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WO1999039914A1 - Feuille pour encrage - Google Patents

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Publication number
WO1999039914A1
WO1999039914A1 PCT/US1999/000870 US9900870W WO9939914A1 WO 1999039914 A1 WO1999039914 A1 WO 1999039914A1 US 9900870 W US9900870 W US 9900870W WO 9939914 A1 WO9939914 A1 WO 9939914A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
multipurpose
latex
monomer
sheet according
Prior art date
Application number
PCT/US1999/000870
Other languages
English (en)
Inventor
Mahfuza B. Ali
Charles M. Leir
Andrew C. Lottes
Manisha Sarkar
Donald J. Williams
Original Assignee
Minnesota Mining And Manufacturing Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining And Manufacturing Company filed Critical Minnesota Mining And Manufacturing Company
Publication of WO1999039914A1 publication Critical patent/WO1999039914A1/fr

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Classifications

    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/0013—Inorganic components thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/0033—Natural products or derivatives thereof, e.g. cellulose, proteins
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/004—Organic components thereof being macromolecular obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G7/00—Selection of materials for use in image-receiving members, i.e. for reversal by physical contact; Manufacture thereof
    • G03G7/0006—Cover layers for image-receiving members; Strippable coversheets
    • G03G7/002—Organic components thereof
    • G03G7/0026—Organic components thereof being macromolecular
    • G03G7/0046—Organic components thereof being macromolecular obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5281—Polyurethanes or polyureas
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/529—Macromolecular coatings characterised by the use of fluorine- or silicon-containing organic compounds

Definitions

  • the invention relates to materials that are useful as ink-receptive sheets for imaging, especially transparent materials having ink-receptive layers which exhibit improved curl and mordant properties.
  • Imaging devices such as ink jet printers and pen plotters are established methods for printing various information including labels and multi-color graphics. Presentation of such information has created a demand for ink-receptive imageable sheets useful for commercial graphics, and for transparent ink receptive imageable receptors that are useful as overlays in technical drawings and as transparencies for overhead projection. Imaging with either the ink jet printer or the pen plotter involves depositing ink on the surface of these receptors. These imaging devices conventionally utilize inks that can remain exposed to air for long periods of time without drying out.
  • compositions useful as liquid-absorbent receptors have been formed by blending and coating a liquid-soluble polymeric material with a liquid-insoluble polymeric material.
  • a liquid-soluble polymeric material for example, U.S. Patent No.
  • 4,371,582 discloses an ink jet recording sheet having an ink receptive layer containing a basic latex polymer and other water soluble polymers such as gelatin wherein the latex preferably includes at least 10 mol% of a copolymerizable monomer having a tertamino or a quaternary ammonium group.
  • U.S. Patent No. 4,578,285 discloses an ink jet printing sheet with a transparent support bearing a layer containing a major proportion of a polyurethane latex and a minor proportion of a water soluble polymer.
  • U.S. Patent No. 4,849,286 discloses a plotter film having an ink receptive coating comprising from 40 to 65 percent by weight of a polyurethane latex.
  • Many basic polymers may be included in ink receptive layers for ink jet recording, as well as basic nonpolymeric materials.
  • U.S. Patent No. 5,589,269 discloses a polymeric mordant containing, as an active entity, a guanidine function.
  • U.S. Patent No. 5,518,821 discloses an ink jet recording medium comprising a water-soluble quaternary ammonium polymer and compounds and polymers containing multiple hydroxy groups.
  • U.S. Patent No. 4,554,181 discloses an ink jet recording sheet containing a combination of a water soluble polyvalent metal salt and a cationic polymer, the cationic groups being present for the insolubilization of an anionic dye such as is likely to be present in an ink jet ink.
  • insolubilization may be considered to be equivalent to the term "mordanting”. It is generally believed that the anionic dyes present ink jet inks form a salt with the quaternary ammonium entity that is either water insoluble or of such a large size that diffusion in the polymeric matrix is reduced or eliminated.
  • U.S. Patent No. 4,740,420 claims a recording medium for ink-jet printing that contains a cationic organic material selected from the classes of alkyl amines, quaternary ammonium salts and polyamines.
  • European Patent Application 0 767 071 -A discloses an ink jet recording sheet containing a pigment and a binder, the binder being a self-emulsifying cationic resin consisting of essentially of at least one water-insoluble acrylic copolymer having cationic functional groups.
  • European Patent Application 0 763 433 A2 claims an ink jet recording medium containing at least one nitrogen-containing component.
