EP0569285A2 - Kolloide zur Steigerung des Reibungskoeffizienten von Beschichtungen auf Blocken kohlefreien Papieres - Google Patents

Kolloide zur Steigerung des Reibungskoeffizienten von Beschichtungen auf Blocken kohlefreien Papieres Download PDF

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Publication number
EP0569285A2
EP0569285A2 EP93401145A EP93401145A EP0569285A2 EP 0569285 A2 EP0569285 A2 EP 0569285A2 EP 93401145 A EP93401145 A EP 93401145A EP 93401145 A EP93401145 A EP 93401145A EP 0569285 A2 EP0569285 A2 EP 0569285A2
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Prior art keywords
pad
sheet
friction
weight percent
paper
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French (fr)
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EP0569285B1 (de
EP0569285A3 (en
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Keith A. C/O Minnesota Mining And Kraft
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3M Co
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Minnesota Mining and Manufacturing Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components

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  • the invention relates to pad coats or release coatings for carbonless copy papers and in particular, this invention relates to pad coats or release coatings which contain, in part, an inorganic colloid and an abherent. This invention also relates to carbonless paper constructions which are at least partially coated with the inventive pad coat or release coating.
  • Carbonless impact marking papers for the transfer of images are papers which are capable of producing an image upon application of pressure.
  • Products employing this chemistry generally contain at least two substrates (for example, two sheets of paper) and involve coating one reactant, known as a color-former, on one substrate, and the other reactant, known as a developer, on another "mating" substrate.
  • One surface, or side, of each substrate is coated with one of the two primary reactants.
  • the two substrates are often referred to as a donor sheet and a receptor sheet.
  • Means for preventing the reacting of the two until intended i.e., until activating pressure is applied
  • This is typically accomplished by encapsulation of one of the reactants.
  • a fill solution of the color-forming compound(s) in a hydrophobic solvent is encapsulated or contained in microcapsules and is coated on the back side of one sheet of paper to form a donor sheet. This is then mated with a receptor sheet coated with a developer or reactant for the color-forming compound.
  • the microcapsules serve the purpose of isolating the reactants from one another and preventing reaction.
  • the two substrates come into contact under sufficient pressure so that the capsules rupture (i.e., those capsules corresponding to the pattern of applied pressure) and the solution of encapsulated color-former is released and transferred from the donor sheet to the receptor sheet.
  • the receptor sheet On the receptor sheet, a reaction between the previously separated reactants occurs. Since the color-former and the developer form a deeply colored image when reacted, an image forms on the receptor sheet. In general, the resulting reaction will, of course, form a colored image corresponding to the path traveled by the stylus or the pattern of pressure provided by the stylus or key.
  • activating pressure includes, but is not limited to, pressure applied by hand with a stylus or pressure applied by a business machine key (for example, a typewriter key); and the term “encapsulation” and “encapsulated compounds” refer to microcapsules enclosing a fill material.
  • a preferred construction contains an encapsulated color-former dissolved in appropriate hydrophobic solvent(s) within microcapsules and coated with a suitable binder onto a back side of the donor sheet, sometimes referred to as a "coated back” (CB) sheet.
  • a developer also optionally in a suitable binder such as a starch or latex, is coated onto the front side of the receptor sheet sometimes referred to as a “coated front” (CF) sheet.
  • suitable binder refers to a material, such as starch or latex, that allows for dispersion of the reactants in a coating on a substrate.
  • Each CB coating contains rupturable capsules which, when ruptured, release reagents to produce a color-changing reaction at the adjacent CF coating.
  • the preparation of such carbonless sheets is disclosed by Gale W. Matson in U.S. Patent Nos. 3,516,846 and 3,516,941, incorporated herein by reference.
  • microcapsules can be manufactured. These varied processes provide different techniques for producing capsules of varying sizes, alternative materials for the composition of the capsule shell, and various different functional materials within the shell. Some of these various processes are disclosed in U.S. Patent Nos. 2,800,427; 2,800,458; 3,416,441; 3,429,827; 3,516,846; 4,087,376; 4,100,103; 4,909,605; and British Patent Specification Nos. 950,443 and 1,046,409. A wide variety of capsule materials can be used in making the capsule shells, including gelatin and synthetic polymeric materials.
  • a popular material for shell formation is the product of the polymerization reaction between urea and formaldehyde, or between melamine and formaldehyde, or the polycondensation products of monomeric or low molecular weight polymers of dimethylolurea or methylolated urea with aldehydes.
  • a variety of capsule forming materials are disclosed, for example, in U.S. Patent Nos. 2,800,458; 3,429,827; 3,516,846, 4,087,376; 4,100,103 and British Patent Specification Nos. 1,046,409; 2,006,709 and 2,062,570.
  • the two sheets are positioned such that the back side of the donor sheet faces the developer coating on the front side of the receptor sheet.
  • the uncoated surface of the donor (CB) sheet contains a form of some type and the activating pressure is generated by means of a pen or other writing instrument used in filling out the form.
  • the image appearing on the receptor (CF) sheet is a copy of the image applied to the top sheet.
  • Constructions containing a first substrate surface, on which is coated the encapsulated color-former, and a second substrate surface, on which is coated a developer, are often prepared.
  • the coated first substrate surface is positioned within the construction in contact with the coated second substrate surface.
  • Such a construction is known as a "set” or a "form-set” construction.
  • Substrates with one surface, on which is coated the encapsulated color-former, and a second, opposite surface, on which is coated a developer, can be placed between the CF and CB sheets in a construction involving a plurality of substrates.
  • Such sheets are generally referred to herein as "CFB" sheets (i.e., coated front and back sheets).
  • CFB sheets are also typically used in form-sets. In some applications, multiple CFB sheets have been used in form-sets. These contain several intermediate sheets, each having a developer coating on one side and a coating with capsules of color-former on the opposite side.
  • the sheets in the form-set are sequenced in the order (from top to bottom) CB, CFB(s), and CF. This insures that in each form-set a color former and a color developer will be brought into contact when the microcapsules containing the color-forming material are ruptured by pressure.
