with ring texture that uses in core are identical, omit its explanation at this.
(2) function endowing agent
In order to widen the dislocation-free temperature range and further to improve the dislocation-free performance on toner-particle surface, the identical functions imparting agent that uses in above-mentioned core (wax, silicone oil) also can be incorporated in the shell material.The preferred forms of above-mentioned application etc. are also applicable to the function endowing agent of waiting to be incorporated in the shell material.
(3) charge control agent
The identical charges controlling agent that uses in above-mentioned core can be incorporated in the shell material.
(4) external application adjuvant
The surperficial available required external application adjuvant of the shell material of toner-particle is coated with.
The example of external application adjuvant comprises the lubricant of flowable such as colloidal silica (comprising fumed silica), aluminium oxide, titanium dioxide etc. and fatty acids slaine such as barium stearate, calcium stearate or barium laurate etc. and this external application adjuvant can use separately or be used in combination with the form of two or more types.Preferred these adjuvants are hydrophobic.
The consumption of employed external application adjuvant is 0.01-10 with respect to per 100 weight portion toner-particles, preferred 0.05-5 weight portion.
If be coated with shell material by the external application adjuvant, the solution coat that then will contain the external application adjuvant adheres to the external application adjuvant on the surface of particle to the surface of particle or by other method.
(5) amounts of components to be mixed
The consumption of the said components in shell material sees the above table, and different is colorant to be mixed.
The microcapsules toner-particle has and resembles capsule or said core-shell structure, and wherein core is coated with shell material.
The preferred 3-10 micron of the mean grain size of whole particle (diameter), the thickness of shell { [(external diameter of capsule)-(diameter of core)] * preferred 0.1-0.5 micron of 1/2}.
According to the present invention, there is the combination of the core and the resin that shell material is used of following three kinds of patterns.
(a) core: olefin polymer (20 ℃≤Tg＜60 ℃, 100≤Mn≤20000) with ring texture
Shell material: the coating resin that photographic fixing is used
(b) core: the adhesive resin that adhesive resin that hot photographic fixing is used and pressure photographic fixing are used
Shell material: olefin polymer (60 ℃≤Tg≤180 ℃, 1000≤Mn≤100000) with ring texture
(c) core: olefin polymer (20 ℃≤Tg＜60 ℃, 100≤Mn≤20000) with ring texture
Shell material: olefin polymer (60 ℃≤Tg≤180 ℃, 1000≤Mn≤100000) with ring texture
As given example in above-mentioned photographic fixing resin [A] (1) and [B] (1), at least a shell material or core, mix alkene and mix various crystallizations and the result of noncrystalline resin (they are compatible with olefin polymer) is the further feature (these features are important to the toner performance) that can demonstrate transparency, low-temperature fixing ability, mechanical shock resistance and have the olefin polymer of ring texture with ring texture.
In pattern (c), in shell material and core, all use olefin polymer with ring texture, above-mentioned feature is shown as the performance of toner fully.
The most preferred form of toner-particle is the following olefin polymer with ring texture, be that glass transition temperature (Tg) is between 40-59 ℃, number-average molecular weight (Mn) is 10 or lower between 1000-10000 and polydispersity (weight-average molecular weight (Mw)/number-average molecular weight (Mn)), and the copolymerization mol ratio of ethene and norborene is 85/15 to 95/5 the ethylene-norbornene copolymer adhesive resin as core, and following olefin polymer with ring texture, promptly (MEK) is solvable in MEK, glass transition temperature (Tg) is between 60-80 ℃, between 4-10, and the copolymerization mol ratio of ethene and norborene is 75/25 to 85/15 the ethylene-norbornene copolymer coating resin as shell material to number-average molecular weight (Mn) between 2000-50000 and polydispersity (Mw/Mn).
Preferably prepare the microcapsules toner-particle by intermediate processing again.More particularly, be that good solvent solution is splashed in the poor solvent solution of coating resin of shell material, the solvent that causes shell material precipitation around core is intermediate processing again, and wherein said good solvent solution has adhesive resin and the colorant that is dissolved in wherein.
Also can prepare the microcapsules toner-particle according to the phase disengagement method shown in for example JP-B-08-16793 and the JP-B2-2631019.
(1) passes through again the method (solvent is intermediate processing again) that intermediate processing prepares
After 16-20wt% being constituted the olefin polymer with ring texture and the 1-2wt% function endowing agent adding of core under 25-30 ℃ temperature and being dissolved in the 76-80wt% solvent (mixed solvent of toluene and cyclohexane etc.), the colorant of dispersion 1-2wt% such as use bowl mill prepares solution (solution A).