  • the nitrogen-containing component is to be selected from poly(vinylpyrrolidone), polyimines, gelatins or quaternary polymers. It should be assumed that one or more of these nitrogen-containing entities can function at least partially as a mordant.
  • Inkjet recording media are also known to contain materials best described as plasticizers. These plasticizers are materials whose primary function is to control mechanical properties of the final film. By mechanical properties, it is meant those characteristics that do not influence image characteristics such as color brightness, bleed, and resolution.
  • a mechanical property of importance to the user of ink jet films is curl. Curl is regarded as undesirable in that films having this characteristic may not lay flat on the stage of an overhead projector, or may not be easy to store, or to feed into imaging devices such as printers. In extreme cases, films with humidity-dependent curl have been known to burst packaging. Small amounts of curl may be acceptable, if still generally undesirable.
  • U.S. Patent No. 5,006,407 selects plasticizers that in addition to those of U.S. Patent No. 5,118,570, include phosphates, substituted phthalic anhydrides, pyrrolidinones and others.
  • Japanese Kokai No. Sho 62[1987]-156984 discloses an ink-jet recording method using a recording material characterized by containing a compound that has both 3 or more hydroxy groups and a molecular weight of 500 or less on the recording surface. This material was disclosed to provide good ink absorbency dot shape and high resolution.
  • the material may be coated onto paper or synthetic film substrates.
  • other imaging devices such as laser printers and xerographic copying machines, and color copiers have differing requirements, such as heat resistance, toner adhesion, and image haze.
  • materials which are designed for use with one type of imaging device are frequently, if not useless with other imaging devices, less useful, having been optimized for one type of device. If imageable, the image may be of lesser quality, lesser resolution, lack shelf stability, etc.
  • Electrophotographic copying machines require materials for which the coefficient of friction must be controlled within a certain range. Very low Coefficients of Friction cause difficulty in handling, the sheets being too slippery. High Coefficients of Friction may prevent the top sheet of a stack being removed in the process of feeding. Thus the surface of the sheets are adjusted to be in an intermediate range. Such adjustment is most easily performed by the addition to the surface coating of a suitable particulate. A lubricant may also be included.
  • a cationic latex emulsion having less than 10 mol% of a copolymerizable monomer having a tertamino or a quaternary ammonium functionality, and an average particle size of from 50 nm to 400 nm provides an imageable coating with good imaging resolution, and reduced curl, along with quick drying properties.
  • an imageable coating is useful not only for ink-jet imaging but as a universal, or multipurpose imaging film, also useful with devices such as xerographic copiers, color laser copiers, laser printers and the like.
  • the invention provides a universal imaging material comprising at least one cationic latex emulsion having less than 10 mol% of a copolymerizable monomer having a tertamino or a quaternary ammonium functionality.
  • the invention further provides a universal imaging sheet comprising a substrate having two major surfaces, wherein at least one of such surfaces has coated thereon an imageable composition having been formed from at least one cationic latex emulsion having less than 10 mol% of a copolymerizable monomer having a tertamino or a quaternary ammonium functionality.
  • universal imaging materials of the invention comprise latex emulsions containing up to 10 mol % of a monomer possessing cationic or quaternary ammonium functionality, and which in addition may contain greater than 10 mol % of a monomer having hydroxy functionality.
  • the universal imaging sheet is formed in two stages.
  • the first stage is concerned with the synthesis of a specific cationic latex emulsion.
  • the second stage is concerned with the incorporation of the latex of the first stage into a formulation to be subsequently coated onto a suitable substrate.
  • Synthesis of the latex is achieved by formulating a premix of monomers intended as the components of the final polymer, together with an initiator. A small portion of this
  • premix is then added to a vessel containing water, a surfactant and more initiator.
  • the reaction vessel is heated until formation of a polymer emulsion starts, and then the remainder of the premix added over an extended time period.
  • the whole mixture may be maintained at a predetermined temperature for a suitable time period to ensure complete reaction of all monomers.
  • all the reactants should be degassed, and the entire reaction carried out in a nitrogen atmosphere.
  • the latex may be added to a solution of other suitable polymers, mixing carefully, followed by the addition of other materials such as additional mordants, surfactants, particulates, and if desired, pigments.
  • the final formulation may then be coated by any of a number of well-known techniques onto film base or other substrate, and the coated layer dried. The dried sheets may then be imaged in a wide variety of imaging devices.
  • synthetic latex means a latex formed by emulsion polymerization and having a small particle size; a true colloidal suspension.
