CA2037154A1 - Receiver for thermally-transferable fluorescent europium complexes - Google Patents
Receiver for thermally-transferable fluorescent europium complexesInfo
- Publication number
- CA2037154A1 CA2037154A1 CA002037154A CA2037154A CA2037154A1 CA 2037154 A1 CA2037154 A1 CA 2037154A1 CA 002037154 A CA002037154 A CA 002037154A CA 2037154 A CA2037154 A CA 2037154A CA 2037154 A1 CA2037154 A1 CA 2037154A1
- Authority
- CA
- Canada
- Prior art keywords
- image
- europium
- complex
- coordinate
- electron
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/38235—Contact thermal transfer or sublimation processes characterised by transferable colour-forming materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
- B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
- B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/142—Dye mordant
Abstract
RECEIVER FOR THERMALLY-TRANSFERABLE
FLUORESCENT EUROPIUM COMPLEXES
Abstract of the Disclosure A receiving element for thermal transfer comprising a support having thereon a polymeric image-receiving layer which also contains a monodentate or bidentate ligand capable of reacting with a 6-coordinate europium(III) complex, transferred from a donor element, to form a higher coordinate complex in situ having the formula:
-B
wherein. D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
FLUORESCENT EUROPIUM COMPLEXES
Abstract of the Disclosure A receiving element for thermal transfer comprising a support having thereon a polymeric image-receiving layer which also contains a monodentate or bidentate ligand capable of reacting with a 6-coordinate europium(III) complex, transferred from a donor element, to form a higher coordinate complex in situ having the formula:
-B
wherein. D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
Description
7 ~ ~r~
RE OEIVER FOR T~ERMALLY-TRANSFERABLE
FLUORESCENT EUROPI~M COMPLEXES
This invention relates to a receiving element which i8 used~with a donor element containing a 6-coordinate europium(III) complex to form a higher coordinate 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 i~ first ~ubjected to color separation by color filters. The respective color-separated images are then converted into elec-trical signals. These signals are then operated on to produce cyan, magenta and yellow electrical sig-nals. These signals are then transmitted to a ther-mal 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 i9 used to apply heat ~rom the back of the dye-donor sheet. The thermal printing head has many heating elements and i~ heated up sequentially in response to the cyan, magenta and yellow signals. The process is then repeated ~or the other two colors. A color hard copy is thus obtained which corresponds to the original picture viewed on a screen. Further details o~ this process and an apparatus for carryin~ it out are contained in U.S. Patent No. 4,621,271 by Brownstein entitled "Apparatus and Method For Controlling A
Thermal Printer Apparatust" issued November 4t 1986.
The system described above has been used to obtain visible dye images. ~owever, for ~tecurity purposes, to inhibit forgeries or duplication, or to encode con~idential in~ormation, it would be ~7~
advantageous to create non-visual ultraviolet absorbing images that Pluoresce with visible emi3sion when illuminated with ultraviolet light.
U.S. Patents 4,876,237, 4,871,714, 5 4,876,234, 4,866,025, 4,860,027, 4,891,351, and 4,891,352 all relate to thermally-transferable fluorescent materials used in a continuou~ tone system. ~owever, none of those materials fluoresce a visible red color when illuminated with ultraviolet light, and none of them describe ligand3 for use in the receiving element. A red color is desirable for many security applications U.S. Patent 4,627,997 discloses a fluorescent thermal transfer recording medium comprising a thermally-meltable, wax ink layer. It i8 an object of this invention to provide a receiving element which contains ligands to react with `!
fluorescent materials transferred from a donor element.
Theæe and other objects are achieved in accordance with this invention which comprises a receiving element for thermal transfer comprising a support having ~hereon a polymeric image-receiving layer, characterized in that the image-receiving layer also contains a monodentate or bidentate ligand capable of reacting with a 6-coordinate europium(III~
complex to form a higher coordinate complex, the higher coordinate complex which is formed in situ in the receiving layer having the following formula:
D, ~C ~ C 0\ ~ u- - B
/c=o/
_ J _ 3 wherein: D and J are defined as above and ~
represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom, e.g., ~ri-n-oCtylphosphine oxide, pyridine-N-oxide or triphenylphosphine oxide; or at least one bidentate ligand with two electron-donating oxygen, nitrogen or ~ulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom, e.g., 2,2'-bipyridine, l,10-phenanthroline, ethylene diamine or 1,2-diaminobutane.
In a pre~erred embodiment of the invention, the 6-coordinate europium(III) complex, which is generally supplied from a donor element, has the formula:
D~
~ C --~0\ ~ u _ J _ 3 wherein: D i~ a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heteroeyclic moiety, e.g. t phenyl, 2-thienyl, 2-furyl, 3-pyridyl, etc.; and The above ~luorescent europium comple~es are essentially non-visible, but emit with a unigue red hue in the xegion of 610 to 625 nm when irradiated with 360 nm ultraviolet light. This red hue is highly desirable ~or security-badging applications.
~uropium(III) is the only rare-earth known to be ~uitable for the practice o~ the invention.
~ s~
Rare earth metals, including europium, are described in the literature such as S, Nakamura and N. Suzuki, Polyhedron, S, 1805 (1986); T. Taketatsu, Talanta, 29, 397 (1982); and E Brittain, J.C.S. Dalton, 1187 - 5 (1979).
Diketone ligands ~rom which the 6-coordinate complexes are derived include the following within the scope of the invention:
6-coQ-rdinat-~-comple~ Diketone Li~rLd Compound l 0 0 \s/o e - CH2 - e - CF3 COmpOund 2 ~o/ !1--e--CE2--e~CF3 Compound 3 o~ ~--C-CH -C-CF
O O
Compound 4 \ _ /-- e - CH2~e - CF3 2.~
O O
Compound 5 \ ~o e - GH2 - e - C~3 =--Compound 6 CH30~-C-CH2- e - CF3 Compound 7 C~30 0 ~--R 11 il ~ ~U--C--CH2--C -CH3 r.,~ J
Suitable monodentate and bidentate ligands within the scope of the invention for incorporation in the receiving element include:
O ~ 2,2~-Bipyridine (Kodak Lab. Chemicals ~ _ ~ ~ No. 4397) ~=D~
10 J~ ~--~ ,10-Phenanthroline (Kodak Lab.
\=N/ \N=D/ Chemicals Ii~o. 3289) H~NC~2CE2NH2 Ethylene diamine (Kodak Lab.
