EP0895130A1 - A receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups - Google Patents
A receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups Download PDFInfo
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- EP0895130A1 EP0895130A1 EP98202303A EP98202303A EP0895130A1 EP 0895130 A1 EP0895130 A1 EP 0895130A1 EP 98202303 A EP98202303 A EP 98202303A EP 98202303 A EP98202303 A EP 98202303A EP 0895130 A1 EP0895130 A1 EP 0895130A1
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- EP
- European Patent Office
- Prior art keywords
- toner
- polyester
- layer
- receiving layer
- acid
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- 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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- 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
- G03G7/0086—Back layers for image-receiving members; Strippable backsheets
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- 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
- G03G7/0026—Organic components thereof being macromolecular
- G03G7/0046—Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to a receptor element for non-impact printing comprising an imaging layer. More particularly, this invention relates to a receptor element for electrostatographic printing with dry toner particles.
- Receptor elements for use in non-impact printing by electrostatographic methods using toner particles, especially, but not exclusively, dry toner particles (i.e. electrophotography, ionography, direct electrostatic printing, magnetography) are well known in the art.
- dry toner particles i.e. electrophotography, ionography, direct electrostatic printing, magnetography
- hydrophobic image receiving layers have been described : e.g. polyamides in US-A-3 535 112 , vinylidene chloride copolymers in US-A-3 539 340 .
- EP-A-104 074 a receiving layer for toner particles comprising a polymethylmethacrylate resin and being coated from a solution containing methyl ethyl ketone and toluene is disclosed.
- an image receiving layer comprising a film forming binder as e.g. poly(vinylalcohol) or cellulose derivatives, and hardening said binder.
- an image receiving layer comprising a polyester resin as binder resin is disclosed, the polyester being coated from a coating solution in methyl ethyl ketone and toluene.
- EP-A-240 147 a toner receiving layer comprising polymethylmethacrylate as binder is disclosed. Again this binder is coated from a solution in methyl ethyl ketone and toluene.
- image receiving layers comprising resins being adapted to the toner particles.
- EP-A-349 227 it is disclosed to coat a toner receiving layer comprising a polyester predominantly having terephthalic acid moieties and bisphenol-A moieties on a polyester support for receiving toner particles having as toner resin a polyester with predominantly fumaric acid moieties and bisphenol-A moieties.
- the advantage is that the binder of the image receiving layer has good compatibility with the toner resin and has a larger elasticity than the toner resin. When used as an image receiving layer for making transparencies for overhead projection with dry toner particles, this provides a smooth fixed image with sharp edges and no scattering of light occurs, giving a clear projected image. Again the toner receiving layer is coated from a volatile organic solvent.
- a toner receiving sheet comprising on a paper support a layer consisting essentially of a thermoplastic acrylic-styrene copolymer with acid value between 10 and 170 and hydrophobic silica.
- EP-A-613 056 a toner receiving layer coated from an aqueous dispersion has been disclosed and the binder of the toner receiving layer is a cross-linked urea-formaldehyde resin powder.
- Image receiving layers, well suited for ink-jet printing and comprising polymeric latices together with other polymeric compounds have been disclosed in e.g. US-A-5 624 743 .
- the toner receiving layers containing polymeric latices seem to have a rather complicated structure and constitution, therefore further toner receiving layers that can be produced via aqueous coating solution, especially when coated on a plastic substrate, are still desirable.
- a toner receiving element comprising a support with a first and second major face and an image receiving layer on said first major face, characterised in that said image receiving layer contains at least 80 % by weight of a polyester containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form.
- the objects are further realised by providing a method for forming a toner image on a substrate comprising the steps of :
- a polyester wherein sulphonic acid groups in free acid form were present as main component of an image receiving layer, a very good toner receiving layer could be prepared.
- a polyester comprising between 0.5 and 20 mole % of sulphonic acid groups is used in the manufacture of a receptor material according to this invention
- receiving layers comprising other polymers with sulphonic acid groups did not have the same very good properties with respect to projection quality of an OHP as receiving layer comprising a polyester comprising sulphonic acid groups in free acid form.
- an image receiving layer comprising at least 80% by weight with respect to the total weight of the layer of a polyester containing between 0.5 and 20 mole % of moieties carrying sulphonic acid groups, can easily be coated on a support from an aqueous dispersion and yield a toner receiving material that gives good toner adhesion and sharp images.
- an image receiving layer according to this invention is coated on a transparent support, the receptor element is very well suited for producing full colour images for use in overhead projection.
- the images made on materials according to this invention are upon projection sharp, show low fog and even the most critical colour (yellow) is rendered very faithfully.
- toner receiving layers according to this invention could be coated from a dispersion containing a dispersion of a polyester containing between 0.5 and 20 mole % of moieties carrying sulphonic acid groups and a surfactant. No other ingredients were necessary to produce a toner receiving layer that shows acceptable coating quality with good imaging properties.
- the surfactant used in the coating solution can be any surfactant know in the art, it is however preferred to use an anionic surfactant as e.g. RHODAFAC RM-710, trade name of RHONE POULENC CHIMIE.
- the sulphonic acid groups can be present as free acid groups, as sodium salt, as ammonium salt or as amine salt. In the most preferred embodiment of the invention, the sulphonic acid groups are present as free acid group.
- a receptor layer wherein the sulphonic acid groups are present as an ammonium salt or as amine salt give useful results, it was surprisingly found that receptor layers wherein the sulphonic acid groups were present as free acid gave better printing results.
- the polyester or copolyester comprising between 0.5 and 20 mole % of sulphonic acid groups can be a polyester comprising di- or polycarboxylic acids and di- or polyols.
- the sulphonic acid moieties can be introduced by adding in the polycondensation mixture a di- or polyol carrying sulphonic acid groups or a di- or polycarboxylic acid carrying sulphonic acid groups or both. It is preferred to use a dicarboxylic acid carrying sulphonic acid groups for introducing moieties with sulphonic acid groups in the polyester used in an image receiving layer according to this invention.
- the polyester for use in an image receiving layer according to this invention preferably obtained by reacting a diol mixture containing ethylene glycol in an amount between 0 and 95 mole % percent with respect to the total diol content and polyethylene glycol in an amount between 0 and 5 mole % percent with respect to the total diol content and an acid mixture containing (i) terephthalic acid, (ii) isophthalic acid, (iii) 5-sulpho-isophthalic acid.
- the polyethylene glycol has a molecular weight of 1500.
- the polyethylene glycol is present in said diol mixture in an amount between 0 to 5 mole % with respect to the total diol content.
- the polyester, used in an image receiving layer according to the present invention is a copolyester obtained by reacting a diol mixture containing ethylene glycol in an amount between 0 and 95 mole % percent with respect to the total diol content and polyethylene glycol in an amount between 0 and 5 mole % percent with respect to the total diol content and an acid mixture containing terephthalic acid, isophthalic acid and 5-sulphoisophthalic acid, said acid mixture consisting essentially of from 20 to 60 mole % of isophthalic acid, 0.5 to 20 mole % of said sulphoisophthalic acid, the remainder in said acid mixture being terephthalic acid. More preferably said mixture comprises between 1 and 10 mole % of said sulphoisophthalic acid.
- the sulpho groups in a polyester for use in an image receiving layer according to this invention are after the polycondensation reaction usually present in the form of their sodium salt.
- the sulpho groups can be converted to the free acid form by treating an aqueous dispersion of the polyester with the sulpho groups in the form of their sodium salt with an ion exchange resin as e.g. LEWATITE S100MB, trade name of Bayer AG, Leverkusen Germany.
- the dispersion of the polyester with the sulpho groups in free acid form can be converted to a dispersion of the polyester with the sulpho groups in ammonium salt form by neutralising the dispersion with ammonia or in the form of an amine salt by neutralising the dispersion with an amine, e.g., morpholine.
- a receptor element according to this invention could also be prepared, with good coating quality, when the receptor layer, coated from an aqueous dispersion, is dried a fairly low temperatures (between 20 and 40 °C) when the coating solution was given a viscosity above 1.25 mPa.s, preferably above 2 mPa.s.
- This can be achieved by using any thickener known in the art, e.g. gelatine, derivatives of cellulose, polysaccharides, polystyrenesulphonic acid, carboxylated poly(meth)acrylates, polyacrylamides, polyurethanes, etc.
- Gelatine is the preferred thickener for forming an image receiving layer according to this invention, since it is a very good thickener for the coating dispersion, giving after coating and drying a very clear receiving layer.
