MXPA97001762A - Sheet for printing with it jet - Google Patents

Abstract

This invention relates to a sheet for ink jet printing suitable for use in signaling, archiving and other applications comprising a plastic substrate, including a particulate one as a means to produce stain resistant images with inks for jet printing.

Description

SHEET FOR PRINTING WITH INK JET Technical Field This invention relates to sheets for inkjet printing, suitable for use in the marking application and in particular to a printing sheet having a release surface in contact with an adhesive layer. This invention is further related to a printing method using the printing sheet of this invention.

Background of the Invention Various suitable processes are known in the art to produce durable signs on exteriors, for example by the electrostatic printing process, receivers and transfer methods for signaling materials. These processes have produced useful materials in a variety of applications such as advertising, billboards, vehicle signage. However, they suffer from the disadvantage that the machinery requirements for those processes and articles are expensive and the REF: 24164 Machinery requires relatively high maintenance and skilled operators. The process of inkjet printing is now well known. The examples of those applications are: sno computer printers for the production of documents and transparencies for retroreproducers. Recently wide-format printers have become commercially available, therefore the printing of large items such as large engineering drawings, cyanographic copies and posters and color markings have become feasible. These printers are relatively expensive compared to many other devices that produce hard copies, for example digital electrostatic printers. However, : _5 printers have all the. usual advantages of devices that produce computer-managed print copies, wherein the image as a transparency or positive photographic print can be explored using the scanning devices known in the art, or stored on the computer disk, manipulated and printed, etc. Generally inkjet inks are wholly or partially water based and the receivers of these inks are typically flat papers or preferably ink jet receptive papers. specials, which are treated or coated to recover the receiving properties or the quality of the images resulting therefrom. Many ink jet receiving compositions suitable for applications such as overhead projector transparencies are known in the art. These are composed of transparent plastic materials such as polyester, which will not only accept aqueous inks and are coated with receptor layers. Pipically, these receptor layers are composed of mixtures of water-soluble polymers that can absorb the aqueous mixture of ink for ink-jet printing. Examples of inkjet receptor compositions used for transparencies for retroreflectors are disclosed in U.S. Patent No. 4,935,307 (Iqbal et al.); U.S. Patent No. 5,208,092 (Iqbal); U.S. Patent No. 5,342,688 (Kitchin et al.); and EPO Publication 0 484 016 Al. A common problem with ink jet images is the subsequent diffusion of the dyes, often particularly under bad hot and humid conditions. Therefore, many receiving materials contain portions that react with, or in other circumstances immobilize the dyes after printing. Alternative methods to avoid Diffusion of the dyes are modify the formulations of inta. Another disadvantage with many compositions for ink jet printing is the deviation of color or discoloration of the dyes in the images with the subsequent loss of archiving capacity, change in the quality of the image over time, and a time to life. Short for relatively high quality images in direct sunlight. This is not a problem in applications such as : "short-term signaling, for example for announcements or notifications." However, these disadvantages make images unsuitable for long-term applications such as archival prints or images and durable signage outdoors .5 Other materials for jet recording of ink are described in U.S. Patent No. 5,132,146 (Maruyama et al.) and U.S. Patent No. 5,302,437 (Idei et al.). ink jet that provide high density, low ink-shift images with dye-based inkjet inks and at the same time provide discoloration-resistant images with pigmented ink jet printing inks.

