CA2035760A1 - In situ dye generation for thermal transfer printing - Google Patents
In situ dye generation for thermal transfer printingInfo
- Publication number
- CA2035760A1 CA2035760A1 CA002035760A CA2035760A CA2035760A1 CA 2035760 A1 CA2035760 A1 CA 2035760A1 CA 002035760 A CA002035760 A CA 002035760A CA 2035760 A CA2035760 A CA 2035760A CA 2035760 A1 CA2035760 A1 CA 2035760A1
- Authority
- CA
- Canada
- Prior art keywords
- substituted
- electrophile
- carbon atoms
- unsubstituted
- alkenyl
- 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
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
-
- 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
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
- B41M5/3854—Dyes containing one or more acyclic carbon-to-carbon double bonds, e.g., di- or tri-cyanovinyl, methine
-
- 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
Abstract
IN SITU DYE GENERATION FOR THERMAL
TRANSFER PRINTING
Abstract In situ dye generation in a thermal transfer system is achieved by reacting an electrophile with a coupler compound to form an arylidene dye. The electrophile and/or the coupler compound are transferred from a donor element to a receiver element where they react to form a colored dye. The invention comprises a dye image recording element comprising a support bearing the electrophile which has the structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
-ii-B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
TRANSFER PRINTING
Abstract In situ dye generation in a thermal transfer system is achieved by reacting an electrophile with a coupler compound to form an arylidene dye. The electrophile and/or the coupler compound are transferred from a donor element to a receiver element where they react to form a colored dye. The invention comprises a dye image recording element comprising a support bearing the electrophile which has the structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
-ii-B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
Description
3~7~
XN SITU DYE GENERATION FOR THER~IAL
TRANSFI:R PRINTING
This invention relates to receiving and donor elements used in thermal transfer pri~ting, and more particularly to the use of reactive compounds (electrophiles and couplers) for in situ dye genera~ion in a thermal transfer ~ystem.
In recent years, thermal transfer systems have been developed to obtAin prints from pictures which have been generated electronically ~rom a eolor video camera. Aecording to one way of obtaining 3uch prints, an electronic picture is firæt Rubjected to color separation by coior filters. The respective color-separated images are then converted into elec-trical si~,nals. These signals are then operated on toproduce 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 ~ace - to-face with a ~o 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 ~rom the back of the dye-donor sheet. The thermal printing head has many hleating 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 thu~ obtained which corresponds to the original picture viewed on a screen. Further detail~ 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 thermal transfer systems deæcribed above routinely use the imagewise tranæfer of a preformed -' ~ :
XN SITU DYE GENERATION FOR THER~IAL
TRANSFI:R PRINTING
This invention relates to receiving and donor elements used in thermal transfer pri~ting, and more particularly to the use of reactive compounds (electrophiles and couplers) for in situ dye genera~ion in a thermal transfer ~ystem.
In recent years, thermal transfer systems have been developed to obtAin prints from pictures which have been generated electronically ~rom a eolor video camera. Aecording to one way of obtaining 3uch prints, an electronic picture is firæt Rubjected to color separation by coior filters. The respective color-separated images are then converted into elec-trical si~,nals. These signals are then operated on toproduce 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 ~ace - to-face with a ~o 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 ~rom the back of the dye-donor sheet. The thermal printing head has many hleating 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 thu~ obtained which corresponds to the original picture viewed on a screen. Further detail~ 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 thermal transfer systems deæcribed above routinely use the imagewise tranæfer of a preformed -' ~ :
-2- ~35'~6~
dye from a dye-donor element to a dye-receiYing element. One of the problems in selecting dyes for such systems is obtaining good transfer efficiency to produce high ma~imum density. Preformed dye ~olecules of high molecular weight require large amount~ of energy for æufficient transfers.
U.S. Patent No. 4,824,822 of ~amamoto et al disclose~ a thermosensitive recording method compri~ing ~ubliming or evaporating a compound A
and/or a compound B onto a recording sheet and then reacting compounds A and B together on the recording sheet in order to form colorin~ matter in situ on the recording sheet. Examples of compound B are aromatic amines, and e~amples of compound A are material~
forming free radicals. The3e compoundq react together upon exposure to light to form coloring matter. While this system may require less energy to tran~fer compounds A and/or B compared to transfer of a preformed dye, the chemistry usecl requires the additional time, egpense and inconvenience of a light exposure step.
In situ ge~eration of a color image in a recording element by reaction of a leuco dye and a developer i~ also well ~nown as may be ~een from the following U.S. Patents: No. 4,740,494, No. 4,703,335, No. 4,622,565, No. ~,500,896, No. 4,39~,616, No.
4,388,362, as well as many others.
Leuco dye~, however, generally have nearly the ~ame molecular weight as the resulting colored dye. Therefore, no energy savings is achieved by transferring a leuco dye compared to a preformed dye.
Also, leuco dyes are generally capable of forming only a single dye hue, thuq limiting their u~e in forming multi-color image~.
It would be desirable to provide a thermal dye transfer system having minimum energy requirements, which would al~o allow for the formation . , " ~ .
~;35~6 of multi-color images, and alæo require a minimum number of ~teps.
These and other objects are achieved in accordance wlth the invention, which comprise~ a dye image recording element compri~ing a ~upport bearin~
an electrophile capable of reacting with a coupler compound to form an arylidene dye, the electrophile having the following etructure:
~ nC ~ 2 B
~_B~
15 wherein X is halogen, ~ub~tituted or unsub~tituted alkyl~ulfonyloxy, ~ubstituted or unsubstituted arylsulfonyloxy, or subætituted or un~ub~tituted acyloxy;
El, E2, E3, and E4 are each independently hydro~en, sub~tituted or unsubstituted alkyl or alkenyl having up to about 8'i~ carbon atoms, ~ub~tituted or unsubstituted aryl having up to about ten carbon atom~, halogen, eyano, benzo~azolyl, nitro, -C02R, --COR, -CONH2, -COMHR, -CONRR, or -S02R, wherein each R i8 independently substituted or unsubstituted alkyl or alkenyl having up to about æi~ carbon atom~, or substituted or unsub~tituted aryl having up to about ten carbon atoms, with the proviso that at lea8t two of the E groups are other than h7drogen, alkyl, alkenyl, aryl or halogen;
Bl and B2 represent the atoms neces~ary to complete optional five- or sig-member ri~g~ formed with carbonyl moieties of El, E2 or E3;
B3 represents hydrogen or the atoms ~ecessary to complete an optional five- or six-member ring with a carbonyl moiety o~ El;
and n iB zero or one.
