AU6541999A - Transfer media - Google Patents

Description

P/00/011 Regulation 3.2

AUSTRALIA

Patents Act 1990 COMPLETE SPECIFICATION FOR A STANDARD PATENT

ORIGINAL

TO BE COMPLETED BY APPLICANT

I,

Name of Applicant: E.I. DU PONT DE NEMOURS AND COMPANY performing it known to me:- So Address for Service: CALLINAN LAWRIE, 711 High Street, Kew, Victoria 3101, Australia Invention Title: TRANSFER MEDIA The following statement is a full description of this invention, including the best method of performing it known to me:- 20/12/99,tdl 1043.cs.doc,l IM-1255 TRANSFER MEDIA This Invention relates to a transfer media for transferring an image to a permanent substrate.

Ink-jet printing is a non-impact method for recording information in response to an electronic signal, such as that generated by a computer. In the printer, the electronic signal produces droplets of ink that are deposited on a media, such as paper or transparent film. Ink-jet printers have found broad commercial acceptance due to their reliability, relatively quiet operation, graphic capability, print quality, and low cost.

In current ink-jet printing applications, several inks (typically having colors of black, cyan, magenta and yellow) are used to print textual and graphic information on a printing media, typically ordinary paper. The inks primarily are composed of water, and contain a colorant that may be a dye or pigment dispersion. The inks generally also contain a polyhydric alcohol to prevent nozzle clogging, and may contain various adjuvants. Such inks and ordinary paper are well suited for desk-top publishing, as currently practiced, wherein only a small portion of the paper receives printed text and graphic information.

It also is desired to reproduce high quality colored pictoral information (such as photographs and the like) using ink-jet technologies for applications such as commercial printing and dcsk-tup publishing. In these applications, however, the printing media will receive substantially more of the black and colored inks in order to accurately reproduce the various hues, tints, and colors contained in a typical colored picture. For example, the printing media will be expected to .:25 receive up to 200% or more coverage in conventional commercial printing applications.

Ordinary paper stock is usually not suitable for such high quality applications for a number of reasons, Water disrupts the paper structure, causing cockle" that affects appearance of the paper and, in extreme cases, may actually cause the paper to distort to the extent that it contacts the ink-jet pen, disrupting the printing process. Also, the paper may not absorb water sufficiently quickly to achieve the desired printing speed, or may cause flooding of the paper surface, which adversely affects image quality. Moreover, wicking of ink into the paper may cause the paper to "show through" into the printed image, detracting from image quality. There is a need for the printed text and pictures to be more robust; exhibit better handleability, water fastness, and smear resistance after printing.

Special ink-jet media have been developed to achieve high quality images lain inkjet printing. In applications such as proofing, an image is printed on an image receptor element and then transferred to a permanent'substrate.

There is still a need for development of transfer media that improves the appearance of the final imaged article.

The present invention provides a transfer media for receiving printed images involving an ink, particularly an aqueous ink-jet ink containing a dye or pigment colorant, and more particularly a dye-based ink jet ink. The printed image is readily transferred to a permanent substrate, which may be paper, plastic, glass, aluminum foil, etc., due to the components contained in the ink receptive layer of the media and the presence of a matting agent in the release layer. This media has improved gloss characteristics, and therefore exhibits reduced image distortion.

Accordingly, in one embodiment, the invention provides a transferable image media comprising, in order: a carrier support; a release layer comprising at least one release agent selected from the group consisting of thermoplastic polyamide polymers and polyamide copolymers and combinations thereof; cellulose ethers; polyethylene oxides; and blends of water-soluble polymers with polyethylene oxide; and at least one matting agent in an amount of from about 3 to about 30% by weight, based upon the weight of the release layer; a hydrophobic protection layer having a surface adjacent the release layer, said protection layer comprising at least one compound selected from acrylate or methacrylate polymers, epoxy resins, diene rubbers, polyolefm 25 elastomers, polyurethane elastomers, polyvinyl chloride, polyvinyl butyral, polycarbonates, cellulose esters, and combinations thereof; and an ink receptive layer comprising at least 15% of a water soluble binder and a hydrophilic thermoplastic polymer having at least one carboxylic acid group and a molecular weight of at least 6000.

The media and process provide special utility in applications involving printing of pictoral information, particularly in demanding ink-jet printing applications which require more ink than normally used in printing text In another embodiment of the invention the transferable image media excludes a protection layer.

Another aspect of the invention relates to the process for preparing an inked image by using the transferable image media described above.

In a preferred application, the media has, in order, an ink receptive layer, a hydrophobic protection layer, a release layer, and a carrier support.