Summary of the Invention In brief, in one aspect of the present invention, there is provided a sheet for inkjet printing, comprising a substrate and a layer receiving the image in contact with the substrate, wherein the layer receiving the image is comprised of: at least one penetrating protective layer of a composition and at least one ink jet receiving layer of a second composition, and wherein _) both the protective penetrating layer and the ink jet receiving layer contain dispersed particles or particles of a size large enough to roughen both a surface of the protective penetrating layer and a surface of the receiving layer of the protective layer. .5 ink jet. Optionally, one side of the substrate opposite the layer receiving the image, in sequential order, is an adhesive layer and has a release liner. The sheet is useful in inkjet printing processes that are substrates that can be used in signage, archiving or other imaging applications. Advantageously, the layer receiving the image (whether comprised of a single layer or multiple layers) can be used with a wide variety of substrates, such as l- > Thermoplastic, thermosetting substrates, papers coated with plastic, fabrics, fabrics covered with elastic, thick or thin, provided that the substrates re covered are capable of being loaded in an ink jet printing system. The printed receiving sheet, either overlaminated with a protective or coated film or otherwise treated to provide a durable surface may be used for commercial signage, archiving or imaging applications. An advantage of the present invention is an ink jet printing sheet wherein the substrate and the adhesive are durable for periods of several years in an outdoor environment where the materials and images may be exposed to rain, sun, and variations in the temperature found in outdoor environments and on surfaces in outdoor environments. Typically, the article of the present invention has some flexibility so that it can adhere on surfaces that have some curvature or are not uniform for example walls or surfaces with screw heads or rivets, without easily tearing the material or cracking or delaminating the layers that receive the image, overlaminated layers, other coatings or "stretched" material on the projection. degrees of water resistance, protection When placed in the image against scratches, splashes and the like, a glossy finish may optionally be provided to the printed sheet, for example 2 overlaying a transparent protective layer. Finally, the articles of the present invention maintain other desirable properties of an ideal ink-jet printing sheet, such as dye-slip resistance and low background color. I also know -0 observe good saturation and color density in the printed images. Printed items do not excessively puff with exposure to moisture or during the ink jet printing process, and printed images exhibit fast ink drying times after _5 of printing with a good image definition. As used in this application: "colorant" means any substrate that imparts color to another material to be mixed and perhaps to dyes or pigments; "Durable" means that the substrates used in the present invention are capable of withstanding the wear and tear associated with the signs and can be from 2 to 5 years in outdoor environments; "plastic" means a material that is capable of being formed or molded with or without heat application and It includes thermoplastic types, thermosetting types, which can be flexible, semi-rigid or - ^) Ü, fragile or ductile; "stain resistant" as used in this application means the resistance of the ink for inkjet printing to staining according to what is described in the following test, printing an image with black lines, allowing a minimum time of five minutes to dry, touch up the line with the fingertip with a light to moderate pressure, such as could be used during normal handling of the images, and observe if line diffusion occurs.

Brief Description of the Drawings Figure 1 is an end, plan view of a two-layer image receiving layer construction after printing and overlamination.

Description of the Preferred Modalities Referring to Figure 1 therein is illustrated a sheet for inkjet printing of the present invention comprising (a) a layer that receives the image 11-12) on (b) a substrate (10), wherein the sheet can optionally have (c) a layer of adhesive (13) coated or laminated to the substrate (10) on the surface away from the 2 layer that receives the image (11-12). The adhesive layer (13) may or may not be backed with a release liner .'14). In this embodiment (Figure 1), the layer receiving the image (11-12) comprises at least two layers, wherein one layer is a protective penetrating layer (12) and the other layer is .0 an ink jet receiving layer (11). Once the ink jet printing sheet has been printed (15) using an inkjet printing process, the printed sheet (100) can be overlaminated with a transparent protective layer (16). The transparent protective layer (16) can be a transparent plastic sheet containing on one side a pressure sensitive adhesive or hot melt adhesive (thermal), or a transparent coating, or a processing technique that could affect the surface of the sheet : 0 printed (100). The typical release liner (14) comprises a sheet material of paper or plastic or other suitable material coated or otherwise treated with a release material such as a material of the • 5 silicone or fluorocarbon on at least one surface in contact with the adhesive layer, so that the adhesive layer = adheres or the release layer but is easily removed from the release liner where desired, so that the adhesive layer is exposed. The substrates are preferably made of durable material that resists the damaging effects of outdoor signage environments including wide ambient temperature ranges - 60 ° C to + 107 ° C, direct exposure to the sun and is optionally conformable to be fixed to . ? external surfaces where it can adhere on surfaces with some curvature or non-uniform, for example, walls or surfaces with screw heads or rivets that protrude slightly on the surface without easily tearing the material or "stretch". However, the Although the invention does not need to be limited to those, a less durable plastic is useful for indoor signage applications such as those that can be used when printed images have been printed with dye-based ink jet printing inks. ^ 3 The substrates may be transparent, translucent, or opaque depending on the application of the invention. Opaque substrates are useful for observing an image from one side of the image of the printed sheet under lighting conditions such as artificial lighting "5 or with sunlight, translucent substrates are particularly useful for use in luminous supports, for example, a light signaling. Substrates useful in the practice of the present invention are commercially available and can be designed to be durable to outdoor, which is preferred. Non-limiting examples of such substrates include the Scotchcal ™ Marking Films and the Short Term Removable Film (STR) Scotchcal ™ Series 9000 available from 3M Company, Avery1 Long Series GL! 'R Films, Avery Long Term Films. * Series XLMR, AveryR Series SXMR Long Term Films, suitable films from the FasCalMR or FasFlex1"1 movie range or any other films to mark, graphics or. promotional materials available from Fasson, Avery or Meyercord. However, there are other manufacturers of suitable materials and the invention should not be limited to the foregoing. Almost any material composed of a plastic sheet could be used depending on the use of the final image, for example, if outdoor durability is required, as long as the lower coating of the ink jet receiver can adhere to the surface of the film sufficiently all right. Useful substrates can have a variety of surface finish such as a matte finish such as that provided with the Short Term Removable Film 31 ?; 5cocchcal, < Series 9000 or glossy finish as provided by ScotchcalHR 3650 Marking Film. Plastic films can be extruded, calendered, or used - "different molded plastic materials, such as those exemplified by Scotchcal plasticized vinyl chloride '"1R or Surlyn, a polyolefin. Any suitable plastic material can be used. Non-limiting examples include the polyester materials exemplified by Mylar ™ available from E. I. Du Pont de Nemours & Company, Melinex ™ available from Imperial Chemicals, Inc., and Celanar ™ available from Celanese Corporation. Other examples include polyolefins such as polyethylene and polypropylene, polycarbonates, polymerized acrylates, polystyrene, polysulfones, polyether sulfones, cellulose triacetate, cellophane, poly (vinyl fluoride), polyimides, Teslin ™ available from PPG Industries, polymers with similar properties to those of rubber such as styrene-butadiene copolymers, or nitrile or butyl rubbers, polybutadienes. Preferred materials for the substrates may include those which are plasticized polyvinyl chloride or ionomers although the invention is not limited thereto. The preferred materials are white opaque or translucent materials although the transparent materials and the opaque colored materials, Translucent or transparent may be useful in special applications. Typical thicknesses of the substrate are in the range of 0.05 to 0.75 mm. However, the thickness may be outside this range and almost any thickness may be useful as long as the film resists tearing or cutting during printing and the application process. Given all considerations, any thickness is useful as long as the substrate is not too thick to be fed into an ink jet printer of choice. The cap that receives the image is comprised of at least two layers, so that at least one of the layers functions as a receiver of the ink jet. When the layer receiving the image is comprised of at least two layers, the uppermost layer functions as the protective penetrating layer and the lower coating layer functions as the ink jet receiver. A two-layer construction is preferred as shown in Figure 1. Although a layer that receives the image is described as a multilayer construction, the use of the term "multiple layers" does not necessarily imply that the layers are totally different, it is say, that there is a discernible demarcation interface, although it can be. There may be, for example, some mixing between layers especially at the interface during the coating process.