- thickener it is preferred to neutralise the sulphonic acid groups in the polymer before the polymer is added to the aqueous gelatine solution. By doing so the risk of flocculation is diminished.
- a thickener it is preferably present in an amount between 1 and 10 % by weight with respect to the total weight of the dry layer.
- a coating dispersion or solution
- a coating dispersion or solution
- This plasticiser or softener is preferably a polyhydroxy compound and more preferably a polyhydroxy compound selected from the group consisting of glycerine, sorbitol, glucose, mannitol, 1,1,1-tris-(hydroxymethyl)propane or 1,2,3,4-butane-tetrol.
- Receptor layers wherein a polymer containing sulphonic acid groups, a thickener , a surfactant and a plasticiser or softener are present give the better printing results (printing quality is assessed on basis of the projection quality of the overhead projectable slide) when the sulphonic acid groups in the polymer are present in the receiving layer as free acid groups, as ammonium salt or as amine salt.
- a plasticiser or softener is used it is preferably present in an amount between 1 and 10 % by weight with respect to the total weight of the dry layer.
- An image receiving layer according to the present invention can further comprise matting agents or spacing agents for enhancing the transportability of the receptor element in the non-impact printing machines.
- Said spacing particles can be inorganic, e.g. silica particles, both hydrophobic and hydrophilic and both crystalline and amorphous.
- Typical useful silica particles are amorphous silica particles sold under trade name SYLOID by GRACE GMBH, Worms, Germany. It can be the untreated particles, e.g. SYLOID 72 or an amorphous silica with special inorganic treatment, e.g. SYLOID 378.
- Said spacing particles can also be organic polymeric beads.
- Very useful organic polymeric beads for use as spacing particles in this invention are the beads prepared by dissolving in an aqueous solvent mixture at least one ⁇ - ⁇ -ethylenically unsaturated monomer(s) capable of forming a polymer that is soluble in the monomer(s) present in said aqueous solvent mixture but which is insoluble in said aqueous solvent mixture, a free radical-forming polymerisation initiator, and a graft-polymerizable polymer containing hydrophilic groups, heating the solution to a temperature from 50 °C to the reflux temperature thereof with stirring so as to from said polymer beads.
- Such polymeric beads have been disclosed in EP-A-080 225.
- cross-linked polymeric beads prepared by dissolving in a solvent mixture of water and water-miscible polar organic solvent an ⁇ - ⁇ -ethylenically unsaturated monomer (1) capable of forming a polymer that is soluble in the monomer(s) present in said solvent mixture but which is insoluble in said solvent mixture, a monomer (2) carrying COOH group(s), a monomer (3) carrying halogen atom(s), a free radical-forming polymerisation initiator, and a graft-polymerizable polymer containing hydrophilic groups, heating the solution obtained to a temperature from 50 °C to the reflux temperature thereof with stirring to form said beads, converting said COOH group(s) by reaction with a hydroxide into a carboxylic acid salt group, and causing said carboxylic acid salt group to react with said halogen atom to form ester cross-linkages.
- polymeric beads useful as spacing particles in the present invention are polymeric beads as disclosed in EP-A-698 625 .
- Such beads are heat resistant and are prepared in an aqueous reaction medium wherein said polymer beads are formed by the simultaneous reaction of a silane monomer comprising an ⁇ - ⁇ -ethylenically unsaturated group, at least one ⁇ - ⁇ -ethylenically unsaturated monomer, different from said silane monomer, capable of forming a polymer that is soluble in the monomer(s) present in said aqueous solvent mixture but which is insoluble in water, a free radical-forming polymerisation initiator that is soluble in the aqueous solvent mixture, and a graft-polymerizable polymer containing hydrophilic groups, and capable of forming a graft polymer that remains soluble in the aqueous reaction mixture.
- the toner receiving layer of the present invention comprises preferably at least 80 % by weight with respect to the total weight of the layer, more preferably at least 90 % by weight with respect to the total weight of the layer of a dispersion of a polyester containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form, the rest of the weight of the layer optionally being made up by a compound selected from the group of surfactants, matting agents, hydrophilic colloids, plasticizers, lubricants, antistatic agents and coloiadal silica.
- the toner receiving layer comprises at least 95 % by weight with respect to the total weight of the layer of the a polyester containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form and the rest of the weight of the layer optionally being made up by a compound selected from the group of surfactants, matting agents, plasticizers, lubricants, antistatic agents and coloiadal silica.
- aqueous dispersions of waxes are used as lubricants.
- the toner receiving layer comprises at least 97 % by weight with respect to the total weight of the layer of the a polyester containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form and the rest of the weight of the layer optionally being made up by a compound selected from the group of surfactants, matting agents and antistatic agents.
- An image receiving layer according to the present invention can be coated on any support known in the art. It can be coated on paper, polyethylene coated paper, plastic supports as, e.g., polyethyleneterephthalate, polyethylenenaphthalate, syndiotactic polystyrene, polyamides, polyimides, polyvinylchloride, polypropylene, etc. It is preferred to coat the receiving layer according to this invention on a thermally stable support as, e.g., a polyester support. By thermally stable is meant that the heat distortion temperature of the support is at least 145 °C.
- the receiving layer according to the present invention can be used on an opaque support as well as on a transparent support.
- the receiving layer, according to this invention, being very transparent, is preferably used on a transparent support.
- a receptor element according to this invention comprises preferably a transparent support and an image receiving layer according to this invention and is used for producing transparencies for e.g. overhead projection (OHP).
- OHP overhead projection
- This primer layer can be any primer layer known in the art. E.g. it can be a vinylidene chloride polymer in latex form as described in e.g. US-A-3 649 336 or a primer layer comprising a polyester as disclosed in, e.g., EP-A-559 244 .
- the image receiving layer according to this invention is preferably coated so as to have a dry thickness between 0.5 and 3 ⁇ m, preferably between 0.75 and 2 ⁇ m both limits included.
- the printing quality in electrostatic printing engines in electrophotography as well as in ionography as in Direct Electrostatic Printing as described in e.g. US-A-3 689 935) on a material containing an image receiving layer according to this invention in terms of evenness of printing of even density patches could largely be enhanced by applying a backing layer on the support having a resistivity between 5.10 8 ⁇ /square and 5 10 11 ⁇ /square measured at 30 % Relative Humidity (RH).
- the backing layer comprises as conductive polymer a polythiophene prepared by oxidative polymerisation of thiophene in the presence of a polyanion compound. This latter compound is preferably polystyrene sulphonic acid.
- polythiophene as a conductive polymer (an electronic conductive polymer) lays in the fact that the conductivity of a backing layer containing such an electronically conducting polymer is almost independent on the relative humidity wherein the material is used.
- the polythiophene used has preferably a formula : in which :
- the resistivity of the backing layer could at 30 % RH not be lower than 5.10 8 ⁇ /square since then the printing density becomes too low, which is, without being bound to any theory, probably due to a less effective transfer from the toner particles from the latent image bearing member to the toner receiving material.
- the upper limit posed on the resistivity of the backing layer depended on the resistivity of the image receiving layer the product of the resistivity of the image receiving layer and of the backing layer is, both measured at 30 % RH, preferably lower than 10 25 ⁇ /square, more preferably lower than 10 23 ⁇ /square.
- the resistivity of the image receiving layer and of the backing layer may be beneficial to introduce an antistatic agent in the toner receiving layer since when the resistivity of the image receiving layer is lower, the resistivity of the backing layer can be higher and still deliver very good evenness.
- any antistatic agent known in the art can be used in a toner receiving layer according to this invention, it is preferred, when an antistatic agent is used in the toner receiving layer, to use polythiophene with formula : in which :
- a receptor element for non-impact printing according to the present invention can be use in several non-impact printing techniques, e.g. ink-jet printing, ionography, magnetography, electrophotography, direct electrostatic printing (as described in e.g. US-A-3 689 935), etc.
- non-impact printing techniques e.g. ink-jet printing, ionography, magnetography, electrophotography, direct electrostatic printing (as described in e.g. US-A-3 689 935), etc.
- the receiving layer according to this invention is however especially useful in non-impact techniques where the image is formed by image-wise applying toner particles, having a toner resin and optionally a pigment, to the image receiving layer and by fixing said image to said receiving layer by fusing the resin in the toner particles to the receiving layer.
- Such techniques are, e.g., ionography, magnetography, electrophotography and direct electrostatic static printing.
