EP0633509A1 - Toner - Google Patents

Toner Download PDF

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Publication number
EP0633509A1
EP0633509A1 EP94114757A EP94114757A EP0633509A1 EP 0633509 A1 EP0633509 A1 EP 0633509A1 EP 94114757 A EP94114757 A EP 94114757A EP 94114757 A EP94114757 A EP 94114757A EP 0633509 A1 EP0633509 A1 EP 0633509A1
Authority
EP
European Patent Office
Prior art keywords
toner
surface tension
binder resin
temperature
reducing agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP94114757A
Other languages
English (en)
French (fr)
Other versions
EP0633509B1 (de
Inventor
Yoshimichi Katagiri
Yuzo Horikoshi
Norio Sawatari
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujitsu Ltd
Original Assignee
Fujitsu Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujitsu Ltd filed Critical Fujitsu Ltd
Priority claimed from EP91305642A external-priority patent/EP0463822B1/de
Publication of EP0633509A1 publication Critical patent/EP0633509A1/de
Application granted granted Critical
Publication of EP0633509B1 publication Critical patent/EP0633509B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08713—Polyvinylhalogenides
    • G03G9/0872—Polyvinylhalogenides containing fluorine
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08773—Polymers having silicon in the main chain, with or without sulfur, oxygen, nitrogen or carbon only