. ~ . , ' ~3~
_~_ The X substituent of uch compounds iB ehosen to be reactive with an active hydrogen atom of a preselected coupler compound and to split-off the electrophile when it and the coupler are reacted together. The remaining portion of the electrophile combine~ with the coupler compound at it~ acti~e hydro~en position to form a resulting arylidene dye.
The dye image recording elementQ of the invention comprising the above-defined electrophiles may take the form of a donor element or a receiver element.
In the process according to the invention, electrophiles in a donor element may be imagewise transferred to a receiving element containing coupler com~ounds by imagewise heating the donor element~ and reacted to~ether with the coupler compounds to form a dye lmage. Alternatively, coupler compounds may be imagewise transferred from a donor element to a receiving element containing electrophiles. The electrophiles are suf~iciently reactive with the couplers described below ~uch that an additional light exposure ~tep ls not required aft:er bringing the electrophile and coupler together to react to ~orm a dye. Further, a single coupler may be reacted with different electrophiles to ~orm dyes of difEerent hues. Alternatively, a ~ingle electrophile may be reacted with different coupler~ to form dyes of different hues.
A further embodiment of the invention comprises a dye image recording assembla~e comprising a first element comprising a ~upport bearing a preselected coupler compound, and a second element comprisin~ a support bearing an electrophile a~
defined above. The ~irst and second elements of the assemblage may be either a receiving element and a donor element, respectively, or a donor element and a receiving element.
_5_ ;21[~35i7 In an alternative embodiment of the invention, both the electrophiles and coupler compounds may be present in geparate adjacent areas of a donor element. A dye image may then be formed by sequentially transferring the electrophile3 and coupler compounds fsom the donor element to a receiving element where they are reacted ~ogether to form a dye image. At least one of the electrophile and the coupler compound is tran~ferred imagewise, while the other may be transferred either imagewise or non-imagewise (uniformly).
By transferring both the electrophiles and coupler compounds from a donor element to a recei~er element, the advantage of lower power requirement due to transfer of smaller molecules is retained while the need for a special receiver element containing an e~ectrophile or coupler compound is eliminated. Also, where both the electrophiles and coupler compounds are transferred imagewise, there is the additional advantage of eliminating the pre~ence of large amounts of residual unreacted electrophile or coupler compound in low density area~ of the image. Where a single coupler compound is transferred to react ~ith multiple individually imagewise transferred electrophiles to form an image with multiple hues~ the density data for all the individually transferred electrophiles can be added to obtain the required density data for the coup~er compound to be tra~sferred i~agewise.
Similarly, a single electrophile may be transferred imagewise corresponding to the total density data for multiple individually imagewise transferred coupler compounds.
In a preferred embodiment of the invention, the electrophile has one of the following structures:
26~35~6 X\ /CN
0~ 0 ~CN
0~ C(CN)2 X~ ~CN
l/-Q~\
where Rl is hydrogen, or ~ubstituted or unsubstitu~ed alkyl or alkenyl having up to about 8iX
carbon atoms, or aryl having up to about 10 carbon atoms. Specific examples of these electrophiles include:
Cl\ /C~
I I (EL-l);
0~ ~ ~0 H
which may be prepared as described in Wiley, R. and Slaymaker, JACS, 80, 1385-~ (1958);
~:; Cl\ /CN
: ~ ~ I (EL-2~;
O \N~ ~(CN)2 which may be prepared as described in U.S. Patent No.
dye from a dye-donor element to a dye-receiYing element. One of the problems in selecting dyes for such systems is obtaining good transfer efficiency to produce high ma~imum density. Preformed dye ~olecules of high molecular weight require large amount~ of energy for æufficient transfers.
U.S. Patent No. 4,824,822 of ~amamoto et al disclose~ a thermosensitive recording method compri~ing ~ubliming or evaporating a compound A
and/or a compound B onto a recording sheet and then reacting compounds A and B together on the recording sheet in order to form colorin~ matter in situ on the recording sheet. Examples of compound B are aromatic amines, and e~amples of compound A are material~
forming free radicals. The3e compoundq react together upon exposure to light to form coloring matter. While this system may require less energy to tran~fer compounds A and/or B compared to transfer of a preformed dye, the chemistry usecl requires the additional time, egpense and inconvenience of a light exposure step.
In situ ge~eration of a color image in a recording element by reaction of a leuco dye and a developer i~ also well ~nown as may be ~een from the following U.S. Patents: No. 4,740,494, No. 4,703,335, No. 4,622,565, No. ~,500,896, No. 4,39~,616, No.
4,388,362, as well as many others.
Leuco dye~, however, generally have nearly the ~ame molecular weight as the resulting colored dye. Therefore, no energy savings is achieved by transferring a leuco dye compared to a preformed dye.
Also, leuco dyes are generally capable of forming only a single dye hue, thuq limiting their u~e in forming multi-color image~.
It would be desirable to provide a thermal dye transfer system having minimum energy requirements, which would al~o allow for the formation . , " ~ .
~;35~6 of multi-color images, and alæo require a minimum number of ~teps.
These and other objects are achieved in accordance wlth the invention, which comprise~ a dye image recording element compri~ing a ~upport bearin~
an electrophile capable of reacting with a coupler compound to form an arylidene dye, the electrophile having the following etructure:
~ nC ~ 2 B
~_B~
15 wherein X is halogen, ~ub~tituted or unsub~tituted alkyl~ulfonyloxy, ~ubstituted or unsubstituted arylsulfonyloxy, or subætituted or un~ub~tituted acyloxy;
El, E2, E3, and E4 are each independently hydro~en, sub~tituted or unsubstituted alkyl or alkenyl having up to about 8'i~ carbon atoms, ~ub~tituted or unsubstituted aryl having up to about ten carbon atom~, halogen, eyano, benzo~azolyl, nitro, -C02R, --COR, -CONH2, -COMHR, -CONRR, or -S02R, wherein each R i8 independently substituted or unsubstituted alkyl or alkenyl having up to about æi~ carbon atom~, or substituted or unsub~tituted aryl having up to about ten carbon atoms, with the proviso that at lea8t two of the E groups are other than h7drogen, alkyl, alkenyl, aryl or halogen;
Bl and B2 represent the atoms neces~ary to complete optional five- or sig-member ri~g~ formed with carbonyl moieties of El, E2 or E3;
B3 represents hydrogen or the atoms ~ecessary to complete an optional five- or six-member ring with a carbonyl moiety o~ El;
and n iB zero or one.
. ~ . , ' ~3~
_~_ The X substituent of uch compounds iB ehosen to be reactive with an active hydrogen atom of a preselected coupler compound and to split-off the electrophile when it and the coupler are reacted together. The remaining portion of the electrophile combine~ with the coupler compound at it~ acti~e hydro~en position to form a resulting arylidene dye.
The dye image recording elementQ of the invention comprising the above-defined electrophiles may take the form of a donor element or a receiver element.