  • CB, CF, and CFB sheet are self-contained (SC), or autogenous, carbonless paper in which both the color-former and developer are applied to the same side of the sheet and/or are incorporated into the fiber lattice of the paper sheet.
  • SC self-contained
  • carbonless paper in which both the color-former and developer are applied to the same side of the sheet and/or are incorporated into the fiber lattice of the paper sheet.
  • Carbonless paper is widely used in the forms industry and carbonless paper forms have been printed in the past by conventional printing techniques such as offset printing, lithography, etc.
  • conventional printing techniques such as offset printing, lithography, etc.
  • electrophotographic copiers having dependable, high capacity collating systems and enhanced copy quality
  • compatibility of the carbonless paper with the machine is critical.
  • the base sheets upon which carbonless paper coatings are applied to form carbonless papers conventionally imaged via offset printing do not have sufficient stiffness or sufficient sensitivity to machine conditions for curl and moisture control to be handled in copier processors and sorters.
  • Carbonless paper is often used in the form of printed form-sets for preparing multiple copies of receipts, bills, and other business forms and form-sets are prepared by collating from 2 to 8 sheets.
  • Form-sets are typically made by applying an adhesive to the edge of a stack of the carbonless paper.
  • Each of the coated sheets in a form-set is somewhat porous and permits the adhesive to penetrate into the pores of the paper, such penetration being necessary to attain satisfactory adhesion of sheets within the form-set.
  • Adhesives useful for edge-padding carbonless papers are described, for example, in U.S. Patent No. 5,079,068, the disclosure of which is incorporated herein by reference.
  • the adhesively bound papers are then "fanned-out” to separate into individual form-sets.
  • carbonless copy paper form-sets often have a release coating (for example, a fluorocarbon or silicone coating) applied to at least one of the outer faces of each form-set.
  • a release coating for example, a fluorocarbon or silicone coating
  • Pad coats function as an abhesive (or non-adhesive) to provide low adhesion properties to the outer faces of a form-set; act as a release agent for the edge-padding adhesive; and promote "fan-out properties" in edge padding to allow the adhesively edge-padded stack to "fan-out” or “fan-apart” and separate into individual form-sets upon fanning.
  • Pad coats are also necessary to counteract curling that otherwise would result from stresses induced in the paper by the CB and CF functional coatings on the opposite surface of the sheet.
  • the surface of the paper coated with capsules or developer may be referred to, respectively, as the CB and CF coated surface or as CB fc and CF fc representing the "functional coated surface” or "functional coated face" of the sheet.
  • the pad coat is applied to the front face of the capsule coated (CB) sheet and/or to the back face of the developer coated (CF) sheet.
  • CB pc refers to the front, pad-coated surface of the CB sheet.
  • CF pc refers to the back, pad-coated surface of the CF sheet.
  • Pad coats are by nature low surface energy materials which operate by preventing wetting of the paper surface by the adhesive. Unfortunately, low surface energy, pad coated surfaces also lower the coefficient of friction of the sheet surface and is one cause of double or multiple sheet feeds and paper misfeeds. The low surface energy, pad-coated surface also reduces toner powder adhesion, resulting in low image density and poor toner anchorage to electrophotographically produced images on the pad coat surfaces. Because of differences in the fluorocarbon coatings, an adhesive that affords fan-apart edge-padding of a certain carbonless copy paper may not be operative with other carbonless copy papers manufactured by different companies.
  • “Fan-out” is a method of separating a stack or pad of multiple form-sets into individual sets.
  • One method of “fanning-out” or “fanning-apart” a stack of collated sheets involves gripping the edge-padded end of the stack with one hand and the unpadded edge with the other and then bending the stack into a "U" shape. While holding the stack horizontally, the padded end is released and allowed to droop downward. This provides enough stress on the adhesive to separate the pad or stack into individual form-sets.
  • Carbonless papers often must contain information such as contract terms or instructions printed onto various faces of the sheets. Thus, all sheet faces must be ink and/or toner receptive.
  • carbonless papers often have pad coats to promote fan-out properties of form-sets. However, these pad coats tend to decrease ink and toner receptivity of the pad coated surface, thus making ink and/or toner adhesion difficult. This results in low adhesion of toner powder to the pad coat surfaces and results in low density images.
  • carbonless paper is prepared and packaged in precollated form-sets.
  • the sheets are arranged in the order in which they will appear in the finished form.
  • the coated back (CB) is first in the form-set
  • the coated front sheet (CF) is last
  • the required number of CFB sheets are in between.
  • the paper may be prepared and packaged in precollated form-sets referred to as "reverse sequence form-sets,” wherein sheets of various colors and surfaces are arranged opposite to their normal functional order.
  • the coated front sheet (CF) is first in the form-set, the coated back sheet (CB) is last, and the required number of CFB sheets are in between.
  • a second problem encountered when precollated carbonless papers are used in friction fed machines results from coefficient of friction mismatch of contacting surfaces and results in the development of dense, noticeable smudge marks on CF sheets. Smudging occurs when two or more carbonless paper sheets enter the feed mechanism together and is believed caused by inadvertent capsule rupture and transfer of color-former from CB to CF surface. This problem is particularly acute when the copier uses a pressure roller or belt for pick up and feeding the sheet into the copier. This problem was addressed by Beery who attributed the smudge to mechanical locking between the sheets due to the relatively high coefficient of friction between the sheet surfaces (see J. Beery, WO 89/04804).
  • His solution was to modify the feed rollers in the machine to make them softer, so that the pressure exerted on the capsule coated surface was reduced and less pressure was placed over the areas of the sheet engaged by the feed mechanism. While photocopier modification by changing the configuration and hardness of the feeding system represents one solution, machine modification is often costly and requires cooperation of the machine manufacturer. It would be advantageous to decrease smudge mark formation without machine modification. A more desirable solution would be to modify the paper surface to machine operation to eliminate smudging.
  • colloidal silica to prevent skidding by increasing the coefficient of friction of linerboard was taught by Inoue and coworkers (M. Inoue, N. Gurnagul, and P. Aroca, Tappi Journal 1990, 72(12), 81-85). They related coefficient of friction with surface free energy and reported increased friction with use of colloidal silica and increase of surface energy from 26.8 dyne/cm to 39.8 dyne/cm.
