EP0768577B1 - Verfahren zur elektrostatografischen Reproduktion von Bildern mit kontinuierlichen Tönen - Google Patents

Verfahren zur elektrostatografischen Reproduktion von Bildern mit kontinuierlichen Tönen Download PDF

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Publication number
EP0768577B1
EP0768577B1 EP95202768A EP95202768A EP0768577B1 EP 0768577 B1 EP0768577 B1 EP 0768577B1 EP 95202768 A EP95202768 A EP 95202768A EP 95202768 A EP95202768 A EP 95202768A EP 0768577 B1 EP0768577 B1 EP 0768577B1
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EP
European Patent Office
Prior art keywords
toner
toner particles
types
particles
image
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Expired - Lifetime
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EP95202768A
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English (en)
French (fr)
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EP0768577A1 (de
Inventor
Dirk Broddin
Serge Tavernier
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP95202768A priority Critical patent/EP0768577B1/de
Priority to DE69507144T priority patent/DE69507144T2/de
Priority to US08/724,065 priority patent/US5825504A/en
Priority to JP8287314A priority patent/JPH09226177A/ja
Publication of EP0768577A1 publication Critical patent/EP0768577A1/de
Priority to US09/047,263 priority patent/US6175374B1/en
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Publication of EP0768577B1 publication Critical patent/EP0768577B1/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/01—Electrographic processes using a charge pattern for multicoloured copies
    • G03G13/016—Electrographic processes using a charge pattern for multicoloured copies in which the colour powder image is formed directly on the recording material, e.g. DEP methods
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/01—Electrographic processes using a charge pattern for multicoloured copies
    • G03G13/013—Electrographic processes using a charge pattern for multicoloured copies characterised by the developing step, e.g. the properties of the colour developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/01—Electrographic processes using a charge pattern for multicoloured copies
    • G03G13/013—Electrographic processes using a charge pattern for multicoloured copies characterised by the developing step, e.g. the properties of the colour developers
    • G03G13/0133—Electrographic processes using a charge pattern for multicoloured copies characterised by the developing step, e.g. the properties of the colour developers developing using a step for deposition of subtractive colorant developing compositions, e.g. cyan, magenta and yellow
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/06—Developing
    • G03G13/08—Developing using a solid developer, e.g. powder developer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G13/00—Electrographic processes using a charge pattern
    • G03G13/22—Processes involving a combination of more than one step according to groups G03G13/02 - G03G13/20

Definitions

  • the invention relates a method for reproducing continuous tone images.
  • the printing proceeds on opaque reflecting supports as well as on transparent supports.
  • ink-jet printing a convenient printing system for use in an office environment, it has been proposed in EP-A 606 022 to use different inks, with different pigmentation and to use the ink with low pigmentation to print the low densities and the ink with high pigmentation to print the high densities.
  • ink drops with volumes ranging from 25 to 100 ⁇ l in the so called bubble jet based systems, or with volumes in the range of 5 to 10 ⁇ l in the so called continuous jet systems.
  • the images are built up by combining in an appropriate way such drops on the substrate, and although the addressability of each drop typically lies in the range of 11.81 dots per mm (300 dpi dots per inch) to 47.27 dots per mm (1200 dpi), the not fully reproducible way the dot spreads and penetrates in the substrate limits the real resolution in the printed image.
  • Electro(stato)graphic methods are evenly well accepted imaging methods in an "office environment" as ink-jet printing since these methods, e.g. electrophotographic copiers, electrographic printers, Direct Electrostatic Printing (DEP), are convenient, fast, clean and do not need aqueous solutions. Since electro(stato)graphic methods may use solid particles that typically have a particle diameter between 1 and 10 ⁇ m as marking particle, it is possible to achieve very high resolution in electro(stato)graphy.
  • US-A-5 142 337 discloses a mixture of opaque black, opaque white and clear toner, to obtain a mixed toner.
  • the mixed toner is printed on top of a black toner in a binary printing process.
  • Patent Abstracts of Japan, vol. 7, no. 290 (P-245)[1435] & JP-A-58 162 970 discloses a mixture of a first and a second toner, to obtain a mixed toner.
  • the mixed toner is applied to the recorded copy image.
  • the chromaticity of toner particles, fused to a substrate may be different from that of the original toner particles, the chromaticity referred to is that of the toner particles appearing on the final substrate.
  • Those two toner types may be identical, but preferentially the colouring power of each toner type is different.
  • each toner type is applied in a subsequent toning step, e.g. by a different toner station.
  • the different colouring power is obtained by a different degree of pigmentation.
  • at least two achromatic toners are used, i.e. greyish or black toners of which the chromaticity is substantially zero.
  • cells are printed by applying a number (N) of different types of toner particles, said toner particles having an average volume diameter d v50 ⁇ m, and wherein said number N fulfils the relation N ⁇ 0.3 ⁇ d v50 and wherein N is determined by adding 0.5 to 0.3 ⁇ d v50 and rounding to the next lower integer.
  • N ⁇ 0.4xd v50 and N is determined by adding 0.5 to 0.4 ⁇ dv50 and rounding to the next lower integer.
  • This application is concerned with any printing method wherein an image is formed by the deposition of particulate marking species.
  • this application is concerned with two electro(stato)graphic printing methods.
  • One is the classical electrography where an electrostatic latent image, on a latent image bearing member, is developed by toner particles, whereafter the developed image can, but may not, be transferred to a final substrate.