The carrier support is a material having sufficient stiffness and dimensional stability to support a printed image without having the'image distort or misalign, and sufficient water resistance that it can be exposed to an aqueous ink without warping or shrinkage. The material also should withstand heat and pressure applied during the lamination steps described below. The support typically has a thickness of about 25 to about 250 microns (1.0 to 10 mils), preferably about 50 to 200 microns (2 to 8 mils). Suitable materials include polymeric films, such as polyethylene terephthalate and polyethylene naphthanate, polyamides, polycarbonates, fluoropolymers, polyacetals, and polyolefins. Thin 0o metal sheets may be selected, as well as natural or synthetic paper treated to be water resistant. The substrate may be transparent, translucent, or opaque. It may be colored and can have components, such as antihalation dyes, incorporated therein to meet the needs of specific applications. Polyethylene terephthalate films are a preferred support material.

Conventional antistat coatings may be present on one or both sides of the support to reduce static if the support is later separated by "peeling", as discussed below. The antistatic coatings may also contain materials such as colorants, antihalation dyes, optical brighteners, surfactants, plasticizers, coating aids, and the like.

20 Conventional back-coating on carrier support may be applied to the media carrier support in order to reduce curl. Additionally, the carrier support may have a backing layer, to improve transport properties of the media in the ink-jet printer, if the material selected as the first substrate does not possess the desired handling properties. The backing layer may have antistatic agents, matting agents, and the 25 like that are commonly employed in the art. For example, the carrier support may have an abrasion resistant coating as disclosed in U.S. Patent No. 5,069,942.

An anchor layer may be used to ensure adequate adhesion of the release layer to the carrier support. The term "anchor layer", as employed in the art, means a layer that is adhesively bonded to the layers on both sides of it. Adhesive materials for bonding different types of materials are well known in the art and are discussed in Handbook of Adhesives. 2nd Edition, Irving Skeist, Ed. (Van Nostrand Reinhold Co., New York, 1977). Any conventional adhesive material can be used in the anchor layer or layers so long as it is not adversely affected by the printing step. Examples include ethylene/vinyl acetate copolymers, vinyl chloride/vinyl acetate copolymers, vinyl chloride/vinylidene chloride copolymers, thermoplastic polyamides, and the like. The choice of adhesive will depend on the compositions of the release layer and the support. The anchor layer or layers may contain materials such as antistats, colorants, antihalation dyes, optical brighteners, surfactants, plasticizers, coating aids, and the like. The anchor layer(s) generally has a thickness in the range of 0.01 to 10 microns, preferably 0.05 to 5 microns.

The release layer facilitates removal of the carrier support from the rest of the transfer media component layers after imaging.

The release layer includes a release agent selected from cellulose ethers; polyethylene oxides; and blends of water-soluble polymers with polyethylene oxide, thermoplastic polyamides and copolymers thereof such as Ultramid®lC.

Examples of water soluble polymers include polyvinyl alcohol, polyvinyl pyrrolidone, polysaccharides, cellulosic compounds like hydroxy methyl cellulose, starch and gum. An example of cellulose ether include ethyl cellulose.

It has been found that matting agents added to release layer can be used to adjust the gloss characteristics of the layer adjacent to the release layer the image reception layer or, where the media contains a protection layer, the protection layer).

Preferably, the release layer contains a matting agent having a preferred particles size of from about 3 to about 45 microns, preferably from about 8 to about 20 microns, in an amount of from about 3 to about 30 percent by weight, preferably from about 5 to about 10 percent by weight, based on the weight of the 20 release layer.

The matting agent used should be chemically inert and may be either inorganic or organic. Some suitable matting agents for use in the release layer include inorganic fillers such as silica or silicates, zeolites, calcined kaolin, diatomaceous earth, barium sulfate, aluminum hydroxide or calcium carbonate, S. 25 glass beads, mica, tin oxide and titanium dioxide and organic matting agents such as polymeric particles, for example, particles of homo- or copolymers of styrene or styrene derivatives such as divinyl benzene, fluorcarbon polymers, and crosslinked polyacrylates and other materials that would be readily apparent to one skilled in the art. The preferred matting agent is silica.

The release layer may also contain other components such as antistats, colorants, antihalation dyes, surfactants, plasticizers, coating aids, and the like.

The release layer generally has a thickness in the range of from about 2 to about 20 microns, preferably from about 3 to about 6 microns. In other words, the dry coating weight of the release range from about 20 to about 200 mg/dm 2 preferably from about 30 to about 60 mg/dm z The hydrophobic layer includes at least one compound selected from acrylate or methacrylate polymers such butyl methacrylates having a glass transition temperature of 15°C and 35°C; epoxy resins, diene rubbers such as polyisoprene, polybutadiene, styrene-butadiene rubbers, chioroprene rubber; polyolefin elastomers; polyurethane elastomers; polyvinyl chloride; polyvinyl butyral; polycarbonates; cellulose esters. The preferred compounds include butyl methacrylates having Tgs. of 15'C and 35'C, or mixtures thereof.