- ionography, magnetography and electrophotography an electrostatic or magnetic (in magnetography) latent image is formed on a latent image bearing member and that latent image is developed by toner particles (both by dry and liquid development).
- the developed latent image is then transferred to the toner receiving layer.
- direct electrostatic printing a flow of toner particles (mostly originating from a dry developer) from a toner source to the receiving layer is image-wise modulated by a printhead structure interposed in said flow. In this case there is no latent image formed.
- the receiving layer according to the present invention is very well suited for use with dry toner particles, and therefore the invention also encompasses a method for forming a toner image on a substrate comprising the steps of :
- the receptor element can be used in any method wherein any kind of dry toner particles are deposited on the toner receiving layer, it is preferred to use a receptor element according to this invention in methods wherein the toner particles that are deposited to the receiving layer comprise at least 50 % by weight, with respect to the total toner resin, of a polyester in the toner resin. More preferably the toner particles deposited on an imaging layer according to this invention, comprise at least 50 % by weight, with respect to the total toner resin, of a polyester with acid value (AV) or hydroxyl value (HV) higher than 2.5 mg KOH/g of the polyester in the toner resin.
- AV acid value
- HV hydroxyl value
- the reaction mixture was then subjected to a reduced pressure of 1 hPa. Under these conditions polycondensation took place within a period of about 60 to 120 minutes.
- the polyester melt was allowed to settle on an aluminium foil and cooled to 25°C. A transparent and brittle solid was obtained.
- the solidified copolyester PA was then milled into a powder.
- the intrinsic viscosity of the copolyester was from 0.20 to 0.30 dl/g, measured at 25 °C in a 60/40-mixture of phenol and o-dichloro-benzene.
- the Tg (glass transition temperature) of the copolyester was 52 °C, measured by DSC (Differential Scanning Calorimetry).
- copolyester dispersion DPA was treated with an ion exchange resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen, Germany).
- a stable copolyester dispersion was obtained with sulphonic groups in the free acid form.
- a stable copolyester dispersion was obtained with sulphonic groups in the ammonium salt form.
- polyester PA The preparation of polyester PA was repeated except for the supplementary addition of 820 mg sodium acetate to the reaction mixture at the beginning of the re-esterification reaction. As a result, the formation of diethyleneglycol was suppressed and the Tg of the copolyester resin increased to 70 °C.
- copolyester dispersion DPB was treated with an ion exchange resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen, Germany).
- a stable copolyester dispersion was obtained with sulphonic groups in the free acid form.
- a stable copolyester dispersion was obtained with sulphonic groups in the ammonium salt form.
- copolyester PA The preparation of copolyester PA was repeated except for the supplementary addition of 112.5 g polyethyleneglycol 1500 (0.75 mole) in the reaction mixture. As a result, copolyester resin PC was obtained.
- the intrinsic viscosity of the copolyester was from 0.20 to 0.30 dl/g when measured at 25°C in a 60/40-mixture of phenol and o-dichloro-benzene.
- the Tg of the copolyester was 53°C when measured by DSC.
- copolyester dispersion DPC was treated with an ion exchange resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen, Germany).
- a stable copolyester dispersion was obtained with sulphonic groups in the free acid form.
- a stable copolyester dispersion was obtained with sulphonic groups in the ammonium salt form.
- a stable copolyester dispersion was obtained with sulphonic groups in the morpholine salt form.
- a coating solution was made containing 640 ml of water, 324 ml of polyester dispersion DPA, 6 ml of an aqueous solution (10 g solids/100 ml) of a surfactant (RHODAFAC RM-710, trade name of RHONE-POULENC CHIMIE, Paris - France, for a mixture of polyoxyethylene-nonylphenyl-etherphosphates) and 30 ml of an aqueous dispersion (1 g solids/100 ml) of a matting agent (SYLOID 72, trade name of GRACE GMBH, Worms, Germany, for amorphous silica with average particle size 4 ⁇ m).
- a surfactant RHODAFAC RM-710, trade name of RHONE-POULENC CHIMIE, Paris - France, for a mixture of polyoxyethylene-nonylphenyl-etherphosphates
- SYLOID 72 trade name of GRACE GMBH, Wor
- the coating solution was coated on a 100 ⁇ m thick clear polyethyleneterephthalate film, subbed with a known subbing layer comprising vinylidene chloride. No backing layer was present.
- the coated layer had a wet thickness of 33 ⁇ m and was dried at 120°C for 2 minutes. This yielded a dry toner receiving layer comprising :
- receptor element 1 The preparation of receptor element 1 was repeated except for the presence of polyester dispersion DPA1 instead of polyester dispersion DPA.
- receptor element 1 was repeated except for the presence of polyester dispersion DPB instead of polyester dispersion DPA.
- receptor element 1 The preparation of receptor element 1 was repeated except for the presence of polyester dispersion DPB1 instead of polyester dispersion DPA.
- receptor element 1 The preparation of receptor element 1 was repeated except for the presence of polyester dispersion DPC1 instead of polyester dispersion DPA.
- receptor element 1 was repeated except for the presence of a latex of a copolymer of n-butylacrylate (47 wt%), styrene (46 wt%) and methacrylic acid (7 wt%) (dispersion AMA1) instead of polyester dispersion DPA.
- a latex of a copolymer of n-butylacrylate (47 wt%), styrene (46 wt%) and methacrylic acid (7 wt%) (dispersion AMA1) instead of polyester dispersion DPA.
- receptor element 1 was repeated except for the presence of a latex of a copolymer of methylmethacrylate (50 wt%), n-butylacrylate (43 wt%) and 2-acrylamido-2-methylpropane sulphonic acid sodium salt (7 wt%) (dispersion AMA2) instead of polyester dispersion DPA.
- comparative receptor element CRE1
- a latex of a copolymer of n-butylacrylate 47 wt%), styrene (46 wt%) and methacrylic acid (7 wt%) with the carboxylic group of the methacrylic resin was present as sodium salt instead of as free acid.
- comparative receptor element CRE2 The preparation of comparative receptor element CRE2 was repeated except for the presence of a latex of a copolymer of methylmethacrylate (50 wt%), n-butylacrylate (43 wt%) and 2-acrylamido-2-methylpropane sulphonic acid sodium salt (7 wt%) treated with an ion exchange resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen, Germany). So the dispersion of the polymer had the sulphonic acid groups in the free acid form. (dispersion AMA4)
- a coating solution was made containing 3.33 g gelatine, that was swelled for 30 minutes in 668 ml of water. The solution was then heated while stirring. Then were added 5.6 ml of an aqueous solution (10 g solids/100 ml) of a surfactant (RHODAFAC RM-710, trade name of RHONE-POULENC; Paris - France, for a mixture of polyoxyethylenenonyl-phenyl-ether-phosphates), 0.28 g of a matting agent (SYLOID 378, trade name of GRACE GMBH; Worms - Germany, for an amorphous silica with special inorganic treatment and with average particle size 4 ⁇ m) and 300 ml of polyester dispersion DPA2.
- a surfactant RHODAFAC RM-710, trade name of RHONE-POULENC; Paris - France, for a mixture of polyoxyethylenenonyl-phenyl-ether-phosphates
- the coating solution was coated on a 100 ⁇ m thick clear polyethyleneterephthalate film, subbed with a known subbing layer comprising vinylidene chloride. No backing layer was present.
- the coated layer had a wet thickness of 33 ⁇ m and was dried at 35 °C and 25 % relative humidity for 2 minutes. This yielded a dry toner receiving layer comprising :
- RE7 RECEPTOR ELEMENT 7
- receptor element 6 was repeated except for the addition of glycerine to the coating solution in such an amount that the dry layer contained 0.05 g/m 2 of glycerine.
- receptor element 6 was repeated, but in the coating solution glycerine was added in such an amount that the dry layer contained 0.10 g/m 2 of glycerine.
- receptor element 6 was repeated, but in the coating solution glycerine was added in such an amount that the dry layer contained 0.15 g/m 2 of glycerine.
- RE10 RECEPTOR ELEMENT 10
- receptor element 6 was repeated, but in the coating solution glycerine was added in such an amount that the dry layer contained 0.20 g/m 2 of glycerine.
- receptor element 10 was repeated, but in the coating solution instead of glycerine, sorbitol was added in such an amount that the dry layer contained 0.20 g/m 2 of sorbitol.
- receptor element 10 was repeated, but in the coating solution instead of glycerine, glucose was added in such an amount that the dry layer contained 0.20 g/m 2 of mannitol.