  • Another method is the method of Direct Electrostatic Printing (DEP), wherein toner particles are imagewise deposited on a substrate without the use of an electrostatic latent image.
  • DEP Direct Electrostatic Printing
  • a monochrome image or a colour image may be reproduced.
  • a monochrome image may be referred to as a black and white image, with continuous tone grey levels.
  • the monochrome image may also be obtained by capturing a colour image by only one spectral band, such that a digital image is obtained for which each picture element or pixel can have one value, corresponding to a specific tone level.
  • colour separations giving a yellow, magenta, cyan and black image of a continuous tone colour image are, in the present invention also designated by monochrome image.
  • a colour image may be obtained by superposition of different colour separations.
  • the traditional colour components cyan, magenta and yellow are augmented with at least one extra colour component according to one toner type.
  • This extra colour component may have another density or colouring power of either cyan, magenta or yellow.
  • a traditional black component is added to the three usual colour components and a grey component is added to vary the black and grey components according to the method of the current invention.
  • at least a second colour component, having a lower pigmentation level, C'M'Y'(K') is added for each traditional colour component, CMY or CMYK.
  • tone levels per colour component is chosen to be 256, and the pixel values vary from 0 to 255 accordingly.
  • An electrographic device can address different locations on the substrate in order to supply to each location a specific amount of toner.
  • a dot of toner particles may be deposited by the electrographic device. Because such location constitutes the smallest dot that can be addressed and deposited by the electrostatic device, such location is called a microdot.
  • the whole substrate can now be partitioned in a plurality of adjacent, non-overlapping or disjunctive microdots. Usually the shape of each microdot is square.
  • 300 up to 600 microdots may be arranged side by side on 25.4 mm (one inch), in which case the "resolution" of the device is said to be 11.81 dots per mm, respectively 23.62 dots per mm (300, respectively 600, dots per inch (dpi)).
  • Microdots may also have a rectangular shape, and/or may be arranged on the substrate in oblique directions rather than in two orthogonal directions. Microdots may also have a hexagonal shape and an appropriate arrangement in order to fill up the complete substrate.
  • toner particles are deposited according to a Gaussian distribution, having its centre close to the centre of the microdot. It is possible that toner particles, intended for a specific microdot, partially or fully fall within a neighbouring microdot. Although the microdots are disjunctive from each other, it is possible that toner particles of adjacent microdots are not disjunctive.
  • the electrographic device may supply at least three different amounts of one toner to each microdot.
  • the amount of toner is meant the concentration or toner deposition level, which may be expressed in milligram toner per square centimetre [mg/cm 2 ].
  • a different concentration may be obtained by pulse width modulation of an electronic signal e.g. when monitoring the exposure of a photosensitive semiconductor drum by a laser beam ; or by pulse height or amplitude modulation ; or any other measure in order to modulate the concentration within or attributable to one microdot.
  • a microdot may get no toner at all or a "low amount” of toner, which means that the toner concentration, measured by the amount of toner deposited for that microdot and related to the area of that microdot, is less than 10% of the maximum toner concentration (e.g. 10 mg/cm 2 ) ; a microdot may get a "high amount” of toner, which means that the toner concentration within such microdot is higher than 70% of the maximum toner concentration for the current application ; a microdot may get also a "medium amount” of toner, which means that the toner concentration is between 10% and 70% of the maximum toner concentration. Preferentially, apart from these three toner concentrations, more toner concentrations may be available. In a preferred embodiment, sixteen levels of toner concentration for each microdot and for each toner type are established.
  • halftone dot size modulation halftone dots, comprising a plurality of microdots, are laid out on a periodic grid having a screen ruling and a screen angle. In order to achieve a higher optical density, more microdots carrying toner are added to the halftone dot.
  • halftone dots are created from a fixed number of microdots, maybe just one microdot, and the distance between such halftone dots is varied, rather than their size.
  • adjacent microdots are preferentially, but not necessarily, arranged in cells, called halftone cells for autotypical screening techniques.
  • adjacent is meant that microdots touch each other by one side or by a corner.
  • a plurality of microdots may be arranged in one cell. Each cell comprises preferentially the same number of microdots, has the same shape and the cells are arranged such that the whole substrate may be tiled by adjacent cells.
  • some tone levels of the original image are reproduced by applying two different toners, having substantially the same chromaticity, or more specifically two achromatic toners, to one cell.
  • An achromatic toner is a greyish or black toner. If a low density must be realised within a cell on the substrate, just one toner may be applied to the cell. A higher optical density within that cell, may be realised by applying a large amount of greyish toner and a low amount of black toner to the cell. It is important to select the distribution of each toner type over the cell such, that the stability of the electrographic process is not jeopardized.
  • microdots In order to exploit the multilevel capabilities of the electrographic device, at least one microdot within a cell or region, comprising adjacent microdots, must have the possibility to get a medium amount of toner.
  • a medium amount of toner typically, for a cell consisting of four microdots, arranged in a 2X2 fashion, three microdots, i.e. a large majority of microdots, preferentially get a "stable amount" of toner, i.e. they may get no or a minimum amount of toner or a maximum amount of toner.
  • the other microdots being a minority, in this example just one microdot, may be supplied with a medium amount of toner.
  • a cell may comprise as much as 256X256 microdots.
