Red dye mixture for thermal color proofing

Abstract: A red dye-donor element for thermal dye transfer comprising a support having thereon a dye layer comprising a mixture of a magenta dye and two yellow dyes dispersed in a polymeric binder, the magenta dye having the formula A the first yellow dye having the following formula B: and the second yellow dye having the formula C:

Description: This invention relates to use of a mixture of dyes for thermal dye transfer imaging which is used to obtain a color proof that accurately represents the hue of a printed color image obtained from a printing press. In order to approximate the appearance of continuous-tone (photographic) images via ink-on-paper printing, the commercial printing industry relies on a process known as halftone printing. In halftone printing, color density gradations are produced by printing patterns of dots or areas of varying sizes, but of the same color density, instead of varying the color density continuously as is done in photographic printing. There is an important commercial need to obtain a color proof image before a printing press run is made. It is desired that the color proof will accurately represent at least the details and color tone scale of the prints obtained on the printing press. In many cases, it is also desirable that the color proof accurately represent the image quality and halftone pattern of the prints obtained on the printing press. In the sequence of operations necessary to produce an ink-printed, full-color picture, a proof is also required to check the accuracy of the color separation data from which the final three or more printing plates or cylinders are made. Traditionally, such color separation proofs have involved silver halide photographic, high-contrast lithographic systems or non-silver halide light-sensitive systems which require many exposure and processing steps before a final, full-color picture is assembled. Colorants that are used in the printing industry are insoluble pigments. By virtue of their pigment character, the spectrophotometric curves of the printing inks are often unusually sharp on either the bathochromic or hypsochromic side. This can cause problems in color proofing systems in which dyes, as opposed to pigments, are being used. It is very difficult to match the hue of a given ink using a single dye. In U.S. Patent 5,126,760, a process is described for producing a direct digital, halftone color proof of an original image on a dye-receiving element. The proof can then be used to represent a printed color image obtained from a printing press. The process described therein comprises: a) generating a set of electrical signals which is representative of the shape and color scale of an original image; b) contacting a dye-donor element comprising a support having thereon a dye layer and an infrared-absorbing material with a first dye-receiving element comprising a support having thereon a polymeric, dye image-receiving layer; c) using the signals to imagewise-heat by means of a diode laser the dye-donor element, thereby transferring a dye image to the first dye-receiving element; and d) retransferring the dye image to a second dye image-receiving element which has the same substrate as the printed color image. In the above process, multiple dye-donors are used to obtain a complete range of colors in the proof. For example, for a full-color proof, four colors: cyan, magenta, yellow and black are normally used. By using the above process, the image dye is transferred by heating the dye-donor containing the infrared-absorbing material with the diode laser to volatilize the dye, the diode laser beam being modulated by the set of signals which is representative of the shape and color of the original image, so that the dye is heated to cause volatilization only in those areas in which its presence is required on the dye-receiving layer to reconstruct the original image. Similarly, a thermal transfer proof can be generated by using a thermal head in place of a diode laser as described in U.S. Patent 4,923,846. Commonly available thermal heads are not capable of generating halftone images of adequate resolution but can produce high quality continuous tone proof images which are satisfactory in many instances. U.S. Patent 4,923,846 also discloses the choice of mixtures of dyes for use in thermal imaging proofing systems. The dyes are selected on the basis of values for hue error and turbidity. The Graphic Arts Technical Foundation Research Report No. 38, "Color Material" (58-(5) 293-301, 1985) gives an account of this method. An