Definitions

  • the present invention is concerned with a toner used for developing an electrostatic latent image in, for example, electrophotography.
  • the toner used for developing the electrostatic latent image includes particles obtained by pulverizing binder resin made of a natural or synthetic high molecular weight substance dispersing colorant such as carbon black. Usually the diameter of the toner particles is about 5 to 20 ⁇ m.
  • the toner used for the development of an electrostatic latent image may consist of these particles alone, or may comprise the particles mixed with a carrier such as iron powder or glass beads.
  • Developing methods are either one-component developing methods or two-component developing methods.
  • the toner used in the former method usually contains magnetic powder, which is frictionally charged by friction between the wall and the developing roller surfaces and is held on the developing roller by the magnetic force of a magnet incorporated in the roller.
  • the toner is developed on to the latent image portion of a photoconductive insulator by the rotation of the roller, whereby the charged toner alone adheres to the latent image by electric attraction to carry the development of the image.
  • developer consisting of toner and carrier is frictionally charged by being mixed and stirred in a developing device.
  • the toner is conveyed to the latent image portion of photoconductive insulator while being carried on the carrier, whereupon the charged toner alone is selectively adhered to the latent image by an electric attraction to carry out the development of the image.
  • a hot roller fixing method is conventionally employed for fixing the toner, although a flash fixing method utilizing light energy generated by a Xenon lamp is now under development. This method has the following favourable characteristics:
  • the toner transferred to a recording medium is adhered to the medium in powdered state and forms a picture image.
  • the image can be destroyed if rubbed with a finger.
  • the toner absorbs energy from the light.
  • the temperature of the toner is accordingly elevated and the toner softens and melts and thus becomes closely adhered to the recording medium.
  • the temperature of the toner begins to fall and the toner solidifies, whereby a fixed picture image is formed.
  • a necessary condition for a toner is that the toner resin becomes soft at a comparatively low temperature and, at the same time, the picture image formed by the toner is not deformed even when the toner is in a molten state.
  • oligomers are generally employed as a binder resin in a toner due to their low melting temperature and good thermal stability.
  • the oligomer however, has defects such that a fixed picture image formed of such an oligomer is easily deformed due to the low melt viscosity and storage stability thereof, and thus the image quality is lowered. Further, when the light energy adsorbed by the toner is too strong, explosive fixing is liable which causes white voids called "image void", whereby the photographic density of the image is lowered.
  • FIGS 1-(a), (b) and (c) of the accompanying drawings illustrate how image void is formed.
  • These figures show that, when a strong light 3 (see Fig. 1(b)) is irradiated onto a toner 1 (see Fig. 1(a)) arranged in multiple columns on a sheet of recording paper 2, the toner 1 is easily melted due to the low softening temperature thereof, and a void 5 is formed inside the toner for the reasons described as follows.
  • numeral 4 in Fig. 1 represents a fixed picture image.
  • the void 5 formed according to the above mechanism is formed by explosive fixing.
  • the toner 1 absorbs energy strong enough to melt it, if the melt viscosity and storage stability of the binder resin 1 are too low compared with the surface tension thereof, the toner aggregates due to the surface tension thereof before the melted toner 1 solidifies, and thus a void 5 may be formed.
  • One way of solving the above problems is to increase the molecular weight of the binder resin. Although the melt viscosity and storage elastic modulus of the toner 1 become higher, the melting point thereof also becomes higher, so that the fixability of toner 1 is decreased.
  • the toner 1 for the light fixing often uses a low molecular weight resin with a lower softening temperature than the polymeric binder resin used in the toner 1 for a hot roller fixing method.
  • a blocking phenomenon may occur such that the toner surface softens when exposed to a high temperature environment and the toners merge.
  • the fluidity of the toner 1 becomes extremely low, and not only is the toner not smoothly supplied into the developing vessel but also the particle diameter, etc., thereof changes. Thus the electrification property of the toner also changes and a good developed image cannot be obtained.
  • an epoxy resin represented by bisphenol A diglycidyl ether, etc is employed as the binder.
  • an oligomer with a low softening temperature i.e. a comparative low molecular weight
  • Such an oligomer is liable to cause explosive fixation due to thermal decomposition thereof, and has a defect such that, owing to the high surface tension and melt viscosity thereof, voids are produced due to the aggregation of the toner particles and the image quality is lowered. Further, the blocking phenomenon occurs when the toner is exposed to a high temperature environment.
  • melt viscosity of the binder resin may be increased, the melting point thereof is also elevated. Therefore, although void formation may be prevented, the fixability is often degraded.
  • melt viscosity of the binder resin may be increased without elevating the melting point thereof, the blocking resistance is often greatly worsened, and the glass transition point of the binder resin is lowered in this case.
  • the present invention has been created in order to solve the problems as described above, and the object thereof is to provide a novel toner having an excellent void forming resistance without lowering the fixability and blocking resistance thereof.
  • the present inventors studied the afore-described problems, and found that these problems could be solved by adopting a binder resin with certain physical property values.