  • a large majority is meant 66% or more.
  • a large majority ( ⁇ 66%) of microdots within a region is supplied with either a high or low amount of one toner, whereas the other microdots (a minority) are supplied with a medium amount of said toner.
  • only a minority of microdots i.e. no microdots or any number ⁇ 34%) within a region or cell is supplied with a medium amount of toner.
  • Implementations of frequency modulation are tile-based, where the tiles correspond to periodic cells of typically a few hundred by a few hundred microdots. Implementations which are not tile based are generally based on some variant of an error-diffusion algorithm.
  • a cell may comprise 256X256 microdots or there may be no cell at all if an error diffusion algorithm is used. In these cases it makes sense to replace the notion of cell by a local environment or "region" of a particular microdot. The extent of the environment is to be chosen such that several halftone dots are within the environment. For such an environment one can determine the number of microdots which get a stable amount of toner.
  • microdots get a 'stable' amount of toner.
  • a hybrid error diffusion technique may be used, based on cell level, instead of based on microdot level, wherein each multilevel halftone cell comprises a plurality of adjacent microdots.
  • microdot gets a low, medium or high amount of the first type of toner, whereas the same microdot may get also a low, medium or high amount of the second toner type. It is important that per toner type a large majority of microdots within a cell gets either a high or low amount of that specific toner. Examples below will show that one microdot within a cell may get a medium amount of first toner, while another microdot within the same cell may get a medium amount of second toner.
  • At least one microdot within that cell preferentially has a low amount of toner, at least one microdot has a high amount of toner and, in order to achieve fine tone gradations, at least one microdot has a medium amount of toner.
  • a low-concentration or a high-concentration ink is deposited on one microdot.
  • the perceived noise level of the reproduced image may be substantially improved by printing at least two toner types having substantially the same chromaticity on top of each other within one microdot for specific density levels.
  • the reproducing or printing method can be practised both with liquid electrostatographic development (using a dispersion of solid toner particles in a dielectric liquid) and with dry electrostatographic developers.
  • the dry developers can be mono-component developers (comprising toner particles, but no carrier particles) as well as multi-component developers (comprising toner and carrier particles).
  • N should at least be equal to 0.3 ⁇ d v50 , wherein N is determined by adding 0.5 to 0.3 ⁇ d v50 and rounding to the next lower integer.
  • N is at least 2.
  • N toning steps where N is at least equal to 0.4 ⁇ d v50 , wherein N is determined by adding 0.5 to 0.4 ⁇ d v50 and rounding to the next lower integer.
  • N is at least 3.
  • the toner compositions of the number N types of toner particles preferably differ in degree of colouring power (i.e. the density achievable in the final image).
  • the colouring power of the type of toner having the lowest colouring power (T 1 ) is, for a given amount of deposited toner, preferably such that T 1 gives, between 10 and 50 % of the density given by the toner particles having the highest colouring power (T max ), when the same amount of particles (expressed in mg/cm 2 ) is deposited.
  • said toner composition T 1 not only has the lowest degree of colouring power, but comprises also toner particles having a particle size distribution showing the lowest volume average diameter.
  • the toner particles comprised in toner composition T 1 have a d v50 that is at least 1.5 to 2.5 times smaller than the d v50 of the toner particles comprised in the toner having the highest colouring power (T max ).
  • the colouring power of the toner particles comprised in the various toner compositions is chosen such that in the final image between 0.1 and 2 mg/cm 2 of toner is present.
  • the dynamic range of the original exceeds the dynamic range of the recording medium, since the R min achievable on an opaque reflecting substrate is around 0.01, amounting to a maximum density around 2.00.
  • the difference between the highest and lowest reflectance is around a factor 100, whereas an original medical image can have a difference in intensities around 1000. Therefore it may be beneficial to divide the dynamic range of the original into several portions each of these portion not having a dynamic range exceeding the dynamic range of the recording medium. A way of doing so has been described in EP-A-0 679 015.
  • the opaque reflecting support used in the present invention can be paper, polyethylene coated paper, an opaque polymeric reflecting substrate, etc.
  • Opaque reflecting polymeric substrates useful as a final substrate to be used according to this invention, are e.g. polyethyleneterephthalate films comprising a white pigment, as described in e.g. US-P 4,780,402, EP-B 182 253.
  • Preferred however are polyethyleneterephthalate films comprising discrete particles of a homopolymer or copolymer of ethylene or propylene as described in e.g. US-P 4,187,113.
  • opaque reflecting final substrates comprising a multi-ply film wherein one layer of said multi-ply film is a polyethyleneterephthalate film comprising discrete particles of a homopolymer or copolymer of ethylene or propylene and at least one other layer is a polyethyleneterephthalate film comprising a white pigment as described in e.g. EP-A-0 582 750 and Japanese non-examined application JP-A-63 200 147.
  • This toner receiving layer comprises a binding agent or mixture of binding agents.
  • binding agent preferably thermoplastic water insoluble resins are used wherein the ingredients can be dispersed homogeneously or form therewith a solid-state solution.
  • binding agent preferably thermoplastic water insoluble resins are used wherein the ingredients can be dispersed homogeneously or form therewith a solid-state solution.
  • all kinds of natural, modified natural or synthetic resins may be used, e.g.