Chemicals No. 1915 (n C8H17)3P0 Trioctylphosphine Oxide (Kodak Lab.
C~emicals No. 7440) These emission enhancing ligands are incorporated in the receiver at up to 70 weight percent 7 preferably 10 to 25 weight percent of the receiving layer polymer. This corresponds to from 0.1 to 10 g/m .
A visible dye can also be used in a separate or the same area o~ the donor element used with the receiving element of the invention provided it is transferable to the dye-receiving layer by the action of heat. Especiall~ good results have been obtained with sublimable dyes. ~xample~ o~ sublimable dyes include anthraquinone dyes, e.g., Sumikalon Violet RSTM (product of Sumitomo Ghemical Co., Ltd.), Dianix Fast Violet 3R-FSTM (product of Mitsubi~hi Chemical Indu~tries, Ltd.), and Kayalon Polyol Brilliant ~lue N-BGMTM and KST Black 146TM
(products of Nippon Kayaku Co., Ltd.); azo dyes such as Kayalon Polyol Brilliant Blue BMTM, Kayalon Polyol Dark Blue 2BMTM, and KST Black ~RTM
Sproducts of Nippon ~ayaku Co., Ltd.), Sumickaron Diazo Black 5GTM (product of Sumitomo Chemical Co., Ltd.), and Miktazol Black 5GHTM (product of Mit~ui Toatsu Chemicals, Inc.); direc.t dyes such as Direct . ~ ~
. ' , ~ :
'- ~` "i ~ P
Dark Green BTM (product of Mitsubishi Chemical Industries, Ltd.) and Direct Brown MTM and Direct Fast Black DTM ~products of Nippon Kayaku Co.
Ltd.); acid dyes such.as Kayanol Milling Cyanine 5R (product of Nippon Kayaku Co. Ltd.); basic dyes such as Sumicacryl Blue 6GTM ~product of Sumitomo Chemical Co., Ltd.), and Aizen Malachite GreenTM (product of Hodogaya Chemical Co., Ltd.~;
CH - -CN
FLUORESCENT EUROPI~M COMPLEXES
This invention relates to a receiving element which i8 used~with a donor element containing a 6-coordinate europium(III) complex to form a higher coordinate 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 i~ first ~ubjected to color separation by color filters. The respective color-separated images are then converted into elec-trical signals. These signals are then operated on to produce cyan, magenta and yellow electrical sig-nals. These signals are then transmitted to a ther-mal 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 i9 used to apply heat ~rom the back of the dye-donor sheet. The thermal printing head has many heating elements and i~ heated up sequentially in response to the cyan, magenta and yellow signals. The process is then repeated ~or the other two colors. A color hard copy is thus obtained which corresponds to the original picture viewed on a screen. Further details o~ this process and an apparatus for carryin~ it out are contained in U.S. Patent No. 4,621,271 by Brownstein entitled "Apparatus and Method For Controlling A
Thermal Printer Apparatust" issued November 4t 1986.
The system described above has been used to obtain visible dye images. ~owever, for ~tecurity purposes, to inhibit forgeries or duplication, or to encode con~idential in~ormation, it would be ~7~
advantageous to create non-visual ultraviolet absorbing images that Pluoresce with visible emi3sion when illuminated with ultraviolet light.
U.S. Patents 4,876,237, 4,871,714, 5 4,876,234, 4,866,025, 4,860,027, 4,891,351, and 4,891,352 all relate to thermally-transferable fluorescent materials used in a continuou~ tone system. ~owever, none of those materials fluoresce a visible red color when illuminated with ultraviolet light, and none of them describe ligand3 for use in the receiving element. A red color is desirable for many security applications U.S. Patent 4,627,997 discloses a fluorescent thermal transfer recording medium comprising a thermally-meltable, wax ink layer. It i8 an object of this invention to provide a receiving element which contains ligands to react with `!
fluorescent materials transferred from a donor element.
Theæe and other objects are achieved in accordance with this invention which comprises a receiving element for thermal transfer comprising a support having ~hereon a polymeric image-receiving layer, characterized in that the image-receiving layer also contains a monodentate or bidentate ligand capable of reacting with a 6-coordinate europium(III~
complex to form a higher coordinate complex, the higher coordinate complex which is formed in situ in the receiving layer having the following formula:
D, ~C ~ C 0\ ~ u- - B
/c=o/
_ J _ 3 wherein: D and J are defined as above and ~
represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom, e.g., ~ri-n-oCtylphosphine oxide, pyridine-N-oxide or triphenylphosphine oxide; or at least one bidentate ligand with two electron-donating oxygen, nitrogen or ~ulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom, e.g., 2,2'-bipyridine, l,10-phenanthroline, ethylene diamine or 1,2-diaminobutane.
In a pre~erred embodiment of the invention, the 6-coordinate europium(III) complex, which is generally supplied from a donor element, has the formula:
D~
~ C --~0\ ~ u _ J _ 3 wherein: D i~ a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heteroeyclic moiety, e.g. t phenyl, 2-thienyl, 2-furyl, 3-pyridyl, etc.; and The above ~luorescent europium comple~es are essentially non-visible, but emit with a unigue red hue in the xegion of 610 to 625 nm when irradiated with 360 nm ultraviolet light. This red hue is highly desirable ~or security-badging applications.
~uropium(III) is the only rare-earth known to be ~uitable for the practice o~ the invention.