  • a pad coat for carbonless paper was disclosed in U.S. Patent No. 5,092,927 as comprising a binder, an aqueous pigment dispersion, and an abhesive component for promoting fan-out.
  • This pad coat is purported to improve printability of the pad coated surface of the form-set.
  • the pigments were chosen for their ink receptive properties and included calcium carbonate, clay, calcined clay, silicates, and alumina trihydrate.
  • the enumerated pigment, Hydral 710B has a particle size of 800 -1,000 nm.
  • the patent did not disclose the use of colloidal size particles.
  • a high shear mixer and optionally, a dispersing aid, were used to disperse the pigment particles.
  • EPO Publication No. 464,681 discloses a dye receiving element for thermal dye transfer in which the backside of the dye receiving element is composed of polyethylene oxide, submicron colloidal inorganic particles, and polymeric particles larger than the colloidal inorganic particles (1-10 ⁇ m in diameter).
  • the purpose of the backside coating is to provide adequate friction for a pick roller to feed one sheet at a time from a supply tray, to minimize interactions between the front and back surfaces of sheets stacked in a supply tray, and to minimize sticking between dye donor element and the receiving element backside layer when the receiver element is accidently inserted into a thermal printer wrong side up. No requirements for printability, toning, or fan-out were mentioned or are required for this system.
  • Silicas and silicates are known and used as CF developers for leuco dyes in carbonless papers.
  • U.S. Patent No. 4,461,494 discloses the use of magnesium-aluminum silicate as a color developer for pressure sensitive carbonless copy paper. The material gives good color retention with freedom from greying or yellowing on storage.
  • U.S. Patent No. 4,732,991 teaches the use of silica gel as a CF material useful as a developer for carbonless papers.
  • U.S. Patent No. 4,075,224 teaches the use of silica gels, acidic clays, or phenolic resins as developers for carbonless papers.
  • inorganic colloidal particles into carbonless paper pad-coats or release coatings results in an increase in the coefficient of friction of the pad coated surface and in toner adhesion and ink receptivity of the pad-coated surface; promotes uniform feeding of carbonless paper sheets into photocopiers and printing presses by reducing misfeeds and double feeds; and reduces feeder induced smudging. It does this without loss of the abhesive release effect provided by the pad-coat and without loss of the fan-out ability to produce form-sets.
  • the present invention provides a composition suitable for use as a pad-coat or release coating for carbonless papers, the composition consisting essentially of about: 0.1-10 weight percent inorganic colloid having a particle size in the range of about 1-125 nm; 0.01-2.5 weight percent abhesive material; and 65.0-99.9 weight percent water; and 0-25 weight percent binder, based upon the total weight of the coating composition.
  • the composition may further contain a pH adjuster, a defoamer, an optical brightener, and the like.
  • the present invention further provides a carbonless paper construction having a pad-coat or release coating applied over at least a portion of at least one outer surface of the carbonless paper construction.
  • the pad coat or release coating consists essentially of about: 2.0-95.0 weight percent inorganic colloid having a particle size in the range of 1-125 nm; 2.0-50.0 weight percent abhesive; and 0-95.0 weight percent binder, based upon the total dry weight of the coating composition.
  • Such inventive carbonless constructions are particularly suitable for use in printing and electrophotographic applications.
  • the invention may be more easily understood in reference to the drawing, the single Figure of which schematically indicates in cross section the edge-padding of a stack of form-sets of collated sheets of carbonless copy paper.
  • FIG. 10 Shown in the drawing is a stack 10 of 4-part carbonless copy paper sheets including top CB sheets 11 , intermediate CFB sheets 12 and 13 and bottom CF sheet 14 resting on table 15 .
  • Each CB coating contains rupturable microcapsules which when ruptured release reagents to produce a color-forming reaction at the adjacent CF coating.
  • the outer faces of the top CB sheets 11 and the bottom CF sheets 14 of each 4-part form-set have been treated with an abhesive release coating, 16 and 17 , of the present invention.
  • a flat plate (not shown) can be used to afford a smooth edge 18 with a steel bar 19 .
  • An edge-padding adhesive composition 20 has been applied to the edge of the stack and has flowed into the stack between the sheets of each form-set to produce a stack of adhesively edge-padded form-sets. The adhesive has not flowed into the stack between the sheets separating each form-set due to the abhesive release coating 16 and 17 .
  • the pad coat or release coating composition of the present invention contains an inorganic colloid, an abhesive material, and water. If desired, the pad coat or release coating composition can also include a binder, a pH adjuster, a defoamer, an optical brightener, and the like.
  • the inorganic colloid can be any inorganic colloid.
  • Preferred inorganic colloids are silica, alumina, titania, zirconia, antimony pentoxide, or calcium carbonate. Most preferably, colloidal silica is utilized.
  • colloidal silica is utilized.
  • colloidal particles means a state of subdivision of matter which comprises either single large molecules or aggregations of smaller molecules. Colloidal particles are of ultramicroscopic size and are dispersed.
  • the size range of colloidal particles generally are from about 1 to 125 nm; preferably, from about 1 to 100 nm; and more preferably, from about to 5 to 75 nm.
  • the effective particle size for most pigments should be at least half the wavelength of light. For visible light this means the lower limit of the effective pigment particle size should be about 200-400 nm.
  • the lower size limit of colorless inorganic pigment particles is usually considered to be about 200 nm (see Kirk-Othmer, "Encyclopedia of Chemical Technology", Volume 17, Wiley Interscience, New York, 1982, pages 788-838).
  • pages 795 and 808 of the foregoing reference show colorless inorganic pigments to have particle sizes ranging from 150-100,000 nm (0.150-100 ⁇ m).
  • colloids and pigment dispersions are also important in coating operations.
  • Colloid compositions have lower viscosities and are stable in the dispersed phase.
  • Pigment compositions tend to be viscous and require high shear agitation and/or suspending aids to maintain pigment dispersion in the coating solution.