  • cellulose derivatives such as ethylcellulose, cellulose esters, carboxymethylcellulose, starch ethers, polymers derived from ⁇ , ⁇ -ethylenically unsaturated compounds such as styrene, polyvinyl chloride, after-chlorinated polyvinyl chloride, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and vinyl acetate, polyvinyl acetate and partially hydrolysed polyvinyl acetate, polyvinyl alcohol, polyvinyl acetals, e.g.
  • polyvinyl butyral copolymers of acrylonitrile and acrylamide, polyacrylic acid esters, polymethacrylic acid esters and polyethylene or mixtures thereof.
  • a particularly suitable ecologically interesting (halogen-free) binder is polyvinyl butyral.
  • Polyvinyl butyral containing some vinyl alcohol units is marketed under the trade name BUTVAR B79 of Monsanto USA.
  • the printing of a continuous tone image on a transparent substrate proceeds basically as described above for the printing of a continuous tone image on an opaque reflecting support.
  • the transparent supports can be made of glass or of a polymeric resin.
  • the polymeric resin substrate can be a polyester, e.g. polyethyleneterephthalate, polyethylenenaphthalate, polycarbonates, polyolefinic film, etc.
  • the final substrate either transparent or opaque, whereon the printing, according to the method of the present invention proceeds, can be present as sheet or as web material.
  • the obtainable maximum transmission density is around 2.00. This is due to the definite size of the toner particles, the limited amount of pigment that can be incorporated in toner particles without negatively influencing the quality of the toner particles and to the finite amount of toner particles that can be deposited on the electrostatic latent image.
  • the amount of toner particles that can be deposited in classical electro(photo)graphy is typically between 5 g/m 2 to 10 g/m 2 , i.e. 0.5 to 1 mg/cm 2 . This transmission density level is acceptable in e.g. transparencies for overhead projection, but is not satisfactory for e.g.
  • the toner composition T N comprises one or more ingredients that together or in cooperation with ingredients comprised in the final substrate are capable of forming a light absorbing substance and said toner particles optionally comprise a light absorbing pigment or dye.
  • said ingredients, comprised in said toner particles that together or in cooperation with ingredients comprised in said final substrate are capable of forming a light absorbing substance, are at least one reductant (compound A) and at least one substantially light insensitive silver salt (compound B).
  • said reductant (compound A) is incorporated in said toner particles and said substantially light insensitive silver salt (compound B) is incorporated in said final substrate.
  • the reaction between reductant (compound A) and substantially light insensitive silver salt (compound B) is aided by an auxiliary reductant C.
  • the pigmentation refers to the amount of pigments added to the toner during the fabrication process.
  • the colouring power refers to the optical density in reflection or transmission obtained for a specific concentration [mg/cm 2 ] of the toner as applied and fused to the substrate, thus after reaction if any.
  • said substantially light insensitive silver salt is a silver salt of a fatty acid, wherein the aliphatic carbon chain has preferably at least 12 C-atoms and said reductant is a di- or tri-hydroxy compound.
  • Substantially light insensitive organic silver salts suited for use according to the present invention are silver salts of aliphatic carboxylic acids known as fatty acids, wherein the aliphatic carbon chain has preferably at least 12 C-atoms, e.g. silver laurate, silver palmitate, silver stearate, silver hydroxystearate, silver oleate and silver behenate, and likewise silver dodecyl sulphonate described in US-P 4,504,575 and silver di-(2-ethylhexyl)-sulfosuccinate described in published EP-A-0 227 141. It is most preferred to use silverbehenate in the method according to the present invention.
  • organic reducing agents for use in the reduction of said substantially light insensitive silver salts are catechol-type reducing agents, by which is meant reducing agents containing at least one benzene nucleus with two hydroxy groups (-OH) in ortho-position, e.g., catechol, 3-(3,4-dihydroxyphenyl) propionic acid, 1,2-dihydroxybezoic acid, methyl gallate, ethyl gallate, propyl gallate, tannic acid and 3,4-dihydroxy-benzoic acid esters.
  • Preferred reductants are gallic acid or derivatives thereof.
  • the reductant to be used in an electrostatographic method according to the present invention can in fact be a mixture of
  • toning agents known from thermography or photo-thermography may be added in the process. Said toning agents can be incorporated in the toner particles or in the final image receiving substrate.
  • the transparent final substrate comprises a toner receiving layer coated on a transparent support.
  • Said toner receiving layer comprises a binding agent or mixture of binding agents, that can be the same as those mentioned above. Since printing of high densities (D > 2.00) is preferred, it is preferred that said toner receiving layer comprises also compounds A, B or C, or mixtures thereof and optionally toning agents (compound D).
  • the toner receiving layer can also comprise waxes or "heat solvents” also called “thermal solvents” or “thermosolvents” improving the penetration of the reducing agent(s) and thereby the reaction speed of the redox-reaction at elevated temperature.
  • the transparent support is preferably a polymeric support.
  • Such supports include, for example, transparent supports as those used in the manufacture of photographic films including cellulose acetate propionate or cellulose acetate butyrate, polyesters such as poly(ethyleneterephthalate), poly(ethylenenaphthalate), polyamides, polycarbonates, polyimides, polyolefins, poly(vinylacetals), polyethers and polysulfonamides.
  • Polyester film supports and especially poly(ethyleneterephthalate) and poly(ethylenenaphthalate) are preferred because of their excellent properties of dimensional stability.