- receptor element 10 was repeated, but in the coating solution instead of glycerine, butanetetrol was added in such an amount that the dry layer contained 0.20 g/m 2 of 1,1,1-tris(hydroxymethyl)propane.
- receptor element 10 was repeated except for the presence of polyester dispersion DPC2 instead of polyester dispersion DPA2.
- receptor element 10 was repeated except for the presence of polyester dispersion DPC instead of polyester dispersion DPA2.
- receptor element 10 was repeated except for the presence of polyester dispersion DPC3 instead of polyester dispersion DPA2.
- the receptor elements (RE1 to RE16, CRE1 to CRE4 were used, for producing overhead projection sheets, in a CHROMAPRESS (trade name of Agfa-Gevaert NV, Mortsel, Belgium) full colour digital printing press with toners and developers as follows :
- the solidified mass was pulverised and milled using an ALPINE Fliessbettarnastrahlmühle type 100AFG (trade name) and further classified using an ALPINE multiplex zig-zag classifier type 100MZR (trade name).
- the average particle size of the separated toner was measured by Coulter Counter model Multisizer (trade name) 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 melt viscosity at 120 °C of 500 Pa.s.
- 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.
- receptor element 2 (RE2) was repeated except for the presence of a backing layer comprising in the dried layer 6 mg/m 2 a polythiophene and polyanion compound.
- This polythiophene was applied from an aqueous dispersion, prepared as follows :
- the backing layer had a resistivity of 1.10 11 ⁇ /square and the toner receiving layer had a resistivity of 9.10 11 ⁇ /square.
- Receptor element 17 was repeated except for a different composition of the backing layer :
- Receptor element 17 (RE17) was repeated except for the fact that the toner receiving layer further contained 0.02 mg/m 2 of dispersion PT1.
- the toner receiving layer had a resistivity of 2.10 10 ⁇ /square.
- Receptor element 22 was repeated except for a different composition of the backing layer :
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Abstract
A receptor element for non-impact printing is provided comprising a
support and an image receiving layer containing at least 80 % by
weight with respect to the total weight of the layer of a polymer
with between 0.5 and 20 mole % of moieties carrying sulphonic acid
groups. Preferably the polymer is a polyester comprising between
0.5 and 20 mole % with respect to the total acid content of moieties
provided by sulphoisophthalic acid and the sulpho groups are present
in free acid form.
Description
The present invention relates to a receptor element for non-impact
printing comprising an imaging layer. More particularly, this
invention relates to a receptor element for electrostatographic
printing with dry toner particles.
Receptor elements for use in non-impact printing by
electrostatographic methods, using toner particles, especially, but
not exclusively, dry toner particles (i.e. electrophotography,
ionography, direct electrostatic printing, magnetography) are well
known in the art. Typically hydrophobic image receiving layers have
been described : e.g. polyamides in US-A-3 535 112, vinylidene
chloride copolymers in US-A-3 539 340.
In e.g. US-A-4 320 186 the use of acrylic polymers in toner
receiving layers is disclosed. In that disclosure it is taught to
coat the polymeric layer from a coating solution with toluene as
solvent.
In EP-A-104 074 a receiving layer for toner particles comprising
a polymethylmethacrylate resin and being coated from a solution
containing methyl ethyl ketone and toluene is disclosed. In
US-A-4 415 626 it is disclosed to use an image receiving layer
comprising a film forming binder as e.g. poly(vinylalcohol) or
cellulose derivatives, and hardening said binder.
In US-A-4 621 009 an image receiving layer comprising a
polyester resin as binder resin is disclosed, the polyester being
coated from a coating solution in methyl ethyl ketone and toluene.
In EP-A-240 147 a toner receiving layer comprising
polymethylmethacrylate as binder is disclosed. Again this binder is
coated from a solution in methyl ethyl ketone and toluene.
For imaging materials to be used for non-impact printing with
electrostatographic methods using dry toner particles, it has been
disclosed to use image receiving layers comprising resins being
adapted to the toner particles. In e.g. EP-A-349 227 it is disclosed
to coat a toner receiving layer comprising a polyester predominantly
having terephthalic acid moieties and bisphenol-A moieties on a
polyester support for receiving toner particles having as toner
resin a polyester with predominantly fumaric acid moieties and
bisphenol-A moieties. The advantage is that the binder of the image
receiving layer has good compatibility with the toner resin and has
a larger elasticity than the toner resin. When used as an image
receiving layer for making transparencies for overhead projection
with dry toner particles, this provides a smooth fixed image with
sharp edges and no scattering of light occurs, giving a clear
projected image. Again the toner receiving layer is coated from a
volatile organic solvent.
In US-A-5 208 093 it is disclosed to provide a toner receiving
layer on a support wherein the toner receiving layer contains a
polymer with equal or lower storage elasticity modulus than the
toner resin. Again the image receiving layer is coated from a
solution in organic solvents.
As stated above, many image receiving layers for dry toner
particles are coated from an organic solvent, which is nowadays
undesirable, both from the view point of safety in the workplace and
of environmental concerns.
Therefore layers comprising a resin that can be coated from an
aqueous medium are very desirable and such layers have been
disclosed.
In US-A-4 168 338 a toner receiving layer comprising an acrylic
polymer with a carboxyl group content between 2 and 30 % by weight
and an epoxy resin has been disclosed.
In US-A-4 245 025 a toner receiving sheet is disclosed
comprising on a paper support a layer consisting essentially of a
thermoplastic acrylic-styrene copolymer with acid value between 10
and 170 and hydrophobic silica.
In EP-A-613 056 a toner receiving layer coated from an aqueous
dispersion has been disclosed and the binder of the toner receiving
layer is a cross-linked urea-formaldehyde resin powder. Image
receiving layers, well suited for ink-jet printing and comprising
polymeric latices together with other polymeric compounds have been
disclosed in e.g. US-A-5 624 743.
The toner receiving layers containing polymeric latices seem to
have a rather complicated structure and constitution, therefore
further toner receiving layers that can be produced via aqueous
coating solution, especially when coated on a plastic substrate, are
still desirable.
It is an object of the invention to provide a receptor element
with an image receiving layer that is highly compatible with dry
toner particles and that can be produced from an aqueous solution or
dispersion.
It is a further object of the invention to provide a receptor
element with an image receiving layer that is highly compatible with
toner particles comprising a polyester as toner resin and that can
be produced from an aqueous solution or dispersion.
It is an other object of this invention to provide a method for
producing a toner image on a receiving element comprising an image
receiving layer coated from an aqueous solution or dispersion.
Further objects and advantages will become clear from the
detailed description hereinafter.
The objects of the invention are realised by providing a toner
receiving element comprising a support with a first and second major
face and an image receiving layer on said first major face,
characterised in that said image receiving layer contains at least
80 % by weight of a polyester containing between 0.5 and 20 mole %
of moieties having sulphonic acid groups in free acid form.
The objects are further realised by providing a method for
forming a toner image on a substrate comprising the steps of :
- providing a substrate with a support and a toner receiving layer containing at least 80 % by weight with respect to the total weight of the layer of a polyester, containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form,
- image wise depositing dry toner particles on said toner receiving layer and
- fixing said toner particles to said toner receiving layer.
It was found that by using a polyester wherein sulphonic acid
groups in free acid form were present, as main component of an image
receiving layer, a very good toner receiving layer could be
prepared. Preferably a polyester comprising between 0.5 and 20 mole
% of sulphonic acid groups is used in the manufacture of a receptor
material according to this invention
Although other sulphonic acid containing polymers could be used,
it was found that receiving layers comprising other polymers with
sulphonic acid groups did not have the same very good properties
with respect to projection quality of an OHP as receiving layer
comprising a polyester comprising sulphonic acid groups in free acid
form. E.g. a receiving layer comprising an addition copolymer of
methylmethacrylate (50 wt%), n-butylacrylate (43 wt%) and 2-acrylamido-2-methylpropane
sulphonic acid sodium salt (7 wt%) or a
layer comprising the same polymer but coated after desalting the
dispersion so that the sulphonic acid group is in free acid form,
did not give satisfactory results.
It was found that an image receiving layer comprising at least
80% by weight with respect to the total weight of the layer of a
polyester containing between 0.5 and 20 mole % of moieties carrying
sulphonic acid groups, can easily be coated on a support from an
aqueous dispersion and yield a toner receiving material that gives
good toner adhesion and sharp images. When an image receiving layer
according to this invention is coated on a transparent support, the
receptor element is very well suited for producing full colour
images for use in overhead projection. The images made on materials
according to this invention are upon projection sharp, show low fog
and even the most critical colour (yellow) is rendered very
faithfully.