~ s~
Rare earth metals, including europium, are described in the literature such as S, Nakamura and N. Suzuki, Polyhedron, S, 1805 (1986); T. Taketatsu, Talanta, 29, 397 (1982); and E Brittain, J.C.S. Dalton, 1187 - 5 (1979).
Diketone ligands ~rom which the 6-coordinate complexes are derived include the following within the scope of the invention:
6-coQ-rdinat-~-comple~ Diketone Li~rLd Compound l 0 0 \s/o e - CH2 - e - CF3 COmpOund 2 ~o/ !1--e--CE2--e~CF3 Compound 3 o~ ~--C-CH -C-CF
O O
Compound 4 \ _ /-- e - CH2~e - CF3 2.~
O O
Compound 5 \ ~o e - GH2 - e - C~3 =--Compound 6 CH30~-C-CH2- e - CF3 Compound 7 C~30 0 ~--R 11 il ~ ~U--C--CH2--C -CH3 r.,~ J
Suitable monodentate and bidentate ligands within the scope of the invention for incorporation in the receiving element include:
O ~ 2,2~-Bipyridine (Kodak Lab. Chemicals ~ _ ~ ~ No. 4397) ~=D~
10 J~ ~--~ ,10-Phenanthroline (Kodak Lab.
\=N/ \N=D/ Chemicals Ii~o. 3289) H~NC~2CE2NH2 Ethylene diamine (Kodak Lab.
Chemicals No. 1915 (n C8H17)3P0 Trioctylphosphine Oxide (Kodak Lab.
C~emicals No. 7440) These emission enhancing ligands are incorporated in the receiver at up to 70 weight percent 7 preferably 10 to 25 weight percent of the receiving layer polymer. This corresponds to from 0.1 to 10 g/m .
A visible dye can also be used in a separate or the same area o~ the donor element used with the receiving element of the invention provided it is transferable to the dye-receiving layer by the action of heat. Especiall~ good results have been obtained with sublimable dyes. ~xample~ o~ sublimable dyes include anthraquinone dyes, e.g., Sumikalon Violet RSTM (product of Sumitomo Ghemical Co., Ltd.), Dianix Fast Violet 3R-FSTM (product of Mitsubi~hi Chemical Indu~tries, Ltd.), and Kayalon Polyol Brilliant ~lue N-BGMTM and KST Black 146TM
(products of Nippon Kayaku Co., Ltd.); azo dyes such as Kayalon Polyol Brilliant Blue BMTM, Kayalon Polyol Dark Blue 2BMTM, and KST Black ~RTM
Sproducts of Nippon ~ayaku Co., Ltd.), Sumickaron Diazo Black 5GTM (product of Sumitomo Chemical Co., Ltd.), and Miktazol Black 5GHTM (product of Mit~ui Toatsu Chemicals, Inc.); direc.t dyes such as Direct . ~ ~
. ' , ~ :
'- ~` "i ~ P
Dark Green BTM (product of Mitsubishi Chemical Industries, Ltd.) and Direct Brown MTM and Direct Fast Black DTM ~products of Nippon Kayaku Co.
Ltd.); acid dyes such.as Kayanol Milling Cyanine 5R (product of Nippon Kayaku Co. Ltd.); basic dyes such as Sumicacryl Blue 6GTM ~product of Sumitomo Chemical Co., Ltd.), and Aizen Malachite GreenTM (product of Hodogaya Chemical Co., Ltd.~;
CH - -CN
3 R i-N-N-~ -N(C2~5~(CH2C6H5) N~COC~3 C~3\ ~C~3 0 I~ /0 ~ =CH-CH=./ I 6 5 (yellow) N~ CE3 ) 2 o ~ ~ ,!~ ~CoN~IcH3 I O O (cyan) ~./ \./
N \ _ /~-N(C~H5)2 or any of the dyes disclosed in U.S. Patent 4,541,830. The above dyes may be employed singly or 30 in combination to obtain a monochrome. The above image dyes and fluorescent dye may be used at a coverage of from about 0.01 to about 1 g/m2, preferably 0.1 to about 0.5 g/m2.
The fluorescent material in the above donor element is dispersed in a polymeric binder such as a cellulose deri~ative, e.g., cellulose acetate 6 ~ 3 hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate; a polycarbonate;
poly(styrene-co-acryl~nitrile), a poly(sulfone) or a poly(phenylene oxide). The binder may be used at a coverage of from about 0.1 to about 5 g/m2.
Any material can be used as the support ~or the donor element used with the receiver of the invention provided it is dimensionally stable and can 10 withstand the heat of the thermal printing heads.
Such materials include polyesters such as poly(ethylene terephthalate); polyamides;
polycarbonates; glassine paper; condenser paper;
cellulose e~ters such as cellulose acetate; ~luorine polymers such as polyvinylidene fluoride or poly(tetrafluoroethylene-co~hexafluoropropylene);
polyethers such as polyoxymethylene; polyacetals;
polyolefins such as polystyrene, polyethylene, polypropylene or methylpentane polymers; and 20 polyimides such as polyimide-amides and polyether-imides. The support generally has a thickness of from about 2 to about 30 ~m. It may also be coated with a subbing layer, if desired.
When using the donor element of the invention with a resistive head, the reverse side oî
the donor element is coated with a slipping layer to prevent the printing head from sticking to the donor element. Such a slipping layer would comprise a lubricating material such as a surface active agent, a li~uid lubricant, a solid lubricant or mi~tures thereof, with or without a polymeric binder.
Preferred lubricating materials include oils or semi-crystalline organic solids that melt below 100C
such as poly(vinyl stearate~, beeswa~, perfluorinated alkyl ester polyethers, poly(caprolactone~, silicone oil, poly(tetrafluoroethylene), carbowax, _9_ poly(ethylene glycols), or any of those materials disclosed in U. S. Patents 4,717,711, 4,737,485, 4,738,950, 4,824,050 or 4~717,712. Suitable polymeric binders for.the slipping layer include poly~vinyl alcohol-co-butyral), poly~vinyl alcohol-co-acetal), poly(styrene), poly(vinyl ace~ate), cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate or ethyl cellulose.
