EP0821280A1 - Method for producing cross-linked fixed toner images - Google Patents
Method for producing cross-linked fixed toner images Download PDFInfo
- Publication number
- EP0821280A1 EP0821280A1 EP97201900A EP97201900A EP0821280A1 EP 0821280 A1 EP0821280 A1 EP 0821280A1 EP 97201900 A EP97201900 A EP 97201900A EP 97201900 A EP97201900 A EP 97201900A EP 0821280 A1 EP0821280 A1 EP 0821280A1
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- EP
- European Patent Office
- Prior art keywords
- toner particles
- reactive group
- toner
- substrate
- groups
- 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.)
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
- G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
- G03G7/002—Organic components thereof
-
- 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
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
-
- 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
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
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- 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
- G03G9/09—Colouring agents for toner particles
- G03G9/0926—Colouring agents for toner particles characterised by physical or chemical properties
-
- 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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09758—Organic compounds comprising a heterocyclic ring
-
- 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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/09775—Organic compounds containing atoms other than carbon, hydrogen or oxygen
Definitions
- the present invention relates to a method for producing toner images, wherein the toner images are strongly attached to the substrate and are highly resistant to wear.
- a latent image is formed that is developed by attraction of so called toner particles. Afterwards the developed latent image (toner image) is transferred to a final substrate and fused to this substrate. In DEP the so called toner particles are imagewise deposited directly on a final substrate and fused to this substrate.
- Toner particles are basically polymeric particles comprising a polymeric resin as main component and various ingredients mixed with said toner resin. Apart from colourless toners, which are used e.g. for finishing function, the toner particles comprise at least one black and/or colouring substances, e.g., coloured pigment.
- the toner particles can be present in a liquid or in a dry developer composition.
- a capsule toner having a core comprising a polymerisable compound, a polymerization initiator and other normal toner ingredients.
- the core is surrounded by a hard shell that breaks during the fixing step.
- the polymerisable compound is polymerized, in this particular disclosure, by low energy visible light.
- the objects of this invention are realized in a first embodiment of this invention by providing a method for forming a toner image on a substrate comprising the steps of :
- the objects of this invention are realized in a second embodiment of this invention by providing a method for forming a toner image on a substrate comprising the steps of :
- a so called “cross-linker” or “hardening” agent comprising reactive groups RGB
- RGA reactive groups contained in the toner particles.
- An "image on a substrate” is, in the context of this invention, meant to include a substrate carrying human readable or/and machine readable text, a substrate carrying figures, a substrate carrying pictures (both coloured and monochromatic) as well as a substrate carrying a combination of at least two of the above.
- a specific chemical interaction between the toner particles and a substrate is used to enhance the mechanical strength of a toner image and/or of the binding between toner image and substrate.
- Both said reactive groups RGA and said reactive groups RGB are preferably members selected from the group consisting of epoxy groups, aldehyde groups, hydroxyl groups, carboxyl groups, mercapto groups, amino groups and amide groups.
- the reactive groups RGA and RGB are preferably chosen such as to form a reaction pair that reacts easily (i.e. fast, at relatively low temperature) together.
- Both reactive groups (RGA and RGB) can be part of a polymeric, oligomeric or low molecular weight (molecular weight lower than 2000) molecule.
- the molecule carrying reactive groups RGA and reactive groups RGB can carry one or more of these reactive groups.
- the toner particles and/or the substrate can comprise, if so desired, a mixture of compounds carrying reactive groups. E.g.
- the toner particles can comprise a compound comprising hydroxyl groups together with a compound comprising epoxy groups.
- different compounds carrying reactive groups can be present, it can e.g. be useful to mix in the substrate a polymeric compound comprising reactive groups with a low molecular weight molecule comprising reactive groups.
- the reaction between the reactive groups results in cross-linking of the toner particles, in chemically fixing the toner particles to the substrate or in both cross-linking the toner particles and chemically fixing them to the substrate.
- the reactive groups RGA in the toner particles are comprised in a polymeric compound and the reactive groups RGB in the substrate in a low molecular weight molecule carrying e.g. two reactive groups RGB, then, during fusing of the toner particles to the substrate, the low molecular weight molecule can migrate from the substrate and cross-link two polymeric compounds, carrying reactive groups RGA, present in the toner particles.
- the reactive groups RGA and RGB are contained in polymeric compounds, then during fusing the reaction between RGA and RGB will rather result in a chemical fixing of the (fused) toner particles to the substrate.
- the ratio between the cross-linking and chemical fixing reaction can be adapted to the needed hardness of the toner layer and to the needed strength of fixing of the fused toner particles to the substrate.
- Typical reaction pairs, comprising reactive groups RGA or RGB, and very useful in the present invention are e.g. :
- the compounds comprising reactive groups RGA are preferably solids that do not deteriorate the mechanical strength of the toner particles in which they are incorporated.
- said reactive groups RGA are part of a polymer used as toner resin (either alone or in mixture with other known toner resins) and said resin carrying reactive groups RGA has preferably a Tg ⁇ 35 °C, preferably larger than 40 °C.
- the polymeric compounds carrying reactive groups are preferably incorporated in the toner particles.
- Very suitable polymers having an acid value > 2.5 mg KOH/g and/or a hydroxyl value > 2.5 mg KOH/g, for use in toner particles used in the method of this invention, can be polycondensation polymers as well as addition polymers, typical examples are tabulated in table 1.
- the reactive groups RGA can also be part of an epoxy-resin that is incorporated in or is the toner resin of the toner particles. Typical examples of useful epoxy resins (polymers) are e.g.
- ARALDITE GT 7203 (trade name for an epoxy resin of Ciba-Geigy of Switserland) and EPIKOTE 1004 (trade name of Shell Company, UK).
- the compound carrying reactive groups RGA and incorporated in the toner particles can also be a polyamide resin or a polyester/polyamide copolymer.
- Chemical structure AV HV Tg °C Mn Mw 1. Polyester resin of terephthalic acid, ethyleneglycol and DIANOL 22 3 31.1 62 3.6 10 2. Polyester resin of fumaric acid and DIANOL 33 17 5.2 55 4.4 12 3. Polyester resin of terephthalic acid, isophthalic acid and DIANOL 22 and ethyleneglycol 18 20.9 60 4 18 4.
- Copoly(styrene-butylacrylate-butylmethacrylate-stearylmethacrylate-methacrylic acid) (65/5/21/5/4) 12 0 58 6 108 5.
- Copoly(styrene-butylmethacrylate-acrylic acid) (80/15/5) 5 0 63 5.5 180 6.
- DIANOL 22 is a trade name of AKZO CHEMIE of the Netherlands for bis-ethoxylated 2,2-bis(4-hydroxyphenyl)propane.
- DIANOL 33 is a trade name of AKZO CHEMIE of the Netherlands for bis-propoxylated 2,2-bis(4-hydroxyphenyl)propane.
- the chemical compound (polymeric, oligomeric or single molecule) carrying reactive groups RGA can be present in the bulk of the toner particles, on the surface of the toner particles or both in the bulk and on the surface of the toner particles.
- Toner particles comprising compounds with reactive groups RGA in the bulk of the particle can be prepared by melt kneading the toner ingredients (e.g. toner resin, charge control agent, pigment, etc) and said compounds with reactive groups RGA. After the melt kneading the mixture is cooled and the solidified mass is pulverized and milled and the resulting particles classified. Also the "emulsion polymerisation” and “polymer emulsion” techniques for toner preparation can be used to prepare toner particles wherein compounds with reactive groups RGA are incorporated in the bulk of the toner particles.
- toner ingredients e.g. toner resin, charge control agent, pigment, etc
- emulsion polymerization a water-immiscible polymerizable liquid is sheared to form small droplets emulsified in an aqueous solution, and the polymerization of the monomer droplets takes place in the presence of an emulsifying agent; such a technique is described e.g. in US P 2,932,629, US P 4,148,741, US P 4,314,932 and EP-A 255 716.
- polymer emulsion a preformed polymer is dissolved in an appropriate organic solvent that is immiscible with water, the resulting solution is dispersed in an aqueous medium that contains a stabilizer, the organic solvent is evaporated and the resulting particles are dried; such a technique is described in, e.g., US P 4,833,060.
- Toner particles having compounds carrying reactive groups at the surface can be prepared as described in EP-A 725 317.
- a method for producing toner particles comprising the steps of :
- preferred stabilizer (co)polymers are being copolymers of vinyl acetate and crotonic acid (90/10 by weight) having a total acid number of 50 to 300, and copolymers of styrene and maleic acid anhydride having a total acid number of 250 to 500, both said copolymers being used, at least partially, transformed into their ammonium salt form.
- the water-soluble stabilizing (co)polymer is precipitated on to the particles, produced by the method according to this invention, by chemical reaction, e.g. acidification of the aqueous medium, the water-soluble (co)polymer adhering to the dispersed polymer particles can be transformed into a water-insoluble species that precipitates on the particles. By doing so carboxylic acid groups are present at the surface of the toner particles.
- the hardening reaction proceeds easily when the interpenetration between toner particles and substrate is quite high.
- This interpenetration is reached by heating the toner particles on the substrate (during fixing or after fixing in an additional heating step) to a temperature that preferably is at most 150 °, most preferably at most 120 °C. Therefore it is preferred to use toner particles, comprising compounds carrying reactive groups RGA, that have a meltviscosity at 120 °C between 50 and 2000 Pas, preferably between 100 and 1000 Pas. All melt viscosities mentioned herein are measured in a RHEOMETRICS dynamic rheometer, RVEM-200 (One Possumtown Road, Piscataway, NJ 08854 USA).