  • emulsion means a stable mixture of two or more immiscible liquids held in suspension by small percentages of emulsifiers, and having a continuous phase and a disperse phase.
  • universal imaging material means a material which is imageable on a variety of types of imaging devices, including but not limited to inkjet, plain paper copier, colored and black/white laser printers and copiers, and is synonymous with "multipurpose”. The use of this term with regard to a material does not mean that the material will invariably be imageable on each and every imaging device, or type thereof commercially available or imaginable, but rather than it will provide quality images on more than one type of device.
  • cationic means having a net positive charge.
  • mudcrack is used in the industry, and refers to an image defect that appear under a mixroscope as a series of cracks in a solid image. This has an appearance similar to that seen when wet mud dries. It is thought to be caused by low cohesion of imaging layers.
  • mol% means wt % mol wt.
  • Latex emulsions are useful for a number of convenient reasons.
  • the conditions of reaction need not be overly severe, indeed many of the preparations may be carried out at or near room temperature, and pressurized reaction vessels may not be needed.
  • Water is the most widely-used reaction medium, providing a heat transfer means, that with reasonable reaction rates, may only necessitate the provision of a condenser system attached to the reaction vessel to ensure adequate cooling.
  • the final product being a suspension in a liquid, is easily transported, has a high concentration of polymer present and, due to the form of the polymer being in small particles dispersed in an aqueous medium, has a relatively low viscosity. Latex materials have proved valuable in such environmentally sensitive products as paints, where the high concentration of polymer, in an innocuous carrier vehicle, has resulted in a superior and widely-used product.
  • the form of the polymer particles in a latex emulsion is generally spherical with mean particle sizes of below 500 nanometers. Suspensions containing particle sizes in this range, i.e. below the wavelength of light are nearly or completely transparent.
  • one monitoring means used during the early part of the polymerization reaction is to look for the appearance of a slight blue coloration to the reaction bulk. This indicates that particulate is forming at approximately the correct particle size.
  • a colloidal suspension of a monomer is generated in an aqueous medium by agitating a liquid monomer and a surfactant with water.
  • the surfactant enables the monomer to be dispersed as very fine globules of liquid, and the presence of an initiator causes polymerization of each globule independent of other globules.
  • the result is to generate a dispersion in water of very small polymer particles. Size of the solid particles may be much less than that of the liquid monomer globules, and it may be hypothesized that on polymerization of the monomer, the formed polymer is rendered insoluble in the monomer, and is ejected from the original globule into the aqueous environment where it is stabilized by the surfactant.
  • Size may be quite variable, but typical particle diameters are 50-400 nanometers, preferably from 50 to 150, more preferably from 75 to 125 nm. Particles are preferred for this invention that are considerably below the wavelength of light, as these particles scatter only a minimum of light resulting in clear coatings.
  • -6- A wide variety of monomers may be used as starting materials for latex emulsion manufacture.
  • Vinyl monomers such as vinyl acetate, vinyl butyrate, vinyl chloride, and the like may be employed as components of latex emulsions, as may urethane monomers, acrylate monomers and many others.
  • acrylate monomers such as ethyl acrylate, methyl acrylate, butyl acrylate, methyl methacrylate, hydroxypropyl acrylate, hydroxyethyl acrylate, and quaternary salts of dimethylaminoethyl acrylate.
  • a key feature of this invention is the presence in the latex emulsion of quaternary nitrogen entities. These are present as a positively charged quadruple-bonded nitrogen atom, and associated therewith a negatively-charged counter ion. These may be selected from a wide variety of anionic entities, for example chloride and other halide ions, sulfate ions, phosphate ions, organic acid ion, such as acetic and propionic, ions combining both traditionally organic entities and traditionally inorganic entities in combination such as methyl sulfate ions and the like.
  • anionic entities for example chloride and other halide ions, sulfate ions, phosphate ions, organic acid ion, such as acetic and propionic, ions combining both traditionally organic entities and traditionally inorganic entities in combination such as methyl sulfate ions and the like.
  • Cross linking may also be employed to improve layer strength either covalently or ionically. Such constructions give rise to highly effective coatings, possessing rapid water-absorption characteristics, but also having excellent wet strength.
  • mordant a material designed to react with the dyes contained in the ink and render them non-diffusing. Diffusion of the dyes after imaging results in the spreading of colors from one area to another, often seen as apparent broadening of fine lines during storage. Such effects are often amplified by storage in high humidity and temperature conditions.