It was found that toner receiving layers according to this
invention could be coated from a dispersion containing a dispersion
of a polyester containing between 0.5 and 20 mole % of moieties
carrying sulphonic acid groups and a surfactant. No other
ingredients were necessary to produce a toner receiving layer that
shows acceptable coating quality with good imaging properties. The
surfactant used in the coating solution can be any surfactant know
in the art, it is however preferred to use an anionic surfactant as
e.g. RHODAFAC RM-710, trade name of RHONE POULENC CHIMIE.
In a receptor element according to this invention, the sulphonic
acid groups can be present as free acid groups, as sodium salt, as
ammonium salt or as amine salt. In the most preferred embodiment of
the invention, the sulphonic acid groups are present as free acid
group. Although a receptor layer wherein the sulphonic acid groups
are present as an ammonium salt or as amine salt give useful
results, it was surprisingly found that receptor layers wherein the
sulphonic acid groups were present as free acid gave better printing
results.
The polyester or copolyester comprising between 0.5 and 20 mole
% of sulphonic acid groups can be a polyester comprising di- or
polycarboxylic acids and di- or polyols. The sulphonic acid
moieties can be introduced by adding in the polycondensation mixture
a di- or polyol carrying sulphonic acid groups or a di- or
polycarboxylic acid carrying sulphonic acid groups or both. It is
preferred to use a dicarboxylic acid carrying sulphonic acid groups
for introducing moieties with sulphonic acid groups in the polyester
used in an image receiving layer according to this invention. The
polyester for use in an image receiving layer according to this
invention preferably obtained by reacting a diol mixture containing
ethylene glycol in an amount between 0 and 95 mole % percent with
respect to the total diol content and polyethylene glycol in an
amount between 0 and 5 mole % percent with respect to the total diol
content and an acid mixture containing (i) terephthalic acid, (ii)
isophthalic acid, (iii) 5-sulpho-isophthalic acid. When
polyethylelene glycol is present, the polyethylene glycol has a
molecular weight of 1500. Preferably the polyethylene glycol is
present in said diol mixture in an amount between 0 to 5 mole % with
respect to the total diol content.
In a particularly preferred embodiment the polyester, used in an
image receiving layer according to the present invention, is a
copolyester obtained by reacting a diol mixture containing ethylene
glycol in an amount between 0 and 95 mole % percent with respect to
the total diol content and polyethylene glycol in an amount between
0 and 5 mole % percent with respect to the total diol content and an
acid mixture containing terephthalic acid, isophthalic acid and 5-sulphoisophthalic
acid, said acid mixture consisting essentially of
from 20 to 60 mole % of isophthalic acid, 0.5 to 20 mole % of said
sulphoisophthalic acid, the remainder in said acid mixture being
terephthalic acid. More preferably said mixture comprises between 1
and 10 mole % of said sulphoisophthalic acid.
The sulpho groups in a polyester for use in an image receiving
layer according to this invention, are after the polycondensation
reaction usually present in the form of their sodium salt. The
sulpho groups can be converted to the free acid form by treating an
aqueous dispersion of the polyester with the sulpho groups in the
form of their sodium salt with an ion exchange resin as e.g.
LEWATITE S100MB, trade name of Bayer AG, Leverkusen Germany. The
dispersion of the polyester with the sulpho groups in free acid form
can be converted to a dispersion of the polyester with the sulpho
groups in ammonium salt form by neutralising the dispersion with
ammonia or in the form of an amine salt by neutralising the
dispersion with an amine, e.g., morpholine.
It has been found that a receptor element according to this
invention could also be prepared, with good coating quality, when
the receptor layer, coated from an aqueous dispersion, is dried a
fairly low temperatures (between 20 and 40 °C) when the coating
solution was given a viscosity above 1.25 mPa.s, preferably above 2
mPa.s. This can be achieved by using any thickener known in the
art, e.g. gelatine, derivatives of cellulose, polysaccharides,
polystyrenesulphonic acid, carboxylated poly(meth)acrylates,
polyacrylamides, polyurethanes, etc. Gelatine is the preferred
thickener for forming an image receiving layer according to this
invention, since it is a very good thickener for the coating
dispersion, giving after coating and drying a very clear receiving
layer. When gelatine is used as thickener, it is preferred to
neutralise the sulphonic acid groups in the polymer before the
polymer is added to the aqueous gelatine solution. By doing so the
risk of flocculation is diminished. When a thickener is used it is
preferably present in an amount between 1 and 10 % by weight with
respect to the total weight of the dry layer.
It was further found that the quality of a receptor element
according to this invention, could further be increased when a
coating dispersion (or solution) was used that not only comprised a
dispersion of a polymer containing between 0.5 and 20 mole % of
moieties having sulphonic acid groups, a surfactant and a thickener,
but also a plasticiser or softener. This plasticiser or softener is
preferably a polyhydroxy compound and more preferably a polyhydroxy
compound selected from the group consisting of glycerine, sorbitol,
glucose, mannitol, 1,1,1-tris-(hydroxymethyl)propane or 1,2,3,4-butane-tetrol.
Receptor layers wherein a polymer containing
sulphonic acid groups, a thickener , a surfactant and a plasticiser
or softener are present give the better printing results (printing
quality is assessed on basis of the projection quality of the
overhead projectable slide) when the sulphonic acid groups in the
polymer are present in the receiving layer as free acid groups, as
ammonium salt or as amine salt. When a plasticiser or softener is
used it is preferably present in an amount between 1 and 10 % by
weight with respect to the total weight of the dry layer.
An image receiving layer according to the present invention can
further comprise matting agents or spacing agents for enhancing the
transportability of the receptor element in the non-impact printing
machines. Said spacing particles can be inorganic, e.g. silica
particles, both hydrophobic and hydrophilic and both crystalline and
amorphous. Typical useful silica particles are amorphous silica
particles sold under trade name SYLOID by GRACE GMBH, Worms,
Germany. It can be the untreated particles, e.g. SYLOID 72 or an
amorphous silica with special inorganic treatment, e.g. SYLOID 378.
Said spacing particles can also be organic polymeric beads. Very
useful organic polymeric beads for use as spacing particles in this
invention, are the beads prepared by dissolving in an aqueous
solvent mixture at least one α-β-ethylenically unsaturated
monomer(s) capable of forming a polymer that is soluble in the
monomer(s) present in said aqueous solvent mixture but which is
insoluble in said aqueous solvent mixture, a free radical-forming
polymerisation initiator, and a graft-polymerizable polymer
containing hydrophilic groups, heating the solution to a temperature
from 50 °C to the reflux temperature thereof with stirring so as to
from said polymer beads. Such polymeric beads have been disclosed
in EP-A-080 225. Also cross-linked polymeric beads prepared by
dissolving in a solvent mixture of water and water-miscible polar
organic solvent an α-β-ethylenically unsaturated monomer (1) capable
of forming a polymer that is soluble in the monomer(s) present in
said solvent mixture but which is insoluble in said solvent mixture,
a monomer (2) carrying COOH group(s), a monomer (3) carrying halogen
atom(s), a free radical-forming polymerisation initiator, and a
graft-polymerizable polymer containing hydrophilic groups, heating
the solution obtained to a temperature from 50 °C to the reflux
temperature thereof with stirring to form said beads, converting
said COOH group(s) by reaction with a hydroxide into a carboxylic
acid salt group, and causing said carboxylic acid salt group to
react with said halogen atom to form ester cross-linkages. Such
beads have been disclosed in US-A-5 252 445. Other polymeric beads
useful as spacing particles in the present invention are polymeric
beads as disclosed in EP-A-698 625. Such beads are heat resistant
and are prepared in an aqueous reaction medium wherein said polymer
beads are formed by the simultaneous reaction of a silane monomer
comprising an α-β-ethylenically unsaturated group, at least one α-β-ethylenically
unsaturated monomer, different from said silane
monomer, capable of forming a polymer that is soluble in the
monomer(s) present in said aqueous solvent mixture but which is
insoluble in water, a free radical-forming polymerisation initiator
that is soluble in the aqueous solvent mixture, and a graft-polymerizable
polymer containing hydrophilic groups, and capable of
forming a graft polymer that remains soluble in the aqueous reaction
mixture.