On the other hand, the charge control agent of olefin polymer with ring texture by 1.8-2.2wt% being constituted shell material and 0.015-0.025wt% is dissolved in the MEK of 98wt% or other solvent and prepares solution (solution B).
In next step, solution A is splashed into the solution B of high-speed stirred from the nozzle that has a plurality of 20-30 micron diameter holes, obtain precipitation, then it is flow through 2 microns, 0.5 micron and 0.2 micron multistep filtrator, thereby from solvent, separate.In one step of back, form particle by using the high-temperature vacuum exsiccator to remove residual solvent.
Obtain the particle size distribution of mean diameter spherical in shape basically, as to have the 4-10 micron and 2-12 micron thus (corresponding to 3 σ, and shell material thickness is the microcapsules toner-particle of 0.2-0.5 micron (based on the weight measurement by solvent fractionation method) σ=standard deviation wherein).
Externally add hydrophobic silica then as developer.
(2) method for preparing by the gas phase separation method
Melt kneading have ring texture olefin polymer, have olefin polymer, wax, colorant and the charge control agent of the sour modification of usefulness of ring texture.In hot water; under high-speed stirred, make after hydrophilic silicon dioxide looses as the protecting colloid differential, be cured, then dissolve silica and be removed by alkaline aqueous solution by cooling off fast with big water gaging; with obtain core material particles by water/methyl alcohol drip washing, filter then.
Olefin polymer, wax and the charge control agent that will have ring texture independently are dissolved in ketone solvent, among the preferred MEK, the above-mentioned core material particles of disperseing scheduled volume with homomixer, the acetate that adds scheduled volume, under degree of depth cooling, drip water at a predetermined velocity shell material is deposited on the core material particles surface more then.
Then, the mixed solution drip washing of water and methyl alcohol, filter and carry out drying, obtain the microcapsules toner-particle.
Externally add hydrophobic silica then as developer.
Can find out from more above-mentioned two kinds of preparation methods, intermediate processing is more suitable for commercial production again, the solvent that reason is to use general cheaply purpose to use, and because the difference of the recessive heat of solvent and water causes more easily carrying out drying, and mutual coalescent the tailing off of toner-particle.
Implement optimal mode of the present invention
Although the mode by embodiment and comparative example has been described the present invention in more detail, these embodiment and comparative example do not limit effective range of the present invention at all.
Be prepared as follows dry monocomponent toner and dry bi-component toner.
Embodiment 1-4 is that the embodiment and the embodiment 5 that prepare microcapsules by intermediate processing again are the embodiment that prepare microcapsules by phase disengagement method.
Embodiment 1
Preparation solution A (core)
That 17wt% is made by Ticona GmbH and to have 49 ℃ glass transition temperature (Tg) and number-average molecular weight (Mn) be that 2000 " Topas T-936 " is used as the olefin polymer with ring texture, that 1wt% is made by Ticona GmbH and to have 58 ℃ glass transition temperature (Tg) and number-average molecular weight (Mn) be the olefin polymer that 3700 " Topas AG-07 " is used as the sour modification of usefulness with ring texture, 0.5wt% is used as the function endowing agent by " BNT22H " and the 0.5wt% that Nippon Seika makes by " Ceridust 3715 " (trade name) that Clariant makes, with under the stirring rate of 30 ℃ and 200rpm, these components are joined gradually and are dissolved in the mixed solvent (weight ratio 50: 50) of 80wt% toluene and cyclohexane.
In above-mentioned solution, add bead then (by the powder of stainless steel of Ashizawa manufacturing, particle diameter: 500 microns), and add 1wt% black colorant (" Carbon Black MA-7 " that Mitsubishi Chemical makes) gradually and use the stirring rate of 500rpm to disperse, obtain solution A.
Preparation solution B (shell material)
That 2wt% is made by Ticona and to have 67 ℃ glass transition temperature (Tg) and number-average molecular weight (Mn) be that 4600 " Topas AG-09 " is used as olefin polymer with ring texture and with itself and 0.02wt% charge control agent (" Copy Charge NX " (trade name); Make by Clariant) be dissolved in together in about 98wt% MEK, obtain solution B.
Granulating technique
Above-mentioned solution A is splashed into the solution B of high-speed stirred from the nozzle that has a plurality of 30 micron diameter holes, form particle.