  • mordants are known to dye technology. Inorganic oxides, hydroxides and salts may be used, and their mode of action is predicated on their ability to react with water soluble dyes, to form what are described in the textile industry as "lakes", these generally being considered to be the inorganic salt of a dye.
  • the inks employed in ink jet printing generally contain organic dyes rendered water soluble by the incorporation in the dye structure of an acid function, a preferred acid function being a sulfonic acid group.
  • a preferred acid function being a sulfonic acid group.
  • One or more of these acid groups attached to an organic dye may render it sufficiently soluble in water to render the dye suitable for formulating an aqueous ink.
  • Incorporation of the sulfonic acid group in the dye structure is not the only way in which a dye may be rendered more water soluble.
  • Carboxylic acid groups can perform a similar function, as may quaternary ammonium groups, or hydroxy groups.
  • Sulfonic acid groups have found considerable favor in ink jet inks, and accordingly coatings have been formulated containing components specifically selected to react with the sulfonic acid-containing dyes.
  • Alumina and aluminum hydroxides have been used as mordants, as being relatively innocuous materials, as have salts of long alkyl-chain quaternary ammonium compounds, and polymeric quaternary ammonium compounds.
  • mordant that has found particular favor in the compositions of this invention, is disclosed in U.S. Patent Number 5,342,688. This patent describes a family of mordants based around a polymer having multiple guanidine functionalities.
  • Imageable coatings may beneficially contain other components, including, for example, plasticizers, surfactants and particulates.
  • Plasticizers found particularly beneficial for the constructions of this invention include polyhydroxy materials exemplified by xylitol, glycerol, mannitol, pentaerythritol gluconic acid and trimethylol propane. Surfactants may be added to aid both the coating process and the ink wetting and distribution properties of the final product.
  • surfactants and wetting agents are those containing fluorocarbon functions, for example Zonyl FSO 100 (CAS # 65545-80-4) made by DuPont Company, and having a CA index name of poly(oxy-l,2- ethanedial), .alpha.-hydro-.omega.-hydroxy-, ether with .alpha.-fluoro-omega.-(2- hydroxy ethy l)poly (difluoromethylene) (1 :1).
  • fluorocarbon functions for example Zonyl FSO 100 (CAS # 65545-80-4) made by DuPont Company, and having a CA index name of poly(oxy-l,2- ethanedial), .alpha.-hydro-.omega.-hydroxy-, ether with .alpha.-fluoro-omega.-(2- hydroxy ethy l)poly (difluoromethylene) (1 :1).
  • Particulates found useful in these constructions include polymeric microspheres or beads including poly(methyl methacrylate) beads and other made by the methods of U.S. Pat. No. 5,238,736.
  • Coating methods for materials of this type include knife coating, wire bar coating, gravure coating, extrusion coating and any process suitable for coating layers of the required thickness.
  • While the practice of this invention is primarily directed towards receptor coatings for inks, the universal features of this invention make it suitable for use with other imaging processes.
  • imaging processes is to be included electrophotographic methods, as embodied in the copier products of the, among others, Xerox Company, and the Laser Printer products of many companies, for example those of the Hewlett Packard Company and Canon, Inc. These processes function by the photo-initiated removal of electrostatic charge from the surface of a photoconductor, and by using the remaining charge to attract an appropriately-charged toner powder. An image-wise distribution of colored or black toner powder is achieved, which is then transferred by any one of a number of means to a receptor sheet.
  • Fusing may be by means of pressure, solvent vapor, heat or the presently preferred method of heating under moderate pressure. It can be argued that the requirements for successful fusing depend on the development of adhesion of the toner to the receptor sheet, rather than by the absorption into the bulk of the layer of a dyestuff carried by a solvent. Mechanisms for toner adhesion to a receptor sheet include, compatibility and intermixing of the toner and
  • toner receptive coatings such as those embodied by U.S. Patent Nos. 5,310,595 and 5,310,591, coatings tailored specifically for toner adhesion under heat and mild pressure are disclosed, and may use the core-shell components disclosed in U. S. Patent No. 5,500,457. These are coatings designed to promote adhesion and have little or no capacity for absorption of inks. Such materials function poorly as ink jet receptor films.
  • the practice of the invention may be divided into two stages, which may be separate in both space and time; the formation of the latex and the making and coating of the imageable coating onto a substrate.
  • the latex emulsion made in the first stage is stable for a considerable period of time, so that it may be manufactured at some convenient facility and if needed shipped to a second facility and stored until it is needed for the second stage of practice of the invention.
  • the two stages will be described sequentially in detail.