alternative and more precise method for color measurement and analysis uses the concept of uniform color space known as CIELAB in which a sample is analyzed mathematically in terms of its spectrophotometric curve, the nature of the illuminant under which it is viewed and the color vision of a standard observer. For a discussion of CIELAB and color measurement, see Principles of Color Technology , 2nd Edition, F. W. Billmeyer, p. 25-110, Wiley-Interscience and Optical Radiation Measurements , Volume 2, F. Grum, p. 33-145, Academic Press. In using CIELAB, colors can be expressed in terms of three parameters: L*, a* and b*, where L* is a lightness function, and a* and b* define a point in color space. Thus, a plot of a* vs. b* values for a color sample can be used to accurately show where that sample lies in color space, that is, what its hue is. This allows different samples to be compared for hue if they have similar density and L* values. In color proofing in the printing industry, it is important to be able to match the printing inks. For additional information on color measurement of inks for web offset proofing, see "Advances in Printing Science and Technology", Proceedings of the 19th International Conference of Printing Research Institutes, Eisenstadt, Austria, June 1987, J. T. Ling and R. Warner, p.55. U.S. Patent 5,023,229 relates to a magenta dye-donor element comprising a mixture of a magenta dye, as disclosed herein, along with one of the yellow dyes, as disclosed herein, for color proofing. However, there is no disclosure in this reference of how to make a red dye-donor element. It is an object of this invention to provide a red dye donor element comprising a mixture of a magenta dye and two yellow dyes for color proofing which will match a red, pigmented printing ink. These and other objects are obtained by this invention which relates to a red dye-donor element for thermal dye transfer comprising a support having thereon a dye layer comprising a mixture of a magenta dye and two yellow dyes dispersed in a polymeric binder, the magenta dye having the formula A wherein: R 1 represents a substituted or unsubstituted alkyl or allyl group of from 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, cinnamyl or methallyl; X represents an alkoxy group of from 1 to 4 carbon atoms or represents the atoms which when taken together with R 2 forms a 5- or 6-membered ring, such as morpholino; R 2 represents any of the groups for R 1 or represents the atoms which when taken together with X forms a 5- or 6-membered ring, such as tetrahydropyridine; R 3 represents a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, such as those listed above for R 1 , or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms, such as phenyl, naphthyl, p-tolyl, m-chlorophenyl, p-methoxyphenyl, m-bromophenyl, o-tolyl, and so forth; J represents CO, CO 2 , -SO 2 - or CONR 5 -; R 4 represents a substituted or unsubstituted alkyl or allyl group of from 1 to 10 carbon atoms, such as those listed above for R 1 , or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms, such as those listed above for R 3 ; and R 5 represents hydrogen, a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, such as those listed above for R 1 , or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms, such as those listed above for R 3 ; the first yellow dye having the following formula B: wherein: R 13 represents a substituted or unsubstituted alkyl or alkoxy group having from 1 to 10 carbon atoms, such as methoxy, ethoxy, methoxyethoxy or 2-cyanoethoxy; or a substituted or unsubstituted aryloxy group having from 6 to 10 carbon atoms such as phenoxy, m-chlorophenoxy or naphthoxy; R 14 represents a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms or a cycloalkyl group of from 5 to 7 carbon atoms or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms, such as those listed above for R 3 ; and R 15 and R 16 each independently represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group having from 1 to 4 carbon atoms; and the second yellow dye having the formula C: wherein: R 8 , R 9 and R 11 each independently represents a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, such as those listed above for R 1 ; a cycloalkyl group of from 5 to 7 carbon atoms; a substituted or unsubstituted allyl group; or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms, such as those listed above for R 3 ; or R 8 and R 9 can be joined together to form, along with the nitrogen to which they are attached, a 5-or 6-membered heterocyclic ring, such as a pyrrolidine