The toner receiving layer of the present invention comprises
preferably at least 80 % by weight with respect to the total weight
of the layer, more preferably at least 90 % by weight with respect
to the total weight of the layer of a dispersion of a polyester
containing between 0.5 and 20 mole % of moieties having sulphonic
acid groups in free acid form, the rest of the weight of the layer
optionally being made up by a compound selected from the group of
surfactants, matting agents, hydrophilic colloids, plasticizers,
lubricants, antistatic agents and coloiadal silica.
In a highly preferred embodiment the toner receiving layer
comprises at least 95 % by weight with respect to the total weight
of the layer of the a polyester containing between 0.5 and 20 mole %
of moieties having sulphonic acid groups in free acid form and the
rest of the weight of the layer optionally being made up by a
compound selected from the group of surfactants, matting agents,
plasticizers, lubricants, antistatic agents and coloiadal silica.
Preferably aqueous dispersions of waxes (both synthetic and
natural) are used as lubricants.
In a most preferred embodiment of this invention the toner
receiving layer comprises at least 97 % by weight with respect to
the total weight of the layer of the a polyester containing between
0.5 and 20 mole % of moieties having sulphonic acid groups in free
acid form and the rest of the weight of the layer optionally being
made up by a compound selected from the group of surfactants,
matting agents and antistatic agents.
An image receiving layer according to the present invention can
be coated on any support known in the art. It can be coated on
paper, polyethylene coated paper, plastic supports as, e.g.,
polyethyleneterephthalate, polyethylenenaphthalate, syndiotactic
polystyrene, polyamides, polyimides, polyvinylchloride,
polypropylene, etc. It is preferred to coat the receiving layer
according to this invention on a thermally stable support as, e.g.,
a polyester support. By thermally stable is meant that the heat
distortion temperature of the support is at least 145 °C.
The receiving layer according to the present invention can be
used on an opaque support as well as on a transparent support. The
receiving layer, according to this invention, being very
transparent, is preferably used on a transparent support. Thus a
receptor element according to this invention comprises preferably a
transparent support and an image receiving layer according to this
invention and is used for producing transparencies for e.g. overhead
projection (OHP).
When the image receiving layer is coated on a plastic support,
it may be beneficial to provide a subbing or primer layer between
the plastic support and the image receiving layer. This primer
layer can be any primer layer known in the art. E.g. it can be a
vinylidene chloride polymer in latex form as described in e.g.
US-A-3 649 336 or a primer layer comprising a polyester as disclosed
in, e.g., EP-A-559 244.
The image receiving layer according to this invention is
preferably coated so as to have a dry thickness between 0.5 and
3 µm, preferably between 0.75 and 2 µm both limits included.
It was found that the printing quality in electrostatic printing
engines (in electrophotography as well as in ionography as in Direct
Electrostatic Printing as described in e.g. US-A-3 689 935) on a
material containing an image receiving layer according to this
invention in terms of evenness of printing of even density patches
could largely be enhanced by applying a backing layer on the support
having a resistivity between 5.108 Ω/square and 5 1011 Ω/square
measured at 30 % Relative Humidity (RH). Is was preferred that the
backing layer comprises as conductive polymer a polythiophene
prepared by oxidative polymerisation of thiophene in the presence of
a polyanion compound. This latter compound is preferably
polystyrene sulphonic acid. The advantage of using polythiophene as
a conductive polymer (an electronic conductive polymer) lays in the
fact that the conductivity of a backing layer containing such an
electronically conducting polymer is almost independent on the
relative humidity wherein the material is used.
The preparation of said polythiophene and of aqueous
polythiophene polymeric polyanion dispersions containing said
polythiophene is described in EP-A-440 957 and corresponding
US-A-5,300,575.
It was found that the resistivity of the backing layer could at
30 % RH not be lower than 5.108 Ω/square since then the printing
density becomes too low, which is, without being bound to any
theory, probably due to a less effective transfer from the toner
particles from the latent image bearing member to the toner
receiving material.
It was found that the upper limit posed on the resistivity of
the backing layer depended on the resistivity of the image receiving
layer the product of the resistivity of the image receiving layer
and of the backing layer is, both measured at 30 % RH, preferably
lower than 1025 Ω/square, more preferably lower than 1023 Ω/square.
For adjusting the product of the resistivity of the image
receiving layer and of the backing layer to the values disclosed
above it may be beneficial to introduce an antistatic agent in the
toner receiving layer since when the resistivity of the image
receiving layer is lower, the resistivity of the backing layer can
be higher and still deliver very good evenness. Although any
antistatic agent known in the art can be used in a toner receiving
layer according to this invention, it is preferred, when an
antistatic agent is used in the toner receiving layer, to use
polythiophene with formula :
in which :
A receptor element for non-impact printing according to the
present invention can be use in several non-impact printing
techniques, e.g. ink-jet printing, ionography, magnetography,
electrophotography, direct electrostatic printing (as described in
e.g. US-A-3 689 935), etc.
The receiving layer according to this invention is however
especially useful in non-impact techniques where the image is formed
by image-wise applying toner particles, having a toner resin and
optionally a pigment, to the image receiving layer and by fixing
said image to said receiving layer by fusing the resin in the toner
particles to the receiving layer. Such techniques are, e.g.,
ionography, magnetography, electrophotography and direct
electrostatic static printing. In ionography, magnetography and
electrophotography an electrostatic or magnetic (in magnetography)
latent image is formed on a latent image bearing member and that
latent image is developed by toner particles (both by dry and liquid
development). The developed latent image is then transferred to the
toner receiving layer. In direct electrostatic printing a flow of
toner particles (mostly originating from a dry developer) from a
toner source to the receiving layer is image-wise modulated by a
printhead structure interposed in said flow. In this case there is
no latent image formed.
The receiving layer according to the present invention is very
well suited for use with dry toner particles, and therefore the
invention also encompasses a method for forming a toner image on a
substrate comprising the steps of :
- providing a substrate with a support and a toner receiving layer containing at least 80 % by weight with respect to the total weight of the layer of a polymer, containing between 0.5 and 20 mole % of moieties having sulphonic acid groups,
- image wise depositing dry toner particles, with a toner resin, on said toner receiving layer and
- fixing said toner particles to said toner receiving layer.
Although the receptor element can be used in any method wherein
any kind of dry toner particles are deposited on the toner receiving
layer, it is preferred to use a receptor element according to this
invention in methods wherein the toner particles that are deposited
to the receiving layer comprise at least 50 % by weight, with
respect to the total toner resin, of a polyester in the toner resin.
More preferably the toner particles deposited on an imaging layer
according to this invention, comprise at least 50 % by weight, with
respect to the total toner resin, of a polyester with acid value
(AV) or hydroxyl value (HV) higher than 2.5 mg KOH/g of the
polyester in the toner resin.
A reaction mixture of 1028.2 g of dimethyl terephthalate (5.3
moles), 776.0 g of dimethyl isophthalate (4.0 moles), 207.2 g of 5-sulphoisophthalic
acid dimethylester sodium salt (0.7 mole), 1240 g
of ethylene glycol (20 moles), 220 mg of zinc acetate dihydrate and
292 mg of antimone(III)oxide was heated to 160°C whilst stirring
under nitrogen atmosphere. Re-esterification took place and methanol
was distilled. The temperature was gradually raised in 3 to 4 hours
to 250°C, until methanol distillation ceased. 652 mg of triphenyl
phosphate was added as a thermal stabiliser. The reaction mixture
was then subjected to a reduced pressure of 1 hPa. Under these
conditions polycondensation took place within a period of about 60
to 120 minutes. The polyester melt was allowed to settle on an
aluminium foil and cooled to 25°C. A transparent and brittle solid
was obtained. The solidified copolyester PA was then milled into a
powder. The intrinsic viscosity of the copolyester was from 0.20 to
0.30 dl/g, measured at 25 °C in a 60/40-mixture of phenol and o-dichloro-benzene.
The Tg (glass transition temperature) of the
copolyester was 52 °C, measured by DSC (Differential Scanning
Calorimetry).
In a 1 litre round-bottomed flask were introduced 100 g powder
of copolyester PA and 400 ml of water. The mixture was heated to
95°C whilst stirring. The mixture transformed from a viscous phase
into a dispersion. After 2 to 4 hours the dispersion was cooled to
25°C and was filtered. A stable aqueous dispersion (DPA) was
obtained with sulphonic groups in the sodium salt form.
The copolyester dispersion DPA was treated with an ion exchange
resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen,
Germany). A stable copolyester dispersion was obtained with
sulphonic groups in the free acid form.