Hydrophilic or water-soluble adhesives or typical water-absorbent polymers used in the art are poly (vinyl pyrrolidone), vinyl pyrrolidone copolymers, for example with ethylene or styrene, polyvinyl alcohol, polyacrylic acids, polymethacrylic acids or (1-alkyl) acrylic acid copolymers and the inorganic salts thereof such as the alkali metal salts derived therefrom, poly (alkylene oxides) or polyglycols, carbohydrates, alkyl and hydroxyalkyl cellulose derivatives, starch and derivatives thereof. starch such as hydroxyalkyl starches, carboxyalkyl celluloses and their salts, gum arabic, xanthan gum, carrageenan gum, proteins and polypeptides. One or more polymers can be crosslinked using other reagents or catalysts. Preferred constituents of the lower coating layer include the copolymers described in EP 0484016 Al, poly (vinyl pyrrolidone), poly (ethylene oxide), and mordants such as those described in U.S. Patent No. 5,342,688 for migration of dye hidden in images after printing. However, mordants are not required in the printing sheet designed for use with pigment-based ink jet printing inks.

Preferred constituents of the topcoat layer are hydrophilic or water soluble polymers, gums and surfactants, which are less sensitive to moisture and touch wetting than for example poly (vill pyrrolidone). These include poly (vinyl alcohol), the aforementioned particulate matter such as corn starch or its derivatives or modified corn starches, Xanthan gum and surfactants such as Triton X-100. A similar top coat is described in U.S. Patent No. 4,935,307 and such a description is incorporated herein by reference. It is preferable to use an image receiving layer having a two layer construction wherein both the lower coating and top coating layers contain particles or dispersed particulate matter, so that the surface of the ink jet sheet is made rough The roughened surface is characterized by scattered particles and / or by being particulate so that images printed using pigment-based inkjet inks in the ink jet printing process are essentially non-stainable or stain resistant. By achieving the lower coating with particulate matter a rough receiving surface can be achieved. Other advantages such as better grip on the printer can also be obtained. ink cnorro and better transport of the article of the invention through the printer and the prevention of "or loqueos". However, the smoothest materials are also colas, when they are intended to be used with inks for printing with dye-based ink core. In addition, constructions having at least two layers are also useful when the layers are not loaded with dispersed or particulate particles, and / or only one of the layers contains particles or is particulate. In addition, the thickness of the upper coating layer is much thinner than that of the lower coating layer. Depending on the printing application, the thickness may vary. In mutual relation, the particles and / or particulate matter contained in the lower coating layer could preferably be greater than the thickness of the upper coating layer. Preferred materials for such dispersed particles and particulate material include materials that are insoluble or of sufficiently low solubility in the remainder of the ink jet coating mixture which is typically aqueous. Materials that have some water absorption are preferred. Non-limiting examples of particulate material include corn starch or modified corn starch, silica, alumina, titanium dioxide or other inorganic oxide or hydroxide materials white, cotton or flocs and other particles gives cellulose or modified cellulose, calcium carbonate or calcium silicate and other white inorganic silicates, sulfides and carb? -natos, clays, and talc. The size of the dispersed particulate or particulate matter is typically in the range of about 1 to 40 micrometers in diameter, preferably in the range of about 2 to 20 micrometers in diameter. However, it is not intended that the invention be limited to this range but that there be sufficient particles that are large enough to roughen the surface of the lower coating and top coat layers. The size distribution listed is a typical range, although it is allowed to use particles or particulate matter that is outside the range of sizes set forth above. The particles and / or particulate matter are added to the layer receiving the image in the range of 10 to 60 * by weight of total solids, preferably in the range of 15 to 25% by weight of total solids. In addition, the particles or dispersed particulate matter are generally available in a size distribution, although it is not intended to be closed to the use of a single particle size or particulate matter, provided that the size is sufficiently large as described above.