In the process according to the invention, electrophiles in a donor element may be imagewise transferred to a receiving element containing coupler com~ounds by imagewise heating the donor element~ and reacted to~ether with the coupler compounds to form a dye lmage. Alternatively, coupler compounds may be imagewise transferred from a donor element to a receiving element containing electrophiles. The electrophiles are suf~iciently reactive with the couplers described below ~uch that an additional light exposure ~tep ls not required aft:er bringing the electrophile and coupler together to react to ~orm a dye. Further, a single coupler may be reacted with different electrophiles to ~orm dyes of difEerent hues. Alternatively, a ~ingle electrophile may be reacted with different coupler~ to form dyes of different hues.
A further embodiment of the invention comprises a dye image recording assembla~e comprising a first element comprising a ~upport bearing a preselected coupler compound, and a second element comprisin~ a support bearing an electrophile a~
defined above. The ~irst and second elements of the assemblage may be either a receiving element and a donor element, respectively, or a donor element and a receiving element.
_5_ ;21[~35i7 In an alternative embodiment of the invention, both the electrophiles and coupler compounds may be present in geparate adjacent areas of a donor element. A dye image may then be formed by sequentially transferring the electrophile3 and coupler compounds fsom the donor element to a receiving element where they are reacted ~ogether to form a dye image. At least one of the electrophile and the coupler compound is tran~ferred imagewise, while the other may be transferred either imagewise or non-imagewise (uniformly).
By transferring both the electrophiles and coupler compounds from a donor element to a recei~er element, the advantage of lower power requirement due to transfer of smaller molecules is retained while the need for a special receiver element containing an e~ectrophile or coupler compound is eliminated. Also, where both the electrophiles and coupler compounds are transferred imagewise, there is the additional advantage of eliminating the pre~ence of large amounts of residual unreacted electrophile or coupler compound in low density area~ of the image. Where a single coupler compound is transferred to react ~ith multiple individually imagewise transferred electrophiles to form an image with multiple hues~ the density data for all the individually transferred electrophiles can be added to obtain the required density data for the coup~er compound to be tra~sferred i~agewise.
Similarly, a single electrophile may be transferred imagewise corresponding to the total density data for multiple individually imagewise transferred coupler compounds.
In a preferred embodiment of the invention, the electrophile has one of the following structures:
26~35~6 X\ /CN
0~ 0 ~CN
0~ C(CN)2 X~ ~CN
l/-Q~\
where Rl is hydrogen, or ~ubstituted or unsubstitu~ed alkyl or alkenyl having up to about 8iX
carbon atoms, or aryl having up to about 10 carbon atoms. Specific examples of these electrophiles include:
Cl\ /C~
I I (EL-l);
0~ ~ ~0 H
which may be prepared as described in Wiley, R. and Slaymaker, JACS, 80, 1385-~ (1958);
~:; Cl\ /CN
: ~ ~ I (EL-2~;
O \N~ ~(CN)2 which may be prepared as described in U.S. Patent No.
3,013,0I3; and .
Cl\ /CN
/- ~ \ (EL-3);
Cl CN
which may be prepared as described in 30sey, A., et al, J. Org. Chem. 32, 194:1 (1967).
. , -,~
'' . ~ .
~35~
O~her repre~eIItatiYe electrophiles suitable for use in the dye image recording element of the ~ nvention include:
~~ ~ /CN
(~5I~4 );
~ CN
Cl\ ~CN
~::N/ CN (E~5 );
Br\ /CN
O~ N ( EL--6 );
02N--~ ~o CF3C02, ,CO , ~o ._. O=~ (E~7 ~;
CN~ C~
Cl~
(E~8 );
0~ ~ ~0 l4H~
~r\ ,CONHC2H5 ( EL--9 );
0~ 0 H
Cl\ _ /C2c~3 ~ ,Co2OE[3 (EL~10 ); and H CN
50Z ~ II~sl (IS~ll).
.
.
-8- ~ ~35 As ~et forth above, ~he preselected coupler compound~ f~r use in the invention are ma~erial~ with an active hydrogen atom that wi:ll react with the electrophiles described above to form an arylidene dye. Examples of classes o~ æuch compounds include aromatic amines, aromatic hydro2yl compounds, compounds comprising a five-member unsaturated hetero-ring having at least one N, O, or S atom, and compounds of the formula Gl-C~2-G2 wherein Gl and G are each independently cyano, substituted or unsubstituted aryl, five- or ~ix-member N, O, or S
containing unsaturated hetero-rlngs, -C02R2, ~COR2, or -CoNR2R3, wherein Gl and G2 may together optionally form a carbocyclic ring, and where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms.
The possible variation~ for the coupler compound structures are diverse, and examples of the aromatic amines and hydroxyl compounds include substituted or unsubstituted derivatives or monomer units of:
D
, where D is -0~ or -NR2R3, where R2 and R3 are a~ defined above, and A represents the members necessary to complete an optional five- or six-member carbocyclic or heterocyclic ring; and R ~__ , o r \ ~ .
~9- ~35~
where R~ i8 as defined above, and J represents the members necessary to complete a five- or ix-membel heterocyclic ring. Example of compounds comprising a five-member unsaturated hetero - ring include substituted or unsubstituted derivatives or monomer units of:
~ r ~ ~
11~,11 ,~ .
where ~ is -S-, -O-, or -NR2, and where R2 and A
are as defined above.
SpeciEic representative coupler compounds suitable for use in the invention are listed below, wherein (M*) is u~ed to indicate the position on the coupler compound of the active hydrogen that ~ill react with the electrophiles described above to ~orm an arylidene dye:
c~3 (~*)\I~\o,l~ CH (C-l) ~-~ \ ~ \CH
H
l~\N/c2H5 I~D~ C-2) (~' >
N(C2~5)2 ~l~ ~OCH3 ~ (C-3) :~
C~30 T
~* ) .
.~ :
.
.. -.
-lo~ ~3~7~
E[N--C2~4C02C2H5 ~1~ ,OC~I3 C~ o~ (C-4) ,(1~* ) N(C2E[5 )2 lo I~ ,0~ ~I (C-53 (H* ) C2H5--l_C2E[4t)2CCH3 (C-6) C2~5--1--C2~40H
I O (C-7 ~t/
(H* ?
lEIN--C2H5 3 (::H3 0, ~l, I~ ,0~ (C-8) (~* ) - ., ~57~io ~1l~
1 (C~I2C6H5)2 I~ ,11~ (c-g) ~ C~3 (~* ) (EI*)\I~o\~ C~ (C-10) ~ \N~ CH3 C2H402CC~3 C2~5--1--C2H4cN
I û (C-ll) ~T~ \Cl (H* ) ~:' -(H* )/ ~o~ \o~ (C--12 ) ' .:
51, ~
1~ ,D~ ,~ C~(H*)--CN (C--13) .