Preferably, the hydrophobic protection layer may also contain UV absorbers. Suitable ISV absorbers often contain groups such as, for example, benzoates, bezophenones, salicylates, cinnaiates, ditheocarbainates, benzotriazoles, propenoic esters, diphenylarcrylates and combinations thereof.

Examples of suitable UV absorbers inclade: propoxylated ethyl paraaminobenzoate; propoxylated ethyl para-aminobenzoate; dipropylene glycol salicylate; 4-dodecylox-2-hydroxybelzophelofe; 2-ethyihexyl paradimethylaminobenzoate; 2-ethylhexyl-p-methoxycinlfflate; 2-hydroxymethoxybenzophenone; 2-hydroxy-4-n-actoxybenzophelofe; hydroxybenzoatc type; nickel dibutyl dithiocarbamate; N.-e-thoxycarbon-ylphenyl)-N'-ethyl-Nphenylforinamidin blends of benzophenone and 1-hydroxycyclohexyl phenyl ketone; 2-methyl-l-(4-methylthio)phelyl)-2-morpholflopropaflonel1 2-ethylhexyl-p-methoxy cixinamate; 2-hydroxy-4-methoxybenzo-phfOfle; dihydroxybenzo-phenone; 2-hydroxy4-methoxybenzophenone-5-sulfofllG acid; 2-hydroxy-4-n-octoxybenzophelone; 2-(2'hydroxy-5-'-methylphenyl)benzotriazole; 2,2',4,4'-tetrahydroxy benzophenone; Sodium 2,2'-dihydroxy-4,4' dixnethoxy-5-sulfobenzophenone; 2-hydroxy-4-methoxy benzophenone; 2-hydroxy-4-methoxy benzophenone-5-sulfonic acid; ethyl-2cyano-3,3-diphenylacrylate; ethylhexyl-2-cyano-3,3-diphenylacrylate; 2,4-diluydroxy benzophenone; 2-propenoic acid, 2-eyano-3,3-diphenyl-2-ethyl .:25 hexyl ester- The hydrophobic protection layer may contain conventional ingredients such as matte agents. Since the printed image is viewed through the hydrophobic protection layer, the layer is transparent and preferably has no yellowness that might shift color balance of the printed image.

The hydrophobic protection layer generally has a thickness in the range of from about 3 to about 40 microns, preferably from about 7 to about 20 microns.

The ink-receptive layer is constructed of a composition having a balance of properties. The ink-receptive layer is releasably affixed to the hydrophobic protection layer where present or the adjacent layer release layer in order that it may be readily separated after being imaged and the image transferred, preferably by lamination, to a permanent substrate. Since the printed image is viewed through the ink receptive layer, the layer is transparent and preferably has no yellowness that might shift color balance of the printed image.

It is desirable that the ink receptive layer not be so tacky at ambient temperatures that it presents a handling problem. However, materials should be avoided that are so slippery that the material presents a registration problem during lamination to the permanent substrate. For many applications, it will be desirable to employ an ink receptive layer that is scratch and abrasion resistant when wet or dry, and is resistant to cracking or creasing from folding.

The ink receptive layer typically has a thickness of from about 3 to about microns, preferably from about 5 to about 20 microns. It contains at least of a water soluble binder, preferably selected from the group consisting of to polyvinyl alcohol, polyvinyl pyrrolidone, cellulose compounds such as polyhydroxymethyl cellulose, polyhydroxyethyl cellulose, polyhydroxypropyl cellulose, polyhydroxypropyl methyl cellulose, starch, gelatin, gum arabic, and combinations thereof; and a hydrophilic thermoplastic polymer having at least one carboxylic acid group, preferably in an amount of from 15 to 85%, and a molecular weight of at least 6000.

The polymer-containing carboxylic acid groups conveniently is a copolymer of(l) at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, and olefinic dicarboxylic acid maleic or itaconic acid), and an olefinic dicarboxylic anhydride maleic or itaconic 20 anhydride), and at least one monomer selected from the group consisting of an acrylate or methacrylate ester having 1 to 6 carbon atoms, a dialkylamine acrylate or methacrylate, styrene, vinyl acetate, vinyl methyl or ethyl ether, vinyl pyrrolidone, ethylene oxide, or the like. Some copolymers that may be selected are methyl methacrylate (37%)/ethyl acrylate (56%)/acrylic acid terpolymer, .i 25 acid no. 76-85, molecular weight 260,000; methyl methacrylate (61.75%)/ethyl acrylate (25.75%)/acrylic acid terpolymer, acid no. 100, molecular weight 200,000; styrene/maleic anhydride half ester copolymers, having styrene to maleic anhydride ratios of 1.4/1 to 1.0/1 and molecular weights from 60,000 to 215,000 *i and poly(methyl vinyl ether/maleic acid).