  • a toner comprising a surface tension reducing agent and one or more binder resins, characterized in that the melt viscosity and the surface tension of said toner, at a temperature of 200°C are, respectively, 30 poises or more and below 15 dyne/cm.
  • the present inventors found after intensive studies that, even when a binder resin with a comparatively low melt viscosity is employed to prevent the lowering of the fixability of a binder resin accompanying the elevation of the melting point thereof and the lowering of blocking resistance thereof accompanying the lowering of the glass transition point thereof, void formation arising from aggregation can be controlled by employing at least a substance for lowering the surface tension of the binder resin or an intermolecular force acting between the molecules constituting the binder resin, i.e., by employing a toner having its surface tension diminished by dispersing a surface tension decreasing agent in the binder resin, and thus achieved the present invention.
  • the present invention is concerned with a toner containing binder resins, in which a surface tension lowering agent is contained and as the surface tension decreasing agent, there may be employed a non-ionic surface active agent.
  • a surface active agent having hydrophilic and hydrophobic groups and exhibiting surface activity e.g. polydimethylsiloxane-polyether, polydimethylsiloxane-polyester represented by the following general formulae: R: an alkyl group or H 0.1 ⁇ b/a ⁇ 10 R: an alkyl group or H, 0.1 ⁇ b/a ⁇ 10, or fluorine polymers represented by the following formula R: an alkyl group or H 0.1 ⁇ a/b ⁇ 10, R: an alkyl group or H 0.1 ⁇ a/b ⁇ 10 etc. may be employed.
  • a surface active agent having hydrophilic and hydrophobic groups and exhibiting surface activity e.g. polydimethylsiloxane-polyether, polydimethylsiloxane-polyester represented by the following general formulae: R: an alkyl group or H 0.1 ⁇ b/a ⁇ 10 R: an alkyl group or H, 0.1 ⁇ b
  • the silicone polymer used as the surface tension reducing agent may be added to the binder resins at the stage of polymerizing the binder resins from monomers or at the stage of melting and kneading the toner-constituting materials.
  • the surface tension reducing agent is added to the binder resins at the stage of the polymerization of the binder resins, the surface tension reducing agent must be a material that does not impede the polymerization of the binder resins and that does not induce a secondary reaction.
  • the number-average molecular weight of the silicone polymer is preferably from 5 x 102 to 5 x 104, and as the number average molecular weight is increased, the dispersibility of the silicone polymer into the binder resins is lowered.
  • the surface tension reducing agent is determined according to the material of the surface tension reducing agent and the surface tension of the binder resins, the surface tension is preferably below 15 dyne/cm at a temperature of 200°C when a polyester resin (polyethylene terephthalate) is employed, which value corresponds to 0.01 to 2.00 wt% based on the weight of the toner.
  • the reason why the amount of added silicone polymer should be below 2.00 wt% is that, if the amount exceeds this limit, due to the surface tension reducing agent's effect of lowering the melt viscosity of the binder resin, the melt viscosity thereof becomes too low and therefore the void formation preventing ability thereof is lowered.
  • the lower limit of the amount of added silicone polymer should be 0.01 wt% is that, if the amount is below said value, the void formation preventing ability resulting from the lowering of the surface tension cannot be obtained.
  • polyethylene glycol ether or polyethylene glycol polyester represented by the following formula RCOO (CH2 CH2 O) n OR' wherein R and R', respectively, indicates an alkyl group or a hydrogen atom and 40 ⁇ n ⁇ 10 or RCOO (CH2 CH2 O) n COR' , wherein R and R', respectively, indicates an alkyl group or a hydrogen atom and 40 ⁇ n ⁇ 10.
  • these aliphatic non-ionic surface active agents When these aliphatic non-ionic surface active agents are employed, it is necessary to add them in a proportion of 5 wt% or more (normally within the range of from about 10 to about 20 wt%) to reduce the surface tension to a sufficient degree.
  • the melt viscosity is also markedly lowered, so that the void formation preventing ability is also degraded. Therefore, the amount of polyethylene glycol ether or polyethylene glycol ester should be below 50 wt%.
  • polyethylene glycol ether or polyethylene glycol ester used as the surface tension reducing agent is hydrolysed under high temperature conditions, it is impossible to add it to and disperse it in the binder resin when synthesizing the binder resin.
  • polyethylene wax and polypropylene wax (number average molecular weight: 2 x 103 to 2 x 104) represented by the following general formula wherein R is a hydrogen atom or group CH3 may be employed as the surface tension reducing agent.
  • the amount of added surface tension reducing agent should be from 2 to 20 wt%.
  • toner binder resin used in the present invention any employable for electrophotography, e.g., styrene acryl, epoxy resin, polyester resin, etc., may be employed independently or in combination.
  • a binder resin with a surface tension reducing agent dispersed therein is combined with another binder resin
  • a binder resin mixture with a surface tension reducing agent added only to one binder resin may be employed, as long as a required amount of surface tension reducing agent is added to the whole of the binder resin mixture.
  • the toner employed in the present invention may be produced by a known process. That is, binder resins, a colouring agent, surface tension decreasing agent, carbon, an charge control agent etc. are melted and kneaded by, e.g., a pressure kneader, roll mill, extruder, etc., and thereby dispersed uniformly, following which the uniformly dispersed mixture is finely pulverized, e.g., by a jet mill etc., and the thus obtained powder is classified by a classifier such as an air classifier to thereby obtain the desired toner.
  • a classifier such as an air classifier
  • the various physical properties were determined by the following measuring methods.
  • Surface tension is the value determined at a temperature of 200°C by employing a Wilhelimie method surface tension measuring equipment equipped with a constant-temperature sample holder with a temperature controlling range of + 0.5°C, "Digiomatic ESB-V" (manufactured by Kyowa Kagaku K.K.).