:: :
-12- ~35~6~
o~
l~ ,(H* ) a~ (C-14~
C~3 OH
10 CH3, ,l ~ ,CH3 ~,T~I (C 15) ~H* ) (H*) ~ ~l~ ,OH
,0 (C-16) ~0 (C-17) (H* )/ \o CH3 ~-- ~ (C-18) ;::~
0 0 (C--19) ~/ \N~ ~ ' H
11 ~ (C-20) y (H* ) i7fi~
~* ~ 2 ~3 * ) I~ ,0~0 (C-22) ~3 --~ (C-23 ) ~H* ) S OCEI3 ,Cl ., U (C-24) (H* ) S CH3 O--11 (C-25 ) (~' ) \N~ 0CH3 C6~4(P-0C~3) ~ :
C6~5C0--CH(H*)--C0--NHC4H9 (C--26) C~H502C--C~(~* )--C0~C2H5 (C~27 ) 02N \ , C~I(H ) CN (C--?.8) .: . ., .
~14-~C~*) ~ (C-2O
(~*) S~ N~C4~9)2 ~C-30) 10 Donor element~ cf the invention comprise a support bearin~ an electrophile or e~upler compound, or both an electrophile and coupler compound in ~epa~ate adjacent areas. Preferably, the elec~rsphile and/or coupler compound i~ disper~ed in a polymeric b~nder layer on the donor element support. The donor polymeric binder may be, for example, a cellulose derivative, e.g., eellulose aeetate hydrogen phthala~e, cellulo~e acetate, cellulose acetate propionate, cel~ulose acetate butyrate, cellulose triacetate, cellulose tripropionate; a polycarbonate;
poly(styrene-co-acrylonitrile), a poly(~ul~one> or a poly(phenylene o~ide~. The binder may be used at a coverage of ~xom about 0.1 to about 5 g/m2.
Any material can be used as the BUpport for the don3r element provided it iQ dimensionally Etable and can withstand the heat of th~e thermal printing heads. Such material~ include polyesters ~uch as poly(ethylene terephthalate); polyamid~B;
polycarbonates; glassine paper; condenser paper;
cellulose e~ters such as cellulose acetate; fluorine polymers such as polyvinylidene fluoride or poly-(tetrafluoroethylene-co-hexafluoropropylene); poly-ether~ such as polyoxymethylene; polyacetal~; poly-olefin~ such as polystyrene, polyethylene, poly-propylene or methylpentane polymers; and polyimidessuch as polyimide-amides and polyether-imideæ. The suppor~ generally has a thickness of from about 2 to :: !
~:01357~
abvut 30 ~m. It may al~o be coated with a subbing layer, if deRired.
A barrier layer compri~ing a hydrophilic polymer ~ay al~o be employed in the donor elemen~
between it~ ~upport and the electrophile or coupler layer which provide~ improved tranofer den~itie3.
Such barrier layer material~ include those deseribed and claimed in U.S. Patent No. 4,700,208 of Yanier et al, issued Oc~ober 13, 1987.
The reverse eide of the donor element may be coated ~ith a ~lipping layer to prevent the printing head from ~ticking to the donor element. Such a slipping layer would compri~e a lubricating material such a~ a ~urface active agent, a liquid lubricant9 a solid lubricant or mixture~ thereof, ~ith or ~ithout a polymeric binder. Preferred lubricatin~ materials ~:
include oil~ or semi-crystalline organic solid~ that melt below 100C ~uch as poly(vinyl ~tearate), beeswax, perfluorinated alkyl ester polyethers, ~0 phosphoric acid esters ~ #ilicone oil8, poly(caprolactone), carbowax or poly(ethylene glycols). Suitable polymeric binders for the slipping layer include poly(vinyl alcohol--co-butyral), poly(vinyl alcohol-co-acetal), poly(~tyrene), poly(~tyrene-co acrylonitrile), poly(vinyl acetate), cellulose acetate butyrate, cellulose acetate or ethyl celluloae.
The amount of the lubricating material to be u~ed in the slipping layer depends largely on the type 30 of lubricating material, but i8 generally in the range of about .001 to abou~ ~ g/m2. If a polymeric binder i~ employed, the lubricating materia~ i~
present in the range of 0.1 to 50 weight ~b, prefer ably 0.5 to 40, of the polymeric binder employed.
Receiving elements of the invention compri~e a support bearing an electrophile or coupler ~ 5 ~6 compound. Preferably, the electrophile or coupler compound is disper~ed in a polymeric binder layer on the receiving element support. Such a receiving element binder layer also functions as a receivin~
S layer ~or the electrophile or coupler compound transferred from the donor element. Where both the electrophile and coupler compound are to be transferred from a donor element, a conventiona~
thermal dye trans~er receiving element comprising a support having thereon a receiving layer may be u~ed.
The receiving element binder and receiving layer may comprise, for e~ample, a polycarbonate, a polyurethane, a polyester, polyvinyl chloride, poly(styrene-co-acrylonitrile), poly(c~prolactone) or mixtures thereof, and may be present in any amount which is effective for the intended purpo~e. In general, good results have been obtained at a concentration of from about 1 to about 5 g/m2.
The receiving element support may be a transparent film such as a poly(ether sul~one?, a polyimide, a cellulose ester such as cellulose acetate, a poly(vinyl alcohol-co--acetal) or a poly(ethylene terephthalate). The ~upport for the receiving element may also be reflective such as baryta-coated paper, white polye~ter (polyester with white pigment incorporated therein), an ivory paper, a condenser paper or a 3ynthetic paper æuch as du Pont Tyvek The electrophiles and coupler compounds may be employed in the donor and receiving elements at any concentration which is e~fective for the intended purpose. To provide a Status A image density of above 1.0, the electrophiles are employed at 0.01 to 1.0 g/m2 in the donor or the receiver element, and the coupler compounds are employed at 0.03 to 3.0 g/m in the donor or the receiver element.
' ~ ~3 ~ ~6 The donor element employed in certain embodiments 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 one electrophile and/or coupler compound thereon or may have alternating areas of different electrophiles and/or coupler compounds chosen to generate dyes of different hues such as cyan, magenta, yellow, black, etc., to enable full color prints to be produced.
Thermal printing heads which can be used to transfer electrophiles or coupler compounds from the donor elements employed in the invention are available co~mercially. There can be employed, for example, a Fujitsu Thermal ~ead (ETP-040 MCS001), a TDK Thermal ~ead F415 ~7-1089 or a Rohm Thermal Head KE 2008-F3.
Alternatively, other energy sources may be used to transfer the electrophiles or coupler compounds such as laser or ultrasound.