or morpholine ring; or either or both of R 8 and R 9 can be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring, thus forming a polycyclic system, such as 1,2,3,4-tetrahydroquinoline, julolidine, 2,3-dihydroindole, or benzomorpholine; R 10 represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, such as those listed above for R 1 ; a cycloalkyl group of from 5 to 7 carbon atoms; a substituted or unsubstituted allyl group; carbamoyl, such as N,N-dimethylcarbamoyl; or alkoxycarbonyl, such as ethoxycarbonyl or methoxyethoxy-carbonyl; R 12 represents a substituted or unsubstituted alkoxy group having from 1 to 10 carbon atoms, such as methoxy, ethoxy, methoxyethoxy or 2-cyanoethoxy; a substituted or unsubstituted aryloxy group having from 6 to 10 carbon atoms, such as phenoxy, m-chlorophenoxy, or naphthoxy; NHR 17 ; NR 17 R 18 or the atoms, such as O, CH 2 , S, NR 17 , and so forth, necessary to complete a 6-membered ring fused to the benzene ring; R 17 and R 18 each independently represents any of the groups for R 8 ; or R 17 and R 18 may be joined together to form, along with the nitrogen to which they are attached, a 5-or 6-membered heterocyclic ring, such as a pyrrolidine or morpholine ring; n is a positive integer from 1 to 5; and G represents a substituted or unsubstituted alkyl or alkoxy group of from 1 to 10 carbon atoms, such as those listed above for R 1 ; halogen; aryloxy; or represents the atoms necessary to complete a 5-or 6-membered ring, thus forming a fused ring system such as naphthalene, quinoline, isoquinoline or benzothiazole; or the second yellow dye having the structure: Compounds included within the scope of formula A employed in the invention include the following: Dye R 1 R 2 R 3 R 4 R 5 X J A1 C 2 H 5 C 2 H 5 CH 3 CH 3 C 4 H 9 -t OCH 3 CO A2 C 2 H 5 C 2 H 5 CH 3 CH 2 CH-OHCH 3 C 4 H 9 -t OCH 3 CO A3 C 3 H 7 C 3 H 7 CH 3 CH 3 C 4 H 9 -t OCH 3 CO A4 C 2 H 5 C 2 H 5 C 4 H 9 -t CH 3 CH 3 OCH 3 - CO A5 C 2 H 5 C 2 H 5 CH 3 C 2 H 5 C 4 H 9 -t OC 2 H 5 SO 2 A 6 C 2 H 5 C 2 H 5 C 2 H 5 CH 3 CH 3 OC 2 H 5 CO A7 C 2 H 5 C 3 H 7 CH 3 CH 3 C 4 H 9 -t OCH 3 CO A8 C 2 H 5 C 2 H 5 CH 3 CH 3 C 4 H 9 -t OCH 3 CO 2 A9 C 2 H 5 C 2 H 5 C 6 H 5 C 3 H 7 C 4 H 9 -t OC 2 H 5 SO 2 A10 H 2 =CH-CH 2 CH 2 =CH-CH 2 CH 3 CH 2 C 6 H 5 C 4 H 9 -t OCH 3 CO A11 C 3 H 7 C 3 H 7 C 2 H 5 C 2 H 5 CH 3 OC 3 H 7 CO A12 C 3 H 7 C 3 H 7 C 2 H 5 C 2 H 5 CH 3 OC 3 H 7 SO 2 In a preferred embodiment of the invention in the above formula A, R 1 and R 2 are each ethyl, X is OCH 3 , J is CO, R 3 is CH 3 , R 4 is CH 3 or CH 2 CHOHCH 3 and R 5 is C 4 H 9 -t. The compounds of formula A above employed in the invention may be prepared by any of the processes disclosed in U.S. Patent 3,336,285, Br 1,566,985, DE 2,600,036 and Dyes and Pigments, Vol 3, 81 (1982). The amounts of dyes used can be varied depending upon the results desired. In general, the ratio of the magenta dye to the yellow dyes is from 3:1 to 1:1. Yellow dyes included within the scope of formula B which may be employed in the invention include the following: Dye R 15 R 16 R 13 R 14 B1 3-CH 3 O 4-CH 3 O CH 3 C 6 H 5 B2 3-CH 3 O H CH 3 C 6 H 5 B3 H 4-CH 3 O CH 3 C 6 H 5 B4 CH 3 4-CH 3 O CH 3 C 6 H 5 B5 CH 3 CH 3 CH 3 C 6 H 5 B6 CH 3 CH 3 CH 3 O C 6 H 5 B7 CH 3 CH 3 CH 3 O C 6 H 5 B8 H 4-CH 3 O CH 3 O C 6 H 5 The above dyes of Formula B are disclosed in U.S. Patent 5,866,509. In a preferred embodiment of the invention, R 14 is phenyl, R 13 is methyl, R 15 is 3-methoxy and R 16 is 4-methoxy. Yellow dyes included within the scope of formula C which may be employed in the invention include the following: In a preferred embodiment of the invention, in formula C, R 11 is phenyl, R 12 is ethoxy or NHR 17 , wherein R 17 is methyl or phenyl, n is 1 and R 10 is hydrogen. In another preferred embodiment, R 12 is O and completes a 6-membered ring fused to the benzene ring. In still another preferred embodiment, R 12 is NR 17 R 18 , wherein each R 17 and R 18 is methyl or R 17 is ethyl and R 18 is phenyl. In still another embodiment, R 12 is NR 17 R 18 , wherein R 17 and R 18 are joined together to form, along with the nitrogen to which they are attached, a pyrrolidine or morpholine ring. The compounds of formula C employed in the invention above may be prepared by any of the processes disclosed in U.S. Patent 4,866,029. The use of dye mixtures in the dye-donor of the invention permits a wide selection of hue and color that enables a closer hue match to a variety of printing inks to be achieved and also permits easy transfer of images to a receiver one or more times if desired. The use of dyes also