- the viscosity measurement is carried out at a sample temperature of 120 °C.
- the sample having a weight of 0.75 g is applied in the measuring gap (about 1.5 mm) between two parallel plates of 20 mm diameter one of which is oscillating about its vertical axis at 100 rad/sec and amplitude of 10 -3 radians.
- the reaction between reactive groups RGA and RGB can beneficially be speeded up by providing catalysers for this reaction.
- Said catalysers are preferably acids (organic or anorganic) or tertiary amines. Typical examples of suitable catalysers are p-toluenesulfonic acid, trimethylamine and triethylamine.
- the catalyser or catalysers can, within the scope of the present invention, be incorporated in the toner particles, the substrate or both in the toner particles and the substrate.
- the catalyser or catalysers can be incorporated in the toner particles, as long as the incorporation of it does not result in a weakening of the mechanical resistance of the toner particles, i.e. when the Tg stays equal to or higher than 35 °C.
- the toner particles not only comprise reactive groups RGA, e.g., a member selected from the group consisting of epoxy groups, aldehyde groups, hydroxyl groups, carboxyl groups, mercapto groups, amino groups and amide groups, but comprise further a compound or mixture of compounds carrying radiation curable groups.
- RGA reactive groups
- the present invention includes also a method for forming toner images on a substrate comprising the steps of :
- the radiation curing can proceed off-line in a separate apparatus wherein the fused layer of toner particles is heated again and irradiated with curing rays.
- the compounds, carrying a radiation curable group, to be incorporated in toner particles for use according to this invention is already an oligomeric or polymeric compound instead of a monomer.
- a monomeric compound may be present in the mixture of radiation curable compounds, as long as the mixture of radiation curable compounds itself has a Tg ⁇ 35 °C.
- electron beam curable groups can be used in the present invention, the radiation curable groups are preferably curable by UV-light.
- Very useful radiation curable polymeric compounds, in toner particles for use in the present invention are UV curable solid epoxy resins with Tg ⁇ 35 °C as disclosed in EP-A 667 381. In this application solid compositions (I) are described containing
- Photoinitiator For the UV curing to proceed it is necessary that a photoinitiator is present.
- Very useful initiators are sulphonium salts as e.g. triarylsulphonium salts, triarylsulphoniumhexafluorophosphate, benzophenones, etc.
- Typical very useful photoinitiators in the context of this invention are, e.g., 2-hydroxy-2-methyl-1-phenylpropan-1-one, compound I, a mixture of compound I and compound II and compound III :
- the initiator can be incorporated in the toner particles together with the UV curable system or can be incorporated in the substrate.
- This embodiment has the advantage that the resins comprised in the fused image are cross-linked (by UV-curing) and attached to the substrate by chemical bonds.
- UV-curable or radiation curable compounds are used in the first embodiment of the present invention, it is possible to do so in various combinations :
- a substrate useful in the first embodiment of the invention comprises reactive groups RGB.
- This reactive groups (RGB) in the substrate, useful in the present invention are in principle a member of the same group of reactive groups as the reactive groups RGA present in the toner particles, i.e. the reactive groups RGB are preferably members selected from the group consisting of epoxy groups, aldehyde groups, hydroxyl groups, carboxyl groups, mercapto groups, amino groups and amide groups.
- the reactive groups RGB can be part of a polymeric, oligomeric or low molecular weight (molecular weight lower than 2000) molecule.
- the molecule carrying reactive groups RGB can carry one or more of these reactive groups.
- the reactive groups RGB are chosen in such a way that they are capable to react with one or more reactive groups RGA present in the toner particles.
- the substrate comprises reactive groups capable of an easy reaction with said hydroxyl and/or carboxyl groups.
- Typical examples of such reactive groups are epoxy groups, aldehyde groups, polyaziridine groups, etc.
- the substrate preferably comprises as reactive group RGB either a hydroxyl, carboxyl, amide or amino group.
- reaction pairs as described above it is preferred to incorporate the low molecular weight compounds or the oligomeric or polymeric compounds having a Tg ⁇ 35 °C in the substrate.
- very suitable compounds carrying reactive groups RGB for incorporation in the substrate are e.g. polyaziridines, polyamidoamine resins, highly methylated melamine resins, hydroxyl group containing epoxy hardening agents, e.g.
- R is alkyl group.
- Further useful epoxy hardening agents are exemplified in e.g. EP-A 495 314 on page 23 to 26. Also epoxy hardening agents represented by formulas A-1 to A-6 can be used in the present invention.
- the compounds with reactive groups can be comprised in a toner receptive layer applied to the substrate.
- the substrate can be paper, cardboard, plastic film, etc.
- Said toner receptive layer can comprise a binder and the compounds with reactive groups RGB can be embedded in said binder.
- the reactive groups RGB can form part of said binder.
- Useful binders, carrying reactive groups RGB are e.g. the same binders as already described herein above as useful binders for the toner particles, i.e. polymers having an acid value > 2.5 mg KOH/g and/or a hydroxyl value > 2.5 mg KOH/g (examples of such polymers are found in table 1) and epoxy polymers. E.g.
- polymers useful as binder in a substrate to be used according to this invention and capable of reacting with a hydroxyl or carboxyl group are epoxy polymers, polymers carrying aldehyde groups, polyaziridines, etc.
- the binder in the image receiving layer of the substrate for use in this invention will preferably comprise hydroxyl, carboxyl and/or amino groups.
- Typical useful binders are gelatin, polyvynilalcohol, etc.
- the binder can also comprise further resinous compounds : e.g. polyamides, carboxyl or sulphonyl group containing polyesters in latex form, etc.
- the substrate can comprise initiators for radiation curing.
- the substrate within the scope of this invention, may further comprise a radiation curable compound and/or a photoinitiator as describe above. It is possible that the substrate comprises said radiation curable compound and that toner particles comprise an initiator for radiation curing as described above.
- the hardening reaction proceeds easily when the interpenetration between toner particles and substrate is quite high.
- This interpenetration is reached by heating the toner particles on the substrate (during fixing or after fixing in an additional heating step) to a temperature that preferably is at most 150 °, most preferably 120 °C.
- the toner receiving layer on the substrate may comprise waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the penetration of the reagents RGA and RGB and thereby the reaction speed of hardening reaction at elevated temperature.
- heat solvent in this invention is meant a non-hydrolyzable organic material which is in solid state at temperatures below 50 °C but becomes on heating above that temperature a plasticizer for the binder of the layer wherein they are incorporated.
- plasticizer for the binder of the layer wherein they are incorporated.
- Useful for that purpose are a polyethylene glycol having a mean molecular weight in the range of 1,500 to 20,000 described in US-P 3,347,675.
- Said toner receiving layer may comprise, apart from a compound comprising reactive groups RGB or mixtures thereof and a binding agent or mixture of binding agents, also stabilizers, toning agents, antistatic agents, spacing particles (both polymeric or anorganic).
- the toner receiving layer may contain other additives such as free fatty acids, antistatic agents, e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H, ultraviolet light absorbing compounds, white light reflecting and/or ultraviolet radiation reflecting pigments, and/or optical brightening agents.
- antistatic agents e.g. non-ionic antistatic agents including a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
- ultraviolet light absorbing compounds e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
- white light reflecting and/or ultraviolet radiation reflecting pigments e.g. in UV light absorbing compounds
- optical brightening agents e.g., a fluorocarbon group as e.g. in F 3 C(CF 2 ) 6 CONH(CH 2 CH 2 O)-H
- This first embodiment of the invention encompasses also an apparatus for forming an image comprising hardened toner particles comprising :
- the first embodiment of the invention comprises further an apparatus for forming an image comprising hardened toner particles comprising :
- the toner particles further comprise a UV curable compound
- said means for fusing said toner images emit infrared radiation and said means for UV curing (e.g. one or more UV emitting lamps) are installed immediately after said fusing means so that the UV curing proceed on the still molten toner image.
- the reactive groups RGB are applied on top of the toner image.
- the same toner particles can be used as those used in the first embodiment of the invention and having been described above.
- the substrate used in this second embodiment can be any substrate known in the art, e.g. plastic film, paper, cardboard, etc. It can also be a substrate comprising reactive groups RGB as described above under the first embodiment of the present invention.
- the reactive compound that is applied on top of the image-wise deposited toner particles is a compound comprising reactive groups RGB that can react with the toner particles.
- the compounds carrying reactive groups RGB are applied to the image in an amount between 1 and 10 g/m 2 , preferably between 2 and 8 g/m 2 .
- Typical couples of compounds, comprising reactive groups RGA or RGB, and very useful in the present invention are the same as those exemplified above.
- the toner particles comprise resins with Tg ⁇ 35 °C containing reactive groups RGA.
- the compounds carrying reactive groups RGB can, in the second embodiment of the invention, be applied to the toner image either before or after fusing of the toner particles to the substrate.
- spray coating techniques it is preferred to use spray coating techniques to apply said compounds.
- These compounds may be applied as such, as a solution or as a dispersion, depending on the physical nature of the compound carrying reactive groups RGB.
- the toner image by an non-image-wise applied layer of clear toner particles wherein said clear toner particles comprise reactive groups RGB and wherein the compounds carrying reactive groups RGB have a Tg ⁇ 35 °C.