  • the toner particles for use in a method for printing a continuous tone image on an opaque reflecting substrate as well as on a transparent substrate according to the present invention can essentially be of any nature as well with respect to their composition, shape, size, and preparation method and the sign of their tribo-electrically acquired charge.
  • the toner particles used in accordance with the present invention may comprise any conventional resin binder.
  • the binder resins used for producing toner particles according to the present invention may be addition polymers e.g. polystyrene or homologues, styrene/acrylic copolymers, styrene/methacrylate copolymers, styrene/acrylate/acrylonitrile copolymers or mixtures thereof.
  • Addition polymers suitable for the use as a binder resin in the production of toner particles according to the present invention are disclosed e.g. in BE 61.855/70, DE 2,352,604, DE 2,506,086, US-P 3,740,334.
  • polyesters prepared by reacting organic carboxylic acids (di- or tricarboxylic acids) with polyols (di- or triol) are the most preferred polycondensation polymers.
  • the carboxylic acid may be e.g. maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, etc or mixtures thereof.
  • the polyolcomponent may be ethyleneglycol, diethylene glycol, polyethylene glycol, a bisphenol such as 2,2-bis(4-hydroxyphenyl)propane called "bisphenol A” or an alkoxylated bisphenol, a trihydroxy alcohol, etc, or mixtures thereof.
  • Polyesters, suitable for use in the preparation of toner particles according to the present invention are disclosed in e.g. US-P 3,590,000, US-P 3,681,106, US-P 4,525,445, US-P 4,657,837, US-P 5,153,301.
  • the toner particles may contain (a) charge control agent(s).
  • the toner powder particles useful in a method according to the present invention may be prepared by mixing the above defined binder resin(s) and ingredients (e.g. an inorganic filler, a charge controlling agent, optionally one of the compounds A, B or C, etc) in the melt phase, e.g. using a kneader.
  • the kneaded mass has preferably a temperature in the range of 90 to 140 °C, and more preferably in the range of 105 to 120 °C.
  • the solidified mass is crushed, e.g. in a hammer mill and the obtained coarse particles further broken e.g. by a jet mill to obtain sufficiently small particles from which a desired fraction can be separated by sieving, wind classification, cyclone separation or other classifying techniques.
  • the toner particles useful according to the present invention may also be prepared by a "polymer suspension” process.
  • the toner resin (polymer) is dissolved in a water immiscible solvent with low boiling point and the toner ingredients (e.g. an inorganic filler, a charge controlling agent, at least one of the compounds A, B or C, etc) are dispersed in that solution.
  • the resulting solution/dispersion is dispersed/suspended in an aqueous medium that contains a stabilizer.
  • the organic solvent is evaporated and the resulting particles are dried.
  • the evaporation of the solvent can proceed by increasing temperature, by vacuum evaporation, by spray-drying as described in, e.g. US-P 3,166,510, US-P 3,338,991, electrostatic pulverizing as described in, e.g. GB 2,121,203, etc.
  • the powder toner particles useful according to the present invention may be used as mono-component developer (magnetic as well as non-magnetic), i.e. in the absence of carrier particles but are preferably used in a two-component system comprising carrier particles.
  • toner particles When used in admixture with carrier particles, 2 to 10 % by weight of toner particles is present in the whole developer composition. Proper mixing with the carrier particles may be obtained in a tumble mixer.
  • Suitable carrier particles for use in cascade or magnetic brush development are described e.g. in GB-P 1,438,110.
  • the carrier particles may be on the basis of ferromagnetic material e.g. steel, nickel, iron beads, ferrites and the like or mixtures thereof.
  • the ferromagnetic particles may be coated with a resinous envelope or are present in a resin binder mass as described e.g. in US-P. 4,600,675.
  • the average particle size of the carrier particles is preferably in the range of 20 to 300 ⁇ m and more preferably in the range of 30 to 100 ⁇ m.
  • iron carrier beads of a diameter in the range of 50 to 200 ⁇ m coated with a thin skin of iron oxide are used.
  • Carrier particles with spherical shape can be prepared according to a process described in United Kingdom Patent Specification 1,174,571.
  • Carrier beads comprising a core and coated with a Si-containing resin are preferred for use according to the present invention.
  • Such carrier beads have been described in e.g. US-P 4,977,054 ; US-P 4,927,728 and EP-A 650 099.
  • the printing can proceed in any electrostatographic printing device that incorporates several toning stations.
  • Typical examples of useful printing device are colour printers having mostly 4 toning stations (one for yellow toner, one for magenta toner, one for cyan toner and one for black toner) wherein monochrome printing with the differently pigmented toners can proceed.
  • apparatus suitable for the implementation of the printing according to the present invention can be named CHROMAPRESS (trade name of Agfa-Gevaert NV Mortsel, Belgium).
  • CHROMAPRESS An apparatus as CHROMAPRESS is very useful, while up to 10 toning stations are present. This opens the possibility for even better monochrome low density printing by using, at least for printing the image I 1 , yellow, magenta and cyan toners with adapted pigmentation to produce grey tones.
  • the amount (e.g. C 1 ) of deposited toner of at least one toner composition is varied in a predefined, preferentially monotonous manner, as the optical density of the result D 0 increases.
  • the amount of deposited toner is not a monotonous function across the complete tone-scale. This is clarified by Fig. 1.