About rate of addition, if in the still of 500 liters of volumes, make under the situation of particle, 100 liters of solution A were joined in 20 minutes in 200 liters of solution B gradually by the mode that from 100 holes, oozes with 5 liters/minute speed, obtain precipitation.
The stirring rate of fixed solution B is 2000rpm, and continues to stir 10 minutes in the back that is added dropwise to complete of solution A.Then precipitation is flow through the multistep filtrator of 2 microns, 0.5 micron and 0.2 micron, thereby from solvent, separate.Then, form the microcapsules toner-particle by using the high-temperature vacuum exsiccator to remove residual solvent.
The mean diameter of gained toner-particle about 6 microns and all distribution of particles are in the particle size range of 2-12 micron.Because the size of corase particles is separated and is not required very thin particle, therefore finds that this method is good in yield aspects.
Observation proof particle by flying-spot microscope is spherical in shape basically and measure following weight according to solvent fractionation method, thereby the thickness that calculates shell material is the 0.2-0.5 micron.
Output about toner, dried output is 21.7kg (productive rate is 92%), with respect to 100 liters of (about 85.6kg, wherein the core polymkeric substance comprises 17.1kg) solution A and 200 liters of (about 162kg, wherein the shell material polymkeric substance comprises 6.5kg) solution B (total solid is 23.6kg).
Flow toner productive rate that method (this method uses high-speed air to flow) obtains of mechanical grinding method by routine and air blast is about 80% and about 75% respectively, wherein forms 1 micron or lower ultrafine particle.Find significantly to improve the productive rate of toner thus by said method.
Measure the mean grain size of toner-particle according to laser diffraction and scattering type size distribution measurement mechanism (by " LA-700 " of Horiba Seisakusho manufacturing).Also account for 95% volume and 75% quantity by identical measurement device size distribution and the particle of finding the 4-10 micron grain size.
In order to measure the thickness of shell material, the 10g toner-particle and being placed in 1 liter of MEK of weighing, by be heated to 50 ℃ and stir made the shell material dissolving in 20 minutes after, filter solvent and measure remaining weight by heat, to calculate the thickness of shell material.
Embodiment 2
Except using yellow colorants " Yellow HG (trade name) " that Clariant makes, obtain the microcapsules toner-particle in the mode identical with embodiment 1 as the colorant.
Embodiment 3
Except using pinkish red colorant " Pink EO2 (trade name) " that Clariant makes, obtain the microcapsules toner-particle in the mode identical with embodiment 1 as the colorant.
Embodiment 4
Except using cyan colorants " Blue BO2G (trade name) " that Clariant makes, obtain the microcapsules toner-particle in the mode identical with embodiment 1 as the colorant.
Embodiment 5
With reference to JP-B1-8-16793 and JP-B2-2631019, be prepared as follows the microcapsules toner-particle by phase disengagement method.
The preparation core material particles
85wt% is used as the olefin polymer with ring texture by " the Topas T-936 " that Ticona makes, " the Topas AG-07 " that 5wt% is made by Ticona is used as the olefin polymer of the sour modification of usefulness with ring texture, the mixed-powder of 2wt% docosanoic acid amide waxe (" BNT22H " (trade name) of being made by Nippon Seika) and 2wt% oxidation and non-oxide Tissuemat E (" Ceridust 3715 " (trade name) made by Clariant) is used as the function endowing agent, with at 120 ℃ down with kneader (" Rheomix 600 " of making by Haake) these components of melt kneading and 5wt% black colorant (" the CarbonBlack MA-7 " that make by Mitsubishi Chemical) and 1wt% charge control agent (by " Copy ChargeNX " (trade name) of Clariant manufacturing) with transfer to the gained potpourri in the rustless steel container of being furnished with well heater and remain under 130 ℃.
Independently water is placed on homomixer (making) neutralization and is heated to and maintains about 95 ℃ by Tokushu Kika.Adding 0.4wt% colloidal silica (" HDK N-30 " that Wacker Chemie makes) then also disperses by stirring fully.
The rotational speed of homomixer is fixed on 8500rpm and adds the above-mentioned molten mixture of about 15 weight portions (phr) in the dispersion medium of hot water, continue stir about 15 minutes then, form microparticle.
Then, dispersion liquid is poured on the good ice of prepared beforehand (amount of ice is the twice of dispersion liquid), so that cool off fast and solidify microparticle.In dispersion liquid, add in equaling then and the sodium hydroxide concentration of colloidal silica amount, stirred 24 hours with propeller agitator under the room temperature, make the colloidal silica dissolving, and separate alkaline solution and solid by centrifugal filter.