Adjuvants for receptor coatings include but are not limited to water soluble polymers or mécelas of water soluble polymers which act as absorbents or binder materials or bos, raticulados materials or other polymers, and optionally other materials such as surfactants, crosslinkers, mordants to avoid the dye shift or otherwise the migration of the dye in the printed image, other entities to prevent the dye shift, and dispersions or emulsions. Materials that absorb ultraviolet radiation, free radical scavengers and antioxidants can also be used. The amounts used of any of the adjuvants are those typical for the selected adjuvant and known to those skilled in the art. Although it is preferred to use a pressure sensitive adhesive, any adhesive that is particularly suitable for the particular substrate selected and the end use application can be used on the sheet for inkjet printing. Such adhesives are those known in the art, any of which include adhesives that are aggressively adhering adhesives, pressure sensitive adhesives, repositionable and / or positionable adhesives, hot melt adhesives and the like. In addition, this allows an ink jet receiving sheet to be manufactured without the addition of an adhesive layer, for example, loaded in a interior signage of short duration in a signaling box. In this application, the overlaid layer refers to any sheet material that can adhere to the surface of any existing coated or non-coated sheet material. "Overlamination" refers to any process to achieve this adhesion, particularly without catching air bubbles, creating creases or other defects that may spoil the appearance of the finished article or with images. The damaging effects of ambient humidity can be retarded by overlaying a transparent protective coating or sheet referred to herein as a overlay. Overlamination has a further advantage that the images are protected from scratching, splashes and sobrelámina can provide a highly glossy or other desired finished or surface finished design, and provide a degree of desired optical dot gain. The overlaminate layer can also absorb ultraviolet radiation or protect the lower layers and image from the damaging effects of direct sunlight or other sources of radiation. The overlamination is as described, for example, in U.S. Patent No. 4,966,804.

After printing an image or design on the ; s? According to the present invention, the image is preferably screened with colorless or almost colorless transparent materials. Suitable overlays include any transparent plastic material that contains an adhesive on a surface. The adhesive of the overlaminate layer could be a hot melt or other thermal adhesive or a pressure sensitive adhesive. The surface of the overlaminate layer can provide a highly glossy or matt texture or other surface. Preferred overlaminate layers are designed for external graphic applications and include materials such as those commercially available from 3M Company and Scotchprint ™ 910 Exterior Protective Film, and 8911 Exterior Protective Film, and 8912 Exterior Protective Film. However, other films or could be manufactured and the invention is not limited to those exemplified. An example of the printing process used in the present invention comprises feeding the material either in the form of a sheet or in a dispersed form from a roller in an ink jet printer, printing a desired color or monochromic image, recovering the image of the printer and, optionally, overlays the image with an overlaminate layer to protect the receptor coatings and The image of the water, scratches and other potential sources of color to the image, and then remove the detached lining, and fix the printed image to a wall, side of a ventricle, title, page or other surface to be seen. Advantageously, the articles of the present invention accept inks for printing with pigment-based inkjet when the substrate is comprised of weather-resistant plastic materials, which allow the construction of images stable to heat and light- under such circumstances they are in outdoor signage environments. The inkjet sheet provides useful images using dye-based printing ink based on dyes and pigments suitable for use, for example, in wide format inkjet printers where both narrow and narrow images can be made. wide by the process of printing with inkjet used in signaling applications. The resulting printed sheet is easily handled without easily staining the image and can be applied, when an adhesive layer is part of the ink jet sheet, to a wall, the side of a vehicle or other surface for pointing or other applications using techniques well known in the art without the use of other devices such as spray adhesives.