Some useful hydrophilic thermoplastic polymers having at least one carboxylic acid group and a molecular weight of at least 6000 include methyl vinyl ether/maleic acid or anhydride; methyl vinyl ether/itaconic acid or anhydride; ethylene/maleic acid or anhydride; styrene/maleic acid or anhydride; polymethacrylic acid and polyacrylic acid.

Where a pigment-based ink is used, the ink receptive layer may also contain a neutralizing component to minimize or avoid cracking of the coating.

Neutralizing agents, for example, ammonia; N,N-dimethylethanolamine; triethanolamine and 2-amino-2-methyl propanol, may be selected to adjust the pH of the solution to approximately which has been found to be advantageous in minimizing the cracking of the inked image formed by a pigment-based ink.

The coating may also contain conventional ingredients such as inorganic filters, humectants, UV absorbers, polymeric dispersants, defoaniers, mold inhibitors, antioxidants, latex dye mordants, optical brighteners, etc.

The ink receptive layer generally has a thickness in the range of 3 to microns, preferably 10 to 20 microns.

In one embodiment, the, ink receptive layer may be placed directly on the release layer containing a matting agent wherein the matting agent has a specified to size and is present in a specified amount. Accordingly, the invention provides a transferable image media comprising, in order: a carrier support; a release layer; and an ink receptive layer.

The hydrophobic protection layer and the ink receptive layer are sequentially applied to the carrier support having thereon a release layer. For high coverage images, the hydrophobic protection layer has a dry coating weight of about 30 mg/din 2 (milligram per square decimeter) to about 400 mg/din 2 similarly, the ink receptive layer has a coating weight from about 30 mng/din 2 to 20 about 400 mg/din 2 Appropriate coating weight is needed to provide sufficient ink vehicle absorbing capacity to prevent ink spread or puddling and to minimize cockle with porous substrates. The layers are applied to the carrier support by conventional coating methods such as roller coating or knife coating methods air knife, trailing blade). All the ingredients can be premixed to form the compositions that are applied to the surface of the release layer at the dry coating weights set out above.

In a different embodiment the hydrophobic protection layer and the ink receptive layer may be laminated, in order, to a release layer that is coated on a carrier support.

The adhesion balance between the various media layers is important if the media is to function as a transfer media. The adhesion force at the point of separation should be lower than the adhesion forces between all other layers remaining at separation. Anchor layers may be present between layers, other than at the point of sepdration, to increase the adhesion force between layers.

The permanent support for the colored image can be chosen from almost any material desired. For most applications a paper permanent support is used.

Other materials which can be used as the permanent support include cloth; wood;, glass; china, polymeric films such as polyethylene terephthalate, polyethylene, polypropylene, etc.; synthetic papers; thin metal sheets or foils; cardboard, etc.

An adhesive may be employed to achieve desired banding strength between the ink receptive layer and the permanent support.

The transfer media provided by this invention may receive ink printed by conventional ink-jet printers, such as thermal or bubble jet printers, piezoelectric printers, continuous flow printers, or valve jet printers. After the ink is printed on the media, the printed.

A transfer process may be used to produce a single or multi-colored image on a permanent substrate. For example, a media may be printed with one or more to colored inks, and then transferred to a permanent substrate, which may have been primed or have an adhesive layer to ensure durable bonding. Then, the media substrate and release layer are readily removed by stripping or peeling, leaving the ink receptive layer and the hydrophobic layer (if present) on the permanent substrate. In a variation, this process may be repeated with the ink receptive layer *0V 15 containing various colors of ink dispersions to build up a multi-colored image. In these applications, it is important that the ink receptive layer have the desired 0 degree of transparency because the colorant is viewed through the layer.

'Me media and processes of the invention have utility for ink-jet printing technologies, with aqueous ink dispersions, to provide high quality printed images .0.020 on a broad variety of substrates. Pictorial as well as textured information may be printed. For multicolored images, yellow, cyan, magenta and black inks may be S used to advantage. Applications include desktop publishing, as well as wide format applications such as the printing of signs, banners, and the like.

Applications fuirther include applying ink jet images to objects having non-planar **25 topography- In accordance to the present invention, the gloss reading of the transfer media can be adjusted to match the gloss reading of the permanent substrate.

0 Matched gloss readings improves the appearance of the final imaged article.

*o

EXAMLES

Table I below lists the name and chemical description of the ingredients used in the Examples.