The ~ollowing examples are provided to illustrate the invention.
Example 1 This example illustrates thermal dye-generation imaging with the electrophile in the donor and the coupler in the receiver.
Donor element~ ~ere prcpared by coating on a ~irst side of a 6 ~m polyethylene terephthalate support:
(1) a subbing layer of a titanium alkoxide (duPont Tyzor TBTTM) ~0.12 g/m2) coated from a n-propyl acetate and l-butanol solvent mixture, and (2) a layer of the indicated electrophile (EL-l, EL-2, or EL-3, illustrated above) (0.22 g/m2) in a cellulose acetate propionate binder (2.5% acetyl, 45%
propionyl) (0.32 g/m~) coated from ethyl acetate.
, ' .
~:~35~
On the reverse side of the donor supports was coated:
(1) a subbing layer of a titanium alkoxide (duPont Tyzor TBTTM) (0.12 g/m2~ coated from a n-propyl acetate and l-butanol solvent mi~ture, and (2) a slipping layer of Emralon 329TM (Acheson Colloids Corp.~ dry film lubricant o~
poly(tetrafluoroethylene) particles in a cellulose nitrate resin binder (0.54 g/m2) coated from propylacetate, toluene, 2-propanol, and l-butanol solvent mixtures.
A receiving element, R-l, was prepared by coating on a white-~eflective support of titanlum dioxide pigmented polyethylene terephthalate a subbing layer of poly(acrylonitrile-co~vinylidene chloride-co-acrylic acid) (79:14:7 wt ratio) (0.07 g/m2~ ~rom a butanone and cyclopentanone so:lvent mixture. This support with subbing layer was sllbjected to electro-static discharge treatment, and a layer of the indicated coupler (0.23 g/m2) in a binder of a polycarbonate resin derived from bisphe~ol A and 1,5-pentanediol (50:50 wt ratio of diol and dihydric phenol) (2.9 g/m2) was then coated from methylene chloride.
A second receiver, R-2, was made as above but used a polyester derived from terephthalic acid, ethylene glycol, and 1?4 bis(~-hydroxyethoxy)benzene (2:1:1 wt ratio) (2.9 g/m2) in place of the polycarbonate binder.
A donor e~ement strip approximately 3 cm x 15 cm in area was placed in contact wi~h the coupler-binder layer side of a receiving element of the same area. This assemblage was clamped to a motor driven 14 mm diameter rubber roller. A TDK Thermal Head L-133 (No. 6-2R16-1) was pressed with a force of 3.6 kg against thc donor element side of the contacted , ; . , ', ~ ,:
.
~tt~3~6 pair pushing it against the rubber roller.
The imaging electronics were activated causing the donor/receiver a~semblage to be drawn between the printing head and roller at 3.1 mm/sec.
Coincidentally the reæistive elements in the thermal print head were pulsed for discrete sequential intervals at per~pixel pulse widths ~rom 0 up to 8 msec ~o generate a ~tepped density image. The vol~age supplied to the print-head was approximately 21 volts representing approximately 1.4 watts/dot ~12. mjoules/dot) for maximum power.
The receiver element was separated from the donor element and the Status A blue, green and red reflection densities of each single color generated image consisting of a series of eight graduated density steps one cm square were read after 1 hour.
Dye generation was observed to be instantaneous in most instances, however, some dyes required ~everal minutes to form completely.
The following ma~imum density, D-max, and minimum density, D-min, data were obtained. Status A
reflection densities are tabulated for the predomi-nate hue only; Rt G, or B. Spectral absorption curves were also obtained to determine the ~-max of each in situ generated dye.
2~3~7 ¢ a ~
a~ ~P O O O ~~ ~ ~1 0 ~ Ct' ~ o c~ o o v~ O~ ~ ~ cs~ ~ ~ O ,_ O ~
o ~ ~~ ~ ~ c~
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o~ ~ OD O ~1 a:~ o u~ ~ ~~ ~ ~D
i ~ u~
d a ~ ~ a~ ~ ~ o ,_ ~0 ~ O ~ O ~1 ~ O ~1 X P~ ~ ~ h .,1 ~
o O O ~ ,~ N
a a~ ~ ~ oo OQ) ~ ~ > V t~
~) ' O
X~3Si7~i~
.~ p~
n ~ o o o ~ o o ~ o o o ,~G oo ooo ooo oo v~ ~ ~ Oo a~
C ~ ~ ~ C~i ~a Q t~ bll Q~ O r~
~ X
.~, ~ o ~ a ~ 3 ~ ~ ~
a) ~1 ~
h ~I) C~ ~ I I ~ I I I I I I I I
2~357~i~
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~: a~ OO ~
,-d ~ O C:~ o o 1~.1o~ o u~ u~
~ oLr~ ,_1o ~ a bO o ~ ~ Q~ a) ~ o P; P~ ~:
. ~
rq O
) a ~ 3 ~ 3 ~ -1 a ~ Q) ~' ~ ~ o~ C~o o ~,-$ ~ I i I .1 :, ~ ' ~ -:
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-~3-Ex~mple 2 This example is 8 imilar to Example 1 but illustrates dye-generatiorl imaging with the coupler in the donor and the electrophile in the receiver.
Donor elements were prepared as in Egample 1, but in place of the electrophile, the indicated coupler (0.22 g/m2) was coated in a cellulose acetate propionate ~inder (0.32 g/m2) from ethyl acetate.
Receiving elements were prepared similar to R-l of Example l, but in place of the coupler, the electrophile (EL-2~ ~0.23 g/m ) was coated in the polycarbonate binder (2.9 g/m2) from methylene chloride.
The evaluation procedure was as described in Example 1, and the data below ~how that good image discrimination is also obtained with this format with change in location of electrophile and coupler as compared to Example 1.
~ ~Eormed~Pye Electro~hile Coupler ~-max Status A
in Re~elver in Donor U!Q nm D-min/D~max E-31 EL-2 C-19 Magenta 518 1.2/0.18 (G~
E-32 EL-2 5-30 Cyan 612 1.6/0.16 (R) ~0 Example_3 This example illustrates the power re~uire-ments for thermal imaglng with in situ dye generation and for preformed dyes.
Two dye~ were evaluated for compari~on, E-3 and E-4. A dye image was formed as in Examples 1 and 2 using dye generation and compared to the same dye preformed and coated in the donor for transfer.
-24~ i7~
~7 Z `~
~ 1l . _ ., "_~" o O ~ a ~ O
P ~ ~ ID \O
Z\~/ E3 ~e3,/ E!
/ \ o tq ~
~ t Q) Q) ~i ~ ,., .
~ " ~ ~ "o ~
Ir~ Ir~
~r~O ~ ~r~O
U ~ ~
+ + - ~ .