- the word "clear” means herein not giving, in a wavelength range extending from 400 to 700 nm, a visible diffuse density, said visible diffuse density being defined as less than 15 % light reduction integrated over that wavelength range. In this case said toner particles are applied onto the toner image before fusing.
- toner image it is also possible to cover the toner image with a layer of clear toner particles that do not comprises reactive groups RGB capable of reacting with the reactive groups RGA contained in the image forming toner particles, but comprising reactive groups RGA.
- This layer of clear toner particles is then covered with a compound comprising reactive groups RGB. Afterwards, both reactive groups are made to react together to harden the outermost toner layer in the toner image.
- a layer of clear toner particles is applied to toner images made up by the overlay of several layers of different types of toner particles (e.g.
- the present invention includes also an apparatus for forming an image comprising hardened toner particles comprising :
- Said means for applying said compound carrying reactive groups RGB can be rollers, wicks, sprays, etc.
- said means for applying compound carrying reactive groups RGB are rollers, it may be split rollers, e.g. when 5 g/m 2 of compound carrying reactive groups RGB has to be applied, there may be provided four application rollers, the first two applying together 2 g/m 2 of compound carrying reactive groups RGB and the following rollers applying the remaining 3 g/m 2 .
- Preferred means for applying said compound carrying reactive groups RGB are supply rollers with a surface in NOMEX-felt (NOMEX is a trade name of Du Pont de Nemours, Wilmington, US) as described in article titled "Innovative Release Agent Delivery Systems" by R. Bucher et al.
- the compound carrying reactive groups RGB can be delivered to the image directly by supply rollers as described above, or over an intermediate roller, which distributes the compound even more evenly over the image.
- Said means for applying a compound comprising reactive groups RGB on top of a toner image may be installed before said means for fusing said toner particles or after said means for fusing said toner particles to said substrate.
- the apparatus comprises preferably also special means for reacting said reactive groups RGA and RGB so as to harden said fused toner image.
- These special means are heating means, that may be the same means as those used as fusing means.
- these means for applying the compounds with reactive groups RGB are preferably means for non-contact application, e.g. spraying means and no special means for reacting said reactive groups RGA and RGB so as to harden said fused toner image are necessary since the reaction of reactive groups RGA and RGB proceeds during the fusing step.
- the second embodiment of the invention includes a method for forming toner images on a substrate comprising the steps of :
- the step of UV curing can proceed on line, e.g, in the fusing station itself of an electrostatographic apparatus or in a station immediately adjacent to said fusing station.
- the radiation curing can proceed off-line in a separate apparatus wherein the fused layer of toner particles is heated again and irradiated with curing rays.
- an apparatus for forming an image comprising hardened toner particles comprising :
- the means for fusing and the means for UV curing can be the same as described above under the first embodiment of the present invention.
- the present invention can be practised in any electrographic or magnetographic imaging method. It can be useful in classical electrophotography, in ionography, in direct electrostatic printing (DEP), etc.
- the present invention is useful for mono-chromatic toner images as well as for multi-chromatic and full colour toner images.
- the means for image-wise depositing toner particles can be direct electrostatic printing means, wherein charged toner particles are attracted to the substrate by an electrical field and the toner flow modulated by a printhead structure comprising printing apertures and control electrodes.
- Said means for image-wise depositing toner particles can also be toner depositing means wherein first a latent image is formed.
- said means for image-wise depositing toner particles) comprise :
- Said latent image may be a magnetic latent image that is developed by magnetic toner particles (magnetography) or, preferably, an electrostatic latent image.
- an electrostatic latent image is preferably an electrophotographic latent image and the means for producing a latent image are in this invention preferably light emitting means, e.g., light emitting diodes or lasers and said latent image bearing member comprises preferably a photoconductor.
- Toner particles useful in both embodiments of this invention can have an average volume diameter between 1 and 50 ⁇ m, preferably between 3 and 20 ⁇ m. When the toner particles are intended for use in colour imaging, it is preferred that the volume average diameter is between 3 and 10 ⁇ m, most preferred between 3 and 8 ⁇ m.
- the particle size distribution of said toner particles can be of any type. It is however preferred to have an essentially (some negative or positive skewness can be tolerated, although a positive skewness, giving less smaller particles than an unskewed distribution, is preferred) Gaussian or normal particle size distribution, either by number or volume, with a coefficient of variability (standard deviation divided by the average) ( ⁇ ) smaller than 0.5, more preferably of 0.3.
- Toner particles useful in the first embodiment of this invention, can comprise any normal toner ingredient e.g. charge control agents, pigments both coloured and black, anorganic fillers, etc.
- charge control agents, pigments and other additives useful in toner particles, to be used in a toner composition according to the present invention can be found in e.g. EP-A 601 235.
- the toner particles can be used as mono-component developers, both as a magnetic and as a non-magnetic mono-component developer.
- the toner particles can be used in a multi-component developer wherein both magnetic carrier particles and toner particles are present.
- the toner particles can be negatively charged as well as positively charged.
- the solidified mass was pulverized and milled using an ALPINE Fliessbettarnastrahlmühle type 100AFG (tradename) and further classified using an ALPINE multiplex zig-zag classifier type 100MZR (tradename).
- the average particle size of the separated toner was measured by Coulter Counter model Multisizer (tradename) was found to be 8.0 ⁇ m by volume.
- Printing proceeded in an AGFA XC305 colour copier.
- the image was printed both on the part of the paper having a receiving layer and the part not having a receiving layer.
- the resistance of the image against solvents was tested by rubbing the image 10 consecutive times with a cloth soaked with MEK (methylethyleketone).
- MEK methylethyleketone
- the solidified mass was pulverized and milled using an ALPINE Fliessbettarnastrahlmühle type 100AFG (tradename) and further classified using an ALPINE multiplex zig-zag classifier type 100MZR (tradename).
- the average particle size of the separated toner was measured by Coulter Counter model Multisizer (tradename) was found to be 8.0 ⁇ m by volume.
- the toner particles were mixed with 0.5 % of hydrophobic colloidal silica particles (BET-value 130 m 2 /g).
- the preparation of the Yellow toner was repeated, but instead of 2 parts SICOECHTGELB PY13, 2 parts of CABOT REGAL 400 (carbon black, trade name of the Cabot Corp. High Street 125, Boston, U.S.A.) were used.
- the four toners, Y, M, C and K had a meltviscosity at 120 ° C of 500 Pas.
- Clear toner 100 parts of an epoxy resin EPIKOTE 1004 (trade mark of the Shell Chemical Co) were melt-blended for 30 minutes at 110 °C in a laboratory kneader.
- the solidified mass was pulverized and milled using an ALPINE Fliessbettarnastrahlmühle type 100AFG (tradename) and further classified using an ALPINE multiplex zig-zag classifier type 100MZR (tradename).
- the average particle size of the separated toner was measured by Coulter Counter model Multisizer (tradename) was found to be 8.0 ⁇ m by volume.
- the clear toner CT had a meltviscosity at 120 °C of 150 Pas.
- the toner particles were mixed with 0.5 % of hydrophobic colloidal silica particles (BET-value 130 m 2 /g).
- Each of the above prepared toners were used to form carrier-toner developers by mixing said mixture of toner particles and colloidal silica in a 4 % ratio with silicone-coated Cu-Zn ferrite carrier particles having an average diameter of 55 ⁇ m.
- Full colour toner images were produced using a commercial CHROMAPRESS (a trade name of Agfa-Gevaert NV, Mortsel, Belgium). The images were covered with a layer of clear toner such that 0.9 mg/cm 2 clear toner was present. The fusing took place with radiant heat. On top of the layer of clear toner a solution of 20 g of a polyaminoamide resin (UNIREZ 1307 trade name) with amino value between 370 and 410 mg KOH/g and 1.6 g of a catalyser (XB 3130 trade name of Ciba Geigy, Switserland) was applied at a wet thickness of 4 ⁇ m (i.e. 4 g of polyaminoamide resin per m 2 ).
- a polyaminoamide resin UNIREZ 1307 trade name
- the image was kept for 1 minute at 125 °C. After cooling the image, the resistance of the image against solvents was tested by rubbing the image 10 consecutive times with a cloth soaked with MEK (methylethyleketone).
- MEK methylethyleketone
Abstract
A method for forming images is provided, comprising the steps of :
Description
The present invention relates to a method for producing toner
images, wherein the toner images are strongly attached to the
substrate and are highly resistant to wear.
In imaging methods as e.g. electro(photo)graphy,
magnetography, ionography, etc. a latent image is formed that is
developed by attraction of so called toner particles. Afterwards
the developed latent image (toner image) is transferred to a final
substrate and fused to this substrate. In DEP the so called toner
particles are imagewise deposited directly on a final substrate
and fused to this substrate.
Toner particles are basically polymeric particles comprising a
polymeric resin as main component and various ingredients mixed
with said toner resin. Apart from colourless toners, which are
used e.g. for finishing function, the toner particles comprise at
least one black and/or colouring substances, e.g., coloured
pigment.
In the different imaging methods, described above, the toner
particles can be present in a liquid or in a dry developer
composition.
In most cases the use of dry developer compositions is
preferred. The main advantage of using a dry developer
composition resides in the absence of the need to eliminate the
liquid phase after development. The avoidance of the need to
evacuate (mainly organic) liquids is desirable both from an
economical standpoint and from an ecological standpoint.
However, in all techniques using dry particulate material to
form an image, the images are very frequently built up by
application of particulate marking elements in multiple,
superimposed layers onto the substrate. The problems associated
with multiple, superimposed layers of particulate marking
particles that are in one way or another fixed on a substrate are
manifold, not only with respect to image quality but also with
respect to image stability and with respect to mechanical issues.