The copolyester dispersion DPA1 was neutralised to pH = 7.5 with
ammonia. A stable copolyester dispersion was obtained with sulphonic
groups in the ammonium salt form.
The preparation of polyester PA was repeated except for the
supplementary addition of 820 mg sodium acetate to the reaction
mixture at the beginning of the re-esterification reaction. As a
result, the formation of diethyleneglycol was suppressed and the Tg
of the copolyester resin increased to 70 °C.
In a 1 litre round-bottomed flask were introduced 100 g powder
of copolyester PB and 400 ml of water. The mixture was heated to
95°C whilst stirring. The mixture transformed from a viscous phase
into a dispersion. After 2 to 4 hours the dispersion was cooled to
25°C and was filtered. A stable aqueous dispersion of polyester PB
(DPB) was obtained with sulphonic groups in the sodium salt form.
The copolyester dispersion DPB was treated with an ion exchange
resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen,
Germany). A stable copolyester dispersion was obtained with
sulphonic groups in the free acid form.
The copolyester dispersion DPB1 was neutralised to pH = 7.5 with
ammonia. A stable copolyester dispersion was obtained with sulphonic
groups in the ammonium salt form.
The preparation of copolyester PA was repeated except for the
supplementary addition of 112.5 g polyethyleneglycol 1500 (0.75
mole) in the reaction mixture. As a result, copolyester resin PC was
obtained. The intrinsic viscosity of the copolyester was from 0.20
to 0.30 dl/g when measured at 25°C in a 60/40-mixture of phenol and
o-dichloro-benzene. The Tg of the copolyester was 53°C when measured
by DSC.
In a 1 litre round-bottomed flask were introduced 100 g powder
of copolyester PC and 400 ml of water. The mixture was heated to
95°C whilst stirring. The mixture transformed from a viscous phase
into a dispersion. After 2 to 4 hours the dispersion was cooled to
25°C and was filtered. A stable aqueous dispersion of polyester PB
(DPB) was obtained with sulphonic groups in the sodium salt form.
The copolyester dispersion DPC was treated with an ion exchange
resin (LEWATITE S100MB, trade name of BAYER AG, Leverkusen,
Germany). A stable copolyester dispersion was obtained with
sulphonic groups in the free acid form.
The copolyester dispersion DPC1 was neutralised to pH = 7.5 with
ammonia. A stable copolyester dispersion was obtained with sulphonic
groups in the ammonium salt form.
The copolyester dispersion DPC1 was neutralised to pH = 7.5 with
morpholine. A stable copolyester dispersion was obtained with
sulphonic groups in the morpholine salt form.
A coating solution was made containing 640 ml of water, 324 ml
of polyester dispersion DPA, 6 ml of an aqueous solution (10 g
solids/100 ml) of a surfactant (RHODAFAC RM-710, trade name of
RHONE-POULENC CHIMIE, Paris - France, for a mixture of
polyoxyethylene-nonylphenyl-etherphosphates) and 30 ml of an aqueous
dispersion (1 g solids/100 ml) of a matting agent (SYLOID 72, trade
name of GRACE GMBH, Worms, Germany, for amorphous silica with
average particle size 4 µm).
The coating solution was coated on a 100 µm thick clear
polyethyleneterephthalate film, subbed with a known subbing layer
comprising vinylidene chloride. No backing layer was present. The
coated layer had a wet thickness of 33 µm and was dried at 120°C for
2 minutes. This yielded a dry toner receiving layer comprising :
The preparation of receptor element 1 was repeated except for
the presence of polyester dispersion DPA1 instead of polyester
dispersion DPA.
The preparation of receptor element 1 was repeated except for
the presence of polyester dispersion DPB instead of polyester
dispersion DPA.
The preparation of receptor element 1 was repeated except for
the presence of polyester dispersion DPB1 instead of polyester
dispersion DPA.
The preparation of receptor element 1 was repeated except for
the presence of polyester dispersion DPC1 instead of polyester
dispersion DPA.
The preparation of receptor element 1 was repeated except for
the presence of a latex of a copolymer of n-butylacrylate (47 wt%),
styrene (46 wt%) and methacrylic acid (7 wt%) (dispersion AMA1)
instead of polyester dispersion DPA.
The preparation of receptor element 1 was repeated except for
the presence of a latex of a copolymer of methylmethacrylate (50
wt%), n-butylacrylate (43 wt%) and 2-acrylamido-2-methylpropane
sulphonic acid sodium salt (7 wt%) (dispersion AMA2) instead of
polyester dispersion DPA.
The preparation of comparative receptor element (CRE1) was
repeated except for the presence of a latex of a copolymer of n-butylacrylate
(47 wt%), styrene (46 wt%) and methacrylic acid (7
wt%) with the carboxylic group of the methacrylic resin was present
as sodium salt instead of as free acid. (dispersion AMA3)
The preparation of comparative receptor element CRE2 was
repeated except for the presence of a latex of a copolymer of
methylmethacrylate (50 wt%), n-butylacrylate (43 wt%) and 2-acrylamido-2-methylpropane
sulphonic acid sodium salt (7 wt%)
treated with an ion exchange resin (LEWATITE S100MB, trade name of
BAYER AG, Leverkusen, Germany). So the dispersion of the polymer had
the sulphonic acid groups in the free acid form. (dispersion AMA4)
A coating solution was made containing 3.33 g gelatine, that was
swelled for 30 minutes in 668 ml of water. The solution was then
heated while stirring. Then were added 5.6 ml of an aqueous
solution (10 g solids/100 ml) of a surfactant (RHODAFAC RM-710,
trade name of RHONE-POULENC; Paris - France, for a mixture of
polyoxyethylenenonyl-phenyl-ether-phosphates), 0.28 g of a matting
agent (SYLOID 378, trade name of GRACE GMBH; Worms - Germany, for an
amorphous silica with special inorganic treatment and with average
particle size 4 µm) and 300 ml of polyester dispersion DPA2.
The coating solution was coated on a 100 µm thick clear
polyethyleneterephthalate film, subbed with a known subbing layer
comprising vinylidene chloride. No backing layer was present. The
coated layer had a wet thickness of 33 µm and was dried at 35 °C and
25 % relative humidity for 2 minutes. This yielded a dry toner
receiving layer comprising :
The preparation of receptor element 6 was repeated except for
the addition of glycerine to the coating solution in such an amount
that the dry layer contained 0.05 g/m2 of glycerine.
The preparation of receptor element 6 was repeated, but in the
coating solution glycerine was added in such an amount that the dry
layer contained 0.10 g/m2 of glycerine.
The preparation of receptor element 6 was repeated, but in the
coating solution glycerine was added in such an amount that the dry
layer contained 0.15 g/m2 of glycerine.
The preparation of receptor element 6 was repeated, but in the
coating solution glycerine was added in such an amount that the dry
layer contained 0.20 g/m2 of glycerine.
The preparation of receptor element 10 was repeated, but in the
coating solution instead of glycerine, sorbitol was added in such an
amount that the dry layer contained 0.20 g/m2 of sorbitol.
The preparation of receptor element 10 was repeated, but in the
coating solution instead of glycerine, glucose was added in such an
amount that the dry layer contained 0.20 g/m2 of mannitol.
The preparation of receptor element 10 was repeated, but in the
coating solution instead of glycerine, butanetetrol was added in
such an amount that the dry layer contained 0.20 g/m2 of 1,1,1-tris(hydroxymethyl)propane.
The preparation of receptor element 10 was repeated except for
the presence of polyester dispersion DPC2 instead of polyester
dispersion DPA2.
The preparation of receptor element 10 was repeated except for
the presence of polyester dispersion DPC instead of polyester
dispersion DPA2.
The preparation of receptor element 10 was repeated except for
the presence of polyester dispersion DPC3 instead of polyester
dispersion DPA2.
The receptor elements (RE1 to RE16, CRE1 to CRE4 were used, for
producing overhead projection sheets, in a CHROMAPRESS (trade name
of Agfa-Gevaert NV, Mortsel, Belgium) full colour digital printing
press with toners and developers as follows :
49 parts of a polyester resin of fumaric acid and propoxylated
bisphenol A (DIANOL 33, a trade name of AKZO CHEMIE of the
Netherlands for bis-propoxylated 2,2-bis(4-hydroxyphenyl)propane)
and 49 parts of a polyester resin of terephthalic acid, isophthalic
acid and ethoxylated bisphenol A (DIANOL 22, a trade name of AKZO
CHEMIE of the Netherlands for bis-ethoxylated 2,2-bis(4-hydroxyphenyl)propane)
and ethyleneglycol 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 pulverised and milled
using an ALPINE Fliessbettgegenstrahlmühle type 100AFG (trade name)
and further classified using an ALPINE multiplex zig-zag classifier
type 100MZR (trade name). The average particle size of the
separated toner was measured by Coulter Counter model Multisizer
(trade name) 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, trade name 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 melt viscosity at 120 °C
of 500 Pa.s.