The amount of the lubricating matexial to be used in the slipping layer depends largely on the type of lubricating material, but is generally in the range of about .001 to about 2 g/m2. If a polymeric binder is employed, the lubricating 15 material is present in the range of 0.1 to 50 weight %, preferably 0.5 to 40, of the polymeric binder employed.
The receiving element of the invention comprises a support having thereon an image receiving layer and the ligand described above. 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 receiving element may also be re:Elective guch as baryta-coated paper, polyethylene-coated paper, white polyester (polyester with whlte pigment incorporated therein~, an ivory paper, a condenser paper or a synthetic paper such as duPont Tyvek~. -The image-receiving laye~ may comprise, for example, a polycarbonate, a polyurethane, a polyester, polyvinyl chloride, poly(styrene co-acrylonitrile), poly(caprolactone) or mixtures thereof. The 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 about 1 to about 5 g/m~.
As noted above, the donor elements employed in the invention are used to form a transfer image.
Such a process comprises a) imagewise-heating a donor element compri~ing a support having on one side thereof a layer comprising a material dispersed in a polymeric binder, and on the other ~ide thereof a slipping layer comprising a lubricant, and b) transferring an image to a receiving element comprising a support having thereon an image-receiving layer to form the transfer image, and wherein the material is a 6-coordinate europium(III) complex and the image-receiving layer also contains an uncharged monodentate or bidentate ligand capable of reacting with the 6-coordinate europium(III) comple~ to form a higher coordinate complex as described above.
The donor element employed in 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 fluorescent europium comple~
thereon as described above, with or without an image dye, or may have alter~ating area3 of 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. Patents 4,541,830, 4,698,651, 4,695,287, 4,701,439, 4,757,046, 4,743,582, 4,769,360 and 4,753,922. Thus, one-, two-, three- or four-color eiements (or higher numbers also) are included within the scope of the invention.
Thermal printlng heads which can be used to transfer ~luorescent material and dye from the donor element~ employed in the invention are available ::
commercially. There can be employed, for example, a Fujitsu Thermal Head (FTP-040 MCS001), a TDK Thermal Head F415 HH7-1089 or a Rohm Thermal Head KE 2008-~3.
~ r~
If a laser is used to transfer dye from the dye-donor employed in the invention to the receiver, then an absorptive material is used in the dye-donor. Any material that absorbs the laser energy may be used such as carbon black or non-volatile infrared~absorbing dyes or pigments which are well known to those skilled in the art.
Cyanine infrared absorbing dyes may also be employed with infrared diode lasers as described in DeBoer U.S. Patent Number 4,973,572.
Several different kinds of lasers could conceivably be used to effect the thermal transfer of dye from a donor sheet to the dye-receiving element, such as ion gas lasers like argon and krypton; metal vapor lasers such as copper, gold, and cadmium; solid state lasers such as ruby or YAG; or diode lasers such as gallium arsenide emitting in the infrared region from 750 to 870 nm. ~owever, in practice, the diode lasers offer substantial advantages in terms of their 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 laser radiation must be absorbed into the dye layer and converted to hleat by a molecular process known as internal conversion. Thus, the construction of a useful dye layer will depend not only on the hue, sublimability and intensity o~ the image dye, 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 the dye-donor element to the dye image-receiving element are available commercially. There can be employed, for example, Laser Model SDL-2420-~2TM
from Spectrodiode Labs, or Laser Model SLD 304 V/WTM from Sony Corp.
A thermal transfer assemblage of the invention comprises a) a donor element as described above, and b) a receiving element as described above, the receiving elemen~ being in a superpos~d relationship with the donor element so that the fluorescent material layer of the donor element is in contact with the image-receiving layer of the receiving element.
The following example is provided to illustrate the invention.
Example 1 This example shows the enhanced fluo-rescence obtained by transferring 6-coordinate europium complexes from a donor to a receiver containing an auxiliary ligand.
A donor element was prepared by coating the following layers in the order recited on a 6 ~m poly(ethylene terephthalate) support:
~) a subbing layer o~ duPont Tyzor TBTTM
titanium tetra-n-butoxide (0.12 g/m2) from l-butanol; and 2) a layer containing the 6-coordinate europium fluore3cent complex with the diketone ligand, as identified above (0,38 g/m2) or comparison material identified below ~0.16 g/m~) in a cellulose acetate butyrate 17%
acetyl and ~8% butyryl binder (0.43 g/m2 or control at 0.32 g/m ) coated from a cyclopentanone, toluene and methanol solvent mixture.
On ~he back side of the donor-element was coated:
1) a subbing layer of duPont Ty~or TBTTM
titanium tetra-n-butoxide (0.12 g/m2) from l-butanol; and 2) a slipping layer of Emralon 329TM poly-tetrafluoroethylene dry film lubricant (acheson Colloids) ~0.54 g/m2) and S-Nauba 5021 Carnauba Wax (Shamrock Technology) (0.003 g/m2) coated from a n-propyl acetate, toluene, 2 propanol and l-butanol solvent mi~ture.
A receiving element was prepared by coating a solution of Makrolon 5700TM (Bayer A.G. Corpo-ration) a bisphenol-A polycarbonate resin (2.9 g/m2), the auxiliary ligand indicated above (0.38 g/m2) or control material (0.38 g/m2) indicated below, and FC-431T~ surfactant (3M Corporation) (0.16 g/m~) in a methylene chloride and trichloro-1~ ethylene solvent mixture on a transparent 175 ~mpolyethylene terephthalate support subbed with a layer of poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (14:79:7 wt ratio) (0.005 g/m2).
The following control material, lacking coordinating atoms, which was coated in a receiver, is available commercially ~rom ~odak Laboratory Products and Chemicals Division.
~ Biphenyl 0=. .=. .