.
V ~ ~Z ~
/~ g /o g :
a) ~: :
~:~3~76~
Thermal transfer receiver~ were prepared with the coupler in a polycarbonate bi~der 9 R-l, as described in Example 1. Donor~ containing the electrophile were prepared ~imilar to Example 1 except the electrophile, EL-l, for the magenta dye forma~ion was at 0.055 g/m2 (0.36 mmoles/m2) in cellulo~e acetate propionate binder (0.14 g/m2) and the electrophile EL-2 ~or the cyan dye ~ormation was at 0.16 ~/m2 (o 77 mmoles/m2) in cellulose acetate propionate binder (0.28 g/m~).
For preformed-dye thermal transfer, do~ors were prepared as in Example l with the above de-Rcribed e~ternally ~ormed magenta and cyan dye~ at 0.11 g/m ~0.36 mmoles/m2) in cellulose ace*ate propionate binder (0.~7 g/m2) for the magenta and at 0.27 g/m2 ~0,77 ~moles/m2) for the cyan. The mmoles of dye were kept cons~ant for the generated and preformed dyes 80 tbat comparisons ~ere more meaningful. The receiver used with these donors containing preformed dye ~as like the R-l poly-carbonate receiver of Example l Pxcept ~o coupler waæ
added.
The transfer o~ the mag~enta and cyan dyes both preformed and using dye genleration was as de~cribed below. Graduated density 11 ~tep ima~es were each generated at 15, 19, and 23.5 volts. In this manner plots of dye-den~ity ver~u~ a given step number ~or each ~oltage were obtained and compared.
The dye-~ide of a donor element ~trip approximately 10 cm x 13 cm in area wa~ placed in contaet with the polymeric receiver layer ~ide o~ a receiver element of the ~ame area. This assemblage was clamped to a stepper-motor driven 60 mm diameter rubber roller. A TDK Thermal ~ead L-231 (thermo-~tatted at 260C) was pressed with a force ~f 3.6 kgagainst the dye-donor eleme~t side of the contac~ed pair pushing it against the rubber roller.
57~
-2~-The imaging el~ctronic~ were activated eausing the donor-receiver assemblage to be drawn through the printing head/roller nip at 6.9 mm/sec.
Coincidentally the resistive elements in the thermal print head were pulsed for 29 usec/pulse at 128 usec intervals during the 33 msec/dot printing time. A
stepped density image was generated by incrementally increasing the number of pulses/dot from 0 to 255.
The voltage supplied to the printing head was either 15, 19, or 23.5 volts, resulting in an instantaneous peak ~ower of 1.3 watts/dot and maximum total energy of 9.6 mJoules/dot at the maximum voltage of 23.5.
The resulting stepped images were read to Statu~ A
green or red reflection density.
~13 ,~ ., ~ r~ ~ ~u~ c~l~
u a eoQ oo~ o~c~, Q
O
~ ,q~ ooo ooo ooo t: a) v v v v v v .~
~ ,Q
.,~ rd ~D ~ Ln~O
~: I
Q : O C> O O O -1 0 ~1 ~1 : i .r l ~
O ~1~1 r~ ~o~ ' 1~ 0~0 000 000 ~ ~ V V V V V
: ~ ~ :Pi o ~ r~ o ~ O
Q
tt I U~
~) ~ I
P
.
': ", .
~33576~D
--28~
. .
From the volta~e versus density plot~, the voltage required to reach a ma~imum density of 1.0 was estima~ed. The~e values are:
s Magent.a Dye ~y~n Dye Preformed Gener~Q~ Preform~d Genera~ed Volta~e ~o D=l.0 23v l9v * 18v lû
*Not feasible -highe3t density tsansPerred was only 0.3, even at 23.5 volts.
At a given step (~iven energy) at a specified 15 voltage, higher den~itie~ are obtained when the dyes are generated in-situ. The preformed cyan dye in particular was incapable of producing a denæity greater than 0.3. The preformed magenta dye could produce a d~nsity of about 1.0 by trans$er. Den~ities 20 of 2.0 or more were obtained with generation of the same two dyes. Virtually no meaningful density wa~
tran~ferred with the pre~ormed cyan dye unless a head voltage of 23.5 was u~ed.
~5 ~ El~ 4 This example illustrate~ thermal dye-generation imaging with two di~ferent electrophilesl EL-l and EL-2, and a ~ingle coupler, C-1, in the donor used with a "non reagent7' receiver. EL-1, EL-2, and 30 C-l are as illu trated above.
Donors were prepared by coating on a first ~ide of a 6 ~m polyethylene terephthalate support:
(1) a subbing layer as in E~ample 1, and (2) a layer of either the magenta electrophile, EL-l ~0.14 g/m2), the cyan electrophile, EL-2 (0.32 g/m ), or the coupler compound, C-l, (1.3 g/m2) in a cellulo~e acetate propionate binder 35~
(2.5% acetyl, 45% propionyl) (at 0.14, 0.28t or 0.57 g/m2, respecti~ely) from ethyl acetate, 9n the rever~e ~ide of the ~upport~, ~ubbing and ~lipping layerg were coated a~ in ~xample 1. The recei~er used with these donor~ was like the R-l polycarbonate receiver of Example l e~cept no coupler was added.
The dye-3ide of an electrophile donor element approximately 3 cm ~ 15 cm in area was placed in contact with a receiver element of the ~ame area.
This assemblage was elamped to a 6tepper-motor driven 60 mm diameter rubber roller. A TDK Thermal Head L-231 (thermostatted at 26OC) was pre~sed with a force of 3.~ kg agai~st the dye-donor element eide of the contacted pair pushing it against the rubber roller.
The imaging electronic3 were activated causing the donor-receiver assemblage to be drawn through the printing head/roller nip at 6.9 ~m/sec.
Coincidentally the resi~tive elements in the thermal print head were pulsed for 29 usec/pul~e at 128 usee intervals during the 33 msecldot printing time. A
stepped density image was generated by incrementally increasing the number of pulses/dot from 0 to 255.
The voltage supplied to the printing head wa~ 18 volts, resulting in an instantaneous peak power of 1.3 watt8/dot and maximum total energy of 7.8 mJouleg/dot.
After either the magenta or cyan electro-phile-donor was printed, the complete area of the coupler-donor was overprinted non-imagewise on the receiver at 18. volt~. As 800n as this overprinting was done, magenta and cyan dye were observed to form.
For comparison, the magenta and eyan e~ectrophiles were transferred under the ~ame conditions to a receiver already containing the coupler compound (at 0.23 g/m2) coated in the polycarbonate layer a~ in Example 1.
Each receiver ~as separated from the donor and the Statu6 A green (G~ and red (R) reflection ~357~t densities of each ~ingle color ~rans~erred ima~e consisting of a ~eries of eleven ~raduated density ~teps one cm square were read within one hour.