In, e.g. EP-A 471 894, EP-A 554 981, US 4,828,950 and US
4,885,603, it has been disclosed to apply a layer of transparent
toner particles on top of the toner image to provide better
resistance to physical damage. Also other means and ways to
produce toner images that are very resistant to external
influences, (e.g. mechanical influence, heat, contact with
solvents, etc) have been proposed.
In, e.g., US 3,723,114 the problem of storage properties of
fused toner images is addressed, the main problem being the fact
that the toner images can, depending on the storage conditions,
become tacky after storage. The problem is solved by using in the
toner resin a substantial portion of thermosetting polymers.
The use of photo-curable toners has been suggested in, e.g.,
US 5,470,683 to produce toner images having better weather
resistance. In that application, a capsule toner is provided
having a core comprising a polymerisable compound, a
polymerization initiator and other normal toner ingredients. The
core is surrounded by a hard shell that breaks during the fixing
step. After the fixing step the polymerisable compound is
polymerized, in this particular disclosure, by low energy visible
light. Although following the teachings of these disclosures
leads to the production of toner layers that are not easily
damaged, the nature of the solutions itself limits the variety of
resins that can be used in the manufacturing of the toner.
Therefore further improvements along the lines of the disclosures
referred to above are desirable.
It is an object of the invention to provide a method for
producing toner images that are very resistant to external
physical influences wherein the toner particles used do not have
to incorporate a restricted number of specific toner resins.
It is a further object of the invention to provide a method
for forming toner images wherein said toner image is very
resistant to the influence of common organic solvents.
It is an other object of the invention to provide a method for
producing toner images wherein the toner image is strongly bound
to the toner receiving substrate.
It is a further object of the invention to provide a method
for producing toner images that are very weather resistant.
Further objects and advantages of the present invention will
become evident from the detailed description hereinafter.
The objects of this invention are realized in a first
embodiment of this invention by providing a method for forming a
toner image on a substrate comprising the steps of :
The objects of this invention are realized in a second
embodiment of this invention by providing a method for forming a
toner image on a substrate comprising the steps of :
It was found that it was possible to produce on a substrate
toner images with high resistance to external influences (i.e.
mechanical wear, degradation by heat, attack by organic solvents,
weather, etc) by hardening the (fused) toner particles comprised
in said image. This hardening proceeds by reacting reactive
groups RGA present in the toner particles with reactive groups RGB
in order to harden the toner particles.
This hardening can proceed via two methods : in a first method, the toner particles comprise reactive groups RGA and the substrate comprises reactive groups RGB and both reactive groups are chosen such that they interact with each other. In a second method a so called "cross-linker" or "hardening" agent, comprising reactive groups RGB, is applied on top of the toner image and made to react with reactive groups RGA contained in the toner particles.
Although both methods as such did produce toner images that were very resistant to mechanical influences, it is possible, within the scope of the present invention, to combine both methods to further increase the hardness and mechanical resistance of the toner images.
An "image on a substrate" is, in the context of this invention, meant to include a substrate carrying human readable or/and machine readable text, a substrate carrying figures, a substrate carrying pictures (both coloured and monochromatic) as well as a substrate carrying a combination of at least two of the above.
This hardening can proceed via two methods : in a first method, the toner particles comprise reactive groups RGA and the substrate comprises reactive groups RGB and both reactive groups are chosen such that they interact with each other. In a second method a so called "cross-linker" or "hardening" agent, comprising reactive groups RGB, is applied on top of the toner image and made to react with reactive groups RGA contained in the toner particles.
Although both methods as such did produce toner images that were very resistant to mechanical influences, it is possible, within the scope of the present invention, to combine both methods to further increase the hardness and mechanical resistance of the toner images.
An "image on a substrate" is, in the context of this invention, meant to include a substrate carrying human readable or/and machine readable text, a substrate carrying figures, a substrate carrying pictures (both coloured and monochromatic) as well as a substrate carrying a combination of at least two of the above.
In the first embodiment of this invention a specific chemical
interaction between the toner particles and a substrate is used to
enhance the mechanical strength of a toner image and/or of the
binding between toner image and substrate.
We have found that the drawbacks of earlier methods to provide
mechanically strong toner images could be solved by providing
toner particles comprising reactive groups (RGA) and have these
reactive groups (RGA) react with reactive groups (RGB) present in
the substrate. After said reaction said toner particles were
cross-linked and/or chemically bound to said substrate.
Herein after, the word "harden" and words derived from it will be used to mean cross-link and/or chemically fix said toner particles to said substrate.
Herein after, the word "harden" and words derived from it will be used to mean cross-link and/or chemically fix said toner particles to said substrate.
Both said reactive groups RGA and said reactive groups RGB are
preferably members selected from the group consisting of epoxy
groups, aldehyde groups, hydroxyl groups, carboxyl groups,
mercapto groups, amino groups and amide groups. The reactive
groups RGA and RGB are preferably chosen such as to form a
reaction pair that reacts easily (i.e. fast, at relatively low
temperature) together.
Both reactive groups (RGA and RGB) can be part of a polymeric, oligomeric or low molecular weight (molecular weight lower than 2000) molecule. The molecule carrying reactive groups RGA and reactive groups RGB can carry one or more of these reactive groups. The toner particles and/or the substrate can comprise, if so desired, a mixture of compounds carrying reactive groups. E.g. the toner particles can comprise a compound comprising hydroxyl groups together with a compound comprising epoxy groups. Also in the substrate different compounds carrying reactive groups can be present, it can e.g. be useful to mix in the substrate a polymeric compound comprising reactive groups with a low molecular weight molecule comprising reactive groups. The reaction between the reactive groups (RGA and RGB) results in cross-linking of the toner particles, in chemically fixing the toner particles to the substrate or in both cross-linking the toner particles and chemically fixing them to the substrate. The type of reaction that occurs, (cross-linking or chemical fixing), depends on the nature of the compound carrying the reactive groups. When e.g. the reactive groups RGA in the toner particles are comprised in a polymeric compound and the reactive groups RGB in the substrate in a low molecular weight molecule carrying e.g. two reactive groups RGB, then, during fusing of the toner particles to the substrate, the low molecular weight molecule can migrate from the substrate and cross-link two polymeric compounds, carrying reactive groups RGA, present in the toner particles. When e.g. both the reactive groups RGA and RGB are contained in polymeric compounds, then during fusing the reaction between RGA and RGB will rather result in a chemical fixing of the (fused) toner particles to the substrate. Thus by carefully choosing compounds of different nature (polymeric, oligomeric or low molecular weight molecule), carrying reactive groups RGA and also carefully choosing compounds of different nature (polymeric, oligomeric or low molecular weight molecule), carrying reactive groups RGB, the ratio between the cross-linking and chemical fixing reaction can be adapted to the needed hardness of the toner layer and to the needed strength of fixing of the fused toner particles to the substrate.
Typical reaction pairs, comprising reactive groups RGA or RGB, and very useful in the present invention are e.g. :
Both reactive groups (RGA and RGB) can be part of a polymeric, oligomeric or low molecular weight (molecular weight lower than 2000) molecule. The molecule carrying reactive groups RGA and reactive groups RGB can carry one or more of these reactive groups. The toner particles and/or the substrate can comprise, if so desired, a mixture of compounds carrying reactive groups. E.g. the toner particles can comprise a compound comprising hydroxyl groups together with a compound comprising epoxy groups. Also in the substrate different compounds carrying reactive groups can be present, it can e.g. be useful to mix in the substrate a polymeric compound comprising reactive groups with a low molecular weight molecule comprising reactive groups. The reaction between the reactive groups (RGA and RGB) results in cross-linking of the toner particles, in chemically fixing the toner particles to the substrate or in both cross-linking the toner particles and chemically fixing them to the substrate. The type of reaction that occurs, (cross-linking or chemical fixing), depends on the nature of the compound carrying the reactive groups. When e.g. the reactive groups RGA in the toner particles are comprised in a polymeric compound and the reactive groups RGB in the substrate in a low molecular weight molecule carrying e.g. two reactive groups RGB, then, during fusing of the toner particles to the substrate, the low molecular weight molecule can migrate from the substrate and cross-link two polymeric compounds, carrying reactive groups RGA, present in the toner particles. When e.g. both the reactive groups RGA and RGB are contained in polymeric compounds, then during fusing the reaction between RGA and RGB will rather result in a chemical fixing of the (fused) toner particles to the substrate. Thus by carefully choosing compounds of different nature (polymeric, oligomeric or low molecular weight molecule), carrying reactive groups RGA and also carefully choosing compounds of different nature (polymeric, oligomeric or low molecular weight molecule), carrying reactive groups RGB, the ratio between the cross-linking and chemical fixing reaction can be adapted to the needed hardness of the toner layer and to the needed strength of fixing of the fused toner particles to the substrate.
Typical reaction pairs, comprising reactive groups RGA or RGB, and very useful in the present invention are e.g. :
Since toner particles to be used in electrostatographic
printing apparatus have preferably quite a high mechanical
strength in order to be able to withstand the mechanical
influences (pressure, friction, etc) in the printing apparatus
before and during development, it is important to preserve the
mechanical strength of the toner particles. Therefore the
compounds comprising reactive groups RGA are preferably solids
that do not deteriorate the mechanical strength of the toner
particles in which they are incorporated. Thus, in a preferred
embodiment said reactive groups RGA are part of a polymer used as
toner resin (either alone or in mixture with other known toner
resins) and said resin carrying reactive groups RGA has preferably
a Tg ≥ 35 °C, preferably larger than 40 °C.