The fluorescent material layer side of the donor element strip approximately 9 cm x 12 cm in area was placed in contact with the image-receiving layer of a receiver element of the same area. The assemblage was fastened in ~he jaws of a stepper motor driven pulling device. The assemblage was laid on top of a 14 mm diameter rubber roller and a TDK
Thermal Head L-133 (No. 6-2R16~ as pressed wlth a spring at a force of 36 N against the donor element ~ide o~ the contacted pair 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 3.1 mm/sec.
Coincidentally the re,sistive elements in the thermal print head were pulsed at a per pixel pulse width of 8 msec to generate a ma~imum denslty image. The voltage supplied to the print-head was approximately 25 v representing approximately 1.6 watts/dot (13.
mjoules/dot).
The receiving element was separated ~rom the donor element and the relative emission was evaluated with a æpectrofluorimeter using a fixed intensity 360 nm egcitation beam and measuring the relative area under the emission spectrum from 375 to 700 nm. The following results were obtained (all transferred materials emitted between 610 and 625 nm.~:
Table l 20 Complex in Auxiliary Ligand Relative Visual Donor in Receiver ~missiQn* Color None None <l Not Vi 9 ible Comparison* None 100 Blue 25Compound 1 2,2'-Bipyridine 42 Intense red Compound l l,10-Phenanthro- 42 Intense line red Compound 1 Ethylene diamine 51 Intense red Compound 1 Trioctylphosphine 35 Intense oxide red Compound l Biphenyl (control~ 5 Moderate red 35 Compound 1 None (control) 5 Moderate red ~ ~3 Tab~e 1 (continued) Complex in Auxiliary Ligand Rela~ive Visual Donor in Receiver EmisslQn* ÇQlor Compound 2 2,2'-Bipyridine35 Intense red Compound 2 Biphenyl (control> 5 Moderate red Compound 2 None (control) 5 Moderate red Compound 3 2,2'-Bipyridine11 Red Compound 3 Biphenyl (control) 1 Faint red 1 Compound 3 None (control) 1 Faint red Compound 4 2,2~-Bipyridine 7 Red Compound 4 None (control) 3 Moderate red Compound 5 2,2'-Bipyridine 2 Moderate red Compound S None (control~ 1 Faint red * Compared to the Pollowing compound, normalized to 100 (emission between 400-SOO nm).
(C2E~5)2N/ ~ / \0/1~
This compound is the subject of U.S. Patent 4,876,237.
', , , - . , . ,.. : . ,.
The above results show that using an auxiliary ligand in the receiver in accordance with the invention to coordinate with the fluorescent materials supplied by a donor has much more -- 5 fluorescence than the control or comparison compounds.
The invention has been described in detail :
with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and ~cope of the invention.
2~
~5 .. . .: . . . .
.
. .
N \ _ /~-N(C~H5)2 or any of the dyes disclosed in U.S. Patent 4,541,830. The above dyes may be employed singly or 30 in combination to obtain a monochrome. The above image dyes and fluorescent dye may be used at a coverage of from about 0.01 to about 1 g/m2, preferably 0.1 to about 0.5 g/m2.
The fluorescent material in the above donor element is dispersed in a polymeric binder such as a cellulose deri~ative, e.g., cellulose acetate 6 ~ 3 hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate; a polycarbonate;
poly(styrene-co-acryl~nitrile), a poly(sulfone) or a poly(phenylene oxide). The binder may be used at a coverage of from about 0.1 to about 5 g/m2.
Any material can be used as the support ~or the donor element used with the receiver of the invention provided it is dimensionally stable and can 10 withstand the heat of the thermal printing heads.
Such materials include polyesters such as poly(ethylene terephthalate); polyamides;
polycarbonates; glassine paper; condenser paper;
cellulose e~ters such as cellulose acetate; ~luorine polymers such as polyvinylidene fluoride or poly(tetrafluoroethylene-co~hexafluoropropylene);
polyethers such as polyoxymethylene; polyacetals;
polyolefins such as polystyrene, polyethylene, polypropylene or methylpentane polymers; and 20 polyimides such as polyimide-amides and polyether-imides. The support generally has a thickness of from about 2 to about 30 ~m. It may also be coated with a subbing layer, if desired.
When using the donor element of the invention with a resistive head, the reverse side oî
the donor element is coated with a slipping layer to prevent the printing head from sticking to the donor element. Such a slipping layer would comprise a lubricating material such as a surface active agent, a li~uid lubricant, a solid lubricant or mi~tures thereof, with or without a polymeric binder.
Preferred lubricating materials include oils or semi-crystalline organic solids that melt below 100C
such as poly(vinyl stearate~, beeswa~, perfluorinated alkyl ester polyethers, poly(caprolactone~, silicone oil, poly(tetrafluoroethylene), carbowax, _9_ poly(ethylene glycols), or any of those materials disclosed in U. S. Patents 4,717,711, 4,737,485, 4,738,950, 4,824,050 or 4~717,712. Suitable polymeric binders for.the slipping layer include poly~vinyl alcohol-co-butyral), poly~vinyl alcohol-co-acetal), poly(styrene), poly(vinyl ace~ate), cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate or ethyl cellulose.
The amount of the lubricating matexial to be used in the slipping layer depends largely on the type of lubricating material, but is generally in the range of about .001 to about 2 g/m2. If a polymeric binder is employed, the lubricating 15 material is present in the range of 0.1 to 50 weight %, preferably 0.5 to 40, of the polymeric binder employed.
The receiving element of the invention comprises a support having thereon an image receiving layer and the ligand described above. 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 receiving element may also be re:Elective guch as baryta-coated paper, polyethylene-coated paper, white polyester (polyester with whlte pigment incorporated therein~, an ivory paper, a condenser paper or a synthetic paper such as duPont Tyvek~. -The image-receiving laye~ may comprise, for example, a polycarbonate, a polyurethane, a polyester, polyvinyl chloride, poly(styrene co-acrylonitrile), poly(caprolactone) or mixtures thereof. The 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 about 1 to about 5 g/m~.