  • Colloidal dispersions are transparent or translucent due to the minute particle size of the suspended colloidal materials. This contrasts with pigment particles which are added to impart color, whiteness, or opacity to solvents in which they are dispersed.
  • the inorganic colloid is generally present in the inventive pad-coat or release coating composition in an amount (based upon the total weight of the coating composition) of about 0.1 to 10.0 weight percent; preferably, about 0.2 to 5.0 weight percent; and most preferably, about 0.3 to 2.5 weight percent.
  • the inorganic colloid functions to impart roughness to the surface of the paper as well as to improve ink and toner receptivity. It is surprising that inorganic colloidal materials, which have a high surface area, do not interfere with the padding and fan-out promoting properties of the abhesive. It is further surprising that such small amounts of colloid can have a dramatic improvement in toner anchorage or fixation to the pad coated surfaces.
  • the abhesive, material serves to prevent the padding adhesive from penetrating the sheets and is necessary to permit fan-out of the stack.
  • Such abhesive materials include silicones, organic-silicone copolymers and blends, organic polymer coatings, waxes, fluorochemicals, and fluorosilicones.
  • the abhesive is a fluorinated compound.
  • fluorochemical abhesive materials or compositions useful in this invention comprise fluorochemical compounds or polymers containing at least one fluoroaliphatic radical or group, R f .
  • the fluoroaliphatic group R f is a fluorinated stable, inert, preferably saturated, monovalent, non-aromatic aliphatic group. It can be straight chain, branched chain, or cyclic, or combinations thereof. R f is preferably a fully fluorinated radical, but hydrogen or chlorine atoms can be present as substituents provided that not one atom of either is present for every two carbon atoms.
  • the R f group has at least 3 carbon atoms, preferably 3 to 20 carbon atoms, and most preferably about 4 to 10 carbon atoms, and preferably contains about 40% to 70% fluorine by weight.
  • the preferred R f groups are fully or substantially fluorinated and more preferably are perfluorinated aliphatic groups of the formula -C n F 2n+1 .
  • Useful fluorochemical polymers containing R f groups include copolymers of fluorochemical acrylate and/or methacrylate monomers with copolymerizable monomers, including fluorinated and fluorine free monomers, such as methyl methacrylate, butyl acrylate, octadecylmethacrylate, acrylate and methacrylate esters of poly(oxyalkylene)polyol oligomers and polymers.
  • Fluorinated abhesive materials useful in pad coats are sold by 3M company under the trade names of Scotchban Protector FC-808, FC-824, and FC-829.
  • a preferred abhesive material is FC-829.
  • a number of other materials may be used as to provide a low energy surface for the pad coat and prevent the padding adhesive from bonding the paper into blocks.
  • U.S. Patent No. 4,962,072 teaches the use of a sizing agent to prevent adhesion. It discloses sizes of alkyl ketene dimer, alkenyl succinic anhydride, and polyurethane.
  • Another abhesive is taught in WO 90/15719. It relies on the low surface energy of metal salts of long chain fatty acids and incorporates natural pigments to improve printability and ink receptivity of the release coating.
  • Another widely used release material for abhesives well known in the art is a silicone polymer, i.e., a polysiloxane. One such material is taught in Canadian Patent No. 2,042,685.
  • Silicone polymers for use as abhesives are available from several commercial sources for example; SM 2800 (available from General Electric Company), X-27740 and X-27741 (available from Dow Corning), and PC 104 (available from Rhone-Poulenc).
  • SM 2800 available from General Electric Company
  • X-27740 and X-27741 available from Dow Corning
  • PC 104 available from Rhone-Poulenc.
  • the present invention is not limited to the use of a fluorocarbon abhesive, but extends to other known abhesives such as those described above.
  • other components in the pad coat may effect the coefficient of friction, the adhesion of imaging materials such as toner powder deposited in electrophotograhic copiers, and fan-apart.
  • a silicone polymer was chosen as a representative material and evaluated in various formulations.
  • the abherent material is generally present in the inventive pad coat or release coating in an amount (based upon the total weight of the composition) of about 0.01 to 2.5 weight percent; preferably, about 0.05 to 2.0 weight percent; and most preferably, about 0.1 to 1.0 weight percent.
  • the water content of the pad coat or release coating composition of the present invention (based upon the total weight of the composition) is generally in an amount in the range of about 65.0 to 99.9 weight percent; preferably, about 75.0 to 99.8 weight percent; and most preferably, about 85 to 99.6 weight percent.
  • the binder serves the purpose of allowing attachment of the other components to the paper.
  • a preferred binder is starch, but other binders such as polyvinyl alcohol (PVA) and styrene/butadiene latexes may be used.
  • PVA polyvinyl alcohol
  • a corn starch available from Grain Processing Corporation (Muscatine, IA) under the name of GPC Oxidized Corn Starch has been found to work well in the present invention. Phosphated wheat starch may also be used.
  • the binder material is generally present in the inventive pad coat or release coating in an amount (based upon the total weight of the composition) of 0.0 to about 25.0 weight percent; preferably, about 0 to about 20.0 weight percent; and most preferably, about 0 to about 10.0 weight percent.
  • the pad coat solution may require pH control prior to addition of the colloid. If necessary, the pH of the pad coat solution should be adjusted by addition of acid or base to bring it into a pH range in which the colloid is stable.
  • the inventive pad coat or release coating is applied over at least a portion of at least one outer surface of a carbonless paper construction.
  • the coating consists essentially of about 2.0-95.0 weight percent inorganic colloid having a particle size in the range of about 1-125 nm, and preferably, about 5-85.0 weight percent inorganic colloid; and about 2.0-50.0 weight percent abherent, and preferably about 3.0-40.0 weight percent abherent, based upon the total dry weight of the fluorinated abherent.
  • binder is present in an amount of about 0-95.0 weight percent and preferably, about 0-85.0 weight percent.
  • the feeding of paper into printing presses or electrophotographic copiers depends upon individual sheets being fed from a stack of the paper, and the mode of transfer of the sheet into the printing press or photocopier varies with the machine.
  • the success in feeding single sheets depends upon separating each sheet from the sheet underneath cleanly without dragging the second sheet or multiple sheets into the printer.