Thus when using reaction pairs as described above in the first embodiment of this invention, the polymeric compounds carrying reactive groups are preferably incorporated in the toner particles.
Very suitable polymers having an acid value > 2.5 mg KOH/g and/or a hydroxyl value > 2.5 mg KOH/g, for use in toner particles used in the method of this invention, can be polycondensation polymers as well as addition polymers, typical examples are tabulated in table 1.
The reactive groups RGA can also be part of an epoxy-resin that is incorporated in or is the toner resin of the toner particles.
Typical examples of useful epoxy resins (polymers) are e.g. ARALDITE GT 7203 (trade name for an epoxy resin of Ciba-Geigy of Switserland) and EPIKOTE 1004 (trade name of Shell Company, UK). The compound carrying reactive groups RGA and incorporated in the toner particles, can also be a polyamide resin or a polyester/polyamide copolymer.
Thus when using reaction pairs as described above in the first embodiment of this invention, the polymeric compounds carrying reactive groups are preferably incorporated in the toner particles.
Very suitable polymers having an acid value > 2.5 mg KOH/g and/or a hydroxyl value > 2.5 mg KOH/g, for use in toner particles used in the method of this invention, can be polycondensation polymers as well as addition polymers, typical examples are tabulated in table 1.
The reactive groups RGA can also be part of an epoxy-resin that is incorporated in or is the toner resin of the toner particles.
Typical examples of useful epoxy resins (polymers) are e.g. ARALDITE GT 7203 (trade name for an epoxy resin of Ciba-Geigy of Switserland) and EPIKOTE 1004 (trade name of Shell Company, UK). The compound carrying reactive groups RGA and incorporated in the toner particles, can also be a polyamide resin or a polyester/polyamide copolymer.
Chemical structure | AV | HV | Tg °C | Mn | Mw |
1. Polyester resin of terephthalic acid, ethyleneglycol and DIANOL 22 | 3 | 31.1 | 62 | 3.6 | 10 |
2. Polyester resin of fumaric acid and DIANOL 33 | 17 | 5.2 | 55 | 4.4 | 12 |
3. Polyester resin of terephthalic acid, isophthalic acid and DIANOL 22 and ethyleneglycol | 18 | 20.9 | 60 | 4 | 18 |
4. Copoly(styrene-butylacrylate-butylmethacrylate-stearylmethacrylate-methacrylic acid) (65/5/21/5/4) | 12 | 0 | 58 | 6 | 108 |
5. Copoly(styrene-butylmethacrylate-acrylic acid) (80/15/5) | 5 | 0 | 63 | 5.5 | 180 |
6. Polyester resin of DIANOL 33/DIANOL 22, terephthalic acid and trimellitic acid | 30 | 50 | 65 | 2.0 | 14 |
7. Co(Styrene/n-butylmethacrylate), diCOOH terminated (65/35) | 15 | 0 | 48 | 2.1 | 10 |
DIANOL 22 is a trade name of AKZO CHEMIE of the Netherlands for
bis-ethoxylated 2,2-bis(4-hydroxyphenyl)propane. DIANOL 33 is a trade name of AKZO CHEMIE of the Netherlands for bis-propoxylated 2,2-bis(4-hydroxyphenyl)propane. |
The chemical compound (polymeric, oligomeric or single
molecule) carrying reactive groups RGA, can be present in the bulk
of the toner particles, on the surface of the toner particles or
both in the bulk and on the surface of the toner particles.
Toner particles comprising compounds with reactive groups RGA
in the bulk of the particle can be prepared by melt kneading the
toner ingredients (e.g. toner resin, charge control agent,
pigment, etc) and said compounds with reactive groups RGA. After
the melt kneading the mixture is cooled and the solidified mass is
pulverized and milled and the resulting particles classified.
Also the "emulsion polymerisation" and "polymer emulsion"
techniques for toner preparation can be used to prepare toner
particles wherein compounds with reactive groups RGA are
incorporated in the bulk of the toner particles. In the "emulsion
polymerization" technique a water-immiscible polymerizable liquid
is sheared to form small droplets emulsified in an aqueous
solution, and the polymerization of the monomer droplets takes
place in the presence of an emulsifying agent; such a technique is
described e.g. in US P 2,932,629, US P 4,148,741, US P 4,314,932
and EP-A 255 716. In the "polymer emulsion" technique, a preformed
polymer is dissolved in an appropriate organic solvent that
is immiscible with water, the resulting solution is dispersed in
an aqueous medium that contains a stabilizer, the organic solvent
is evaporated and the resulting particles are dried; such a
technique is described in, e.g., US P 4,833,060.
Toner particles having compounds carrying reactive groups at
the surface can be prepared as described in EP-A 725 317. In this
European Application a method for producing toner particles is
disclosed, comprising the steps of :
It is taught that preferred stabilizer (co)polymers are being
copolymers of vinyl acetate and crotonic acid (90/10 by weight)
having a total acid number of 50 to 300, and copolymers of styrene
and maleic acid anhydride having a total acid number of 250 to
500, both said copolymers being used, at least partially,
transformed into their ammonium salt form. The water-soluble
stabilizing (co)polymer is precipitated on to the particles,
produced by the method according to this invention, by chemical
reaction, e.g. acidification of the aqueous medium, the water-soluble
(co)polymer adhering to the dispersed polymer particles
can be transformed into a water-insoluble species that
precipitates on the particles. By doing so carboxylic acid groups
are present at the surface of the toner particles.
The hardening reaction (the reaction between reactive groups
RGA and RGB), according to this invention, proceeds easily when
the interpenetration between toner particles and substrate is
quite high. This interpenetration is reached by heating the toner
particles on the substrate (during fixing or after fixing in an
additional heating step) to a temperature that preferably is at
most 150 °, most preferably at most 120 °C. Therefore it is
preferred to use toner particles, comprising compounds carrying
reactive groups RGA, that have a meltviscosity at 120 °C between
50 and 2000 Pas, preferably between 100 and 1000 Pas. All melt
viscosities mentioned herein are measured in a RHEOMETRICS dynamic
rheometer, RVEM-200 (One Possumtown Road, Piscataway, NJ 08854
USA). The viscosity measurement is carried out at a sample
temperature of 120 °C. The sample having a weight of 0.75 g is
applied in the measuring gap (about 1.5 mm) between two parallel
plates of 20 mm diameter one of which is oscillating about its
vertical axis at 100 rad/sec and amplitude of 10-3 radians.
The reaction between reactive groups RGA and RGB can
beneficially be speeded up by providing catalysers for this
reaction. Said catalysers are preferably acids (organic or
anorganic) or tertiary amines. Typical examples of suitable
catalysers are p-toluenesulfonic acid, trimethylamine and
triethylamine. The catalyser or catalysers can, within the scope
of the present invention, be incorporated in the toner particles,
the substrate or both in the toner particles and the substrate.
The catalyser or catalysers can be incorporated in the toner
particles, as long as the incorporation of it does not result in a
weakening of the mechanical resistance of the toner particles,
i.e. when the Tg stays equal to or higher than 35 °C.
It may be beneficial that the toner particles not only
comprise reactive groups RGA, e.g., a member selected from the
group consisting of epoxy groups, aldehyde groups, hydroxyl
groups, carboxyl groups, mercapto groups, amino groups and amide
groups, but comprise further a compound or mixture of compounds
carrying radiation curable groups.
Thus, the present invention includes also a method for forming
toner images on a substrate comprising the steps of :
The radiation curing can proceed off-line in a separate
apparatus wherein the fused layer of toner particles is heated
again and irradiated with curing rays.
To preserve the mechanical strength of the toner particles, it
is preferred that the compounds, carrying a radiation curable
group, to be incorporated in toner particles for use according to
this invention, is already an oligomeric or polymeric compound
instead of a monomer. A monomeric compound may be present in the
mixture of radiation curable compounds, as long as the mixture of
radiation curable compounds itself has a Tg ≥ 35 °C. Although
electron beam curable groups can be used in the present invention,
the radiation curable groups are preferably curable by UV-light.
Very useful radiation curable polymeric compounds, in toner
particles for use in the present invention are UV curable solid
epoxy resins with Tg ≥ 35 °C as disclosed in EP-A 667 381. In
this application solid compositions (I) are described containing
Other useful UV curable resins for incorporation in toner particles are powders based on unsaturated polyesters and polyurethaneacrylates, a typical example of such a polymeric UV curable system is available through Hoechts High Chem, Hoechts-Sara Pero (Mi) Italy. Such a system comprises a solid unsaturated polyester resin available under trade name AFTALAT VAN 1743, having a Tg ≥ 52 °C and an urethane adduct with acrylic functional groups available under trade name ADDITOL 03546, having a Tg ≥ 47 °C. The properties of this system have be described in European Coating Journal n° 9/95 606-608 (1995). Also non-acrylate binder systems are useful in the present invention, e.g. a powder composed of a mixture of an unsaturated polyester resin in which maleic acid or fumaric acid is incorporated and a polyurethane containing a vinylether. Such a binder system has been developed by DSM resins of the Netherlands and the properties thereof have been described in European Coating Journal n° 3/96 115-117 (1996).