Then with slurry water/methanol solution (50/50wt%) drip washing, filter for per twice, and carry out drying with the hot air dryer that is fixed on 40 ℃, obtain core material particles.
The volume average particle size of these particles is about 8 microns (" LA-700 " that make by Horiba Seisakusho measures).
Preparation shell material solution
Use 95 weight portions above-mentioned " Topas AG-09 " as the mixed-powder of olefin polymer, 2 weight portion docosanoic acid amide waxes with ring texture (" BNT22H " (trade name) of making by Nippon Seika) and 2wt% oxidation and non-oxide Tissuemat E (" Ceridust 3715 " (trade name) made by Clariant) as the function endowing agent, 1 weight portion charge control agent (" Copy Charge NX " (trade name) made by Clariant) and 2400 weight portion MEKs prepare the shell material solution that is used to seal.
The homomixer assembling has the reactor of 20 liters of volume chucks, adds the above-mentioned solution of 7.6kg in reactor, and after under agitation being cooled to-25 ℃, adding 120g acetate also stirred 5 minutes.
Then the above-mentioned core material particles of 2.0kg is joined in the reactor, and after fully disperseing with homomixer, add 0-5 ℃ cold water with the rate of addition of 10g/min.In the end increase rate of addition in the step gradually to 100g/min and the about 3kg water of last adding.About 2 hours of this technology required time.
Then, separate capsule solution and water/methyl alcohol (50/50wt%) drip washing capsule particle by isolated by filtration 2 times by centrifugal filter, isolated by filtration is also dry down at 40 ℃.
About 8.5 microns of the volume average particle size of capsule particle, this is obviously big and owing to seal and cause diameter to become big than core material particles.
The weight of measuring by above-mentioned solvent fractionation method calculates similar basically shell material thickness (0.2-0.3 micron).
Externally the hydrophobic colloidal silica of 0.5 weight portion is joined on the thus obtained microcapsules as developer.
The comparative example 1
Toner is the toner that is available commercially from by air blast Ginding process (jet mill method) preparation, and the toner that is used for duplicating machine " FT-5520 " of more specifically saying so and being made by Ricoh uses this toner and carries out Performance Evaluation with above-mentioned duplicating machine.
The comparative example 2
Toner is the toner that is available commercially from by the mechanical grinding method preparation, the toner that is used for printer " Magicolor 2CX " of more specifically saying so and being made by QMS uses this toner also to carry out Performance Evaluation with the duplicating machine " FT-5520 " that above-mentioned Ricoh produces.
By microcapsules toner that uses gained among the embodiment 1-4 and the toner that comparative example 1 and 2 is purchased, carry out real duplicating with the duplicating machine " FT-5520 " of manufacturing.The results are shown in Table 2.
(a) effect of anti-(antispent) toner that lost efficacy
Use each embodiment and comparative example's toner sample on the high-quality paper, to carry out the real experiment of duplicating.Copy to till the limiting quantity that the toner component adheres on the developing cylinder and photoconductor arrive to allow always, be used in the paper that place copies on the paper and contrast.
(b) transfer performance
Measurement is transferred to efficient on the high-quality paper from photoconductor, is benchmark to duplicate the toner consumption that reclaims the back on 10000 paper, and wherein said paper is a matrix to be duplicated.
(c) photographic fixing ability
Use various toners on high-quality paper, to form image, with one not the paper of equal in quality of printing be placed on paper top of printing and, make it to transfer under external force on the paper that does not print with the image of anti-wiping power test machine wiping printing.
The fixation rate of image is fixed as 150mm/sec and fixing temperature is fixed as 150 ℃.
Anti-wiping power experimental conditions is fixed as carries out 20 times under the load (about 907g) at 2 pounds and moves back and forth.After wiping, use Macbeth type reflection-densitometer to measure initial density of image (A) before wiping, transfer to density (B) on the paper of not printing and density (C) that paper does not have image region, and determine transfer velocity by following formula [(B-C)/A * 100 (%)].The lower limit of the fixing temperature of measurement and comparison 60% or higher transfer velocity and the lower limit of photographic fixing pressure.
(d) Tu Xiang sharpness
The image definition that compares each toner, and following opinion rating, fine rule resolution and OHP transmittance.
Grade
The sample that uses Dataquest Co. to make is by 0-16 level gray scale step opinion rating.