Table 1: Name Available From General Chemical Description Ultrarnid(D IC BASF Corporation, co-polyaxnide of nylon 6 Charlotte, NC and nylon 66 Syloid®D ED2 W. R. Grace and Company, silica particles having Baltmore M ~particle size of 0@

S

U

55.5

S

*5 S S

*SS*

Name Available From General Chemical Description 10-15 microns (J.u) Syloid®V ED5 W. P, Grace and Company, sl particle s of in Baltimore, MD pril ieo 25-30 microns CronarO 471 E. I. du Pont de Nemours and Co., polyester resim

DE

ElvaciteO 2044 E. I. du Pont de Nemours and Co., acrylic polymer ElvaciteQ 2046 Wilmington,

DE

GantrezO ANI 19 ISP, Wayne, NJ poly(methyl vinyl ether/maleic anhydride) Elvanolv 52-22* E. I. du Pont de Nemours and Co., poly vinyl alcohol

DE

Zelec® ECP3010 XC E. I. du Pont do Nemours and Co. particles consisting of Wilmington, DE mica and tin oxide having particle size of 3 to 5 microns PVP-K90 ISP, Wayne, NJ polyvinyl pyrroidone Epon®& 110 1 Shell Chemical, Houston, TX epoxy resin BakeliteQ® VAGH Union Carbide Corp., Danbury, CT vinyl chloride resin ScripsetOD Monsanto Co., St- Louis, MO poly(styrene)maleic Gantrez®0 S97 ISP, Wayne, NJ poly(methyl vinyl ether/maleic acid) P ININGAND LAlyATION Unless otherwise stated, each of the transfer media in the Examples was printed using a HP2000C printer (available from Hewlett-Packard, Palo Alto, CA) 5 using commercial inks (Cyan HP-C4841A; Yellow HP-C4842A;Magenta HP- C4843A; Black HP-4844A) for this printer to form a four-color image. The printed media was then transferred to a permnanent substrate, which is Reflection® paper (Consolidated Papers Inc., Wisconsin Rapids, WI), by lamination. The lamination equipment was a WaterProof® Laminator I. du Pont de Nemours to and Company, Wilmington, DE), at a lamination temperature was I I10 0 C.and a pressure of 400 psi (2.758 x 10' Pa).

GLOSS AND OPTICAL 1ENSITY WASWMNTS Gloss reading of the image transferred to the permanent substrate in the Examples was measured using a Novo-Gloss'" reading meter(Gardcoe, Paul N.

Gardner Company, Inc., Pompano Beach, FL) at 600 angle.

9 Sc. S S S

*SS

S

0S S S S 5 55 5* 5 S S *5

I

Optical density of the image after it has been transferred to the permanent substrate in the Examples was measured using a Macbeth@ RD918 densitometer (Kollmorgen Corp, Newburgh, NY).

Unless otherwise stated, the amount of ingredients in the various component layers are listed in parts by weight, based upon the weight of the component layer.

EXAMPLE 1 Effect Of Matte Agent Particle Size On Release Layer Properties Two transfer media(Samples A and each containing the following components layers were made: a support, a release layer, a hydrophobic protective layer and an ink receiving layer.

The component layers were prepared as described below: Release Layer: Sample A: A 13% coating solution was prepared by adding 24 gms 15 (grams) of Ultramid® 1C into a solvent mixture of 149.6 gms of N-propyl alcohol and 26.4 gms of water. The mixture was stirred with high RPM for 3 hrs.