As noted above, the donor elements employed in the invention are used to form a transfer image.
Such a process comprises a) imagewise-heating a donor element compri~ing a support having on one side thereof a layer comprising a material dispersed in a polymeric binder, and on the other ~ide thereof a slipping layer comprising a lubricant, and b) transferring an image to a receiving element comprising a support having thereon an image-receiving layer to form the transfer image, and wherein the material is a 6-coordinate europium(III) complex and the image-receiving layer also contains an uncharged monodentate or bidentate ligand capable of reacting with the 6-coordinate europium(III) comple~ to form a higher coordinate complex as described above.
The donor element employed in 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 fluorescent europium comple~
thereon as described above, with or without an image dye, or may have alter~ating area3 of 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. Patents 4,541,830, 4,698,651, 4,695,287, 4,701,439, 4,757,046, 4,743,582, 4,769,360 and 4,753,922. Thus, one-, two-, three- or four-color eiements (or higher numbers also) are included within the scope of the invention.
Thermal printlng heads which can be used to transfer ~luorescent material and dye from the donor element~ employed in the invention are available ::
commercially. There can be employed, for example, a Fujitsu Thermal Head (FTP-040 MCS001), a TDK Thermal Head F415 HH7-1089 or a Rohm Thermal Head KE 2008-~3.
~ r~
If a laser is used to transfer dye from the dye-donor employed in the invention to the receiver, then an absorptive material is used in the dye-donor. Any material that absorbs the laser energy may be used such as carbon black or non-volatile infrared~absorbing dyes or pigments which are well known to those skilled in the art.
Cyanine infrared absorbing dyes may also be employed with infrared diode lasers as described in DeBoer U.S. Patent Number 4,973,572.
Several different kinds of lasers could conceivably be used to effect the thermal transfer of dye from a donor sheet to the dye-receiving element, such as ion gas lasers like argon and krypton; metal vapor lasers such as copper, gold, and cadmium; solid state lasers such as ruby or YAG; or diode lasers such as gallium arsenide emitting in the infrared region from 750 to 870 nm. ~owever, in practice, the diode lasers offer substantial advantages in terms of their 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 laser radiation must be absorbed into the dye layer and converted to hleat by a molecular process known as internal conversion. Thus, the construction of a useful dye layer will depend not only on the hue, sublimability and intensity o~ the image dye, 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 the dye-donor element to the dye image-receiving element are available commercially. There can be employed, for example, Laser Model SDL-2420-~2TM
from Spectrodiode Labs, or Laser Model SLD 304 V/WTM from Sony Corp.
A thermal transfer assemblage of the invention comprises a) a donor element as described above, and b) a receiving element as described above, the receiving elemen~ being in a superpos~d relationship with the donor element so that the fluorescent material layer of the donor element is in contact with the image-receiving layer of the receiving element.
The following example is provided to illustrate the invention.
Example 1 This example shows the enhanced fluo-rescence obtained by transferring 6-coordinate europium complexes from a donor to a receiver containing an auxiliary ligand.
A donor element was prepared by coating the following layers in the order recited on a 6 ~m poly(ethylene terephthalate) support:
~) a subbing layer o~ duPont Tyzor TBTTM
titanium tetra-n-butoxide (0.12 g/m2) from l-butanol; and 2) a layer containing the 6-coordinate europium fluore3cent complex with the diketone ligand, as identified above (0,38 g/m2) or comparison material identified below ~0.16 g/m~) in a cellulose acetate butyrate 17%
acetyl and ~8% butyryl binder (0.43 g/m2 or control at 0.32 g/m ) coated from a cyclopentanone, toluene and methanol solvent mixture.
On ~he back side of the donor-element was coated:
1) a subbing layer of duPont Ty~or TBTTM
titanium tetra-n-butoxide (0.12 g/m2) from l-butanol; and 2) a slipping layer of Emralon 329TM poly-tetrafluoroethylene dry film lubricant (acheson Colloids) ~0.54 g/m2) and S-Nauba 5021 Carnauba Wax (Shamrock Technology) (0.003 g/m2) coated from a n-propyl acetate, toluene, 2 propanol and l-butanol solvent mi~ture.
A receiving element was prepared by coating a solution of Makrolon 5700TM (Bayer A.G. Corpo-ration) a bisphenol-A polycarbonate resin (2.9 g/m2), the auxiliary ligand indicated above (0.38 g/m2) or control material (0.38 g/m2) indicated below, and FC-431T~ surfactant (3M Corporation) (0.16 g/m~) in a methylene chloride and trichloro-1~ ethylene solvent mixture on a transparent 175 ~mpolyethylene terephthalate support subbed with a layer of poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (14:79:7 wt ratio) (0.005 g/m2).
The following control material, lacking coordinating atoms, which was coated in a receiver, is available commercially ~rom ~odak Laboratory Products and Chemicals Division.
~ Biphenyl 0=. .=. .
The fluorescent material layer side of the donor element strip approximately 9 cm x 12 cm in area was placed in contact with the image-receiving layer of a receiver element of the same area. The assemblage was fastened in ~he jaws of a stepper motor driven pulling device. The assemblage was laid on top of a 14 mm diameter rubber roller and a TDK
Thermal Head L-133 (No. 6-2R16~ as pressed wlth a spring at a force of 36 N against the donor element ~ide o~ the contacted pair 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 3.1 mm/sec.
Coincidentally the re,sistive elements in the thermal print head were pulsed at a per pixel pulse width of 8 msec to generate a ma~imum denslty image. The voltage supplied to the print-head was approximately 25 v representing approximately 1.6 watts/dot (13.
mjoules/dot).