  • carbonless paper there are several sheets and the sheets have coatings which differ in surface character.
  • the ratio of the sliding force to the force between the sheets which must be overcome to initiate movement is called the "static coefficient of friction.”
  • the ratio of the sliding force to the force between the sheets that must be overcome to maintain sheet movement is called the "kinetic coefficient of friction.” Static coefficient of friction is usually higher than kinetic coefficient of friction. While both coefficients of friction are important, the static coefficient of friction is more important when considering the feeding of paper into copiers and printing presses.
  • Printing presses and electrophotographic copiers are designed to feed paper into the machine by several mechanisms.
  • the paper may be fed by a vacuum pickup and transfer system, by a roller or belt which exerts pressure on the top sheet in the stack, by a roller or belt which exerts pressure on the top sheet in the stack in combination with a retard roller or belt beneath the stack, or by other suitable means.
  • a roller or belt pressed against the top sheet of the paper stack is employed as the feed means.
  • These feed means move into engagement with the top sheet of the stack, exert pressure on the top sheet, usually by buckling the sheet, and releases and separates the sheet from the stack.
  • the sheet can then be fed through "take away rolls” into the copier.
  • the feed means usually remain at a fixed position in relation to the stack during sheet feeding.
  • a forward moving belt removes the top sheet from a stack of paper and advances the sheet to a set of pinch rolls which then feed the sheet into the imaging and toner transfer stations.
  • a retard roller under the feed belt catches any second sheet that begins to transfer with the top sheet.
  • a smudge mark often develops on the CF surface of a sheet. Smudging is caused by coefficient of friction mismatch between contacting surfaces of consecutive sheets of paper and results from CB capsule rupture and color-former transfer to the CF surface. Capsule rupture can be caused by the feed mechanism (such as a belt or roller) sliding across the paper rather then smoothly feeding the paper into the photocopier or printing press. Capsule rupture can also be caused by double or multiple sheet feeds of carbonless papers into the feeder assembly and subsequent abrasion by the retard roller along the CB surface. Transfer of color-former from the CB sheet to the CF surface can take place in the paper feed mechanism as another sheet is fed, within the copier, or in the collection tray as the sheets lie on top of each other.
  • the interfaces are CB against CF and CF pc against CB pc (of the next form-set).
  • the static coefficient of friction ranges from about 0.55 to 0.65.
  • the static coefficient of friction is about 0.35.
  • the interfaces are CB against CF (of the CFB sheet), CB (of the CFB sheet) against CF, and CF pc against CB pc (of the next form-set).
  • the static coefficient of friction is again about 0.55-0.65.
  • the coefficient is again about 0.35.
  • 4-part and larger form-sets only additional CB/CF interfaces are present.
  • the interfaces are CF pc against CB pc and CB against CF (of the next form-set).
  • the static coefficient of friction is about 0.35.
  • the static coefficient of friction ranges from about 0.55 to 0.65.
  • the interfaces are CF pc against CF (of the CFB sheet), CB (of the CFB sheet against CB pc , and CB against CF (of the next form-set).
  • the static coefficient of friction is about 0.50.
  • the coefficient of friction is also about 0.50.
  • the static coefficient of friction ranges from about 0.55 to 0.65.
  • Coefficient of Friction was measured using an Instron Coefficient of Friction Fixture (Catalog No. 2810-005) installed on an Instron Testing Instrument.
  • the fixture comprises a friction table, a sled, and a pulley.
  • One piece of material is attached to the friction table.
  • a second piece of material is attached to the 200 g 23 ⁇ 8'' x 25 ⁇ 8 (6.0 cm x 6.7 cm) sled.
  • the materials are positioned so that the interfaces between which the coefficient of friction is to be measured are in contact.
  • the sled is connected through a low-friction pulley to the Instron load cell which detects the drag or friction.
  • the force needed to draw the sled across the friction table is a measure of the friction between the two contacting surfaces. This force can be plotted, as for example, on a strip chart recorder.
  • Form-sets are prepared by stacking the collated carbonless paper, trimming, edge- padding, and fanning-out.
  • the stack is first trimmed to align the edge to a uniform state.
  • the edge is preferably compressed by a weight. The amount of compression is not material as long as it is not so great as to rupture the capsules contained on the CB sheet [(preferably not more than about 50 psi (340 kPa)]. After 24 hours, the edge is adhesively edge-padded.
  • Edge-padding is accomplished by applying adhesive, as with a brush, along the edge of the stack. Sufficient amounts of padding adhesive are applied until excess adhesive runs down the edge of the stack. This assures complete adhesion between individual sheets of each form-set in the stack. Greater amounts cause no problem except to be wasteful. Compression is maintained for 24 hours while the edge padded sets are allowed to dry. All padding described herein used "3M Brand Padding Adhesive," available from the Carbonless Products Department of 3M Company, St. Paul, MN.
  • CB/CFB bonds are the bonds most likely to break upon fan-out or crash printing.
  • the most stringent testing of the ability to form strong bonds between sheets is in 2-part sets (CB/CF) and in 4-part sets (CFB/CFB), rather than in 3-part sets.
  • the quality of edge padding can be determined by two tests, one showing how readily a stack of collated sheets separates into sets ("Fan-Out Rating Test") and the other showing the strength of the adhesive bond between individual sheets of a set (“Bond Strength Test”).
  • a stack of sets of collated sheets that has been edge-padded is tested for fan-out into sets as follows:
  • the quality of toner adhesion can be determined by three tests, one showing the ease of scraping fused toner off the sheet (“Knife-Rubbing Test”), one showing the ease of toner removal with a repositionable removable tape (“Low-Tack Tape Peel Test”), and one showing the ease of toner removal with a permanent non-removable tape (“High-Tack Tape Peel Test”).
  • Carbonless paper is imaged in a commercial electrophotographic copier such as a Xerox Model 1090. A knife edge is scraped lightly across the fused toner powder image on the paper and the ease of toner removal is subjectively evaluated.
  • Tape peel tests determine toner adhesion to the pad coat of the paper by measuring the approximate toner percentage removed when tape is applied to and pulled off the toned sheet.