2.4 gms of Syloid ED2 were added to the above solution followed by stirring for 20 min. The Sample A coating solution was coated on a sheet of Cronar@ 471, with a 4 mil (101.16 microns knife to form a release layer having a dry 20 thickness of 58 mg/dm 2 with the drying weight composition listed in Table 2 below: Table 2: Sample A Release Layer Composition SINGREDIENT AMOUNT (PARTS BY WEIGHT) Ultramid® IC Syloid® ED2 0.1 25 Sample B: A second release layer was prepared using the same procedure for making Sample A release layer, as described above, with the following exception: Syloid® ED5 was used. The dry weight composition of Sample B is listed in Table 3 below: Table 3: Sample B Release Layer Composition INGREDIENT AMOUNT (PARTS BY WEIGHT) Ultramid® IC Syloid® ED5 Hydrophobic Layer: A 30% coating solution of Elvacite® 2044 was prepared by adding 60 gms (grams) of Elvacite® 2044 into 140 gms of acetone. The mixture was stirred for approximately 3 hrs. The coating solution was coated onto each of Samples A and B, using a 6 mil (152 micron) knife to obtain a dry coating weight of 192 mg/dm 2 Ink Receptive Layer: A 7% Gantrez® AN119 coating solution was prepared by adding 14 gms of GantrezV AN119 into 186 gms of deionized water, stirring for 30 minutes with high RPM and heating up to 80C for 3 hours. 14 gms of triethanolamine (Ashland Chemical Co. Industrial Chemicals and Solvents Div., Columbus, OH) were then added. A 7% solution of Elvanol® 52-22 was prepared by adding 14 gms of Elvanol® 52-22 into 186 gms of cold water, then heating up to 85°C for 3 hrs until the solution became clear and homogeneous. 20 gms of Gantrez® AN119 solution containing triethanolamine and 80 gms of Elvanol® 52-22 solution were then mixed. This coating solution was coated with a 12-mil (0.3 micron) thick knife onto the dried hydrophobic protection layers in 15 Samples A and B to form ink receptive layers with a dry weight of 190 mg/dm 2 The composition of the ink receptive layer is listed in Table 4 below: Table 4: Ink Receptive Layer Composition for Samples A and B INGREDIENT AMOUNT (PARTS BY WEIGHT S" GantrezO AN 119 1 Elvanol® 52-22 3 Triethanolamine 1 An image was printed on each of Samples A and B using an HP2000C printer and to form a four color image. The printed media were then laminated to Reflection® paper (Consolidated Papers Inc., Wisconsin Rapids, WI), using a WaterProof® Laminator I. du Pont de Nemours and Company, Wilmington, DE) at a lamination temperature of 110*C. and a laminating pressure of 400 psi (2,758 kPa). Results of the gloss and optical density measurements are shown in Table 5 below: TABLE 5: Gloss and Optical Density of Image Printed By HP2000C on Samples A and B Matte Agent Particle Sample Size Optical Density Gloss K C M Y R G B 600 A 10-15 1.42 0.83 1.37 1.43 1.25 1.22 0.91 6.9 B 25-35 1.35 0.80 1.32 1.40 1.20 1.18 0.87 8.4 The Sample A media was also printed with a continuous flow ink jet printer, AX4 I. du Pont de Nemours and Company, Wilmington, DE) with a standard commercial ink, and then transferred to Reflection® paper. Results of s the gloss and optical density measurements are shown in Table 6 below: TABLE 6: Gloss and Ootcal Density of Image Printed By AX4 Printer on Sample A Sample Optical Density Gloss K C M Y R 0 B A 1.94 1.63 1.71 1.24 1.77 1.50 1.54 10.2 EXAMPLE 2 Effect Of Amount Of Matte Agent On Gloss Five transfer media (Samples C, D, E, F and G) were prepared as described below.

Release layer coatings were prepared as follows: 15 A 13% solution (Sample C release layer) was prepared by adding 24 gms of Ultramid® 1C into a solvent mixture of 149.6 gms of N-propyl alcohol and 26.4 gns of water. The mixture was stirred with high RPM for 8 hrs. The S: solution was coated on Cronar® 471 with a 4 mil (0.1 micron) knife to have the dry thickness of 61 mg/dm 2 Samples D, E, F and G release layers were prepared following the same procedure used to prepare Sample C release layer, with the S. following exception: the level of Syloid® ED2 was varied as shown in Table 7 below.

Table 7: Release Layer Compositions for Samples C-G .2.

Release Layer Amount Ingredient by weiht) Sample C D E F G Ultramid IC 99 97 95 92 Syloid® ED2 1 3 5 8 A hydrophobic protection layer and an ink receptive layer were then coated over each of the release layers as described in Example 1 above.

Each of the media C through G were printed with an HP2000C printer (Hewlett Packard Co, Palo Alto, CA) to form a four color image on each of the samples. The printed media were then laminated to Reflection® paper using a WaterProof laminator at 110 0 C and 400 psi (2758 kPa). Optical density and gloss level were measured and the results are shown in Table 8 below: TALE 8 Sample Optical Density Gloss K C M Y R 0 B C 2.50 1.02 0.92 0.87 0.98 1.65 1.25 62.4 D 2.25 0.95 0.87 0.82 0.88 1.43 1.13 50.7 E 2.12 0.88 0.82 0.77 0.85 1.38 1.06 41.2 F 1.93 0.85 0.76 0.74 0.80 1.32 1-01 25.6 G 1.57 0.90 0.74 0.72 0.74 1.29 0.95 14.5 As shown in Table 8 above, the gloss decreases with increased dosage of the matte agent, Syloid® ED2.

EXAMPLE 3 Effect of Release Laer Thickness On Gloss Four transfer media (Samples H, I, J and K) were prepared following the procedure for preparing Sample A media with the exception of the release layer thickness: Release layer having the composition of Table 2 above were coated with a 3, 6, 8 and 15 mil (76, 152,203,381 microns) knife onto a Cronar® 471 to obtain the different thicknesses of release layer shown in Table 9 below. The S-gloss measurements of Samples H-K are also listed in Table 9 below.

Table 9 Sample Thickness of Release Ler Gloss (at 600 angle) H 38 mg/din 2 9.7 1 75 mg/dn 2 7.2 J 112 mg/di 2 7.3 K 190 mg/dn 2 12.1 The optical density of Samples H-K were essentially the same.