  • a glass vessel is charged with distilled or deionized water, a chosen mixture of monomers, a surfactant and an initiator. This mixture is then vigorously stirred to create droplets of globules of monomer. At the end of this stage, further monomer and initiator may be added and the vessel heated to initiate the polymerization step. At the commencement of this step, additional monomer mix may be added over an extended period, and when complete the whole may be maintained at the chosen temperature for several hours to ensure complete reaction. The contents of the reaction vessel are then cooled and the finished latex emulsion decanted for storage or shipment.
  • the transparent film substrate is preferably formed from any polymer capable of forming a self-supporting sheet, e.g., films of cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof.
  • cellulose esters such as cellulose triacetate or diacetate, polystyrene, polyamides, vinyl chloride polymers and copolymers, polyolefin and polyallomer polymers and copolymers, polysulphones, polycarbonates, polyesters, and blends thereof.
  • Suitable films may be produced from polyesters obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to about 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2,5-, 2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, with one or more glycols such as ethylene glycol, 1,3- propanediol, 1 ,4-butanediol, and the like.
  • dicarboxylic acids or their lower alkyl diesters in which the alkyl group contains up to about 6 carbon atoms, e.g., terephthalic acid, isophthalic, phthalic, 2,5-, 2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid
  • Preferred film substrates or backings are cellulose triacetate or cellulose diacetate, poly(ethylene naphthalate), polyesters, especially poly(ethylene terephthalate), and polystyrene films. Poly(ethylene terephthalate) is most preferred. It is preferred that film substrates have a caliper ranging from 50 ⁇ m to 200 ⁇ m. Film substrates having a caliper of less than 50 ⁇ m are difficult to handle using conventional methods for graphic materials. Film substrates having calipers over 200 ⁇ m are stiffer, and present feeding difficulties in certain commercially available ink jet printers and pen plotters.
  • polyester film substrates When polyester film substrates are used, they can be biaxially oriented to impart molecular orientation, and may also be heat set for dimensional stability during fusion of the image to the support. These films may be produced by any conventional extrusion method.
  • the substrate may be opaque or transparent; a normally transparent film forming polymeric material may be rendered opaque by the addition of a pigment such as talc,
  • paper substrates are less preferred; however, they may be used if desired.
  • Useful primers include those known to have a swelling effect on a film substrate polymer. Examples include halogenated phenols dissolved in organic solvents.
  • the surface of the film backing may be modified by treatment such as corona treatment or plasma treatment.
  • the primer layer when used, should be relatively thin, preferably less than 2 micrometers, most preferably less than 1 micrometer, and may be coated by conventional coating methods.
  • Transparencies of the invention are particularly useful in the production of imaged transparencies for viewing in a transmission mode, e.g., in association with an overhead proj ector .
  • Curl at 15°C and 20% Relative Humidity is measured by placing a sheet of film in a controlled environment chamber at the conditions mentioned previously, and allowing it to remain there for 24 hours. The film sample is then taken to a controlled environment chamber at 24°C and 50% Relative Humidity, and placed on a horizontal surface. After 30 seconds, the height in millimeters above the surface is measured for each corner, and an average calculated This measurement is repeated at 1, 2, 3, and 4 minutes, and the largest average recorded is reported as the Curl.
  • 80% Relative Humidity is measured in controlled environment chambers set to those conditions.
  • a 3M model 9550 overhead projector is allowed to run for 30 minutes, by which time the stage will have attained an equilibrium temperature.
  • a sheet of unimaged film, imageable side up, is placed on the projector stage, and after one minute the height
  • Toner Adhesion Crease Method Toner adhesion was measured by a test that consists of folding a solid black image area 180 degrees down the center, with the toner image on the outside of the fold, rolling the fold 3 times with a one kilogram rubber roller, and rubbing the crease line with a paper towel. Toner is removed from the crease line, and the width of the removed toner area is a measure of the adhesion of the toner to the coating. When compared to a product specifically formulated for use in a Plain Paper copier similar toner adhesion values were obtained.
  • Example 1 This example discloses the synthesis of a multi-monomer cationic latex polymer. Three monomers were used for this synthesis: ethyl acrylate, (“EA”), (CAS # 140-88-5), Hydroxypropyl acrylate (“HP A”), (CAS # 25584-83-2) and dimethylaminoethyl acrylate methyl chloride quaternary (referred to as "FA”). All quantities will be given as parts by weight unless otherwise stated.