For the UV curing to proceed it is necessary that a photoinitiator
is present. Very useful initiators are sulphonium salts as e.g.
triarylsulphonium salts, triarylsulphoniumhexafluorophosphate,
benzophenones, etc. Typical very useful photoinitiators in the
context of this invention, are, e.g., 2-hydroxy-2-methyl-1-phenylpropan-1-one,
compound I, a mixture of compound I and compound II
and compound III :
The initiator can be incorporated in the toner particles
together with the UV curable system or can be incorporated in the
substrate.
This embodiment has the advantage that the resins comprised in the fused image are cross-linked (by UV-curing) and attached to the substrate by chemical bonds.
This embodiment has the advantage that the resins comprised in the fused image are cross-linked (by UV-curing) and attached to the substrate by chemical bonds.
When UV-curable or radiation curable compounds are used in the
first embodiment of the present invention, it is possible to do so
in various combinations :
A substrate useful in the first embodiment of the invention
comprises reactive groups RGB. This reactive groups (RGB) in the
substrate, useful in the present invention, are in principle a
member of the same group of reactive groups as the reactive groups
RGA present in the toner particles, i.e. the reactive groups RGB
are preferably members selected from the group consisting of epoxy
groups, aldehyde groups, hydroxyl groups, carboxyl groups,
mercapto groups, amino groups and amide groups. The reactive
groups RGB can be part of a polymeric, oligomeric or low molecular
weight (molecular weight lower than 2000) molecule. The molecule
carrying reactive groups RGB can carry one or more of these
reactive groups.
In this invention the reactive groups RGB are chosen in such a
way that they are capable to react with one or more reactive
groups RGA present in the toner particles. When e.g. in the toner
particles, hydroxyl and/or carboxyl groups are present, the
substrate comprises reactive groups capable of an easy reaction
with said hydroxyl and/or carboxyl groups. Typical examples of
such reactive groups are epoxy groups, aldehyde groups,
polyaziridine groups, etc. When e.g. in the toner particles an
epoxy group is present as reactive group RGA, the substrate
preferably comprises as reactive group RGB either a hydroxyl,
carboxyl, amide or amino group. When reaction pairs as described
above are used it is preferred to incorporate the low molecular
weight compounds or the oligomeric or polymeric compounds having a
Tg < 35 °C in the substrate. Thus very suitable compounds
carrying reactive groups RGB for incorporation in the substrate
are e.g. polyaziridines, polyamidoamine resins, highly methylated
melamine resins, hydroxyl group containing epoxy hardening agents,
e.g. reaction products of epichlorohydrin
and HO-(CH2-CHOH-CH2-O-)n-H wherein n is an integer between 3 and
10, reaction products of epichlorohydrin and
HO-(CH2-CHOR-CH2-O-)n-H wherein n is an integer between 3 and 10,
and R is alkyl group. Further useful epoxy hardening agents are
exemplified in e.g. EP-A 495 314 on page 23 to 26. Also epoxy
hardening agents represented by formulas A-1 to A-6 can be used in
the present invention.
The compounds with reactive groups (RGB) can be comprised in a
toner receptive layer applied to the substrate. The substrate can
be paper, cardboard, plastic film, etc. Said toner receptive
layer can comprise a binder and the compounds with reactive groups
RGB can be embedded in said binder. The reactive groups RGB can
form part of said binder. Useful binders, carrying reactive
groups RGB, are e.g. the same binders as already described herein
above as useful binders for the toner particles, i.e. polymers
having an acid value > 2.5 mg KOH/g and/or a hydroxyl value > 2.5
mg KOH/g (examples of such polymers are found in table 1) and
epoxy polymers. E.g. polymers useful as binder in a substrate to
be used according to this invention and capable of reacting with a
hydroxyl or carboxyl group (comprised in the toner particles) are
epoxy polymers, polymers carrying aldehyde groups, polyaziridines,
etc. When the toner particles comprise epoxy groups or aldehyde
groups, then the binder in the image receiving layer of the
substrate for use in this invention will preferably comprise
hydroxyl, carboxyl and/or amino groups. Typical useful binders
are gelatin, polyvynilalcohol, etc. The binder can also comprise
further resinous compounds : e.g. polyamides, carboxyl or
sulphonyl group containing polyesters in latex form, etc.
When the toner particles further comprise radiation curable
(photopolymerizable) monomers, oligomers or polymers, the
substrate can comprise initiators for radiation curing.
The substrate, within the scope of this invention, may further
comprise a radiation curable compound and/or a photoinitiator as
describe above. It is possible that the substrate comprises said
radiation curable compound and that toner particles comprise an
initiator for radiation curing as described above.
As stated above, the hardening reaction (the reaction between
reactive groups RGA and RGB), according to this invention,
proceeds easily when the interpenetration between toner particles
and substrate is quite high. This interpenetration is reached by
heating the toner particles on the substrate (during fixing or
after fixing in an additional heating step) to a temperature that
preferably is at most 150 °, most preferably 120 °C. Thus it is
beneficial when at these temperatures the toner receiving layer
has some fluidity. Therefore, the toner receiving layer on the
substrate may comprise waxes or "heat solvents" also called
"thermal solvents" or "thermosolvents" improving the penetration
of the reagents RGA and RGB and thereby the reaction speed of
hardening reaction at elevated temperature.
By the term "heat solvent" in this invention is meant a non-hydrolyzable
organic material which is in solid state at
temperatures below 50 °C but becomes on heating above that
temperature a plasticizer for the binder of the layer wherein they
are incorporated. Useful for that purpose are a polyethylene
glycol having a mean molecular weight in the range of 1,500 to
20,000 described in US-P 3,347,675. Further are mentioned
compounds such as urea, methyl sulfonamide and ethylene carbonate
being heat solvents described in US-P 3,667,959, and compounds
such as tetrahydro-thiophene-1,1-dioxide, methyl anisate and 1,10-decanediol
described as heat solvents in Research Disclosure,
December 1976, (item 15027) pages 26-28. Still other examples of
heat solvents have been described in US-P 3,438,776, and
4,740,446, and in published EP-A 0 119 615 and 0 122 512 and DE-A
3 339 810.
Said toner receiving layer may comprise, apart from a compound
comprising reactive groups RGB or mixtures thereof and a binding
agent or mixture of binding agents, also stabilizers, toning
agents, antistatic agents, spacing particles (both polymeric or
anorganic).
In addition to said ingredients the toner receiving layer may
contain other additives such as free fatty acids, antistatic
agents, e.g. non-ionic antistatic agents including a fluorocarbon
group as e.g. in F3C(CF2)6CONH(CH2CH2O)-H, ultraviolet light
absorbing compounds, white light reflecting and/or ultraviolet
radiation reflecting pigments, and/or optical brightening agents.
This first embodiment of the invention encompasses also an
apparatus for forming an image comprising hardened toner particles
comprising :
The first embodiment of the invention comprises further an
apparatus for forming an image comprising hardened toner particles
comprising :
When the toner particles further comprise a UV curable compound,
it is preferred that said means for fusing said toner images emit
infrared radiation and said means for UV curing (e.g. one or more
UV emitting lamps) are installed immediately after said fusing
means so that the UV curing proceed on the still molten toner
image.
In the second embodiment of the invention, the reactive groups RGB
are applied on top of the toner image.
In the second embodiment of the invention, the same toner
particles can be used as those used in the first embodiment of the
invention and having been described above.
The substrate used in this second embodiment can be any
substrate known in the art, e.g. plastic film, paper, cardboard,
etc. It can also be a substrate comprising reactive groups RGB as
described above under the first embodiment of the present
invention.
The reactive compound that is applied on top of the image-wise
deposited toner particles is a compound comprising reactive groups
RGB that can react with the toner particles. The compounds
carrying reactive groups RGB are applied to the image in an amount
between 1 and 10 g/m2, preferably between 2 and 8 g/m2.
Typical couples of compounds, comprising reactive groups RGA
or RGB, and very useful in the present invention are the same as
those exemplified above.
In this second embodiment of the invention, it is also
preferred that the toner particles comprise resins with Tg ≥ 35 °C
containing reactive groups RGA.
The compounds carrying reactive groups RGB can, in the second embodiment of the invention, be applied to the toner image either before or after fusing of the toner particles to the substrate. When the compounds comprising reactive groups RGB are applied to the toner image before fusing, it is preferred to use spray coating techniques to apply said compounds. These compounds may be applied as such, as a solution or as a dispersion, depending on the physical nature of the compound carrying reactive groups RGB.
The compounds carrying reactive groups RGB can, in the second embodiment of the invention, be applied to the toner image either before or after fusing of the toner particles to the substrate. When the compounds comprising reactive groups RGB are applied to the toner image before fusing, it is preferred to use spray coating techniques to apply said compounds. These compounds may be applied as such, as a solution or as a dispersion, depending on the physical nature of the compound carrying reactive groups RGB.
In the second embodiment of the invention it is possible to
cover the toner image by an non-image-wise applied layer of clear
toner particles wherein said clear toner particles comprise
reactive groups RGB and wherein the compounds carrying reactive
groups RGB have a Tg ≥ 35 °C. The word "clear" means herein not
giving, in a wavelength range extending from 400 to 700 nm, a
visible diffuse density, said visible diffuse density being
defined as less than 15 % light reduction integrated over that
wavelength range. In this case said toner particles are applied
onto the toner image before fusing.
It is also possible to cover the toner image with a layer of
clear toner particles that do not comprises reactive groups RGB
capable of reacting with the reactive groups RGA contained in the
image forming toner particles, but comprising reactive groups RGA.