Fine rule resolution
The sample that uses Dataquest to make is estimated the fine rule resolution characteristic by the thread pattern of 0-600dpi.
The OHP transmittance
On the ohp film that the PPC that Fuji Xerox makes uses, form image, measure transmittance, and characterize transmittance with A/B * 100% in image region (A) and no image area (B).
(e) storage stability
With the toner of each side method preparation after 60 ℃ and 50%RH (relative humidity) preserve 8 hours down, make toner through regular time section through 100 purpose screen clothes, by characterizing with % except that the value that the screen cloth residue gets with employed sample size.Coalescent this value that will make of toner-particle is higher in the preservation process.Be that 50 ℃ or lower material cause coalescent mainly by fusing point contained in the method for producing toner and toner.Symbol " o " expression 0.5% or lower screen cloth residue and " * " expression surpass 0.5% screen cloth residue.
Table 2
| Assessment item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | The comparative example 1 | The comparative example 2 |
| Anti-inefficacy toner effect | ????50,000 | ????50,000 | ????50,000 | ????50,000 | ????50,000 | ?20,000 | 20,000 |
| The transfer performance of photoconductor (%) | ????99.8 | ????99.8 | ????99.8 | ????99.8 | ????99.8 | ?95 | 99 |
| Photographic fixing ability low pressure limit (kg/cm 2) | ????20 | ????20 | ????20 | ????20 | ????20 | ?400 | 300 |
| Photographic fixing ability lowest temperature (℃) | ????100 | ????100 | ????100 | ????100 | ????100 | ?140 | 130 |
| The image definition grade | ????16 | ????16 | ????16 | ????16 | ????16 | ?8 | 8 |
| Image definition fine rule resolution (dpi) | ????600 | ????600 | ????600 | ????600 | ????600 | ?300 | 300 |
| Image definition OHP transmittance (%) | ????95 | ????95 | ????95 | ????95 | ????95 | ?90 | 92 |
| Storage stability | ????○ | ????○ | ????○ | ????○ | ????○ | ?× | × |
Industrial applicibility
The microcapsules toner-particle that the toner of development static electrification image of the present invention usefulness is comprised of core and shell. In addition, the olefin polymer with circulus with relatively low glass transition temperature and relative low mean molecule quantity is used as the adhesive resin in core, and/or the olefin polymer with circulus with relatively high glass transition temperature and relative high number-average molecular weight is used as coating resin in shell material.
Therefore toner can be used for pressure heating fixation type copying equipment, and it has good storage stability, can produce high-grade sharp image and it is good at anti-inefficacy toner effect, transfer ability, photographic fixing ability and dislocation-free aspect of performance.
In addition, toner of the present invention even in low-temperature heat type copying equipment, show aspect the sufficient photographic fixing ability good.
In addition, even in the situation of using heat roller fixation type equipment, use toner of the present invention can easily realize significantly reducing the heating heat, thereby play a role making energy-conservation copying equipment.
In addition, by will being incorporated into shell material for the function imparting agent of the demoulding, thereby needn't be coated with to the warm-up mill surface unction such as silicone oil or wax.
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.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2000/002782 WO2001084248A1 (en) | 2000-04-11 | 2000-04-27 | Toner for electrostatically charged image development |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1408079A true CN1408079A (en) | 2003-04-02 |
Family
ID=11735980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00816783A Pending CN1408079A (en) | 2000-04-27 | 2000-04-27 | Toner for electrostatically charged image development |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100684062B1 (en) |
| CN (1) | CN1408079A (en) |
| CA (1) | CA2407323A1 (en) |
| DE (1) | DE60031580T2 (en) |
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| CN101067730A (en) * | 2006-05-02 | 2007-11-07 | 夏普株式会社 | Capsulated toner |
| CN100440048C (en) * | 2005-03-15 | 2008-12-03 | 富士施乐株式会社 | Toner for electrostatic charge image developing, developer for electrostatic charge image developing, and image forming apparatus |