?? Examples The invention will be better illustrated by the following examples, but the particular materials and amounts thereof set forth in the examples, as well as other conditions and details, should not be construed to unduly limit this invention. All materials are commercially available or are known to those skilled in the art unless otherwise stated or evident. In the examples described here, the density and optical densities where the reflection densities were measured using a Gretag SPM-50 densitometer, subtracting the density of the unprinted sheet as a base. For reference, the example densities were obtained by printing on Hewlett-Packard HP51631E special inkjet paper using Hewlett-Packard's DesignJet 650C equipped with HP51650 series cartridges (including HP51640A black) as recommended for the printer: 1.365 (cían), 1,154 (magenta), 0.967 (yellow) and 1,247 (black). By reference, the following densities were obtained by printing on Hewlett-Packard HP51631E special inkjet paper using the DesignJet 650C from Hewlett-Packard equipped n cartridges of the HP51640 series (including black 15 0A): 1,247 (cyan), 1,123 (magenta), 0.686 (yellow) and 242 -. 242 -black).

Example l The ink jet printing sheets for dye and pigment inkjet printing inks were prepared by coating the following formulation on Scotchcal Marking Film, 1R Series 3650 available from 3M Company. A formulation was made by mixing thoroughly until a homogeneous mixture was obtained; 810 grams of a 20% aqueous solution of copolymer according to that described in EP 0484016 Al, 469 grams of solid poly (vinylpyrrolidone), K90 (available from ISP Technologies Inc.), 162 grams of Polyethylene Glycol 600 Carbowax (available from Union Carbide Chemicals and Plastics Company Inc.), 108 grams of a 15% solution of mordant (mordant with chloride counterions as described in U.S. Patent No. 5,342,688 and PCT Publication WO 94/20304, PCT Publication WO 94 / 20305, and PCT Publication WO 94/20306, 3560 grams of deionized water and 1638 grams of ethanol 167 grams of LOK-SIZE * 30 Cationic Corn Starch (available from AE Staley) were added to the mixture.

Manufacturing Company). The solution was mixed using a stirrer suspended for four hours, and then homogenized for thirty minutes in a five gallon cylindrical drum using a Silverson high-speed Multi-Purpose Laboratory mixer, equipped with a Disintegrating Head. Before coating, 3.3 grams of 30% aqueous ammonia (available from Aldrich Chemical Ccmpany) and then 24.3 grams of Xama 7, (an aziridine crosslinker available from Hoechst Celanese Corporation) were thoroughly mixed. The above formulation was coated on a device for coating an automated pilot at a fabric speed of 0.10 meters per second on a Marking Scotchcal ™ 3650 Series film of 0.3048 meters in width: a weather-tolerant white vinyl product composed of, in order; a white vinyl layer, a layer of pressure sensitive adhesive, and release paper; available from 3M Co. A knife coating device placed at approximately a distance of 127 microns was used and the weight of the dried coating was measured at 14.90 grams per square meter. The material was passed at 0.10 meters per second through four drying zones; 3.66 meters at 65.6 ° C, 3.66 meters at 79.4 ° C, ^. 66 meters at 93.3 ° C, and 7.32 meters at 121 ° C.

In a second step, an upper coating on the product of the above coating operation was coated onto the coated layer described above by coating the pilot coating device with the knife coating device placed at a distance of 76 micrometers. The upper coating similar to that described in US Patent No. 4,935,307 was composed of 66% by weight (of the total mixture) of deionized water; 1.64% by weight of polyvinyl alcohol Airvol 540 (available from Air Products) 31.17% by weight of denatured alcohol; 0.61% by weight of cationic corn starch LOK-SIZE * (available from AE Staley Manufacturing Company), 0.28% by weight of Xantana gum, a polysaccharide gum known as KELTROL TF 1000 (available from Kelco Division of Merck &Co. Inc.), and 0.3% by weight of Triton X-100 surfactant (available from Union Carbide Chemicals and Plastics Company Ine). This coated article was passed at 0.10 meters per second through four drying zones; 3.66 meters at 65.6 ° C, 3.66 meters at 79.4 ° C, 3.66 meters at 93.3 ° C, and 7.32 meters at 93.3 ° C. The images were printed directly on the side of the receiving coating of the coated material using a HP Jetjet HP650C ink jet printer from Hewlett Packard equipped with standard 51650 series ink cartridges giving Or excellent densities, fast drying time, stain resistant including black (printed cartridge HP51640A containing an ink based on i me to black). An image was overcoated using ScotchprintMR 8910 Exterior Protective Film, luster b ii ^ or available from 3M Co. using techniques known in the art, giving a bright protected image centers splashes. The overlay also provides additional resistance to ink bleeding under humid environmental conditions. Examples of optical densities obtained in non-overlaminated samples were measured with a Gretag SPM-50 manual densitometer 1,294 (cyan), 0.969 (magenta), 0.654 (yellow), and 1,450 (black). Eota sheet for printing was also printed on a wide format Encad Novajet printer equipped with LaserMaster Corp. inks (all based on dyes). Very high densities were obtained, although the drying times were prolonged - of the order of ten minutes to dry to the touch. The optical density samples obtained were 1,857 (cyan), 1,802 (magenta), 1,044 (yellow), and 1,937 (black).