  • the noise level may be reduced by superposition of several types of toner, it is beneficial to restrict the total amount of toner per microdot, preferably to 2 mg/cm 2 . This is especially true if too high concentrations of toner particles tend to crack if the page or substrate is bent.
  • FIG. 2 and 4 show that other toner amounts as a function of the required optical density D 0 are achievable. Boundary points, where monotonicity is disrupted, are indicated by the vertical dashed lines in Fig. 1-4. It is within the scope of the present invention to select different values for the deposited toner mass or amount of toner C i of a particular toner composition i for the different boundary points, while some toner compositions can have arbitrary deposited mass and optionally change the rate of increase at some of the boundary points, as in the example of Fig. 4. In Figures 5-8 configurations are shown for use of three toners, preferentially at three different toner stations.
  • the respective toner concentrations C 1 , C 2 and C 3 may be found by using the three graphs in one of the figures. According to Fig. 5, toner concentrations are never descending. This option requires a serious total amount of toner, but has proven to be the most stable imaging method. According to Fig. 6, the toner amount of the first toner is ascending as a function of increasing density D 0 as long as the toner amounts for the second and third toners are constant. Whenever the toner amount for either the second or the third toner increases, the toner amount for the first toner decreases as a function of increasing density D 0 ⁇
  • Fig. 1-8 it is thus clear that different portions of the tone scale D 0 may be printed with different combinations of layers, where some of the toner compositions may have a fixed deposited amount, some toner compositions or types of toner, having substantially the same chromaticity, may be absent, some toner compositions may have an increasing deposited toner amount, and some toner compositions - preferably having a lower pigmentation - may even decrease the deposited mass or toner amount, while the deposited mass of a higher pigmented toner composition increases as the tone Do to be printed increases.
  • a Cu-Zn ferrite based coated carrier was prepared by coating a Cu-Zn ferrite core with 1 % of dimethylsilicone using a solution spraying technique in a fluidized bed and post curing the coating.
  • the carrier showed a saturation magnetization (M sat ) of 0.41 Tesla.
  • Three developers (Dev 1 , Dev 2 and Dev 3 ) were prepared accordingly by adding 4 % of the respective toner compositions T 1 , T 2 and T 3 to the carrier particles.
  • the toners had a charge of - 3.7 Fc/10 ⁇ m.
  • Chromapress is a trade name of Agfa-Gevaert N.V. in Mortsel Belgium.
  • This printer has ten toner stations, five at each side of the substrate (paper) to be printed. In normal operation, four toner stations at each side are used, in order to overlay cyan, magenta, yellow and black toner, for reproducing colour images.
  • This printer may print 1000 A3 size pages (297 mm X 420 mm) per hour. The resolution is 23.62 dpmm (dots/mm 600 dpi), such that the size of one microdot is about 42 ⁇ m.
  • each microdot and per toner station 64 different energy levels (addressable with six bits) may be applied, in order to vary the amount of toner particles deposited per toner station. Usually, only sixteen levels from these 64 levels are selected in order to achieve density levels which are discernible from each other.
  • the number N of different types of toner was chosen to be 3.
  • the 23.62 dpmm (600 dpi) microdots were grouped 2 by 2 in adjacent halftone cells, in order to have a higher grey-scale resolution per toner printing station at a 11.81 dpmm (300 dpi) resolution than the 64 levels at 23.62 dpmm (600 dpi).
  • a table was built with three amounts of toners - indicated by C 1 , C 2 and C 3 in Fig. 9, where C 1 stand for the amount of toner A, C 2 for the amount of toner B and C 3 for the amount of toner C - and four microdots : microdot 1, microdot 2, microdot 3 and microdot 4.
  • microdots were geometrically arranged as shown in Fig. 9 : microdot 1 top left in the cell, microdot 3 top right in the cell, microdot 4 bottom left and microdot 2 bottom right.
  • the toner concentrations C 1 , C 2 and C 3 were varied according to the graphs in Fig. 9.
  • the concentration of the first toner for microdot 1 was increased from zero to maximum.
  • the concentration of the first toner for microdot 2 increases from zero to maximum. The same happens for microdots 3 and 4 respectively.
  • the concentration of the second toner is increased from zero to maximum, first for microdot 1, then 2, 3 and 4 respectively.
  • concentration of toner C in increased for microdot 1, 2, 3 and 4 respectively from minimum to maximum concentration in order to achieve a higher density on the substrate.
  • the desired overall tone behaviour may be obtained by executing a procedure like the one represented below, including the following steps :
  • An advantage of this method is that the opaque reflecting substrate is always covered by a full layer of toner A (first toner with concentration C 1 ), before any toner of toner composition B (second toner) of higher pigmentation is deposited, such that intentional modulation and noise associated with the tone layer B is reduced in amplitude to the difference in opacity of layer A and the combined layers A+B. Similarly, fluctuations due to toner C have an amplitude limited to the difference in opacity of layer A+B and layer A+B+C.
  • a disadvantage is the significant toner consumption three full layers of toner are deposited to achieve maximum density.
  • the "perceived" standard deviation of a substantially constant density was measured. Patches with microdots having maximum toner concentration were produced. The printing was done on paper and the density patches were measured in reflection mode. In a first test, a visual density of 1.45 was produced by making use of one toner. In a second test, the same visual density was obtained by using three types of achromatic toners in overprinting, according to the method of the current invention. For both the first and second test, the homogeneity of the patches was measured.