  • a piece of tape approximately 2-3 inches (5.1-7.6 cm) long was placed on the sheet of carbonless paper that had been imaged in a Xerox Model 1090 photocopier. The image had both large solid areas and fine line areas.
  • the tape was pressed onto the imaged paper by rolling it 4 times with a 4.5 lb (2.0 kg) roller. The tape was then removed and the approximate amount of toner removed determined.
  • a "low-tack tape test” was run using 3M Scotch Brand #811 Magic Tape. This is a removable tape and uses a Post-It TM repositionable type adhesive.
  • a "high-tack tape test” was run using 3M Scotch Brand #810 Magic Tape. This is a non-removable tape and uses a permanent adhesive. It should be noted that both tapes can be removed from the paper because of the fan-out coating on the paper. It should also be noted that when the high-tack tape peel test was run on paper having no pad coat, the paper was torn by removal of the tape.
  • Examples 1 and 2 show the preparation and evaluation of CF and CB pad coats (CF pc and CB pc ).
  • CF pad coat solutions were prepared by mixing the materials shown below. To the indicated amount of water were added solutions of FC-829, and 32% starch solution. The pH, now about 3, was adjusted to 10 by addition of 50% aqueous NaOH solution, and colloidal silica was added (pH is adjusted prior to addition of the colloid). A control pad-coat was prepared by using no colloid and is labeled 0%. In all cases, the total pad-coat solutions contained 12,000 g of material.
  • the 32% solution of starch binder for the CF pad coat was prepared by adding 3,200 g of GPC Oxidized Corn Starch (available from Grain Products Corporation, Muscatine IA) to 6,800 g of water in a Groden Model TDB/7 Steam Jacket Kettle. The mixture was heated at 200 °F (93°C) for 1 hr.
  • GPC Oxidized Corn Starch available from Grain Products Corporation, Muscatine IA
  • FC-829 is a fluorochemical abhesive material available as a 30% aqueous solution from 3M Company, St. Paul, MN.
  • Nalco 1140 is a colloidal silica solution containing 40% silica and is available from Nalco Corp., Naperville, IL.
  • the weight percent silica of the total solids is the same as the weight percent silica in the dried coating. silica 0% 2.9% 13.0% 42.8% 60.0%
  • the coated paper was dried in a forced air oven at 250 °F (121 °C ) at a coating speed of 200 ft./minute.
  • the coated CF sheets were made into 2-part sets using a CB sheet available from the Carbonless Products Department of 3M Company, St Paul, MN under the name of "3M Blue Purple CB.” This sheet is coated with a pad coat that does not contain colloidal material.
  • the coefficient of friction of the CF pc surface was measured against CB pc surface.
  • the adhesion and fan-apart were measured as described above. Results of the evaluation, shown in Table 1, demonstrate an increase in both coefficient of friction and surface energy of the contacting surfaces. Fan apart and adhesion between the CF and CB sheets of padded form-sets is maintained.
  • CB pad coat solutions were prepared by mixing the materials shown below. To the indicated amount of water were added solutions of FC-829 fluorochemical abhesive, Tinapol PT-150, and Nalco 7569 defoamer. The pH, now between 4 and 5, was adjusted to 10 by addition of 50% aqueous NaOH solution, and colloidal silica was added. A control pad-coat was prepared by using no colloid and is labeled 0%. The weights shown below are gross weights of solution and include water present. In all cases, the total pad-coat solutions contained 6,000 g of material.
  • FC-829 is a fluorochemical abhesive material available as a 30% aqueous solution from 3M Company, St. Paul, MN.
  • Tinapol PT-150 is an optical brightener available from Ciba-Geigy, Inc., Ardsley, NY. It is an aqueous solution containing 28% solids.
  • Nalco 7569 is a defoamer available from Nalco Company, Naperville, IL. It is 100% active liquid.
  • Nalco 1140 is a colloidal silica solution containing 40% silica and is also available from Nalco Corp., Naperville IL.
  • Amount of Silica weight of material (gm) 0.0% 0.1% 0.5% 2.5% 5.0% water 5,927 5,912 5,852 5,552 5,177 FC-829 sol'n 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34 34
  • the weight percent silica of the total solids is the same as the weight percent silica in the dried coating.
  • the coating weights were: 0.0% silica .012 pounds per ream 0.1% silica .016 pounds per ream 0.5% silica .025 pounds per ream 2.5% silica .068 pounds per ream 5.0% silica .143 pounds per ream
  • the coated CB sheet was made into 2-part set using a CF sheet available from the Carbonless Products Department of 3M Company, St Paul, MN under the name of "3M Blue Purple CF". This sheet is coated with a pad coat that does not contain colloidal material.
  • the coefficient of friction of the CB pc surface was measured against CF pc surface which did not contain colloidal particles.
  • the adhesion and fan apart were measured as described above. Results of the evaluation, shown in Table 2, demonstrate an increase in both coefficient of friction and surface energy of the contacting surfaces. Fan apart and bond strength measurements demonstrate that addition of colloidal particles to the pad coat has little effect on these form-set properties.
  • the CF and CB sheets prepared as in Examples 1 and 2 were used to prepare precollated 2-part form sets. These sets have only CB/CF and CB pc /CF pc interfaces.
  • the sheets were imaged in a Xerox Model 1090 electrophotographic copier which uses pressure belts for feeding paper into the copier.
  • the sheets were mated such that the level of colloid loading was the same. That is, each CF pc and CB pc had the same colloid and same percent colloid.
  • the coefficient of friction between the CF pc and CB pc faces were measured.
  • the stack was padded and tested for fan-apart and bond strength. Results are shown in Table 3.
  • Smudging results from CB capsule rupture during paper feed and subsequent color-former transfer to a CF developer sheet. Capsule rupture is caused by the feed mechanism (such as a belt or roller) sliding across the paper rather than smoothly feeding the paper into the photocopier or printing press. Smudging results from coefficient of friction mismatch between consecutive sheets of paper and is caused by dragging the CF sheet over the CB sheet. This commonly takes place under the force of the retard roller and nip rollers of the feed mechanism.