Example 2 The article produced as follows illustrates a different type of substrate reinforced with adhesive that allows the short-term removal of images. The lower coating solution of the same composition as described in Example 1 was coated on a pilot coating device at a fabric speed of 0.10 meters per second on a roll of Short Removable Film.

. ) Term (STR) Scotchcal''R Series 9000 0.30 meters wide, available from 3M Co. and comprising in this order, a white vinyl layer, an adhesive layer (which allows removal for up to two years with little or no adhesive residue from most surfaces), and a release liner.

. : The lower coating was coated on the vinyl using a knife coating device placed at a distance of about 127 microns giving a dry coating with a measured weight at 15.51 grams per square meter. The material was passed to 0.1 meters : 0 per second through four drying zones; 3.66 meters at 65.63C, 3.66 meters at 79.43C, 3.66 meters at 93.3 ° C, and 7.32 meters at 121 ° C. The top coating was as described in Example 1, except that it was further diluted to 1% solids , c with deionized water. In a second pass, the coating The upper coating was coated on the product of the operation or previous coating on the previously coated layer using the pilot coating device of the knife coating device placed at a distance of 127 micrometers. For the top coating the speed of the fabric was approximately 0.076 meters per second. The top coating was applied using a knife transverse flow. The material was passed at approx. 0.076 meters per second through four drying tones; 3.66 meters at 65.6"C, 3.66 meters at 79.4DC, 3.66 meters at 93.3 ° C, and 7.32 meters at 121 ° C. Color test patterns were printed on samples of 21.6 by 27.9 centimeters of those materials using the DesignJet 650C Hewlett-Packard giving fast-drying images with stain-resistant images including the black pigment, and also printed test patterns and larger full-color images using the Hewlett-Packard 51640 DesignJet 650C equipped with Hewlett-Packard 51640 series cartridges, giving fast-drying, stain-resistant images The examples of optical densities measured for the 1002-colored areas are: for HP51650 inks (including HP51640A black) printed on the Hewlett-Packard Design and HP650C printer: 0.970 (cyan), 1.013 (magenta), 0.581 (yellow), and 1.125 (black).

The examples of optical densities measured for the colored areas 100 are: for the HP51640 inks printed on the Design et HP650C printer by Hewlett-Packard: 1367 -c? An,!, 0.9? 7 (magenta), 0.991 (yellow), and 1,185 (black).

Example 3 The following example illustrates the sheet for printing ^ ~) acting as a pigment-based inks only and thus does not require any mordanting method to retard or prevent ink bleeding. A formulation was made by mixing perfectly until obtaining a homogeneous mixture, 59.8 grams of a solution .5 aqueous copolymer 202 as described in EP No. 0484016, 34.6 grams of solid poly (vinyl pyrrolidone) K90 available from ISP Technologies Inc., 12 grams of Carbowax Polyethylene Glycol 600 available from Union Carbide Chemicals and Plastics Company Inc., and 263 grams of deionized water. TO The mixture was added with 121 grams of ethanol and 12.3 grams of LOK-SIZE® Cationic Corn Starch (available from A. E. Staley Manufacturing Company). Cornstarch was homogenized using a Silverson L4R Multi-Purpose Laboratory Mixer equipped with a Head Disintegrating for a period of ten minutes.

To 50 grams of the above solution was added a g.ca ie ammonia ai 305 (available from Aldrich Chemical Co.) / added 0.13 grams of Xama 7 (available from Hoechst elane = e Corporation) and mixed thoroughly. Mix ; The resultant was coated manually using a cutter or notch placed at a fixed distance of about 127 microns, and dried in a 93.3 C oven for four minutes. The above coatings were coated with the : top coating solution described in Example 1 on the blade using a fixed distance of about 16 microns and drying at 93.3 ° C for three minutes. Image areas printed with HP640A Hewlett-Packard DesignJet in black were resistant to 1 spotting and a non-overlaminated sample 8910 (ie at least protected from the effects of moist air) was placed in an oven / chamber for 90 hours at 40 ° C and 85% humidity, and showed no black bleed other obvious harmful effects to the areas or leaves with black images. Four images were made and three were overlaminated with Scotchprintr ™ 8910 Exterior Protective Film, glossy gloss available from 3M Co. using techniques known in the art giving brilliant images.