This layer of clear toner particles is then covered with a
compound comprising reactive groups RGB. Afterwards, both
reactive groups are made to react together to harden the outermost
toner layer in the toner image. When a layer of clear toner
particles is applied to toner images made up by the overlay of
several layers of different types of toner particles (e.g. in full
colour toner images or in a black and white (monochrome) image
with extended tonal range as disclosed in EP-A 768 577 and in
which a relief structure is present, it is possible to apply said
layer of clear toner particles "counter image-wise", such that a
thicker fixed clear finish layer is present in the lower thickness
areas of the image and a thinner fixed clear finish layer is
present in the higher thickness areas of the image.
The present invention includes also an apparatus for forming
an image comprising hardened toner particles comprising :
Said means for applying said compound carrying reactive groups
RGB can be rollers, wicks, sprays, etc. When said means for
applying compound carrying reactive groups RGB are rollers, it may
be split rollers, e.g. when 5 g/m2 of compound carrying reactive
groups RGB has to be applied, there may be provided four
application rollers, the first two applying together 2 g/m2 of
compound carrying reactive groups RGB and the following rollers
applying the remaining 3 g/m2. Preferred means for applying said
compound carrying reactive groups RGB are supply rollers with a
surface in NOMEX-felt (NOMEX is a trade name of Du Pont de
Nemours, Wilmington, US) as described in article titled
"Innovative Release Agent Delivery Systems" by R. Bucher et al. in
The proceedings of IS&T's Eleventh International Congress on
Advances in Non-Impact Printing Technologies, page 219 - 222.
This congress was held in Hilton Head, from 29.10.95 to 03.11.95.
The proceedings are published by IS&T, Springfield, US 1995. The
compound carrying reactive groups RGB can be delivered to the
image directly by supply rollers as described above, or over an
intermediate roller, which distributes the compound even more
evenly over the image.
Said means for applying a compound comprising reactive groups
RGB on top of a toner image may be installed before said means for
fusing said toner particles or after said means for fusing said
toner particles to said substrate.
When said means for applying a compound comprising reactive
groups RGB are installed after the fusing means, the reactive
groups RGB are applied on top of a fused, still warm, toner image
and the apparatus comprises preferably also special means for
reacting said reactive groups RGA and RGB so as to harden said
fused toner image. These special means are heating means, that
may be the same means as those used as fusing means.
When said means for applying the compound comprising reactive
groups RGB are installed before said means for fusing said toner
particles, these means for applying the compounds with reactive
groups RGB are preferably means for non-contact application, e.g.
spraying means and no special means for reacting said reactive
groups RGA and RGB so as to harden said fused toner image are
necessary since the reaction of reactive groups RGA and RGB
proceeds during the fusing step.
Also in this second embodiment of the invention, it is
possible to use toner particles and/or substrates that further
comprise radiation curable, preferably UV-curable compounds as
described above. Thus the second embodiment of the invention
includes a method for forming toner images on a substrate
comprising the steps of :
In this method the step of UV curing can proceed on line, e.g,
in the fusing station itself of an electrostatographic apparatus
or in a station immediately adjacent to said fusing station.
The radiation curing can proceed off-line in a separate
apparatus wherein the fused layer of toner particles is heated
again and irradiated with curing rays.
Also within the scope of the present invention is an apparatus
for forming an image comprising hardened toner particles
comprising :
In such an apparatus the means for fusing and the means for UV
curing can be the same as described above under the first
embodiment of the present invention.
The present invention can be practised in any electrographic
or magnetographic imaging method. It can be useful in classical
electrophotography, in ionography, in direct electrostatic
printing (DEP), etc. The present invention is useful for mono-chromatic
toner images as well as for multi-chromatic and full
colour toner images.
Thus in the apparatus, within the scope of the invention, the means for image-wise depositing toner particles can be direct electrostatic printing means, wherein charged toner particles are attracted to the substrate by an electrical field and the toner flow modulated by a printhead structure comprising printing apertures and control electrodes.
Said means for image-wise depositing toner particles can also be toner depositing means wherein first a latent image is formed. In such an apparatus, within the scope of the present invention, said means for image-wise depositing toner particles) comprise :
Thus in the apparatus, within the scope of the invention, the means for image-wise depositing toner particles can be direct electrostatic printing means, wherein charged toner particles are attracted to the substrate by an electrical field and the toner flow modulated by a printhead structure comprising printing apertures and control electrodes.
Said means for image-wise depositing toner particles can also be toner depositing means wherein first a latent image is formed. In such an apparatus, within the scope of the present invention, said means for image-wise depositing toner particles) comprise :
- means for producing a latent image on a latent image bearing member,
- means for developing said latent image by the deposition of said toner particles, forming a developed image and
- means for transferring said developed image on said substrate.
Said latent image may be a magnetic latent image that is
developed by magnetic toner particles (magnetography) or,
preferably, an electrostatic latent image. Such an electrostatic
latent image is preferably an electrophotographic latent image and
the means for producing a latent image are in this invention
preferably light emitting means, e.g., light emitting diodes or
lasers and said latent image bearing member comprises preferably a
photoconductor.
Toner particles useful in both embodiments of this invention can
have an average volume diameter between 1 and 50 µm, preferably
between 3 and 20 µm. When the toner particles are intended for
use in colour imaging, it is preferred that the volume average
diameter is between 3 and 10 µm, most preferred between 3 and 8
µm. The particle size distribution of said toner particles can be
of any type. It is however preferred to have an essentially (some
negative or positive skewness can be tolerated, although a
positive skewness, giving less smaller particles than an unskewed
distribution, is preferred) Gaussian or normal particle size
distribution, either by number or volume, with a coefficient of
variability (standard deviation divided by the average) (ν)
smaller than 0.5, more preferably of 0.3.
Toner particles, useful in the first embodiment of this
invention, can comprise any normal toner ingredient e.g. charge
control agents, pigments both coloured and black, anorganic
fillers, etc. A description of charge control agents, pigments
and other additives useful in toner particles, to be used in a
toner composition according to the present invention, can be found
in e.g. EP-A 601 235.
The toner particles can be used as mono-component developers,
both as a magnetic and as a non-magnetic mono-component developer.
The toner particles can be used in a multi-component developer
wherein both magnetic carrier particles and toner particles are
present. The toner particles can be negatively charged as well as
positively charged.
49 parts of a polyester of fumaric acid and DIANOL 33 (n° 2 in
Table 1) and 49 parts of a polyester of terephthalic acid,
isophthalic acid and DIANOL 22 and ethyleneglycol (n° 3 in Table
1) were melt-blended for 30 minutes at 110 °C in a laboratory
kneader with 2 parts of Cu-phthalocyanine pigment (Colour Index PB
15:3).
After cooling the solidified mass was pulverized and milled
using an ALPINE Fliessbettgegenstrahlmühle type 100AFG (tradename)
and further classified using an ALPINE multiplex zig-zag
classifier type 100MZR (tradename). The average particle size of
the separated toner was measured by Coulter Counter model
Multisizer (tradename) was found to be 8.0 µm by volume.
On a part of the glossy side of ZANDERS PAPER (tradename) a
solution of 25.9 g melamine-formaldehyde (CYMEL 303,
tradename of American Cyanamid Company USA) and 2.6 g p-toluenesulphonic
acid (catalyser) in 71.5 g Methyl-Ethyleketone
was coated by a bar coater at a wet thickness of 20 µm. After
drying for 30 minutes at 50 °C, the dry layer had a thickness of 6
µm. On an adjacent part of the glossy side of said paper no toner
receiving layer was present.
Printing proceeded in an AGFA XC305 colour copier. The image was
printed both on the part of the paper having a receiving layer and
the part not having a receiving layer. After fixing of the image,
the resistance of the image against solvents was tested by rubbing
the image 10 consecutive times with a cloth soaked with MEK
(methylethyleketone). The image on the part comprising the
receiving layer according to this invention, resisted the rubbing
for ten times, whereas the image on the part not having the
receiving layer disappeared after rubbing once.
49 parts of a polyester with acid value AV of 17 mg KOH/g
(number 2 of Table 1) and 49 parts of a polyester with AV of 18 mg
KOH/g (number 3 of Table 1) were melt-blended for 30 minutes at
110 °C in a laboratory kneader with 2 parts of SICOECHTGELB D
1355 DD (Colour Index PY 13, trade name of BASF AG, Germany).
After cooling the solidified mass was pulverized and milled
using an ALPINE Fliessbettgegenstrahlmühle type 100AFG (tradename)
and further classified using an ALPINE multiplex zig-zag
classifier type 100MZR (tradename). The average particle size of
the separated toner was measured by Coulter Counter model
Multisizer (tradename) was found to be 8.0 µm by volume.
To improve the flowability of the toner mass the toner
particles were mixed with 0.5 % of hydrophobic colloidal silica
particles (BET-value 130 m2/g).
The preparation of the Yellow toner was repeated, but instead of 2
parts SICOECHTGELB PY13, 2 parts of PERMANENT CARMIN FFB 02
(Colour Index PR146, tradename of Hoechst AG, Germany) were used.
The preparation of the Yellow toner was repeated, but instead of 2
parts SICOECHTGELB PY13, 2 parts of HELIOGEN BLAU D7072DD (Colour
Index PB15:3, trade name of BASF AG, Germany) were used.
The preparation of the Yellow toner was repeated, but instead of 2
parts SICOECHTGELB PY13, 2 parts of CABOT REGAL 400 (carbon black,
trade name of the Cabot Corp. High Street 125, Boston, U.S.A.)
were used.