| CN101144991B (en) * | 2006-09-08 | 2010-06-02 | 夏普株式会社 | Functional particle and manufacturing method thereof |
| US7833446B2 (en) | 2006-08-01 | 2010-11-16 | Sharp Kabushiki Kaisha | Method of manufacturing aggregated particles |
| CN101286028B (en) * | 2007-04-09 | 2011-02-16 | 富士施乐株式会社 | Endless belt, endless belt suspending apparatus, and image forming apparatus using the same |
| CN102053518A (en) * | 2009-11-09 | 2011-05-11 | 夏普株式会社 | Toner manufacturing method and toner |
| US8097395B2 (en) | 2007-08-08 | 2012-01-17 | Sharp Kabushiki Kaisha | Method of manufacturing toner particles, toner particles, two-component developer, developing device and image forming apparatus |
| CN101393404B (en) * | 2007-09-20 | 2012-05-30 | 富士施乐株式会社 | Toner for development of electrostatic image, developer for development of electrostatic image, and device and apparatus by using the same |
| US8252501B2 (en) | 2008-07-25 | 2012-08-28 | Sharp Kabushiki Kaisha | Method of manufacturing coalesced resin particles, coalesced resin particles, toner, two-component developer, developing device, and image forming apparatus |
| CN107209465A (en) * | 2015-03-26 | 2017-09-26 | 京瓷办公信息系统株式会社 | Developing toner for electrostatic latent images |
| CN107219733A (en) * | 2016-03-22 | 2017-09-29 | 富士施乐株式会社 | Tone agent for developing electrostatic charge image, electrostatic charge image developer and toner cartridge |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7105263B2 (en) * | 2003-12-30 | 2006-09-12 | Samsung Electronics Company | Dry toner comprising encapsulated pigment, methods and uses |
-
2000
- 2000-04-27 DE DE60031580T patent/DE60031580T2/en not_active Expired - Fee Related
- 2000-04-27 KR KR1020027012799A patent/KR100684062B1/en not_active IP Right Cessation
- 2000-04-27 CA CA002407323A patent/CA2407323A1/en not_active Abandoned
- 2000-04-27 CN CN00816783A patent/CN1408079A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100440048C (en) * | 2005-03-15 | 2008-12-03 | 富士施乐株式会社 | Toner for electrostatic charge image developing, developer for electrostatic charge image developing, and image forming apparatus |
| CN101067730A (en) * | 2006-05-02 | 2007-11-07 | 夏普株式会社 | Capsulated toner |
| US7875413B2 (en) | 2006-05-02 | 2011-01-25 | Sharp Kabushiki Kaisha | Capsulated toner having fine particle cycloolefin copolymer resin shell |
| CN101067730B (en) * | 2006-05-02 | 2013-02-13 | 夏普株式会社 | Capsulated toner |
| US7833446B2 (en) | 2006-08-01 | 2010-11-16 | Sharp Kabushiki Kaisha | Method of manufacturing aggregated particles |
| CN101144991B (en) * | 2006-09-08 | 2010-06-02 | 夏普株式会社 | Functional particle and manufacturing method thereof |
| US8067143B2 (en) | 2006-09-08 | 2011-11-29 | Sharp Kabushiki Kaisha | Functional particle and manufacturing method thereof |
| CN101286028B (en) * | 2007-04-09 | 2011-02-16 | 富士施乐株式会社 | Endless belt, endless belt suspending apparatus, and image forming apparatus using the same |
| US8097395B2 (en) | 2007-08-08 | 2012-01-17 | Sharp Kabushiki Kaisha | Method of manufacturing toner particles, toner particles, two-component developer, developing device and image forming apparatus |
| CN101393404B (en) * | 2007-09-20 | 2012-05-30 | 富士施乐株式会社 | Toner for development of electrostatic image, developer for development of electrostatic image, and device and apparatus by using the same |
| US8252501B2 (en) | 2008-07-25 | 2012-08-28 | Sharp Kabushiki Kaisha | Method of manufacturing coalesced resin particles, coalesced resin particles, toner, two-component developer, developing device, and image forming apparatus |
| CN102053518B (en) * | 2009-11-09 | 2012-10-03 | 夏普株式会社 | Toner manufacturing method and toner |
| CN102053518A (en) * | 2009-11-09 | 2011-05-11 | 夏普株式会社 | Toner manufacturing method and toner |
| CN107209465A (en) * | 2015-03-26 | 2017-09-26 | 京瓷办公信息系统株式会社 | Developing toner for electrostatic latent images |
| CN107219733A (en) * | 2016-03-22 | 2017-09-29 | 富士施乐株式会社 | Tone agent for developing electrostatic charge image, electrostatic charge image developer and toner cartridge |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2407323A1 (en) | 2001-11-08 |
| KR20020092403A (en) | 2002-12-11 |
| DE60031580D1 (en) | 2006-12-07 |
| KR100684062B1 (en) | 2007-02-16 |
| DE60031580T2 (en) | 2007-09-06 |
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