Example 4 The following procedure illustrates the functionality at different lower coating thicknesses. A lower coating formulation was made as described in Example 1 (but twice the amounts of each material). The material was coated on an automated pilot device at a fabric speed of 0.10 meters per second on a roll of Scotchcal ™ 3650 marking film (available from 3M Company) of 0.30 meters in width. For 15 minutes, a knife coating device placed at a distance of about 51 microns was used and the weight of the dry coating was measured at 5.60 grams per square meter. Then for an additional 15 minutes, the blade coating device was placed at a distance of about 76 micrometers, and the weight of the dried coating was measured at 9.16 grams per square meter. Then for another 15 minutes, the blade coating device was placed at a distance of about 102 microns, and the weight of the dry coating was measured at 13.3 and again at 13.5 grams per square meter. All the material was passed at 0.10 meters per second through four drying zones; 0.37 meters at 65.6 ° C, 3.66 meters at 79.4 ° C, 3.66 meters at 93.3 ° C, and 7.32 meters at 121 ° C.

In a second pass, the topcoat formulation as described in Example i) was coated onto the product of the above coating operation on the Vecubierta strain described above using the pilot coating device with the knife coating device placed at a distance of 76 micrometers and at a fabric speed of 0.10 meters per second through four drying zones, 3.66 meters at 65.5 ° C, 3.66 meters at 79.4 ° C, 3.66 meters at 93.3 ° C, and 7.32 meters at 121" C. The test pattern images were printed using the Hewlett-Packard Designjet 650C with Hewlett-Packard Series 51640 cartridges, and giving fast drying stain-resistant images to all coating weights The following table illustrates the optical densities: Example 5 A lower coating formulation containing silica was prepared by mixing thoroughly until having a homogeneous mixture, 11.95 grams of a 20% aqueous solution, of copolymer as described in patent application 3M EP 0484016 Al, 6.92 grams of poly (vinyl pyrrolidone) Solid K90 (available from ISP Technologies Inc.), 2.39 grams of Carbowax Polyethylene Glycol 600 2 available from Union Carbide Chemicals and Plastics Company Inc.), 1.59 grams of aqueous polymeric mordant solution at - fifteen-. (mordant with chloride counterions as described in Example 1, 52.6 grams of deionized water and 24.2 grams of ethanol. The mixture was stirred with an agitator driven by suspended air and 2.46 grams of silica Aerosil 380 (available from Degussa Corporation Silica Division). 0.05 grams of 30% ammonia (available from Aldrich Chemical Co.) and 0.36 grams of Xama 7, (available from Hoechst Celanese Corporation) were added to the above solution, and mixed D perfectly. The resulting mixture was manually coated using a notched bar or blade at a fixed distance of about 127 microns, and dried in a 93.3 ': C oven for four minutes.

The above coatings were coated with the top coat solution described in Example 1 on the blade using a fixed distance of about 51 microns and dried at 93.3 ° C for three minutes. The test patterns were printed on an HP650C equipped with HP51650 series ink cartridges and HP51640A black ink cartridge. Images with good stain resistance and rapid ink drying were obtained. Examples of densities are 0.718 (cyan), 0.663 (magenta), 0.509 (yellow), and 1007 (black).

Comparative Example A The following example illustrates a different mordant, a lower coating without dispersed particulate matter. This formulation gives excellent images with dye-based ink jet printing inks, but images or parts of images printed using pigment-based inkjet inks still have the ability to stain for an unreasonable time, for example that exceeds 48 hours. The lower coating formulation was made as described in Example 1 with twice the amounts of each material. However, a mordant different from that of Example 1 was used.

The mordant used was a 15% solution of mordant with an equivalent of the chloride ion and the trifluoroacetate ion equivalent as described in Example 1. The r, atena2 was coated on an automated pilot coating device at a fabric speed of 0.043. meters per second on a roll of Marking Scotchcal ™ 3650 Series Film (available from 3M Company) of 0.30 meters wide. A knife coating device placed at a distance of approximately 127 micrometers was used and the weight of the dry coating was measured at 10.84 grams per square meter.All coated articles were passed at 0.043 meters per second through three zones. of heat drying, 3.5G meters at 79.4 ° C, 3.66 meters at 121 ° C, and 3.66 1 meters to 121 C. In a second pass, the topcoat • formulation as described in Example 1) was coated on the product of the above coating operation on the above described coated layer using the D pilot coating device with the knife coating device positioned at a distance of 51 micrometers at a fabric speed of 0.043 meters per second through three heat drying zones; 3.66 meters at 65.6 ° C, 3.66 meters at 79.4 ° C, and 3.66 meters at 93.33C. 3o printed test charts directly.-Ocher the resulting material (on one side of the waterborne coating) on a Designjet HP650 printer from Hewlett-Packard equipped cr? - the 51650 Series color cartridges (cyan, magenta and yellow) and the 51640A cartridge (for black ink). Good images were obtained, but not as good as those obtained with the materials of the type exemplified in examples 1, 2, 3, 4, 5 and 6 with respect to the black areas of the images (ie those areas printed with the ink based on HP51640A cartridge pigment), which could easily stain using the method described here considered unreasonable after printing exceeding 48 hours. The examples of densities obtained are 0.320 (cyan), 0.667 (magenta), 0.591 (yellow) and 1.310: egro).