  • Melt viscosity and storage modulus are values obtained by the measurement of a temperature rise from 50°C to 250°C at a programming rate of 10°C/min in a nitrogen atmosphere by employing a cone plate type dynamic viscoelasticity measuring equipment, "MR-3 Soliquid Meter [phonetic]" (manufactured by K.K. Rheology). Note, the frequency in this case was set as 0.5 Hz.
  • the obtained mixture was melted and kneaded in a pressure kneader for 30 min, at a temperature of 130°C, so that a toner cake was obtained, and the toner cake was cooled and pulverized by a rotoprex pulverizer to obtain a rough granular toner with a particle diameter of about 2 mm.
  • the rough granular toner was finely pulverized by a jet mill ("PJM Pulverizer” produced by Japan Newmatic Co., Ltd.) and the thus obtained powder was classified by an air classifier (produced by Alpine Co., Ltd.), so that a positively charged toner (Toner A) with a particle diameter of from 5 to 20 ⁇ m was obtained.
  • JM Pulverizer produced by Japan Newmatic Co., Ltd.
  • An air classifier produced by Alpine Co., Ltd.
  • a developer consisting of 5 parts by weight of toner A and 95 parts by weight of amorphous iron powder, "TSV 100/200" (produced by Nihon Teppun K.K.) was prepared as carrier and with the prepared developing agent, a printing test was carried out by employing an improved "FACOM-6715" laser printer and the optical density of the obtained picture image was determined. The judgement of void formation states was conducted visually.
  • the surface tension of the toner was determined at a temperature of 200°C by employing surface tension measuring equipment ("Digiomatic ESB-V" manufactured by Kyowa Kagaku K.K.).
  • the result of the printing test showed that toner A had an excellent void resistance and a printing density of 1.1, and that the surface tension of toner A was 15 dyne/cm. (refer to the added Table).
  • polyester polyethylene terephthalate; weight-average molecular weight: 1000
  • silicone polymer added, said polyester being employed as the binder resin
  • 5 parts by weight of carbon black and 3 parts by weight of nigrosine dye as colorants.
  • the obtained mixture was melted and kneaded in a pressure kneader for 30 min. at a temperature of 130°C, so that a toner cake was obtained.
  • the obtained toner cake was cooled and was converted into a rough granular toner with a particle diameter of about 2 mm, by a rotoprex pulverizer.
  • the obtained rough granular toner was finely pulverized by a jet mill and the obtained powder was classified by an air classifier, so that a positively charged toner (Toner B) with a particle diameter of from 5 to 20 pm was obtained.
  • toner B had an excellent void resistance.
  • the optical density was 1.2, and the surface tension of toner B was 13 dyne/cm (refer to the table).
  • binder resins 62 parts by weight of styrene acryl with 2.0 parts by weight, based on the resin weight, of silicone polymer added and 30 parts by weight of a polyester resin (polyethylene terephthalate; weight-average molecular weight: 1000) with no silicone polymer added, 3 parts by weight of carbon black (Black Pearls L) and 3 parts by weight of nigrosine dye were further added as colorants to the binder resins.
  • the obtained mixture was melted and kneaded by a pressure kneader for 30 min at a temperature of 130°C, so that a toner cake was obtained.
  • the obtained toner cake was cooled and pulverized into a rough granular toner with a particle diameter of about 2 mm by a rotoprex pulverizer.
  • the obtained rough granular toner was finely pulverized by a jet mill (PJM pulverizer) and the obtained fine powder was classified by an air classifier (manufactured by Alpine Co., Ltd.), so that a positively charged toner (Toner C) with a particle diameter of from 5 to 20 ⁇ m was obtained.
  • JM pulverizer jet mill
  • Air classifier manufactured by Alpine Co., Ltd.
  • toner C had an excellent void resistance.
  • the optical density of 1.3, and the surface tension of toner C was 10 dyne/cm (refer to the table).
  • Example 1 was repeated except that, at the time of melting and kneading the toner, silicone polymer was not added as a surface tension reducing agent, so that a toner D was obtained.
  • silicone polymer was not added as a surface tension reducing agent, so that a toner D was obtained.
  • a printing test and the determination of surface tension of the toner were carried out in the same way as in Example 1, many voids were formed during the printing of this toner and the printing density was 0.8.
  • the surface tension of toner D was 25 dyne/cm (refer to the table).
  • Example 2 was repeated except that silicone polymer was not added as a surface tension reducing agent, so that a toner E was obtained.
  • silicone polymer was not added as a surface tension reducing agent, so that a toner E was obtained.
  • a printing test and the determination of surface tension of the toner were carried out in the same way as in Example 1, many voids were formed during the printing of this toner and the printing density was 0.7.
  • the surface tension of toner E was 23 dyne/cm (refer to the added table).
  • Example 1 was repeated except that 92 parts by weight of an epoxy resin were employed as binder resin and 3 parts by weight of silicone polymer were added thereto as a surface tension reducing agent, so that toner F was obtained.
  • toner F was 9 dyne/cm (refer to the added table).
  • Example 3 was repeated except that silicone polymer was not added to styrene acryl as a surface tension reducing agent, so that a toner G was obtained.
  • silicone polymer was not added to styrene acryl as a surface tension reducing agent, so that a toner G was obtained.
  • a printing test and the determination of surface tension of the toner were carried out in the same way as in Example 1, many voids were formed in the printing of this toner and the printing density was 0.6.
  • the surface tension of toner G was 33 dyne/cm (refer to the added table).
EP94114757A 1990-06-22 1991-06-21 Elektrophotographischer Toner Expired - Lifetime EP0633509B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2165178A JP2735165B2 (ja) 1990-06-22 1990-06-22 トナー
JP165178/90 1990-06-22
EP91305642A EP0463822B1 (de) 1990-06-22 1991-06-21 Toner