The four toners, Y, M, C and K had a meltviscosity at 120 ° C of 500 Pas.
The four toners, Y, M, C and K had a meltviscosity at 120 ° C of 500 Pas.
After cooling the solidified mass was pulverized and milled
using an ALPINE Fliessbettgegenstrahlmühle type 100AFG (tradename)
and further classified using an ALPINE multiplex zig-zag
classifier type 100MZR (tradename). The average particle size of
the separated toner was measured by Coulter Counter model
Multisizer (tradename) was found to be 8.0 µm by volume. The
clear toner CT had a meltviscosity at 120 °C of 150 Pas.
To improve the flowability of the toner mass the toner
particles were mixed with 0.5 % of hydrophobic colloidal silica
particles (BET-value 130 m2/g).
Each of the above prepared toners were used to form carrier-toner
developers by mixing said mixture of toner particles and
colloidal silica in a 4 % ratio with silicone-coated Cu-Zn ferrite
carrier particles having an average diameter of 55 µm.
Full colour toner images were produced using a commercial
CHROMAPRESS (a trade name of Agfa-Gevaert NV, Mortsel, Belgium).
The images were covered with a layer of clear toner such that 0.9
mg/cm2 clear toner was present.
The fusing took place with radiant heat.
On top of the layer of clear toner a solution of 20 g of a polyaminoamide resin (UNIREZ 1307 trade name) with amino value between 370 and 410 mg KOH/g and 1.6 g of a catalyser (XB 3130 trade name of Ciba Geigy, Switserland) was applied at a wet thickness of 4 µm (i.e. 4 g of polyaminoamide resin per m2). The image was kept for 1 minute at 125 °C.
After cooling the image, the resistance of the image against solvents was tested by rubbing the image 10 consecutive times with a cloth soaked with MEK (methylethyleketone). The image on the part being treted with a hardener according to this invention, resisted the rubbing for ten times, whereas the image on the part not being treated layer disappeared after rubbing once.
The fusing took place with radiant heat.
On top of the layer of clear toner a solution of 20 g of a polyaminoamide resin (UNIREZ 1307 trade name) with amino value between 370 and 410 mg KOH/g and 1.6 g of a catalyser (XB 3130 trade name of Ciba Geigy, Switserland) was applied at a wet thickness of 4 µm (i.e. 4 g of polyaminoamide resin per m2). The image was kept for 1 minute at 125 °C.
After cooling the image, the resistance of the image against solvents was tested by rubbing the image 10 consecutive times with a cloth soaked with MEK (methylethyleketone). The image on the part being treted with a hardener according to this invention, resisted the rubbing for ten times, whereas the image on the part not being treated layer disappeared after rubbing once.
Claims (14)
1. A method for forming toner images on a substrate comprising the
steps of :
i) providing a substrate having a support and a toner receiving
layer thereon, said receiving layer containing at least one
reactive group RGB,
ii) providing toner particles containing a least one reactive
group RGA,
iii) image-wise depositing said toner particles on said substrate,
forming an image and
iv) reacting said reactive group RGA with reactive group RGB so as
to harden said toner particles.
2. A method according to claim 1, wherein said toner particles
contain a toner resin carrying said at least one reactive group
RGA.
3. A method according to claim 2, wherein said resin carrying said
reactive group RGA has a Tg ≥ 35 °C.
4. A method according to any of claims 1 to 3, wherein said
reactive group RGA and said reactive group RGB are members
selected from the group consisting of epoxy groups, aldehyde
groups, hydroxyl groups, carboxyl groups, mercapto groups, amino
groups and amide groups.
5. A method according to any of claims 1 to 3, wherein said
reactive group RGA and said reactive group RGB are comprised in
compounds forming reaction pairs said pairs being members selected
from the group consisting of :
polyaminoamide resins having an amine value between 140 and 430
mg KOH/g with compounds comprising epoxy groups,
polymers having an acid value larger than 2.5 mg KOH/g or a
hydroxyl value larger than 2.5 mg KOH/g with compounds carrying
epoxy groups,
polymers comprising epoxy groups with polyaziridines,
polymers having an acid value larger than 2.5 mg KOH/g or a
hydroxyl value larger than 2.5 mg KOH/g with polyaziridines,
polymers having an acid value larger than 2.5 mg KOH/g or a
hydroxyl value larger than 2.5 mg KOH/g with polyabietic acid,
polymers having an acid value larger than 2.5 mg KOH/g or a
hydroxyl value larger than 2.5 mg KOH/g with highly methylated
melamine resins,
polyamide resins with hardening agents comprising epoxy groups
and
polyester/polyamide copolymers with hardening agents comprising
epoxy groups.
6. A method according to any of claims 1 to 5, wherein said
substrate further comprises a catalyser.
7. A method according to any of claims 1 to 6, wherein said toner
particles further comprise a radiation curable compound and an
initiator for radiation curing.
8. A method according to any of claims 1 to 6, wherein said toner
particles further comprise a radiation curable compound and said
substrate comprises further an initiator for radiation curing.
9. A method according to claim 7, wherein said substrate further
comprises a radiation curable compound.
10. A method according to claim 8, wherein said substrate further
comprises a radiation curable compound.
11. A method for forming toner images comprising the steps of :
i) providing toner particles comprising at least one reactive
group RGA,
ii) image-wise depositing said toner particles on a substrate,
forming an image,
iii) applying a compound comprising at least one reactive group
RGB on said image and
iv) reacting said reactive group RGA with said reactive group RGB
so as to harden said toner particles.
12. A method according to claim 11, wherein said reactive group
RGA and reactive group RGB are members selected from the group
consisting of epoxy groups, aldehyde groups, hydroxyl groups,
carboxyl groups, mercapto groups, amino groups and amide groups.
13. A method according to claim 11, wherein said at least one
reactive group RGA is an epoxy group and said at least one
reactive group RGB is part of a polyaminoamide resin having an
amine value between 140 and 430 mg KOH/g.
15. An apparatus for forming image comprising hardened toner
particles comprising :
i) means for image-wise applying toner particles comprising at
least one reactive group RGA on a substrate,
ii) means for fusing said toner particles to said substrate,
forming a fused toner image, characterised in that it further
comprises means for applying a compound carrying at least one
reactive group RGB on top of said image-wise applied toner
particles.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97201900A EP0821280A1 (en) | 1996-07-26 | 1997-06-21 | Method for producing cross-linked fixed toner images |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96202127 | 1996-07-26 | ||
EP96202127 | 1996-07-26 | ||
EP97201900A EP0821280A1 (en) | 1996-07-26 | 1997-06-21 | Method for producing cross-linked fixed toner images |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0821280A1 true EP0821280A1 (en) | 1998-01-28 |
Family
ID=26143045
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97201900A Withdrawn EP0821280A1 (en) | 1996-07-26 | 1997-06-21 | Method for producing cross-linked fixed toner images |
Country Status (1)
Country | Link |
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EP (1) | EP0821280A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1341048A1 (en) * | 2002-02-28 | 2003-09-03 | Xerox Corporation | Curing processes |
EP1437628A1 (en) * | 2003-01-07 | 2004-07-14 | Xeikon International N.V. | UV curable toner particles and toners and developers comprising these |
EP1959304A3 (en) * | 2007-02-16 | 2009-09-09 | Xerox Corporation | Curable Toner Compositions and Processes |
US7807256B2 (en) | 2007-01-30 | 2010-10-05 | Hewlett-Packard Development Company, L.P. | Toner receiving composition |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0104626A1 (en) * | 1982-09-24 | 1984-04-04 | Coulter Systems Corporation | Opaque contact print copy and method of making same |
EP0601235A1 (en) * | 1992-12-07 | 1994-06-15 | Agfa-Gevaert N.V. | Toner composition suited for fixing by non-contact fusing |
EP0667381A2 (en) * | 1994-02-09 | 1995-08-16 | Ciba-Geigy Ag | Ultraviolet curable solid epoxy resin compositions |
US5486436A (en) * | 1993-10-15 | 1996-01-23 | The Standard Register Company | Sealable web or sheet product |
-
1997
- 1997-06-21 EP EP97201900A patent/EP0821280A1/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0104626A1 (en) * | 1982-09-24 | 1984-04-04 | Coulter Systems Corporation | Opaque contact print copy and method of making same |
EP0601235A1 (en) * | 1992-12-07 | 1994-06-15 | Agfa-Gevaert N.V. | Toner composition suited for fixing by non-contact fusing |
US5486436A (en) * | 1993-10-15 | 1996-01-23 | The Standard Register Company | Sealable web or sheet product |
EP0667381A2 (en) * | 1994-02-09 | 1995-08-16 | Ciba-Geigy Ag | Ultraviolet curable solid epoxy resin compositions |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1341048A1 (en) * | 2002-02-28 | 2003-09-03 | Xerox Corporation | Curing processes |
EP1437628A1 (en) * | 2003-01-07 | 2004-07-14 | Xeikon International N.V. | UV curable toner particles and toners and developers comprising these |
US7807256B2 (en) | 2007-01-30 | 2010-10-05 | Hewlett-Packard Development Company, L.P. | Toner receiving composition |
EP1959304A3 (en) * | 2007-02-16 | 2009-09-09 | Xerox Corporation | Curable Toner Compositions and Processes |
US8039187B2 (en) | 2007-02-16 | 2011-10-18 | Xerox Corporation | Curable toner compositions and processes |
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