Example 6 The following example illustrates a different release plastic, adhesive and papermaking material. At the same time as set forth in Example 4, the same formulations were coated using the same pilot scale coating apparatus on a cloth approximately 0.41 meters wide comprising a layer SuriyrR white plastic, a layer of removable adhesive and on release paper as described in US Pat. Nos. 5,198,301; 5,196,246 and 4,994,322. The material e? rc-covered in an automated pilot coating device at a fabric speed of 0.10 meters per second. Various coating weights were used, but in this example the distance of the knife coating device was set at a distance of approximately 102 micrometers. This coated material was passed at 0.10 meters per second through four drying zones; 3.66 meters at 79.4 C, 3.66 meters at 79.4 ° C, 3.66 meters at 93.3 ° C, and 7.32 meters at 93.3 ° C. In a second pass, the topcoat (formulation as described in Example 1 and Example 4) was coated on the product of the above coating operation on the above-described coated layer using the pilot coating device with the coating device of blade placed at a distance of 76 micrometers at a fabric speed of 0.10 meters per second through four drying zones; 3.66 meters at 79.4 ° C, 3.66 meters at 79.4 ': C, 3.66 meters at 93.3 ° C, and 7.32 meters at 93.3 ° C. The images of the test pattern were divided using the Hewlett-Packard Designjet 650C equipped with the Hewlett-Packard 51650 cartridges, giving resistant images . spotting quick drying. Examples of dense densities are: 0.978 (cyan), 0.334 (magenta), 0.624 and arillo 'and 1117 (black).

Comparative Example B The following exemplifies that plastic materials with adhesive and release support without the receiving layer of the invention do not perform satisfactorily as ink jet receiving materials with aqueous inkjet printing inks. Letter-sized sheets (21.6 x 27.9 centimeters) of the following materials were fed into a HP650C Designjet inkjet printer from Hewlett-Packard. Printing was attempted with the printer equipped with the HP51640 placed ink cartridges (with the black cartridge HP51640), and then tried with the HP51650 placed cartridges (including the HP51640A black cartridge). The materials tested were the Film for Mark ScotchprintMR 3650, Marking Film ScotchprintMR 3620, Marking Film Scotchprint "" 11 * 8640 all available from 3M Co. and a material comprising a white Surlyn ™ plastic layer, a layer of adhesive that allows for removal, and a release paper as described in US Pat.

U.S. Patent Nos. 5,198,301; 5,196,246 and 2,354,322. The coating of the latter material to allow receipt of the ink for inkjet printing is described in Example 6. The inks were deposited on the plastic surface, ie they did not penetrate to any degree or all, and they did not moisten the plastic surface giving a discontinuous image and low densities. The most minimal contact of the finger caused the image to become stained. This remained true 18 hours after printing. The above observations were true for both dye-based and pigment-based inks HP51640A. For an appreciation of the scope of the invention, we claim the following. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates. Having described the invention as above, property is claimed as contained in the following:

Claims (5)

1. A sheet for ink jet printing, earaetapcaia because it comprises a substrate and a layer receiving images in contact with the substrate, wherein the image receiving layer is comprised of at least one penetrating protective layer of a composition and at least one layer receiving the ink jet of a second composition, and wherein both the penetrating protective layer and the ink jet receiving layer contain particles or dispersed particulate matter of a size large enough to roughen both the surface of the protective penetrant layer and a surface of the receiving layer of the ink jet.

2. The sheet for printing with ink jet according to claim 1, characterized in that the dispersed particulate matter is a corn starch or modified corn starch.

3. The ink jet recording sheet according to claim 1 or 2, characterized in that the protective penetrating layer is thinner than the larger size of the dispersed particulate matter in the ink jet receiving layer.

4. The sheet for ink jet printing according to claims 1-3, characterized by the substrate is a plastic sheet opaque or translucent to PC-a vinyl chloride case).

5. The sheet for ink jet printing according to claims 1-4, characterized in that it also includes an adhesive layer adjacent to the substrate and on the surface of the substrate opposite the layer receiving the images.