  • EA ethyl acrylate
  • HP A Hydroxypropyl acrylate
  • FA dimethylaminoethyl acrylate methyl chloride quaternary
  • a reaction vessel was fitted with a condenser, a thermometer, a dropping funnel, a mechanical stirrer and a nitrogen purging system.
  • To this vessel was added 393 parts of deionized water, 5 parts of cetyl trimethyl ammonium chloride (as a 25% solution in water) and 0.4 parts of V-50.
  • V-50 is an initiator supplied by Wako Chemicals USA Inc., and is 2,2'-azobis(2-amidinopropane) dihydrochloride, CAS # 2997-92-4. The solution was left to stir at 300 rpm.
  • a pre-mix of 66 parts of ethyl acrylate, 30 parts of hydroxypropyl acrylate, 5 parts of dimethylaminoethyl acrylate methyl chloride quaternary (as 80% solids in water) and 0.4 parts of V-50 was made. 10 parts of this pre-mix were added to the reaction vessel, and the vessel contents heated to 50 C C. A bluish coloration appeared indicating the formation of a latex emulsion. The remainder of the pre-mix was added over a period of 2 hours. The reaction mixture was then maintained at the same temperature for a further 4 hours. The reaction was carried out under a steady purge of nitrogen gas. Completion of the reaction was monitored by
  • Example 2 A series of latex emulsion polymers was made by the method of Example 1. The respective compositions are shown in Table 1 below.
  • DMAEMA-C 16 is Dimethylaminoethyl methacrylate hexadecyl chloride quaternary.
  • 2b contains no quatemizable monomers, but may contain some cetyl trimethyl ammonium chloride.
  • Table 2 gives monomer ratios by mol%.
  • Emulsion #2a was selected for examination in a coating.
  • the various components were first made up into pre-mixes, and quantities of the pre-mixes combined to make the final coating solution.
  • Methocel® K-35 made by Dow Chemical Company; 14%) by weight aqueous solution of a mordant in water, having the following formula;
  • a coating was made of the above formulation, with no addition of a latex emulsion, to produce a coating weight of about 9 g/m 2 .
  • the coating was made on primed polyester film base, having a caliper of 100 microns. This coating served as a control.
  • All coatings had an approximate dry coating weight of 9 g/m 2 .
  • Mudcracking is an image defect that appear under a microscope as a series of cracks in a solid image. It is evaluated visually; a zero value indicates that the defect is not present.
  • Curl was measured under three conditions: 21°C and 50% relative humidity (RH), 35°C and 80% RH, and 18°C and 20% RH.
  • RH relative humidity
  • a low number represents a low degree of Curl, low Curl being desirable.
  • the first set of conditions are those likely to be found in an average office environment, the second set of conditions are representative of tropical environments, and are the most severe conditions likely to be found where ink jet printers are in use, and the third set of conditions may be found in latitudes where winters are cold, resulting in very low humidities.
  • the tropical condition is the one where a coating of this type may be expected to have absorbed much water from the atmosphere, and the winter climate condition where the coating may be expected to have absorbed the least. Under all conditions, an increased quantity of the cationic latex emulsion leads to decreased curl.
  • Example 4 A similar coating to the above was made using a commercially-available cationic resin, i.e., Witcobond W-213, available from the Witco Corporation as a 40% latex emulsion in water. It is described as an "aliphatic urethane with surface cationic functions". The exact chemical nature of this material is not revealed. It was diluted
  • Dispal® 23N4 (alumina dispersion) 35.00 % parts by weigh
  • Methocel® K-35 (cellulose ; derivative) 39.20
  • Witco W-213 (cationic urethane latex) 9.80
  • This formulation was coated at 10% by weight solids at a nominal wet coating thickness of 150 microns, yielding a dry coating weight of 15 g/square meter.
  • This coating was imaged in HP Deskjet 500 printer and gave bright color images, with acceptable dry times. There was only a small degree of curl present.
  • Example 5 A coating was made according to the formulation given in Table 8.
  • This formulation was coated out of water onto 100 micron glossy opaque polyester film using an extrusion coating method to a dry coating weight of 9 g/m 2 .
  • the resulting coating was dried in an air-impingement oven, and converted to 8 1/2 x 11 inch sheets. These sheets were imaged in a Hewlett Packard 870 ink jet printer and in a
  • Example 6 This example shows alternative chemistry for the cationic latex emulsion, namely the use of a cross-linker.
  • This formulation was coated out of water onto 100 micron Polyester film base using an extrusion coating method to a dry coating thickness of 9 microns.
  • the coatings were imaged in HP 690, HP870, Canon BJC-620 and Epson 800 ink jet printers. All printers yielded high-quality color images, suitable for projection on an overhead projector.