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP91305642.0 Division 1991-06-21
EP91305642A Division EP0463822B1 (de) 1990-06-22 1991-06-21 Toner

Publications (2)

Publication Number Publication Date
EP0633509A1 true EP0633509A1 (de) 1995-01-11
EP0633509B1 EP0633509B1 (de) 1999-01-07

Family

ID=15807334

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94114757A Expired - Lifetime EP0633509B1 (de) 1990-06-22 1991-06-21 Elektrophotographischer Toner

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EP (1) EP0633509B1 (de)
JP (1) JP2735165B2 (de)
DE (1) DE69130740T2 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002156775A (ja) * 2000-11-21 2002-05-31 Fujitsu Ltd フラッシュ定着用カラートナー
JP4648187B2 (ja) * 2005-12-27 2011-03-09 株式会社リコー トナー、現像剤、トナーの製造方法、画像形成装置及び画像形成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2386847A1 (fr) * 1977-04-07 1978-11-03 Mita Industrial Co Ltd Revelateur pour images electrostatiques
US4198477A (en) * 1977-02-28 1980-04-15 Xerox Corporation Method of using electrostatographic toner composition with surfactant
DE3039224A1 (de) * 1979-10-18 1981-04-30 Daikin Kogyo Co., Ltd., Osaka Verfahren zum elektrostatischen vervielfaeltigen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51100729A (de) * 1975-03-03 1976-09-06 Kanebo Ltd
JPS548535A (en) * 1977-06-22 1979-01-22 Canon Inc Toner for electrostatic charge developing
JPS5695245A (en) * 1979-12-28 1981-08-01 Canon Inc Pressure fixing composition
JPS6073545A (ja) * 1983-09-30 1985-04-25 Toshiba Corp 静電荷像現像用トナ−
US5691096A (en) * 1989-04-04 1997-11-25 Lexmark International, Inc. Flash fusible toner resins

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4198477A (en) * 1977-02-28 1980-04-15 Xerox Corporation Method of using electrostatographic toner composition with surfactant
FR2386847A1 (fr) * 1977-04-07 1978-11-03 Mita Industrial Co Ltd Revelateur pour images electrostatiques
DE3039224A1 (de) * 1979-10-18 1981-04-30 Daikin Kogyo Co., Ltd., Osaka Verfahren zum elektrostatischen vervielfaeltigen

Also Published As

Publication number Publication date
DE69130740D1 (de) 1999-02-18
DE69130740T2 (de) 1999-05-20
JP2735165B2 (ja) 1998-04-02
JPH0456867A (ja) 1992-02-24
EP0633509B1 (de) 1999-01-07

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