  • CF pc and CB pc pad coat solutions were prepared as in Examples 1 and 2 with three different colloidal silicas differing in particle size and surface areas. Static and Kinetic coefficient of friction measurements and fan apart, bond strength, knife rub, and toner adhesion tests were performed as described above. The results, shown below, indicate colloid size can be varied over a broad range to provide increased coefficient of friction without adversely affecting fan apart or bond strength.
  • Toner anchorage and smudge were also evaluated for the pad coats with the different sized colloids.
  • Pad coat formulations were prepared as described below. In these examples, the starch solution was 20% solids and the total weight of all coating formulations was 35 g. The formulations were mixed, stirred, and coated onto a 15 lb basis weight paper using a #8 Meyer rod. The coatings were dried by passing through a Pako heat roller at 250 °F (121 °C) for 2 min. Samples were left at 72 °F/50% relative humidity overnight. The coated CF pc side of the samples were tested against an identical CF pc sheet for static and kinetic coefficient of friction.
  • drawdown samples usually have a higher coefficient of friction than machine coated samples. This is due to the nature of coating technique.
  • Examples 11-14 demonstrate that binders in addition to starch are useful for preparing CF pad coats of the present invention (CF pc ).
  • Pad coat formulations were prepared as described below. In these examples, the binder solution was as indicated, and the total weight of all coating formulations was 50 g. The formulations were mixed, stirred and coated onto a 15 lb basis weight paper using a #8 wire wound rod (Meyer rod). The coatings were dried by passing through a Pako heat roller at 250 °F (121 °C) for 2 min. Samples were left at 72 °F/50% relative humidity overnight and tested for static and kinetic coefficient of friction.
  • the binder comprised 5% by weight of the coating solution.
  • the colloid used was Nalco 1030, a colloidal silica available from Nalco Chemical Co., Naperville, IL. It contains 30% SiO2 solids and has a particle size of 13 nm and a pH of 10.2. The amount of colloid added is indicated as a percent by weight of the coating solution.
  • the binders used were as follows:
  • GPA Oxidized Corn Starch was used as a 20% starch solution. It was prepared as indicated in Examples 5-9 above.
  • Dow 620 is a 50% solids styrene/butadiene latex from Dow Chemical Company, Midland MI.
  • Vinol 205 is a Polyvinyl Alcohol (PVA) available from Air Products Co., Allentown PA. It was made into a 16% solids solution by heating with stirring at 185°F (85°C).
  • Ecosol 45 is a phosphated wheat starch from Ogilvie Mills, Inc., Minnetonka, MN. It was made into a 10% solids solution by dissolving in water.
  • Example 11 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 37.58 37.08 36.33 35.08 FC-829 sol'n 0.68 0.68 0.68 0.68 Starch sol'n 11.74 11.74 11.74 Nalco 1030 sol'n 0.00 0.50 1.25 2.50
  • Example 12 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 44.32 43.82 43.07 41.82 FC-829 sol'n 0.68 0.68 0.68 0.68 Dow 620 latex 5.00 5.00 5.00 Nalco 1030 sol'n 0.00 0.50 1.25 2.50
  • Example 13 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 33.70 33.20 32.45 31.20 FC-829 sol'n 0.68 0.68 0.68 0.68 Vinol 205 15.63 15.63 15.63 Nalco 1030 sol'n 0.00 0.50 1.25 2.50
  • Example 14 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 24.32 23.82 23.07
  • Examples 15-17 were run as in Examples 11-14 above, except that the binder comprised 2% by weight of the coating solution.
  • the colloid used was again Nalco 1030 and the binders used were again GPA Oxidized Corn Starch, Vinol 205 Polyvinyl Alcohol (PVA), and Ecosol 45 phosphated wheat starch.
  • PVA Polyvinyl Alcohol
  • Example 15 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 44.32 43.82 43.07 41.82 FC-829 sol'n 0.68 0.68 0.68 0.68 Starch sol'n 5.00 5.00 5.00 Nalco 10301 0.00 0.50 1.25 2.50
  • Example 16 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 43.07 42.57 41.82 40.57 FC-829 sol'n 0.68 0.68 0.68 0.68 0.68 Vinol 205 6.25 6.25 6.25 Nalco 10301 0.00 0.50 1.25 2.50
  • Example 17 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 39.32 38.82 38.07 36.82 FC-829 sol'n 0.68 0.68 0.68 0.68 Ecosol 45 10.00 10.00 10.00 10.00 Nalco 1030 0.00 0.50 1.25 2.50
  • Examples 18 and 19 were run as in Examples 11-14 above, except that the binder comprised 10% by weight of the coating solution.
  • the colloid used was again Nalco 1030 and the binders used were GPA Oxidized Corn Starch, and Vinol 205 Polyvinyl Alcohol (PVA).
  • Example 18 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 24.32 23.82 23.07 21.82 FC-829 sol'n 0.68 0.68 0.68 0.68 Starch sol'n 25.00 25.00 25.00 25.00 Nalco 1030 0.00 0.50 1.25 2.50
  • Example 19 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 18.07 17.57 16.82 15.57 FC-829 sol'n 0.68 0.68 0.68 0.68 Vinol 205 31.25 31.25 31.25 31.25 Nalco 1030 0.00 0.50 1.25 2.50
  • Example 20 was run as in Examples 11-14 above, except that the binder was Ecosol 45 phosphated wheat starch and comprised 8% by weight of the coating solution.
  • the colloid used was Nalco 1030. weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 9.32 8.82 8.07 6.82 FC-829 sol'n 0.68 0.68 0.68 0.68 Ecosol 45 40.00 40.00 40.00 Nalco 1030 0.00 0.50 1.25 2.50
  • Example 21 and 22 were run as in Examples 11-14 above, except that in Example 21 the binder was Dow 620 Latex and comprised 1% by weight of the coating solution and in Example 22 the binder was Dow 620 styrene/butadiene latex and comprised 2.5% by weight of the coating solution.
  • the colloid used was Nalco 1030.