  • This example shows alternative chemistry for the cationic latex emulsion, namely the use of a polymer made with acrylic acid (AA) as a monomer according to the method of Example 1.
  • the final composition of this polymer was Ethyl acrylate/Hydroxypropyl
  • Example 8 This example shows alternative chemistry for the cationic latex emulsion, except that a heat-activated cross-linker is incorporated in the latex emulsion.
  • the particular crosslinker used in this example is N-methylol acrylamide (NMA), used in the proportions by weight 64/30/4/2, corresponding to ethyl acrylate/hydroxypropyl acrylate/F A/NMA. It was incorporated in a formulation as shown in Table 11.
  • NMA N-methylol acrylamide
  • This formulation was coated onto 100 micron Polyester film using a knife coater, at a wet coating thickness of 100 microns.
  • the final dry coating thickness was approximately 10 microns.
  • the coating was imaged in a Hewlett-Packard 870 and Canon 620 ink jet printers and yielded bright colorful images of good transparency.
  • Example 9 This Example demonstrates the use of alternative water-soluble resins in combination with the latexes of this invention.
  • 9a illustrates the use of a hydroxypropyl methyl cellulose
  • 9b the use of polyvinyl pyrrolidone (PVP)
  • 9c the use of these two polymers in combination.
  • Formulation composition is given in Table 12.
  • Example 10 A composition found to give particularly acceptable results in inkjet printers is described by Table 13. It was evaluated in an electrophotographic printer, illustrating the versatility of this composition.
  • Emulsion (2a from Example 2) 9.8
  • This formulation was coated by an extrusion bar method onto either white opaque 100 micron film, or onto 100 micron transparent film. Coatings were dried in an impingement oven and evaluated by imaging in a Hewlett Packard Color Laserjet® 5M printer. This is an electrophotographic printer, whereas printers used in previous examples were based on the inkjet printing process.
  • the coating on white opaque film gave reflection color densities, measured by a Macbeth TR 924 densitometer as shown in Table 14, and the coating on transparent film gave density values, measured with the same instrument, also shown in Table 14!
  • Example 11 This example illustrates the use of the transparent film described in Example 10 in a black and white office copier.
  • a sheet of the transparent material of Example 10 was imaged in a Xerox 1090 Office Copier. Viewed on an overhead projector, the image was of good contrast.
  • -22- Toner adhesion was measured by a test that consists of folding a solid black image area 180 degrees down the center, with the toner image on the outside of the fold, rolling the fold 3 times with a one kilogram rubber roller, and rubbing the crease line with a paper towel. Toner is removed from the crease line, and the width of the removed toner area is a measure of the adhesion of the toner to the coating. When compared to a product specificall formulated for use in a Plain Paper copier similar toner adhesion values were obtained. Width in all samples was less than 1 mm, indicating good adhesion.
  • Example 12 This example illustrates the use of the transparent film described in Example 10 as a write-on film.
  • a sheet of the transparent material generated in Example 10 was used as the material for a hand- written overhead visual. It was found to be receptive to both pencil and the pens used for transparency marking. In the case of the marking pen, drying was sufficiently fast that a few seconds after application of the ink, the image could not be smeared by finger pressure.
  • Example 13 This example illustrates the use of latex emulsions which do not contain hydroxypropyl acrylate, but which instead contain A- 174 (3-(trimethoxysilyl) propyl methacrylate).
  • Table 15 details the percentage parts by weight of the monomer used to synthesize the emulsion latex. Otherwise the synthetic method was as outlined in Example 1.
  • each of the above latex emulsions, 13 a to 13e, were formulated in a coating similar to that of Example 10, except that latex emulsion 2a was replaced successively by latex emulsions 13a to 13e.
  • the coating weight of the dried coatings averaged about 9 g/m 2 .
  • Coatings were imaged in a Hewlett Packard 870C inkjet printer, and in a Canon BJC620 inkjet printer, and the color densities measured with a Macbeth TR 924 Densitometer. Tables 16 and 17 shown the measured densities from the Hewlett Packard and Canon printers respectively.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)

Abstract

L'invention concerne une feuille pour la reproduction d'images qui possède un substrat recouvrant au moins un côté de la feuille et comportant un revêtement universel pour la reproduction d'images, formé à partir d'une émulsion de latex contenant jusqu'à 10 mole pour-cent d'un monomère à valence fonctionnelle de cations ou d'ammonium quaternaire. Le revêtement peut en outre comprendre plus de 10 mole pour-cent d'un monomère à valence fonctionnelle hydroxy.