allows easy modification of image density to any desired level. The dyes of the dye-donor element of the invention may be used at a coverage of from 0.02 to 1 g/m 2 . The dyes in the dye-donor of the invention are dispersed in a polymeric binder such as a cellulose derivative, for example, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate or any of the materials described in U. S. Patent 4,700,207; a polycarbonate; poly(vinyl acetate); poly(styrene-co-acrylonitrile); a polysulfone or a poly(phenylene oxide). The binder may be used at a coverage of from 0.1 to 5 g/m 2 . The dye layer of the dye-donor element may be applied by any method such as coating on the support or printing thereon by a technique such as a gravure process. Any material can be used as the support for the dye-donor element of the invention provided it is dimensionally stable and can withstand the heat of the laser or thermal head. Such materials include polyesters such as poly(ethylene terephthalate); polyamides; polycarbonates; cellulose esters such as cellulose acetate; fluorine polymers such as poly(vinylidene fluoride) or poly(tetrafluoroethylene-co-hexafluoropropylene); polyethers such as polyoxymethylene; polyacetals; polyolefins such as polystyrene, polyethylene, polypropylene or methylpentene polymers; and polyimides such as polyimide-amides and polyether-imides. The support generally has a thickness of from 5 to 200 µm. It may also be coated with a subbing layer, if desired, such as those materials described in U. S. Patents 4,695,288 or 4,737,486. The reverse side of the dye-donor element may be coated with a slipping layer to prevent the printing head from sticking to the dye-donor element. Such a slipping layer would comprise either a solid or liquid lubricating material or mixtures thereof, with or without a polymeric binder or a surface-active agent. Preferred lubricating materials include oils or semicrystalline organic solids that melt below 100°C such as poly(vinyl stearate), beeswax, perfluorinated alkyl ester polyethers, polycaprolactone, silicone oil, polytetrafluoroethylene, carbowax, poly(ethylene glycols), or any of those materials disclosed in U. S. Patents 4,717,711; 4,717,712; 4,737,485; and 4,738,950. Suitable polymeric binders for the slipping layer include poly(vinyl alcohol-co-butyral), poly(vinyl alcohol-co-acetal), polystyrene, poly(vinyl acetate), cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate or ethyl cellulose. The amount of the lubricating material to be used in the slipping layer depends largely on the type of lubricating material, but is generally in the range of 0.001 to 2 g/m 2 . If a polymeric binder is employed, the lubricating material is present in the range of 0.1 to 50 weight %, preferably 0.5 to 40 %, of the polymeric binder employed. The dye-receiving element that is used with the dye-donor element of the invention usually comprises a support having thereon a dye image-receiving layer. The support may be a transparent film such as a poly(ether sulfone), a polyimide, a cellulose ester such as cellulose acetate, a poly(vinyl alcohol-co-acetal) or a poly(ethylene terephthalate). The support for the dye-receiving element may also be reflective such as baryta-coated paper, polyethylene-coated paper, an ivory paper, a condenser paper or a synthetic paper such as DuPont Tyvek RTM . Pigmented supports such as white polyester (transparent polyester with white pigment incorporated therein) may also be used. The dye image-receiving layer may comprise, for example, a polycarbonate, a polyurethane, a polyester, poly(vinyl chloride), poly(styrene-co-acrylonitrile), polycaprolactone, a poly(vinyl acetal) such as poly(vinyl alcohol-co-butyral), poly(vinyl alcohol-co-benzal), poly(vinyl alcohol-co-acetal) or mixtures thereof. The dye image-receiving layer may be present in any amount which is effective for the intended purpose. In general, good results have been obtained at a concentration of from 1 to 5 g/m 2 . As noted above, the dye-donor elements of the invention are used to form a dye transfer image. Such a process comprises imagewise-heating a dye-donor element as described above and transferring a dye image to a dye-receiving element to form the dye transfer image. The dye-donor element of the invention may be used in sheet form or in a continuous roll or ribbon. If a continuous roll or ribbon is employed, it may have only the dyes thereon as described above or may have alternating areas of other different dyes or combinations, such as sublimable cyan and/or yellow and/or black or other dyes. Such dyes are