~tatuS A Den~ity QIu~ler Coupler Coated Transferr in ~ceiver ~rom Donor Magent~ Cyan ~g~ Cyan Step (P~lses/~ot2 (G~ (R~ (G2 (R~
100 (Dmin) 0 0.10 0.06 0.12 0.07 4 92 0.12 0.07 0.13 0.09 7 161 0.63 0.2S 0.59 0.37 11 ~Dmax) 255 1.37 Q.87 1.64 1.3 The above data ~hows that high densities can be obtained by delivery of both the coupler compound and the electrophile ~rom a donor elemen~.
The invention has been clescribed in detail with particular reference to preferred embodiments thereof, but it will be under~tood that variations and modif ications can be effected wit;hin the ~pirit and scope of the invention.
., . . ,. -, . . ,~
;" ,','
Cl\ /CN
/- ~ \ (EL-3);
Cl CN
which may be prepared as described in 30sey, A., et al, J. Org. Chem. 32, 194:1 (1967).
. , -,~
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~35~
O~her repre~eIItatiYe electrophiles suitable for use in the dye image recording element of the ~ nvention include:
~~ ~ /CN
(~5I~4 );
~ CN
Cl\ ~CN
~::N/ CN (E~5 );
Br\ /CN
O~ N ( EL--6 );
02N--~ ~o CF3C02, ,CO , ~o ._. O=~ (E~7 ~;
CN~ C~
Cl~
(E~8 );
0~ ~ ~0 l4H~
~r\ ,CONHC2H5 ( EL--9 );
0~ 0 H
Cl\ _ /C2c~3 ~ ,Co2OE[3 (EL~10 ); and H CN
50Z ~ II~sl (IS~ll).
.
.
-8- ~ ~35 As ~et forth above, ~he preselected coupler compound~ f~r use in the invention are ma~erial~ with an active hydrogen atom that wi:ll react with the electrophiles described above to form an arylidene dye. Examples of classes o~ æuch compounds include aromatic amines, aromatic hydro2yl compounds, compounds comprising a five-member unsaturated hetero-ring having at least one N, O, or S atom, and compounds of the formula Gl-C~2-G2 wherein Gl and G are each independently cyano, substituted or unsubstituted aryl, five- or ~ix-member N, O, or S
containing unsaturated hetero-rlngs, -C02R2, ~COR2, or -CoNR2R3, wherein Gl and G2 may together optionally form a carbocyclic ring, and where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms.
The possible variation~ for the coupler compound structures are diverse, and examples of the aromatic amines and hydroxyl compounds include substituted or unsubstituted derivatives or monomer units of:
D
, where D is -0~ or -NR2R3, where R2 and R3 are a~ defined above, and A represents the members necessary to complete an optional five- or six-member carbocyclic or heterocyclic ring; and R ~__ , o r \ ~ .
~9- ~35~
where R~ i8 as defined above, and J represents the members necessary to complete a five- or ix-membel heterocyclic ring. Example of compounds comprising a five-member unsaturated hetero - ring include substituted or unsubstituted derivatives or monomer units of:
~ r ~ ~
11~,11 ,~ .
where ~ is -S-, -O-, or -NR2, and where R2 and A
are as defined above.
SpeciEic representative coupler compounds suitable for use in the invention are listed below, wherein (M*) is u~ed to indicate the position on the coupler compound of the active hydrogen that ~ill react with the electrophiles described above to ~orm an arylidene dye:
c~3 (~*)\I~\o,l~ CH (C-l) ~-~ \ ~ \CH
H
l~\N/c2H5 I~D~ C-2) (~' >
N(C2~5)2 ~l~ ~OCH3 ~ (C-3) :~
C~30 T
~* ) .
.~ :
.
.. -.
-lo~ ~3~7~
E[N--C2~4C02C2H5 ~1~ ,OC~I3 C~ o~ (C-4) ,(1~* ) N(C2E[5 )2 lo I~ ,0~ ~I (C-53 (H* ) C2H5--l_C2E[4t)2CCH3 (C-6) C2~5--1--C2~40H
I O (C-7 ~t/
(H* ?
lEIN--C2H5 3 (::H3 0, ~l, I~ ,0~ (C-8) (~* ) - ., ~57~io ~1l~
1 (C~I2C6H5)2 I~ ,11~ (c-g) ~ C~3 (~* ) (EI*)\I~o\~ C~ (C-10) ~ \N~ CH3 C2H402CC~3 C2~5--1--C2H4cN
I û (C-ll) ~T~ \Cl (H* ) ~:' -(H* )/ ~o~ \o~ (C--12 ) ' .:
51, ~
1~ ,D~ ,~ C~(H*)--CN (C--13) .
:: :
-12- ~35~6~
o~
l~ ,(H* ) a~ (C-14~
C~3 OH
10 CH3, ,l ~ ,CH3 ~,T~I (C 15) ~H* ) (H*) ~ ~l~ ,OH
,0 (C-16) ~0 (C-17) (H* )/ \o CH3 ~-- ~ (C-18) ;::~
0 0 (C--19) ~/ \N~ ~ ' H
11 ~ (C-20) y (H* ) i7fi~
~* ~ 2 ~3 * ) I~ ,0~0 (C-22) ~3 --~ (C-23 ) ~H* ) S OCEI3 ,Cl ., U (C-24) (H* ) S CH3 O--11 (C-25 ) (~' ) \N~ 0CH3 C6~4(P-0C~3) ~ :
C6~5C0--CH(H*)--C0--NHC4H9 (C--26) C~H502C--C~(~* )--C0~C2H5 (C~27 ) 02N \ , C~I(H ) CN (C--?.8) .: . ., .
~14-~C~*) ~ (C-2O
(~*) S~ N~C4~9)2 ~C-30) 10 Donor element~ cf the invention comprise a support bearin~ an electrophile or e~upler compound, or both an electrophile and coupler compound in ~epa~ate adjacent areas. Preferably, the elec~rsphile and/or coupler compound i~ disper~ed in a polymeric b~nder layer on the donor element support. The donor polymeric binder may be, for example, a cellulose derivative, e.g., eellulose aeetate hydrogen phthala~e, cellulo~e acetate, cellulose acetate propionate, cel~ulose acetate butyrate, cellulose triacetate, cellulose tripropionate; a polycarbonate;
poly(styrene-co-acrylonitrile), a poly(~ul~one> or a poly(phenylene o~ide~. The binder may be used at a coverage of ~xom about 0.1 to about 5 g/m2.