PCT/US1999/000870 1998-02-04 1999-01-15 Feuille pour encrage WO1999039914A1 (fr)

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EP1132217A1 (fr) * 2000-03-09 2001-09-12 Eastman Kodak Company Elément pour l'enregistrement par jet d'encre contenant des particules enrobées
US6521325B1 (en) 1999-06-01 2003-02-18 3M Innovative Properties Company Optically transmissive microembossed receptor media
EP1288012A3 (fr) * 2001-08-31 2003-10-15 Eastman Kodak Company Elément pour impression par jet d'encre et procédé d'impression
EP1288008A3 (fr) * 2001-08-31 2003-10-15 Eastman Kodak Company Elément pour impression par jet d'encre et procédé d'impression
US6764725B2 (en) 2000-02-08 2004-07-20 3M Innovative Properties Company Ink fixing materials and methods of fixing ink
US6815020B2 (en) 2001-08-31 2004-11-09 Eastman Kodak Company Ink jet recording element
EP1522416A1 (fr) * 2003-10-08 2005-04-13 Fuji Photo Film Co., Ltd. Support d'information avec surface imprimable
EP1226969A3 (fr) * 2001-01-26 2005-06-01 Eastman Kodak Company Procédé d'impression au jet d'encre
US6974609B2 (en) 2000-02-08 2005-12-13 Engle Lori P Media for cold image transfer
WO2019097469A2 (fr) 2017-11-17 2019-05-23 3M Innovative Properties Company Couches réceptrices d'encre pour étiquettes durables
WO2020003188A2 (fr) 2018-06-29 2020-01-02 3M Innovative Properties Company Couches de réception d'encre pour étiquettes durables

Citations (3)

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Publication number Priority date Publication date Assignee Title
US5624743A (en) * 1996-02-26 1997-04-29 Xerox Corporation Ink jet transparencies
US5693410A (en) * 1996-09-03 1997-12-02 Xerox Corporation Ink jet transparencies
US5709976A (en) * 1996-06-03 1998-01-20 Xerox Corporation Coated papers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5624743A (en) * 1996-02-26 1997-04-29 Xerox Corporation Ink jet transparencies
US5709976A (en) * 1996-06-03 1998-01-20 Xerox Corporation Coated papers
US5693410A (en) * 1996-09-03 1997-12-02 Xerox Corporation Ink jet transparencies

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6521325B1 (en) 1999-06-01 2003-02-18 3M Innovative Properties Company Optically transmissive microembossed receptor media
US6913722B2 (en) 1999-06-01 2005-07-05 3M Innovative Properties Company Method of making an optically transparent inkjet printing medium
US7005162B2 (en) 2000-02-08 2006-02-28 3M Innovative Properties Company Methods of fixing ink
US6764725B2 (en) 2000-02-08 2004-07-20 3M Innovative Properties Company Ink fixing materials and methods of fixing ink
US6974609B2 (en) 2000-02-08 2005-12-13 Engle Lori P Media for cold image transfer
EP1132217A1 (fr) * 2000-03-09 2001-09-12 Eastman Kodak Company Elément pour l'enregistrement par jet d'encre contenant des particules enrobées
EP1226969A3 (fr) * 2001-01-26 2005-06-01 Eastman Kodak Company Procédé d'impression au jet d'encre
EP1288008A3 (fr) * 2001-08-31 2003-10-15 Eastman Kodak Company Elément pour impression par jet d'encre et procédé d'impression
US6815020B2 (en) 2001-08-31 2004-11-09 Eastman Kodak Company Ink jet recording element
EP1288012A3 (fr) * 2001-08-31 2003-10-15 Eastman Kodak Company Elément pour impression par jet d'encre et procédé d'impression
EP1522416A1 (fr) * 2003-10-08 2005-04-13 Fuji Photo Film Co., Ltd. Support d'information avec surface imprimable
WO2019097469A2 (fr) 2017-11-17 2019-05-23 3M Innovative Properties Company Couches réceptrices d'encre pour étiquettes durables
US11905429B2 (en) 2017-11-17 2024-02-20 3M Innovative Properties Company Ink-receptive layers for durable labels
WO2020003188A2 (fr) 2018-06-29 2020-01-02 3M Innovative Properties Company Couches de réception d'encre pour étiquettes durables
US12331213B2 (en) 2018-06-29 2025-06-17 3M Innovative Properties Company Ink-receptive layers for durable labels

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