  • a value for the parameter ⁇ D smaller than 0.045 means acceptable image quality, in terms of homogeneity of even density patterns, a value smaller than 0.030 means excellent quality, a value of 0.025 to 0.020 is typical for offset high-quality.
  • the results of this analysis was 0.030 for the first test, using one single toner type and the result was 0.020 for the second test, using three toner types having substantially the same chromaticity. From these results it is clear that the noise level is substantially lower if more toner types are used.
  • the 23.62 dpmm (600 dpi) microdots were grouped in halftone cells in a 2 by 2 fashion, in order to get a higher grey-scale resolution per toner printing station at a 11.81 dpmm (300 dpi) resolution than the 64 levels at 23.62 dpmm (600 dpi).
  • a concentration scheme was built with three toners and four microdots, using 63 entry levels, per microdot and per printing station, as depicted in Fig. 10.
  • the microdots were numbered according to the geometry in Fig. 10.
  • the numbers in abscissa (0 to 12) may be multiplied by 63 in order to get input-levels from 0 to 756.
  • microdot arrangement in the cell is chosen such that toners A (C 1 ) and C (C 3 ) form horizontal lines when two out of the four pixels are on, while toner B (C 2 ) forms vertical lines when two out of the four microdots are on.
  • This is advantageous to minimise the sensitivity to wrong registration and banding, induced by vibration. This may be understood by the assumption that intersecting perpendicular lines do not change their mutual overlap when one set of lines is shifted with respect to the other.
  • a wedge consisting of patches of 1 cm 2 of the next 19 input levels X i was printed : 0, 42, 84, 126, ... 714, 756 and the measured reflectance densities Y i were represented in a graph.
  • 256 equidistant levels with respect to opacity were selected out of the 757 from Fig. 10. Again a medical image was printed, the image being represented by 256 density levels and having a resolution of 11.81 dpmm (300 dpi). Again, noise levels were substantially reduced.

Claims (19)

  1. Verfahren zum Reproduzieren eines Halbtonbilds durch bildmäßiges Auftragen von Tonerteilchen auf ein Substrat durch eine Druckeinrichtung, umfassend den Schritt des Unterteilens einer Fläche des Substrats in mehrere disjunktive Stellen, die von der Druckeinrichtung für das Auftragen einer bestimmten Menge von Toner adressiert werden können;
       ist gekennzeichnet durch den Schritt des Auftragens, auf mindestens eine adressierbare Stelle, mindestens zwei Arten von Toner, mit einem Farbartunterschied, der folgender Ungleichung genügt: (Δa*2 + (Δb*)2 ≤ 20 wenn in dem CIE-Raum L*a*b* ausgedrückt.
  2. Verfahren nach Anspruch 1, weiterhin umfassend die folgenden Schritte:
    Festlegen eines Gebiets benachbarter adressierbarer Stellen, umfassend die mindestens eine adressierbare Stelle;
    Auftragen einer Tonerkonzentration über 70% der maximalen Tonerkonzentration einer der mindestens zwei Arten von Toner auf mindestens eine adressierbare Stelle innerhalb des Gebiets;
    Auftragen einer Tonerkonzentration von weniger als 10% der maximalen Tonerkonzentration des einen Toners auf mindestens eine andere adressierbare Stelle innerhalb des Gebiets; und
    Auftragen einer Tonerkonzentration zwischen 10% und 70% der maximalen Tonerkonzentration des einen Toners auf die mindestens eine andere adressierbare Stelle innerhalb des Gebiets.
  3. Verfahren nach Anspruch 2, bei dem für jede der mindestens zwei Arten von Toner eine Minderheit von adressierbaren Stellen innerhalb des Gebiets mit einer Tonerkonzentration zwischen 10% und 70% der maximalen Tonerkonzentration versorgt werden.
  4. Verfahren nach einem der Ansprüche 1 bis 3, bei dem jeder adressierbaren Stelle, mit mehreren Tonerarten mit dem Farbartunterschied versorgt, eine Tonerkonzentration über 70% der maximalen Tonerkonzentration mindestens einer Tonerart mit der Farbart zugeführt wird.
  5. Verfahren nach einem der Ansprüche 2 oder 3, bei dem mindestens ein Gebiet, umfassend mindestens eine adressierbare Stelle versorgt mit mehreren Tonerarten, mit dem Farbartunterschied, vollständig mit einer Tonerkonzentration über 70% der maximalen Tonerkonzentration des mindestens einen Tonertyps versorgt wird.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem adressierbare Stellen durch Auftragen einer Anzahl N von Arten von Tonerteilchen mit dem Farbartunterschied gedruckt werden, wobei die Tonerteilchen einer Art den größten durchschnittlichen Volumendurchmesser dv50 µm aufweisen und wobei die Anzahl N die Beziehung N ≥ 0,3xdv50 erfüllt und wobei N durch Addieren von 0,5 zu 0,3xdv50 und Abrunden auf die nächstniedrigere ganze Zahl bestimmt wird.
  7. Verfahren nach einem der Ansprüche 1 bis 5, bei dem adressierbare Stellen durch Auftragen einer Anzahl N von Arten von Tonerteilchen mit dem Farbartunterschied gedruckt werden, wobei die Tonerteilchen einer Art den größten durchschnittlichen Volumendurchmesser dv50 µm aufweisen und wobei die Anzahl N die Beziehung N ≥ 0,4xdv50 erfüllt und wobei N durch Addieren von 0,5 zu 0,4xdv50 und Abrunden auf die nächstniedrigere ganze Zahl bestimmt wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem in einem fertiggestellten Bild pro cm2 maximal 2 mg an Toner vorliegen.