The receiving element was separated ~rom the donor element and the relative emission was evaluated with a æpectrofluorimeter using a fixed intensity 360 nm egcitation beam and measuring the relative area under the emission spectrum from 375 to 700 nm. The following results were obtained (all transferred materials emitted between 610 and 625 nm.~:
Table l 20 Complex in Auxiliary Ligand Relative Visual Donor in Receiver ~missiQn* Color None None <l Not Vi 9 ible Comparison* None 100 Blue 25Compound 1 2,2'-Bipyridine 42 Intense red Compound l l,10-Phenanthro- 42 Intense line red Compound 1 Ethylene diamine 51 Intense red Compound 1 Trioctylphosphine 35 Intense oxide red Compound l Biphenyl (control~ 5 Moderate red 35 Compound 1 None (control) 5 Moderate red ~ ~3 Tab~e 1 (continued) Complex in Auxiliary Ligand Rela~ive Visual Donor in Receiver EmisslQn* ÇQlor Compound 2 2,2'-Bipyridine35 Intense red Compound 2 Biphenyl (control> 5 Moderate red Compound 2 None (control) 5 Moderate red Compound 3 2,2'-Bipyridine11 Red Compound 3 Biphenyl (control) 1 Faint red 1 Compound 3 None (control) 1 Faint red Compound 4 2,2~-Bipyridine 7 Red Compound 4 None (control) 3 Moderate red Compound 5 2,2'-Bipyridine 2 Moderate red Compound S None (control~ 1 Faint red * Compared to the Pollowing compound, normalized to 100 (emission between 400-SOO nm).
(C2E~5)2N/ ~ / \0/1~
This compound is the subject of U.S. Patent 4,876,237.
', , , - . , . ,.. : . ,.
The above results show that using an auxiliary ligand in the receiver in accordance with the invention to coordinate with the fluorescent materials supplied by a donor has much more -- 5 fluorescence than the control or comparison compounds.
The invention has been described in detail :
with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and ~cope of the invention.
2~
~5 .. . .: . . . .
.
. .
Claims (12)
1. In a receiving element for thermal transfer comprising a support having thereon a polymeric image-receiving layer, the improvement wherein said image-receiving layer also contains a coordinate complex having formula:
-B
wherein: D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
-B
wherein: D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
2. The element of Claim 1 wherein B
represents tri-n-octylphosphine oxide, pyridine-N-oxide or triphenylphosphine oxide.
represents tri-n-octylphosphine oxide, pyridine-N-oxide or triphenylphosphine oxide.
3. The element of Claim 1 wherein B
represents 2,2'-bipyridine, 1,10-phenanthroline, ethylene diamine or 1,2-diaminobutane.
represents 2,2'-bipyridine, 1,10-phenanthroline, ethylene diamine or 1,2-diaminobutane.
4. The element of Claim 1 wherein D
represents phenyl, 2-thienyl, 2-furyl or 3-pyridyl.
represents phenyl, 2-thienyl, 2-furyl or 3-pyridyl.
5. In a process of forming a transfer image comprising : a) imagewise-heating a donor element comprising a support having on one side thereof a layer comprising a material dispersed in a polymeric binder, and b) transferring an image to a receiving element comprising a support having thereon an image-receiving layer to form said transfer image, the improvement wherein said material is a
6 coordinate europium(III) complex.
6. The process of Claim 5 wherein said higher coordinate complex having the formula:
-B
wherein: D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
6. The process of Claim 5 wherein said higher coordinate complex having the formula:
-B
wherein: D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
7. In a thermal transfer assemblage comprising:
a) a donor element comprising a support having on one side thereof a layer comprising a material dispersed in a polymeric binder, and b) a receiving element comprising a support having thereon an image-receiving layer, said receiving element being in a superposed relationship with said donor element so that said material layer is in contact with said image-receiving layer, the improvement wherein said material is a 6-coordinate europium(III) complex and said image-receiving layer also contains a mono-dentate or bidentate ligand capable of reacting with said 6-coordinate europium(III) complex to form a higher coordinate complex.
a) a donor element comprising a support having on one side thereof a layer comprising a material dispersed in a polymeric binder, and b) a receiving element comprising a support having thereon an image-receiving layer, said receiving element being in a superposed relationship with said donor element so that said material layer is in contact with said image-receiving layer, the improvement wherein said material is a 6-coordinate europium(III) complex and said image-receiving layer also contains a mono-dentate or bidentate ligand capable of reacting with said 6-coordinate europium(III) complex to form a higher coordinate complex.
8. The assemblage of Claim 7 wherein D
represents phenyl, 2-thienyl, 2-furyl or 3-pyridyl.
represents phenyl, 2-thienyl, 2-furyl or 3-pyridyl.
9. The assemblage of Claim 7 wherein said higher coordinate complex has the formula:
wherein: D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
wherein: D is a substituted or unsubstituted, aromatic, 5- or 6-membered carbocyclic or heterocyclic moiety;
J is -CF3, -CH3, -CH2F or -CHF2; and B represents at least one monodentate ligand with an electron-donating oxygen or nitrogen atom or at least one bidentate ligand with two electron-donating oxygen, nitrogen or sulfur atoms atoms capable of forming a 5-or 6-membered ring with the europium atom.
10. The assemblage of Claim 9 wherein represents tri-n-octylphosphine oxides pyridine-N-oxide or triphenylphosphine oxide.
11. The assemblage of Claim 9 wherein B
represents 2,2'-bipyridine, 1,10-phenanthroline, ethylene diamine or 1,2-diaminobutane.
represents 2,2'-bipyridine, 1,10-phenanthroline, ethylene diamine or 1,2-diaminobutane.