disclosed in U. S. Patent 4,541,830. Thus, one-, two-, three- or four-color elements (or higher numbers also) are included within the scope of the invention. Thermal printing heads which can be used to transfer dye from the dye-donor elements of the invention are available commercially. There can be employed, for example, a Fujitsu Thermal Head (FTP-040 MCSOO1), a TDK Thermal Head F415 HH7-1089 or a Rohm Thermal Head KE 2008-F3. A laser may also be used to transfer dye from the dye-donor elements of the invention. When a laser is used, it is preferred to use a diode laser since it offers substantial advantages in terms of its small size, low cost, stability, reliability, ruggedness, and ease of modulation. In practice, before any laser can be used to heat a dye-donor element, the element must contain an absorbing material which absorbs at the emitting wavelength of the laser. When an infrared laser is employed, then an infrared-absorbing material may be used, such as carbon black, cyanine infrared-absorbing dyes as described in U.S. Patent 4,973,572, or other materials as described in the following U.S. Patents: 4,948,777; 4,950,640; 4,950,639; 4,948,776; 4,948,778; 4,942,141; 4,952,552; 5,036,040; 5,972,838 and 4,912,083. The laser radiation is then absorbed into the dye layer and converted to heat by a molecular process known as internal conversion. Thus, the construction of a useful dye layer will depend not only on the hue, transferability and intensity of the image dyes, but also on the ability of the dye layer to absorb the radiation and convert it to heat. Lasers which can be used to transfer dye from dye-donors employed in the invention are available commercially. There can be employed, for example, Laser Model SDL-2420-H2 from Spectra Diode Labs, or Laser Model SLD 304 V/W from Sony Corp. A thermal printer which uses the laser described above to form an image on a thermal print medium is described and claimed in U.S. Patent 5,268,708. Spacer beads may be employed in a separate layer over the dye layer of the dye-donor in the above-described laser process in order to separate the dye-donor from the dye-receiver during dye transfer, thereby increasing the uniformity and density of the transferred image. That invention is more fully described in U.S. Patent 4,772,582. Alternatively, the spacer beads may be employed in the receiving layer of the dye-receiver as described in U.S. Patent 4,876,235. The spacer beads may be coated with a polymeric binder if desired. The use of an intermediate receiver with subsequent retransfer to a second receiving element may also be employed in the invention. A multitude of different substrates can be used to prepare the color proof (the second receiver) which is preferably the same substrate as that used for the printing press run. Thus, this one intermediate receiver can be optimized for efficient dye uptake without dye-smearing or crystallization. Examples of substrates which may be used for the second receiving element (color proof) include the following: Flo Kote Cover RTM (S. D. Warren Co.), Champion Textweb RTM (Champion Paper Co.), Quintessence Gloss RTM (Potlatch Corp.), Vintage Gloss RTM (Potlatch Corp.), Khrome Kote RTM (Champion Paper Co.), Consolith Gloss RTM (Consolidated Papers Co.), Ad-Proof Paper RTM (Appleton Papers, Inc.) and Mountie Matte RTM (Potlatch Corp.). As noted above, after the dye image is obtained on a first dye-receiving element, it may be retransferred to a second dye image-receiving element. This can be accomplished, for example, by passing the two receivers between a pair of heated rollers. Other methods of retransferring the dye image could also be used such as using a heated platen, use of pressure and heat, external heating, and so forth Also as noted above, in making a color proof, a set of electrical signals is generated which is representative of the shape and color of an original image. This can be done, for example, by scanning an original image, filtering the image to separate it into the desired additive primary colors, that is, red, blue and green, and then converting the light energy into electrical energy. The electrical signals are then modified by computer to form the color separation data which are used to form a halftone color proof. Instead of scanning an original object to obtain the electrical signals, the signals may also be generated by computer. This process is described more fully in Graphic Arts Manual , Janet Field ed., Arno Press, New York 1980 (p. 358ff). A thermal dye transfer assemblage of the invention comprises a) a dye-donor element as described above, and b) a dye-receiving element as described above, the dye-receiving element being in a superposed relationship with the dye-donor element so that the dye layer of the donor element is in contact with the dye image-receiving layer of the receiving element. The above assemblage comprising these two elements may be preassembled as an integral unit when a monochrome image is to be obtained. This may be done by temporarily adhering the two elements together at their margins. After transfer, the dye-receiving element is then peeled apart to reveal the dye transfer image. The following examples are provided to illustrate the invention. Dye-Donor Element 1 On a 100 µm poly(ethylene terephthalate) support having a subbing layer of Tyzor TBT RTM (0.13g/m 2 ) was coated a dye layer containing magenta dye A2 illustrated above (0.09g/m 2 ), yellow dye B1 illustrated above (0.022 g/m 2 ), yellow dye C 1 illustrated above (0.042 g/m 2 ) the cyanine infrared-absorbing dye disclosed in U.S. Patent 5,972,838 (IR2 tributylamine salt column 12, lines 25-40) at 0.043 g/m 2 in a cellulose acetate binder (CAP 480-20 from Eastman Chemical Company) (0.16 g/m 2 ) from a solvent mixture of diethylketone, 1-methoxy-2-propanol and methanol (66/27/6 wt./wt). Dye-Donor Element 2 This was the same as element 1 except that Dye B1 was coated at 0.032g/m 2 and Dye C1 was coated at 0.032g/m 2 . Printing Proof test images were produced on a Creo Trendsetter Spectrum platesetter/proofer equipped for proofing with a modified printhead and a cassette media-loading device. The images were initially formed by transferring the dye from the test donor to a Kodak APPROVAL RTM . Intermediate Color Proofing Film, CAT # 831 5582, mounted on the drum. The test image consisted of 100% dot solid area patches which were produced by an exposure at the film plane of 205 to 315.5 mJ/cm 2 obtained by a combination of laser power and drum rotation rate. The Intermediate film was then laminated to a Vintage Gloss RTM (Potlatch Corp.) paper stock that had been previously laminated with Kodak APPROVAL RTM Prelaminate, CAT # 173 9671 in a Kodak APPROVAL RTM 800XL Laminator to form the final images. Color and density measurements were made using a X-rite[®] RTM 938 portable spectrophotometer set for D 50 illuminant and 2 degree observer angle. Readings were made with black backing behind the samples. In using CIELAB, colors can be expressed in terms of three parameters: L*, a* and b*, where L* is a lightness function, and a* and b* define a point in color space. Thus, a plot of a* vs. b* values for a color sample can be used to accurately show where that sample lies in color space, that is, what its hue is. This allows different samples to be compared for hue if they have similar L* values. The color differences between the samples can be expressed as ΔE, where ΔE is the vector difference in CIELAB color space between the laser thermal generated image and the red ink color aim, according to the following formula: ΔE =square root [(L* e -L* s ) 2 +(a* e -a* s ) 2 +(b* e -b* s ) 2 ] wherein subscript e represents the measurements from the experimental material and subscript s represents the measurements from the red ink color aim. The red ink color aim is the Pantone RTM Formula Guide Red 199 C. The color differences can also be expressed in terms of a hue angle and saturation C* according to the following formulas: Hue angle = arctan b*/a* C* =square root (a* 2 +b* 2 ) A ΔE of less than 4, a ΔHue angle of plus or minus 3° and a Δ C* of less than 3 is acceptable. The results are shown in table 1 with Dye-Donor Elements 1 and 2 being exposed at 315.5 and 205.8mJ/cm 2 respectively: Red Element L* a* b* ΔE Hue angle ΔHue angle C* ΔC* Control Aim 47.6 72.4 34.5 - 25.5 - 80.2 - 1 45.8 70.7 33.6 2.5 25.4 -0.1 78.3 -1.9 2 47.5 69.4 35.2 3.1 26.9 1.4 77.8 -2.4 The above results show that the red dye-donor elements of the invention provided an acceptable match to the red printing ink control. Example 2 Example 1 was repeated with Dye-Donor Element 2 except that the printing device was a Kodak Approval RTM XP Digital Color Proofing System at a film plane power of 350 mw and a drum rotation rate necessary to achieve exposures of 200-315 mJ/cm 2 . The results are shown in the following Table 2, run at 260 mJ/cm 2 . Red Element L* a* b* ΔE Hue angle ΔHue angle C* ΔC* Control Aim 47.6 72.4 34.5 - 25.5 - 80.2 - 2 47.7 69.8 35.1 2.7 26.7 1.2 78.1 -2.1 The above results show that the red dye-donor element of the invention provided an acceptable match to the red printing ink control.