EXAMPLE 4 Transfer Media Including An Alternate Matte Agent A three layer transfer media (Sample L) was prepared as described in Example 2 with the following exceptions: Zelec® ECP3010 XC was used in place of Syloid® ED2; and PVP-K90, which dissolves in cold water was used in place of the Elvanol® 52-22, and Elvacite® 2044 is replaced with a blend of Elvacite® 2044 and 2046 in a 50/50 weight ratio. The media had the component layers and composition listed in Table 10 below: Table 10: Sample Dry Weight Amount Component Layer (mg/dnM 2 Composition (parts by weight) ink receptive layer 195 Gantreze AN 119 1 PVP K-90 3 triethanolamine hydrophobic layer 185 Elvacite® 2044 1 Elvacite® 2046 1 release layer 35 Ultramid® 1C I Zelec® ECP3010CX 0.1 The media was printed using an HP2000C printer, and the printed media was laminated to Reflection® paper, using a WaterProof® laminator at 115°C and 5 400 psi (2758 kPa). Gloss and optical density measurements are shown in Table 11 below: TABLE 11 Sample p0 tieal Density Gloss K C M Y R G B L 2.23 0.87 1.76 2.01 1.40 1.39 093 61.3 EXAMPLE Alternate Hydrophobic Protection Layer A transfer media (Samples M) was prepared as described below.

A release layer was prepared as follows: A 13% Ultramid® 1C solution with Syloid® ED2 was prepared as 15 described in Example 2 and a 4 mil (101 micron) knife was used to coat the solution on 4 mil (101 micron) Cronar® 471 (DuPont) to obtain the matte release layer with a dry coating weight of 55 mg/din 2 A hydrophobic layer was prepared as follows: gns of Elvacite® 2044 and 30 gins ofEpon® 1101 were added to 140 gins of acetone. The mixture was stirred for 3 hrs. A 6 mil (152 micron) knife used to overcoat the solution on top of the release layer to obtain a hydrophobic layer having a coating wieght of 54 mg/din 2 with the composition shown in Table 12 below: Table 12: Sample M Protection Layer Composition Ingredient Elvacite® 2044 Amount (parts by weight) 3 part Epon@~ 110 1 1 part An ink receptive layer was prepared as follows-, A 7% Poly(vinylpyrrolidofle) K-90 (ISP Wayne, NJ) solution was prepared by adding 14 gml of the polymer into 186 gins of cold water, and stirring for approximately I hour. 150 gins of 7% PVP K-90 solution, 150 gmn of 7% ElvanoO® 52-22 solution, 100 gins of 7% (JantrezQ AN 119 solution prepared as described in Example 2, and 7 gins of triethanolamine were mixed and stirred for mi. 12 mil (305 microns) knife was used to overcoat the solution on top of hydrophobic layer to obtain 190 ing/dn 2 ink receptive layer with the dry weight composition as Table 13: Samle M Ink Receptive Layer Composition *Ingredient Amount (parts by weight) PVP K-90 Elvanol®l 52-22 :.Gantrez®g ANl 19 ::Triethanolamine The media was printed and then the image was laminated on to *is Reflection® paper. The gloss and optical density measurements are shown in Table 14 below.

20 TABLE 14 Sample M Measuremnents Optical Density Gloss K KC MIYI RI GIB 1.33 10.75 0.73 0.70 0.79 1.09 0.86 1.

EXAMPLE 6 Alternate Hydrophobic Protection Laver A three layer transfer media (Sample N) was prepared by repeating the steps of Example 5 above with the following exceptions: the ink receptive and hydrophobic layers prepared as described below were used.

The hydrophobic protection layer had the composition shown in Table below: Table 15: Sample N Protection Layer Comoosition Inerdiet Amount (parts by weigt ElvaciteO 2044 3 Bakelite®D VAGH

I

The ink receptive layer was prepared by the following procedure: A 13% Scripset® solution was prepared by adding 14 gms of Scripset@ and 7 gms dimethanolamine (DMEA)into 186 gms of water and stirring for approximately 3 hrs. The dry weight composition is shown Table 16 below: Table 16: Sample N Ink Receptive Layer Composition Ingedient Amount (parts by weight) Scripset® 640 1 Elvanol@ 52-22 3 DMEA 1 The transfer media was printed and laminated. Gloss and optical density were measured. Results are shown in Table 17 below.

TABLE 17 Optical Density Gloss K C M Y R G B At 1.31 0.71 0.72 0.70 0.76 1.08 0.83 12.6 *o° EXAMPLE 7 Transfer Media Without Protection Layer A three-layer transfer media (Sample 0) was prepared as follows: A release layer was prepared as follows: A 10% Elvacite® 2046 solution was prepared by adding 20 gms of Elvacite® 2046 to 180 gms of acetone and stirring for 3 hrs until dissolved. 2 gms of Syloid® ED2 were then added into the solution and the mixture stirred for 1 hr.

until the ingredients were well dispersed. This dispersion was then coated using a 4 mil (101 microns) knife onto a gel-subbed Mylar® (DuPont) at a coating weight of 55 gm/dm 2 The composition is shown in Table 18 below: TABLE 18: Sample O Release Layer Composition Ingredient Amount (parts by weight) Elvacite® 2046 Syloid® ED2 0.1 An ink receptive layer similar to that described in Example 1 was prepared and coated onto the release layer using a 12 mil (304 microns) knife to obtain a coating weight of 190 mg/dm 2 The transfer media was printed and laminated. Gloss and optical density were measured. Results are shown in Table 19 below.