12. The assemblage of Claim 9 wherein D
represents phenyl, 2-thienyl, 2-furyl or 3-pyridyl.
represents phenyl, 2-thienyl, 2-furyl or 3-pyridyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/493,077 US5011816A (en) | 1990-03-13 | 1990-03-13 | Receiver for thermally-transferable fluorescent europium complexes |
| US493,077 | 1990-03-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2037154A1 true CA2037154A1 (en) | 1991-09-14 |
Family
ID=23958809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002037154A Abandoned CA2037154A1 (en) | 1990-03-13 | 1991-02-26 | Receiver for thermally-transferable fluorescent europium complexes |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5011816A (en) |
| EP (1) | EP0446834B1 (en) |
| JP (1) | JPH0764126B2 (en) |
| CA (1) | CA2037154A1 (en) |
| DE (1) | DE69102459T2 (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69506822T2 (en) * | 1994-04-19 | 1999-08-12 | Ilford Imaging Ch Gmbh | RECORDING LAYER FOR INK JET PRINTING |
| KR100195175B1 (en) * | 1996-12-23 | 1999-06-15 | 손욱 | Electroluminescence element and its manufacturing method |
| JP2000173301A (en) * | 1998-12-10 | 2000-06-23 | Seiko Epson Corp | Piezoelectric light emission element, display device and manufacture thereof |
| US6174652B1 (en) * | 1999-09-30 | 2001-01-16 | Eastman Kodak Company | Stable coating composition |
| US6400386B1 (en) | 2000-04-12 | 2002-06-04 | Eastman Kodak Company | Method of printing a fluorescent image superimposed on a color image |
| US20050011405A1 (en) * | 2001-04-09 | 2005-01-20 | Masaaki Ikeda | Red fluorescent material and composition containing the same |
| JP3957162B2 (en) * | 2001-04-27 | 2007-08-15 | 富士フイルム株式会社 | Inkjet recording sheet |
| JP4098970B2 (en) * | 2001-06-19 | 2008-06-11 | 富士フイルム株式会社 | Inkjet recording sheet |
| US7793846B2 (en) | 2001-12-24 | 2010-09-14 | L-1 Secure Credentialing, Inc. | Systems, compositions, and methods for full color laser engraving of ID documents |
| CA2471457C (en) * | 2001-12-24 | 2011-08-02 | Digimarc Id Systems, Llc | Covert variable information on id documents and methods of making same |
| AU2002364036A1 (en) | 2001-12-24 | 2003-07-15 | Digimarc Id Systems, Llc | Laser etched security features for identification documents and methods of making same |
| US7694887B2 (en) | 2001-12-24 | 2010-04-13 | L-1 Secure Credentialing, Inc. | Optically variable personalized indicia for identification documents |
| WO2003088144A2 (en) | 2002-04-09 | 2003-10-23 | Digimarc Id Systems, Llc | Image processing techniques for printing identification cards and documents |
| US7824029B2 (en) | 2002-05-10 | 2010-11-02 | L-1 Secure Credentialing, Inc. | Identification card printer-assembler for over the counter card issuing |
| US7804982B2 (en) | 2002-11-26 | 2010-09-28 | L-1 Secure Credentialing, Inc. | Systems and methods for managing and detecting fraud in image databases used with identification documents |
| DE602004030434D1 (en) | 2003-04-16 | 2011-01-20 | L 1 Secure Credentialing Inc | THREE-DIMENSIONAL DATA STORAGE |
| US7364085B2 (en) * | 2003-09-30 | 2008-04-29 | Digimarc Corporation | Identification document with printing that creates moving and three dimensional image effects with pulsed illumination |
| CN109678896B (en) * | 2019-01-10 | 2021-01-01 | 厦门稀土材料研究所 | Compound containing rare earth europium as well as preparation method and application thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3357353A (en) * | 1966-01-03 | 1967-12-12 | Xerox Corp | Vapor thermography recording process and recording member used therein |
| FR2556867B1 (en) * | 1983-12-14 | 1986-06-06 | Jalon Michel | SECURITY MARKING METHOD, MATERIALS PROVIDED WITH SECURITY MARKS, AND APPLICATIONS THEREOF. |
| US4627997A (en) * | 1984-06-22 | 1986-12-09 | Ricoh Co., Ltd. | Thermal transfer recording medium |
| GB8513088D0 (en) * | 1985-05-23 | 1985-06-26 | Royal Doulton Uk Ltd | Marking of articles |
| FR2585987B1 (en) * | 1985-08-08 | 1989-02-03 | Petrel Sarl | SECURITY MARKING METHOD, MATERIALS PROVIDED WITH SECURITY MARKS |
| US4860027A (en) * | 1988-03-18 | 1989-08-22 | A. B. Dick Company | Ink drop control system with temperature compensation |
| US4876237A (en) * | 1988-08-31 | 1989-10-24 | Eastman Kodak Company | Thermally-transferable fluorescent 7-aminocoumarins |
| US4871714A (en) * | 1988-08-31 | 1989-10-03 | Eastman Kodak Company | Thermally-transferable fluorescent diphenyl ethylenes |
| US4876234A (en) * | 1988-08-31 | 1989-10-24 | Eastman Kodak Company | Thermally-transferable fluorescent oxazoles |
| US4866025A (en) * | 1988-09-30 | 1989-09-12 | Eastman Kodak Company | Thermally-transferable fluorescent diphenylpyrazolines |
| US4891351A (en) * | 1988-12-12 | 1990-01-02 | Eastman Kodak Co. | Thermally-transferable fluorescent compounds |
| US4891352A (en) * | 1988-12-23 | 1990-01-02 | Eastman Kodak Company | Thermally-transferable fluorescent 7-aminocarbostyrils |
-
1990
- 1990-03-13 US US07/493,077 patent/US5011816A/en not_active Expired - Lifetime
-
1991
- 1991-02-26 CA CA002037154A patent/CA2037154A1/en not_active Abandoned
- 1991-03-11 EP EP91103684A patent/EP0446834B1/en not_active Expired - Lifetime
- 1991-03-11 DE DE69102459T patent/DE69102459T2/en not_active Expired - Fee Related
- 1991-03-12 JP JP3046655A patent/JPH0764126B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69102459T2 (en) | 1995-02-02 |
| JPH05193272A (en) | 1993-08-03 |
| EP0446834A1 (en) | 1991-09-18 |
| JPH0764126B2 (en) | 1995-07-12 |
| DE69102459D1 (en) | 1994-07-21 |
| US5011816A (en) | 1991-04-30 |
| EP0446834B1 (en) | 1994-06-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |