THERMALLY-TRANSFERRED NEAR-INFRARED ABSORBING DYES

Abstract: A dye-donor element for thermal dye transfer comprising a support having on one side thereof a near-infrared absorbing dye comprising a dithiolene-­ nickel(II) complex dispersed in a polymeric binder, and on the other side thereof a slipping layer comprising a lubricant, the dye having the formula: wherein each R¹, R², R³ and R⁴ independently represents a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms; a substituted or unsubstituted heterocyclic group; or R¹ and R² may be combined together with the carbon atoms to which they are attached to form a 5- or 6-membered carbocylic or heterocyclic ring; or R³ and R⁴ may be combined together with the carbon atoms to which they are attached to form a 5- or 6-membered carbocyclic or heterocyclic ring.

Description: This invention relates to near-infrared absorbing dye-donor elements used in thermal dye transfer wherein the dye comprises a dithiolene-nickel(II) complex. In recent years, thermal transfer systems have been developed to obtain prints from pictures which have been generated electronically from a color video camera. According to one way of obtaining such prints, an electronic picture is first subjected to color separation by color filters. The respective color-separated images are then converted into electrical signals. These signals are then operated on to produce cyan, magenta and yellow electrical signals. These signals are then transmitted to a thermal printer. To obtain the print, a cyan, magenta or yellow dye-donor element is placed face-to-face with a dye-receiving element. The two are then inserted between a thermal printing head and a platen roller. A line-type thermal printing head is used to apply heat from the back of the dye-donor sheet. The thermal printing head has many heating elements and is heated up sequentially in response to the cyan, magenta and yellow signals. The process is then repeated for the other two colors. A color hard copy is thus obtained which corresponds to the original picture viewed on a screen. Further details of this process and an apparatus for carrying it out are contained in U.S. Patent No. 4,621,271 by Brownstein entitled "Apparatus and Method For Controlling A Thermal Printer Apparatus," issued November 4, 1986. The system described above has been used to obtain visible dye images. There are situations, however, where it is desirable to obtain an image not substantially visible to the naked eye. Bar-code standards for code 3 of the AIAG (Automotive Industry Action Group) Bar Code Symbology Standard AIAG-B-1-1984 specifies image density at 900 nm for reading by near-infrared readers or scanners. A somewhat similar U.S. military standard specifies density at 800 nm. Thus, a bar-code scanner could be used to read bar-codes or striped images if they had a near-infrared density. JP 62/087,388 discloses a particular near-infrared absorbing agent in a thermal transfer sheet which is used with an acceptor sheet having a thermoplastic substance capable of dissolving the near-infrared absorbing agent. There is a problem with using those compounds, however, in that a special acceptor sheet is required in order to dissolve the compounds. It is an object of this invention to provide a dye-donor element which contains a near-infrared absorbing dye which does not require an accepting sheet containing a special compound to dissolve the near-infrared absorbing dye. It is another object of this invention to provide a dye image which could be thermally-transferred by a thermal print head to a receiver which would then be read by a bar-code scanner. An example of such a use would be an identification card having a thermally-transferred near-infrared dye image, serving as a security printing or background logo, to be read only by a bar-code scanner. A forger of such a card might not even be aware of the near-infrared dye image since it would not be visible to the naked eye. These and other objects are achieved in accordance with this invention which comprises a dye-donor element for thermal dye transfer comprising a support having on one side thereof a near-infrared absorbing dye dispersed in a polymeric binder, and on the other side thereof a slipping layer comprising a lubricant, characterized in that the dye has the formula: wherein each R¹, R², R³ and R⁴ independently represents a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms such as -CH₃, -C₂H₅, -CH(CH₃)₂, -CH₂-CH₂-O-CH₃, - n -C₄H₉, i -C₄H₉, t -C₅H₁₁; a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms such as a substituted or unsubstituted heterocyclic group such as or or R¹ and R² may be combined together with the carbon atoms to which they are attached to form a 5- or 6-membered carbocyclic or heterocyclic ring, such as or R³ and R⁴ may be combined together with the carbon atoms to which they are attached to form a 5- or 6-membered ring such as those listed above for R¹ and R²; with the proviso that R¹ and R² cannot both be the same and R³ and R⁴ cannot both be the same. In a preferred embodiment of the invention, each of R¹, R², R³, and R⁴ is a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms. In another preferred embodiment, at least one of R¹, R², R³, and R⁴ is phenyl. The above complexes have substantial absorbance in the near-infrared region (750-1000 nm), minimal visible absorption (as coated or transferred, they generally appear as a light gray-green hue), good solubility for coating from common oxygenated solvents, and good thermal volatility. These properties make these complexes well-suited for printing of designs such as the bars or stripes of a bar-code and reading the near-infrared density by a scanner. The dyes employed in the invention have transferred density having adequate discrimination for a good print contrast signal for such applications. In another embodiment of this invention, the above complexes may be combined with dyes absorbing in the visible region to form a transferred image with improved light stability. The addition of a visible absorbing dye also allows transfer of an image in conformance with military standard MIL-STD-1189A for bar codes which requires a readable image at 633nm and provides for readings at 800 and 900nm in the near infrared. Compounds included within the scope of the invention include the following: These dithiolene complexes may be prepared by established synthetic procedures, such as described in G. N. Schranzer and V. P. Mayweg, J. Am. Chem. Soc., 84 , 3221 (1962). The dye in the dye-donor element of the invention is dispersed in a polymeric binder such as a cellulose derivative, e.g., cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate; a polycarbonate; poly(styrene-co-acrylonitrile), a poly(sulfone) or a poly(phenylene oxide). The binder may be used at a coverage of from 0.1 to 5 g/m². The dye layer of the dye-donor element may be coated on the support or printed thereon by a printing 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 thermal printing heads. Such materials include polyesters such as poly(ethylene terephthalate); polyamides; polycarbonates; glassine paper; condenser paper; cellulose esters, fluorine polymers; polyethers; polyacetals; polyolefins; and polyimides. The support generally has a thickness of from 2 to 30 µm. It may also be coated with a subbing layer, if desired. The reverse side of the dye-donor element is coated with a slipping layer to prevent the printing head from sticking to the dye-donor element. Such a slipping layer would comprise a lubricating material such as a surface active agent, a liquid lubricant, a solid lubricant or mixtures thereof, with or without a polymeric binder. Preferred lubricating materials include oils or semi-crystalline organic solids that melt below 100°C such as poly(vinyl stearate), beeswax, perfluorinated alkyl ester polyesters, poly(caprolactone), silicone oil, poly(tetrafluoroethylene), carbowax or poly(ethylene glycols). Suitable polymeric binders for the slipping layer include poly(vinyl alcohol-co-butyral), poly(vinyl alcohol-co-acetal), poly(styrene), poly(vinyl acetate), cellulose acetate butyrate, 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 .001 to 2 g/m². 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 poly(ethylene terephthalate) or reflective such as baryta-coated paper, polyethylene-coated paper, while polyester (polyester with white pigment incorporated therein), etc. In a preferred embodiment, polyester with a white pigment incorporated therein is employed. The dye image-receiving layer may comprise, for example, a polycarbonate, a polyurethane, a polyester, polyvinyl chloride, poly(styrene- co -acrylonitrile), poly(caprolactone) 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/m². 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 near-infrared dye thereon as described above or may have alternating areas of other different dyes, such as sublimable magenta and/or yellow and/or cyan 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. In a preferred embodiment of the invention, the dye-donor element comprises a poly(ethylene terephthalate) support coated with sequential repeating areas of magenta, yellow, cyan and the near-infrared dye as described above. A thermal dye transfer assemblage using 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. When a multi-color image is to be obtained, the above assemblage is formed on several occasions during the time when heat is applied by the thermal printing head. After the first dye is transferred, the elements are peeled apart. A second dye-donor element (or another area of the donor element with a different dye area) is then brought in register with the dye-receiving element and the process repeated. The other colors are obtained in the same manner. The following examples are provided to illustrate the invention. Example 1 A dye-donor element was prepared by coating the following layers in the order recited on a 6 µm poly(ethylene terephthalate) support: 1) subbing layer of duPont Tyzor TBT® titanium tetra- n -butoxide (0.16 g/m²) from 1-butanol; and 2) a dye layer containing the near-infrared dye as identified above or control dye identified below (0.27 g/m²) in a cellulose acetate butyrate (17% butyryl and 28% acetyl) binder (0.32 g/m²) coated from a tetrahydrofuran, acetone and cyclohexanone solvent mixture. On the back side of the element was coated: 1) a subbing layer of Bostik 7650® (Emhart Corp.) polyester (0.16 g/m²) coated from a toluene and 3-pentanone solvent mixture; and 2) a slipping layer of Gafac RA-600® (GAF Corp.) polymer (0.043 g/m²) and BYK-320® (BYK Chemie, USA) (0.011 g/m²) in a poly(styrene- co -acrylonitrile) binder (70:30 wt. ratio) (0.54 g/m²) coated from a toluene and 3-pentanone solvent mixture. A dye-receiving element was prepared by coating a solution of Makrolon 5705® (Bayer A.G. Corporation) polycarbonate resin (2.9 g/m²) in a methylene chloride and trichloroethylene solvent mixture on a 175 µm polyethylene terephthalate support containing titanium dioxide. The dye side of the dye-donor element strip one inch (25 mm) wide was placed in contact with the dye image-receiving layer of the dye-receiver element of the same width. The assemblage was fastened in the jaws of a stepper motor driven pulling device. The assemblage was laid on top of a 0.55 (14 mm) diameter rubber roller and a TDK Thermal Head L-133 (No. C6-0242) and was pressed with a spring at a force of 8 pounds (3.6 kg) against the dye-donor element side of the assemblage pushing it against the rubber roller. The imaging electronics were activated causing the pulling device to draw the assemblage between the printing head and roller at 0.123 inches/sec (3.1 mm/sec). Coincidentally, the resistive elements in the thermal print head were heated at increments from 0 up to 8.3 msec to generate a graduated density test pattern. The voltage supplied to the print head was approximately 21 v representing approximately 1.7 watts/dot (12 mjoules/dot). The dye-receiving element was separated from the dye-donor element and the reflection density of the transferred image was read from 600 to 1000 nm. The λ-max was calculated and the densities at λ-max and 900 nm were recorded. The following results were obtained: Dye λ-max (nm) Transferred Reflection Density D-max at 900 nm 1 800 1.27 0.54 2 832 1.24 0.87 3 830 0.87 0.59 4 838 0.76 0.55 5 905 0.44 0.44 6 910 0.92 0.92 7 906 0.88 0.87 8 856 0.96 0.79 9 922 0.92 0.87 10 933 0.60 0.87 11 870 1.08 1.05 C-1 900 0.01 0.01 C-2 813 0.16 0.09 Control near-infrared absorbing dyes: The data show that the nickel(II) dithiolene dyes of the invention all have superior transfer and absorption characteristics in the near infrared region compared to two control dyes.

Claims: A dye-donor element for thermal dye transfer comprising a support having on one side thereof a near-infrared absorbing dye dispersed in a polymeric binder, and on the other side thereof a slipping layer comprising a lubricant, characterized in that said dye has the formula: wherein: each R¹, R², R³, and R⁴ independently represents a substituted or unsubstituted alkyl group having from 1 to 10 carbon atoms; a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms; a substituted or unsubstituted heterocyclic group; or R¹ and R² may be combined together with the carbon atoms to which they are attached to form a 5- or 6-membered carbocyclic or heterocyclic ring; or R³ and R⁴ may be combined together with the carbon atoms to which they are attached to form a 5- or 6-membered carbocyclic or heterocyclic ring; with the proviso that R¹ and R² cannot both be the same and R³ and R⁴ cannot both be the same. The element of Claim 1 characterized in that each of R¹, R², R³, and R⁴ is a substituted or unsubstituted aryl group having from 6 to 10 carbon atoms. The element of Claim 1 characterized in that at least one of R¹, R², R³, and R⁴ is phenyl. The element of Claim 1 characterized in that R¹ and R⁴ are each The element of Claim 1 characterized in that said dye donor element comprises sequential repeating areas of magenta, yellow, cyan, and said near-infrared dye.

Inventors: BYERS, GARY WAYNE C/O EASTMAN KODAK COMPANY, CHAPMAN, DEREK DAVID C/O EASTMAN KODAK COMPANY
Applicants: EASTMAN KODAK COMPANY (A NEW JERSEY CORPORATION)
Application year: 1988
Main classification: B41M5
IPC codes: B41M5, D06P5, C09K3