  • Example 21 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 48.32 47.82 47.07 45.82 FC-829 sol'n 0.68 0.68 0.68 0.68 Dow 620 latex 1.00 1.00 1.00 1.00 Nalco 1030 0.00 0.50 1.25 2.50
  • Example 22 weight of material gm Colloid Level 0% 0.3% 0.75 1.5% Water 46.82 46.32 45.57 44.32 FC-829 sol'n 0.68 0.68 0.68 0.68 Dow 620 latex 2.50 2.50 2.50 2.50 2.50 2.50 2.50 Nalco 1030 0.00 0.50 1.25 2.50
  • Examples 23-26 demonstrate the use of silicone abhesives for pad-coatings (pad-coats) for carbonless papers.
  • the silicone system used as an abhesive for evaluation in Examples 23-26 was silicone PC 104 in conjunction with catalyst designated PC 60 and crosslinker PC 31. All are availible from Rhone-Poulenc.
  • PC 104 is beleived to be a polydimethyl siloxane.
  • PC 31 is believed to be a silane hydride crosslinker.
  • PC 60 is believed to be a platinum catalyst. These materials are provided as an emulsion in water at about 40% solids and are very convenient for preparing pad-coats.
  • the effect of adding colloidal particles to a silicone abhesive was determined by measuring and comparing coefficient of friction and fan-apart of a pad-coat formulation made without colloidal particles with a pad-coat formulation made with colloid particles added.
  • a pad-coat solution was prepared by first preparing a solution of a polymer thickener in water.
  • the polymer thickener gives the coating solution good coating properties.
  • Water soluble polymers such as starch, hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), sodium alginate, and polyvinyl alcohol may be used.
  • a 0.75% polymer thickener solution was prepared by heating 198.5 grams of water to about 40°C and then adding 1.5 g of hydroxyethyl cellulose (Natrosol 250 HHR available from the Aqualon Company). The mixture became clear after stirring for 10 minutes; the many small suspended bubbles settled out overnight.
  • Other concentrations of polymer thickener solutions were prepared in a similar manner.
  • Pad-coat solutions were prepared by adding various amounts of polymer thickener solution to the PC 104 in a beaker, then adding the water. PC 31 was added, followed by the PC 60. The mixture was stirred slowly to avoid incorporation of air for about 30 minutes. The solutions were coated on 15 pound basis weight paper with a #8 Meyer rod and dried in a forced air oven at 250°F (121°C) for two minutes. In all, 5 pad-coated papers were made. Fan-apart and coefficient of friction were measured for each coating.
  • the thickener was added to the silicone (PC 104), followed by additional water, colloid, silicone catalyst (PC 31) and crosslinker (PC 60).
  • the concentration of hydroxyethyl cellulose (HEC) thickener was 0.5% in water.
  • Pad-coat solutions were prepared as in Example 23 above.
  • Table 10 demonstrates the effect of colloid addition on pad-coat properties. Addition of colloid is seen to increase toner adhesion while improving both coefficient of friction and fan-apart. In all samples, 2.0% silicone was present in the pad-coat formulation. As shown in samples B and C , at 2-3% colloidal silica good coefficient of friction is achieved while maintaining satisfactory fan-apart. In these experiments, fan-apart was measured with the pad-coated surface mated against bond paper. This results in a lower fan-apart than if two pad-coated surfaces were in contact. This is due to the fan-out adhesive bonding to the outer face of the bond paper. A more satisfactory fan-apart would be expected to result at about 1-2% colloidal silica if both mating surfaces were pad-coated.
  • the choice of thickener will have an effect on the properties of the fan-apart, the coefficient of friction and the toner powder adhesion.
  • the fan-apart as measured between the pad-coat and a 15# bond sheet is lower than would result if two pad-coated sheets were mated.
  • the low coefficient of friction for the starch thickened coating indicates more colloid is needed to obtain a satisfactory result, and the toner adhesion results would also be improved by making this adjustment.
  • the fluorochemical abherent provides better performance, however it should be noted that the silicone abherent was selected as being representative of the class and may well not be the optimum material for this application.
  • Table 13 Comparison of Silicone and Fluorochemical Abherents Silicone Abherent Fluorochemical Abherent Wt% abherent 2.0 0.6 Fan-apart 2.5 3.5 COF 0.55 0.68 Low Tack Tape test 85.% 10.%

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Publication number Priority date Publication date Assignee Title
US5991588A (en) * 1994-04-12 1999-11-23 Imation Corp. Electrophotographic transfer process for transferring toner image onto carbonless paper
EP1960601B2 (de) † 2005-12-14 2015-05-06 BASF Performance Products plc Papierherstellungsverfahren

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US3738957A (en) * 1971-03-18 1973-06-12 Du Pont Coacervates of polyvinyl alcohol and colloidal silica
US3949148A (en) * 1973-11-15 1976-04-06 Xerox Corporation Transparency for multi-color electrostatic copying
JPS5895745A (ja) * 1981-12-02 1983-06-07 Sanyo Kokusaku Pulp Co Ltd 複写用紙製造法
US5092927A (en) * 1988-06-14 1992-03-03 Nekoosa Papers, Inc. Pad coating for carbonless paper products

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US3738957A (en) * 1971-03-18 1973-06-12 Du Pont Coacervates of polyvinyl alcohol and colloidal silica
US3949148A (en) * 1973-11-15 1976-04-06 Xerox Corporation Transparency for multi-color electrostatic copying
JPS5895745A (ja) * 1981-12-02 1983-06-07 Sanyo Kokusaku Pulp Co Ltd 複写用紙製造法
US5092927A (en) * 1988-06-14 1992-03-03 Nekoosa Papers, Inc. Pad coating for carbonless paper products

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5991588A (en) * 1994-04-12 1999-11-23 Imation Corp. Electrophotographic transfer process for transferring toner image onto carbonless paper
EP1960601B2 (de) † 2005-12-14 2015-05-06 BASF Performance Products plc Papierherstellungsverfahren

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EP0569285B1 (de) 1997-07-30
EP0569285A3 (en) 1994-06-01
CA2094004A1 (en) 1993-11-05
DE69312564T2 (de) 1998-02-05
DE69312564D1 (de) 1997-09-04

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