  9. Verfahren nach einem der vorhergehenden Ansprüche, bei dem sich die Arten von Tonerteilchen in ihrem Ausmaß an Färbekraft unterscheiden, wobei Tonerteilchen T1 das niedrigste Ausmaß an Färbekraft aufweisen, Tonerteilchen Tmax die höchste Färbekraft aufweisen.
  10. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Arten von Tonerteilchen einen unterschiedlichen volumenmittleren Durchmesser dv50 aufweisen.
  11. Verfahren nach einem der Ansprüche 9 oder 10, bei dem die Färbekraft von Tonerteilchen T1 derart ist, daß Abscheiden einer Menge von T1 zwischen 10 und 50% der Dichte ergibt, die das Abscheiden einer gleichen Menge von Tonerteilchen Tmax ergibt.
  12. Verfahren nach einem der Ansprüche 9 bis 11, bei dem die Tonerteilchen T1 einen durchschnittlichen Volumendurchmesser dv50 zwischen 5 und 20% unterhalb der Tonerteilchen Tmax aufweisen.
  13. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das Drucken auf einem transparenten endgültigen Substrat vonstatten geht und mindestens eine der Arten von Tonerteilchen einen oder mehr Zusatzstoffe umfaßt, die zusammen oder im Zusammenwirken mit in dem endgültigen Substrat enthaltenen Zusatzstoffen in der Lage sind, eine lichtabsorbierende Substanz zu bilden, und die Tonerteilchen wahlweise ein lichtabsorbierendes Pigment oder einen lichtabsorbierenden Farbstoff umfassen.
  14. Verfahren nach einem der vorhergehenden Ansprüche, bei dem es sich bei den Tonerteilchen um Trockentonerteilchen handelt.
  15. Verfahren nach einem der vorhergehenden Ansprüche, bei dem der Bildreproduktionsprozeß ein elektrografischer Prozeß ist.
  16. Verfahren nach einem der Ansprüche 2 bis 15, in Abhängigkeit von Anspruch 2, bei dem es sich bei dem Gebiet um eine Mehrstufenrasterzelle handelt, die disjunktive Mengen von benachbarten adressierbaren Stellen umfaßt.
  17. Verfahren nach einem der vorhergehenden Ansprüche, bei dem es sich bei dem Halbtonbild um ein Bild aus dem medizinischen Bereich handelt.
  18. Verfahren nach Anspruch 17, bei dem ein transparenter Träger verwendet wird und der Träger ein blauer Polyesterträger ist.
  19. Vorrichtung, die Mittel zum Ausführen des Verfahrens gemäß einem beliebigen der Ansprüche 1 bis 18 umfaßt.
EP95202768A 1995-10-13 1995-10-13 Verfahren zur elektrostatografischen Reproduktion von Bildern mit kontinuierlichen Tönen Expired - Lifetime EP0768577B1 (de)

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Application Number Priority Date Filing Date Title
EP95202768A EP0768577B1 (de) 1995-10-13 1995-10-13 Verfahren zur elektrostatografischen Reproduktion von Bildern mit kontinuierlichen Tönen
DE69507144T DE69507144T2 (de) 1995-10-13 1995-10-13 Verfahren zur elektrostatografischen Reproduktion von Bildern mit kontinuierlichen Tönen
US08/724,065 US5825504A (en) 1995-10-13 1996-09-30 Method for stable electro (stato) graphic reproduction of a continuous tone image
JP8287314A JPH09226177A (ja) 1995-10-13 1996-10-11 連続的色調の像の安定な（静）電記録再現方法
US09/047,263 US6175374B1 (en) 1995-10-13 1998-03-24 Method for stable electro (stato) graphic reproduction of a continuous tone image

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EP95202768A EP0768577B1 (de) 1995-10-13 1995-10-13 Verfahren zur elektrostatografischen Reproduktion von Bildern mit kontinuierlichen Tönen

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US6146799A (en) * 1998-06-17 2000-11-14 Agfa-Gevaert Method for printing continuous tone images with high density resolution
US6025922A (en) * 1998-12-18 2000-02-15 Electronics For Imaging Reduction of banding in printed images
EP1014207A1 (de) * 1998-12-23 2000-06-28 Agfa-Gevaert N.V. Tonerreihenfolge zur Rauschverminderung
AU2000224576A1 (en) 2000-02-06 2001-08-14 Indigo N.V. Method for producing high gloss printed images
US8437037B2 (en) 2008-05-29 2013-05-07 Xeikon Manufacturing N.V. Multilevel clustered dot screening method with improved detail and reduced image noise

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JPS58162970A (ja) * 1982-03-23 1983-09-27 Hitachi Ltd 静電像現像装置
JPS6125365A (ja) * 1984-07-13 1986-02-04 Canon Inc 中間調画像形成方法
DE3786656T2 (de) * 1987-01-19 1994-01-27 Canon Kk Farbtoner und ihn enthaltende Zweikomponentenentwickler.
US5142337A (en) * 1990-10-09 1992-08-25 International Business Machines, Corp. Printing grey scale images

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