TABLE 19 Optical Density Gloss K C M Y R G I At 1.30 0.80 0.75 0.70 0.73 1.05 0.86 12.5 Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or components referred to, but not to preclude -the presence or addition of one or more other feature, integer, e* *c step, component or group thereof.

*o o*

Claims (7)

1. A transferable image media comprising, in order; a carrier support; a release layer comprising at least one release agent selected from polyamide polymers and polyamide copolymers and combinations thereof; cellulose ethers; polyethylene oxides; and blends of water-soluble polymers with polyethylene oxide; and at least one matting agent in an amount of from about 3 to about 30% by weight, based upon the weight of the release layer; optionally, a hydrophobic protection layer having a surface adjacent the release layer, said protection layer comprising at least one compound selected fromacrylate or methacrylate polymers, epoxy resins, diene rubbers, polyolefin elastomers, polyurethane elastomers, polyvinyl chloride, polyvinyl butyral, polycarbonates, cellulose esters, and combinations thereof; and 15 an ink receptive layer comprising at least 15% of a water soluble binder selected from polyvinyl alcohol, polyvinyl pyrrolidone, polysaccharides, cellulosic compounds, gelatin, starch, gum arabic and combinations thereof; and a hydrophilic thermoplastic polymer having at least one carboxylic acid group and a molecular weight of at least 6000. 20

2. The media of Claim 1 wherein the matting agent has a particle size of 3 to 4 5 microns.

3. The media of Claim 1 wherein the matting agent has a particle size of 8 to 20 microns.

4. The media of Claim 1, 2 or 3 wherein the matting agent is selected from silica, silicates, zeolites, calcined kaolin, diatomaceous earth, barium sulfate, aluminum hydroxide or calcium carbonate, glass beads, mica, tin oxide, titanium dioxide, particles of homo- or copolymers of styrene or styrene derivatives, fluorcarbon polymers particles, crosslinked polyacrylates, and combinations thereof.

5. The media of Claim 1 wherein the acrylate or methacrylate polymer is a butyl methacrylate having Tg of 150C, a butyl methacrylate having Tg of or mixtures thereof.

6. The media of Claim 1 wherein the hydrophobic protection layer further comprises UV absorbers selected from 2-propenoic acid, 2-cyano-3,3- diphenyl-2-ethyl hexyl ester; propoxylated ethyl para-aminobenzoate; propoxylated ethyl para-aminobenzoate; dipropylene glycol salicylate; 4-dodeoylox-2-hydroxybenzophenone; 2-ethylhexyl para-dimethylaminobenzoate; 2-ethylhexyl-p-methoxycinnamate; 2-hydroxy-4-methoxybenzophenone; 2.hydroxy-n-octoxybezopheflofl; hydroxybenzoate type; nickel dibutyl dithiocarbamate; N-(phoxycarboflylphenyl)W-thy[N'iphenylforma1dile; blends of benzophenone and I1-hydroxycyclohexyl phenyl ketone; 2-methyl-i methylthio)phenyl)2-mophoflinoppaoflfl-l; 2-ethylhexyl-p-methoxy cinnamate; 2-hydroxy-methoxybenzo-phelofl; dihydroxybcnzo-phenoiie; 2-hydroxy-4-methoxybenzopheloe-5-sulforni acid; 2-bydroxy-4-n- octoxybenzophenone; 2,2',4,4'-tetrahydroxy benizophenone; Sodium 2,2'-dihydroxy-4,4' sulfobenzophenone; 2-hydroxy-4-methoxy benzophenone; 2-hydroxy-4-metboxy benzophenone-5-sulfonic acid; ethyl-2-cyano-3,3-diphenylacrylate; etbylhexyl-2- oyano-3,3-diphenylacrylate; 2,4-dihydroxy benzophenone.

7. The media of Claim I wherein the hydrophilic thermoplastic polymer having at least one carboxylic acid group and a molecular weight of at least 6000 is selected from the group consisting of methyl vinyl ether/maleic acid or anhydride; methyl vinyl etherlitaconic acid or anhydride; ethylene/maleic acid or anhydride; styrene/maleic acid or anhydride; polymethacrylic acid and polyacrylic acid. Dated this 2 0th day of December, 1999 E.I. DU PONT DE NEMOURS AND COMPANY By their Patent Attorneys: CALLINAN LAWRIE 0 0