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.
The printing quality was examined visually during overhead
projection of the sheets prepared in examples 1 to 4. It was found
that the yellow part of the toner image was most critical and thus
the quality is judged on the yellow image with quotation as
hereunder :
The column headed by H, Na, NH4, Amine shows the form under
which the acid is present: H as acid, Na as sodium salt, NH4 as
ammonium salt, amine as morpholine salt.
It is clear that all receiving materials having an image
receiving layer with a polyester dispersion offer good image
quality, especially when the polyester dispersion has sulphonic
groups in the acid form, instead of the sodium salt form. A good
image quality can also be attained if the image receiving layer
contains a polyester dispersion with sulphonic groups in the amine
form, gelatine and a softening agent, e.g. glycerine.
The preparation of receptor element 2 (RE2) was repeated except
for the presence of a backing layer comprising in the dried layer 6
mg/m2 a polythiophene and polyanion compound. This polythiophene
was applied from an aqueous dispersion, prepared as follows :
The backing layer had a resistivity of 1.1011 Ω/square and the
toner receiving layer had a resistivity of 9.1011 Ω/square.
Receptor element 17 (RE17) was repeated except for the fact that
the toner receiving layer further contained 0.02 mg/m2 of dispersion
PT1. The toner receiving layer had a resistivity of 2.1010
Ω/square.
On receptor elements 17 to 26 an even patch of black built up
with y, M, C and K toner (i.e. having 4 toner layers) was printed in
the circumstances as described above.
The patches were evaluated for evenness on a scale between 0
(very even) and 4 (very uneven). Also an even patch of Magenta
toner was printed and the density was measured with a MACBETH TR1224
(trade name) densitometer. The results are summarised in table 2.
It is clear that when the resistivity of the image receiving
layer is lower, the resistivity of the backing layer can be higher
and still deliver very good evenness.
Claims (12)
- A toner receiving element comprising a support with a first and second major face and an image receiving layer on said first major face, characterised in that said image receiving layer contains at least 80 % by weight with respect to the total weight of said layer of a polyester, containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form.
- A toner receiving element according to claim 1, wherein said image receiving layer contains at least 90 % by weight with respect to the total weight of the layer of a polyester, containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form and at most 10 % by weight of a compound selected from the group of surfactants, matting agents, plasticizers, lubricants, antistatic agents and coloiadal silica.
- A toner receiving element according to claim 1, wherein said image receiving layer contains at least 97 % by weight with respect to the total weight of the layer of a polyester, containing between 0.5 and 20 mole % of moieties having sulphonic acid groups in free acid form and at most 3 % by weight of a compound selected from the group of surfactants, matting agents and antistatic agents.
- A toner receiving element according to any of claims 1 to 3, wherein said polyester is a copolyester obtained by reacting a diol mixture containing ethylene glycol in an amount between 0 and 95 mole % percent with respect to the total diol content and polyethylene glycol in an amount between 0 and 5 mole % percent with respect to the total diol content and an acid mixture containing terephthalic acid, isophthalic acid and 5-sulphoisophthalic acid, said acid mixture consisting essentially of from 20 to 60 mole % of isophthalic acid, 0.5 to 20 mole % of said sulphoisophthalic acid, the remainder in said acid mixture being terephthalic acid
- A toner receiving element according to claim 1, wherein said image receiving layer further comprises between 1 and 10 % by weight with respect to the total weight of the layer with respect to said polyester of a hydrophilic colloid.
- A toner receiving element according to claim 1 or 5 , wherein said image receiving layer further comprises between 1 and 10 % by weight with respect to the total weight of the layer with respect to said polyester of a plasticer selected from the group consisting of glycerine, sorbitol, glucose, mannitol, 1,1,1-tris(hydroxymethyl)propane or 1,2,3,4-butane-tetrol.
- A toner receiving element according to any one of the preceding claims, wherein a backing layer is applied to said second major face of said support having a resistivity between 5.108 Ω/square and 5.1011 Ω/square, both limits included.
- A toner receiving element according to claim 7, wherein said backing layer comprises a polythiophene prepared by oxidative polymerisation of thiophene in the presence of a polyanion compound.
- A toner receiving element according to claim 8 wherein said polythiophene corresponds to the formula : in which :each of R1 and R2 independently represents hydrogen or a C1-4 alkyl group or together represent an optionally substituted C1-4 alkylene group or a cycloalkylene group, preferably an ethylene group, an optionally alkyl-substituted methylene group, an optionally C1-12 alkyl- or phenyl-substituted 1,2-ethylene group, a 1,3-propylene group or a 1,2-cyclohexylene group.
- A toner receiving element according to claim 9, wherein R1 and R2 form together a - CH2-CH2- group.
- A method for forming a toner image on a substrate comprising the steps of :providing a toner receiving element according to anyone of claims 1 to 10,image wise depositing dry toner particles, with a toner resin, on said toner receiving element andfixing said toner particles to said toner receiving layer.
- A method according to claim 10, wherein said toner resin comprises at least 50 % by weight with respect to the total weight of said resin of a polyester with acid value (AV) or hydroxylvalue (HV) higher than 2.5 mg KOH/g of the polyester.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP98202303A EP0895130A1 (en) | 1997-08-01 | 1998-07-08 | A receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97202394 | 1997-08-01 | ||
EP97202394 | 1997-08-01 | ||
EP98202303A EP0895130A1 (en) | 1997-08-01 | 1998-07-08 | A receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0895130A1 true EP0895130A1 (en) | 1999-02-03 |
Family
ID=26146753
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98202303A Withdrawn EP0895130A1 (en) | 1997-08-01 | 1998-07-08 | A receptor element for non-impact printing comprising an image receiving layer with a polymer comprising sulphonic acid groups |
Country Status (1)
Country | Link |
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EP (1) | EP0895130A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1041446A1 (en) * | 1999-03-29 | 2000-10-04 | Felix Schoeller Technical Papers, Inc. | Image receiving element with polyester image receiving layer |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0177111A2 (en) * | 1984-10-01 | 1986-04-09 | Toray Industries, Inc. | Method of treating textiles |
EP0368318A2 (en) * | 1988-11-11 | 1990-05-16 | Fuji Photo Film Co., Ltd. | Thermal transfer image receiving material |
US5460874A (en) * | 1994-09-30 | 1995-10-24 | Minnesota Mining And Manufacturing Company | Water-based coating compositions for imaging applications |
US5534478A (en) * | 1995-06-06 | 1996-07-09 | Eastman Kodak Company | Thermal dye transfer system with polyester ionomer receiver |
EP0728801A2 (en) * | 1995-02-27 | 1996-08-28 | Teijin Limited | Laminated film |
US5733694A (en) * | 1995-07-04 | 1998-03-31 | Fuji Xerox Co., Ltd. | Electrophotographic transfer film and color image formation process |
-
1998
- 1998-07-08 EP EP98202303A patent/EP0895130A1/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0177111A2 (en) * | 1984-10-01 | 1986-04-09 | Toray Industries, Inc. | Method of treating textiles |
EP0368318A2 (en) * | 1988-11-11 | 1990-05-16 | Fuji Photo Film Co., Ltd. | Thermal transfer image receiving material |
US5460874A (en) * | 1994-09-30 | 1995-10-24 | Minnesota Mining And Manufacturing Company | Water-based coating compositions for imaging applications |
EP0728801A2 (en) * | 1995-02-27 | 1996-08-28 | Teijin Limited | Laminated film |
US5534478A (en) * | 1995-06-06 | 1996-07-09 | Eastman Kodak Company | Thermal dye transfer system with polyester ionomer receiver |
US5733694A (en) * | 1995-07-04 | 1998-03-31 | Fuji Xerox Co., Ltd. | Electrophotographic transfer film and color image formation process |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1041446A1 (en) * | 1999-03-29 | 2000-10-04 | Felix Schoeller Technical Papers, Inc. | Image receiving element with polyester image receiving layer |
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