Claims: A red dye-donor element for thermal dye transfer comprising a support having thereon a dye layer comprising a mixture of a magenta dye and two yellow dyes dispersed in a polymeric binder, the magenta dye having the formula A wherein: R 1 represents a substituted or unsubstituted alkyl or allyl group of from 1 to 6 carbon atoms; X represents an alkoxy group of from 1 to 4 carbon atoms or represents the atoms which when taken together with R 2 forms a 5- or 6-membered ring; R 2 represents any of the groups for R 1 or represents the atoms which when taken together with X forms a 5- or 6-membered ring; R 3 represents a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms; J represents CO, CO 2 , -SO 2 - or CONR 5 -; R 4 represents a substituted or unsubstituted alkyl or allyl group of from 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms; and R 5 represents hydrogen, a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms; the first yellow dye having the following formula B: wherein: R 13 represents a substituted or unsubstituted alkyl or alkoxy group having from 1 to 10 carbon atoms or a substituted or unsubstituted aryloxy group having from 6 to 10 carbon atoms; R 14 represents a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms, a cycloalkyl group of from 5 to 7 carbon atoms, or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms; and R 15 and R 16 each independently represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group having from 1 to 4 carbon atoms; and the second yellow dye having the formula C: wherein: R 8 , R 9 and R 11 each independently represents a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms; a cycloalkyl group of from 5 to 7 carbon atoms; a substituted or unsubstituted allyl group; or a substituted or unsubstituted aryl group of from 6 to 10 carbon atoms; or R 8 and R 9 can be joined together to form, along with the nitrogen to which they are attached, a 5-or 6-membered heterocyclic ring; or either or both of R 8 and R 9 can be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring, thus forming a polycyclic system; R 10 represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to 10 carbon atoms; a cycloalkyl group of from 5 to 7 carbon atoms; a substituted or unsubstituted allyl group; carbamoyl; or alkoxycarbonyl; R 12 represents a substituted or unsubstituted alkoxy group having from 1 to 10 carbon atoms; a substituted or unsubstituted aryloxy group having from 6 to 10 carbon atoms; NHR 17 ; NR 17 R 18 or the atoms necessary to complete a 6-membered ring fused to the benzene ring; R 17 and R 18 each independently represents any of the groups for R 8 ; or R 17 and R 18 may be joined together to form, along with the nitrogen to which they are attached, a 5-or 6-membered heterocyclic ring; n is a positive integer from 1 to 5; and G represents a substituted or unsubstituted alkyl or alkoxy group of from 1 to 10 carbon atoms; halogen; aryloxy; or represents the atoms necessary to complete a 5- or 6-membered ring, thus forming a fused ring system; or the second yellow dye having the structure: The element of Claim 1 wherein the dye-donor element contains an infrared-absorbing dye in the dye layer. The element of Claim 1 wherein in formula A, R 1 and R 2 are each ethyl, X is OCH 3 , J is CO, R 3 is CH 3 , R 4 is CH 3 or CH 2 CHOHCH 3 and R 5 is C 4 H 9 -t. The element of Claim 1 wherein in formula B, R 14 is phenyl, R 13 is methyl, R 15 is 3-methoxy and R 16 is 4-methoxy. The element of Claim 1 wherein in formula C, R 11 is phenyl, R 12 is ethoxy or NHR 17 , wherein R 17 is methyl or phenyl, n is 1 and R 10 is hydrogen. The element of Claim 1 wherein in formula C, R 12 is O and completes a 6-membered ring fused to the benzene ring. The element of Claim 1 wherein in formula C, R 12 is NR 17 R 18 , wherein each R 17 and R 18 is methyl or R 17 is ethyl and R 18 is phenyl. The element of Claim 1 wherein in formula C, R 12 is NR 17 R 18 , wherein R 17 and R 18 are joined together to form, along with the nitrogen to which they are attached, a pyrrolidine or morpholine ring. A process of forming a red dye transfer image comprising imagewise-heating the red dye-donor element of Claim 1, and transferring a dye image to a dye-receiving element to form the red dye transfer image. A thermal dye transfer assemblage comprising: a) the red dye-donor element of Claim 1, and b) a dye-receiving element comprising a support having thereon a dye image-receiving layer, the dye-receiving element being in a superposed relationship with the red dye-donor element so that the dye layer is in contact with the dye image-receiving layer.

Inventors: CHAPMAN DEREK DAVID, KASZCZUK LINDA A, PEARCE GLENN T, CHAPMAN, DEREK DAVID, KASZCZUK, LINDA A., PEARCE, GLENN T., Chapman, Derek David, Eastman Kodak Company, Kaszczuk, Linda A., Eastman Kodak Company, Pearce, Glenn T., Eastman Kodak Company
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 2001
Main classification: B41M5
IPC codes: C09B23, C09B67, B41M5, G03F3, C09B29