Any material can be used as the BUpport for the don3r element provided it iQ dimensionally Etable and can withstand the heat of th~e thermal printing heads. Such material~ include polyesters ~uch as poly(ethylene terephthalate); polyamid~B;
polycarbonates; glassine paper; condenser paper;
cellulose e~ters such as cellulose acetate; fluorine polymers such as polyvinylidene fluoride or poly-(tetrafluoroethylene-co-hexafluoropropylene); poly-ether~ such as polyoxymethylene; polyacetal~; poly-olefin~ such as polystyrene, polyethylene, poly-propylene or methylpentane polymers; and polyimidessuch as polyimide-amides and polyether-imideæ. The suppor~ generally has a thickness of from about 2 to :: !
~:01357~
abvut 30 ~m. It may al~o be coated with a subbing layer, if deRired.
A barrier layer compri~ing a hydrophilic polymer ~ay al~o be employed in the donor elemen~
between it~ ~upport and the electrophile or coupler layer which provide~ improved tranofer den~itie3.
Such barrier layer material~ include those deseribed and claimed in U.S. Patent No. 4,700,208 of Yanier et al, issued Oc~ober 13, 1987.
The reverse eide of the donor element may be coated ~ith a ~lipping layer to prevent the printing head from ~ticking to the donor element. Such a slipping layer would compri~e a lubricating material such a~ a ~urface active agent, a liquid lubricant9 a solid lubricant or mixture~ thereof, ~ith or ~ithout a polymeric binder. Preferred lubricatin~ materials ~:
include oil~ or semi-crystalline organic solid~ that melt below 100C ~uch as poly(vinyl ~tearate), beeswax, perfluorinated alkyl ester polyethers, ~0 phosphoric acid esters ~ #ilicone oil8, poly(caprolactone), carbowax or poly(ethylene glycols). Suitable polymeric binders for the slipping layer include poly(vinyl alcohol--co-butyral), poly(vinyl alcohol-co-acetal), poly(~tyrene), poly(~tyrene-co acrylonitrile), poly(vinyl acetate), cellulose acetate butyrate, cellulose acetate or ethyl celluloae.
The amount of the lubricating material to be u~ed in the slipping layer depends largely on the type 30 of lubricating material, but i8 generally in the range of about .001 to abou~ ~ g/m2. If a polymeric binder i~ employed, the lubricating materia~ i~
present in the range of 0.1 to 50 weight ~b, prefer ably 0.5 to 40, of the polymeric binder employed.
Receiving elements of the invention compri~e a support bearing an electrophile or coupler ~ 5 ~6 compound. Preferably, the electrophile or coupler compound is disper~ed in a polymeric binder layer on the receiving element support. Such a receiving element binder layer also functions as a receivin~
S layer ~or the electrophile or coupler compound transferred from the donor element. Where both the electrophile and coupler compound are to be transferred from a donor element, a conventiona~
thermal dye trans~er receiving element comprising a support having thereon a receiving layer may be u~ed.
The receiving element binder and receiving layer may comprise, for e~ample, a polycarbonate, a polyurethane, a polyester, polyvinyl chloride, poly(styrene-co-acrylonitrile), poly(c~prolactone) or mixtures thereof, and may be present in any amount which is effective for the intended purpo~e. In general, good results have been obtained at a concentration of from about 1 to about 5 g/m2.
The receiving element support may be a transparent film such as a poly(ether sul~one?, a polyimide, a cellulose ester such as cellulose acetate, a poly(vinyl alcohol-co--acetal) or a poly(ethylene terephthalate). The ~upport for the receiving element may also be reflective such as baryta-coated paper, white polye~ter (polyester with white pigment incorporated therein), an ivory paper, a condenser paper or a 3ynthetic paper æuch as du Pont Tyvek The electrophiles and coupler compounds may be employed in the donor and receiving elements at any concentration which is e~fective for the intended purpose. To provide a Status A image density of above 1.0, the electrophiles are employed at 0.01 to 1.0 g/m2 in the donor or the receiver element, and the coupler compounds are employed at 0.03 to 3.0 g/m in the donor or the receiver element.
' ~ ~3 ~ ~6 The donor element employed in certain embodiments 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 one electrophile and/or coupler compound thereon or may have alternating areas of different electrophiles and/or coupler compounds chosen to generate dyes of different hues such as cyan, magenta, yellow, black, etc., to enable full color prints to be produced.
Thermal printing heads which can be used to transfer electrophiles or coupler compounds from the donor elements employed in the invention are available co~mercially. There can be employed, for example, a Fujitsu Thermal ~ead (ETP-040 MCS001), a TDK Thermal ~ead F415 ~7-1089 or a Rohm Thermal Head KE 2008-F3.
Alternatively, other energy sources may be used to transfer the electrophiles or coupler compounds such as laser or ultrasound.
The ~ollowing examples are provided to illustrate the invention.
Example 1 This example illustrates thermal dye-generation imaging with the electrophile in the donor and the coupler in the receiver.
Donor element~ ~ere prcpared by coating on a ~irst side of a 6 ~m polyethylene terephthalate support:
(1) a subbing layer of a titanium alkoxide (duPont Tyzor TBTTM) ~0.12 g/m2) coated from a n-propyl acetate and l-butanol solvent mixture, and (2) a layer of the indicated electrophile (EL-l, EL-2, or EL-3, illustrated above) (0.22 g/m2) in a cellulose acetate propionate binder (2.5% acetyl, 45%
propionyl) (0.32 g/m~) coated from ethyl acetate.
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On the reverse side of the donor supports was coated:
(1) a subbing layer of a titanium alkoxide (duPont Tyzor TBTTM) (0.12 g/m2~ coated from a n-propyl acetate and l-butanol solvent mi~ture, and (2) a slipping layer of Emralon 329TM (Acheson Colloids Corp.~ dry film lubricant o~
poly(tetrafluoroethylene) particles in a cellulose nitrate resin binder (0.54 g/m2) coated from propylacetate, toluene, 2-propanol, and l-butanol solvent mixtures.
A receiving element, R-l, was prepared by coating on a white-~eflective support of titanlum dioxide pigmented polyethylene terephthalate a subbing layer of poly(acrylonitrile-co~vinylidene chloride-co-acrylic acid) (79:14:7 wt ratio) (0.07 g/m2~ ~rom a butanone and cyclopentanone so:lvent mixture. This support with subbing layer was sllbjected to electro-static discharge treatment, and a layer of the indicated coupler (0.23 g/m2) in a binder of a polycarbonate resin derived from bisphe~ol A and 1,5-pentanediol (50:50 wt ratio of diol and dihydric phenol) (2.9 g/m2) was then coated from methylene chloride.
A second receiver, R-2, was made as above but used a polyester derived from terephthalic acid, ethylene glycol, and 1?4 bis(~-hydroxyethoxy)benzene (2:1:1 wt ratio) (2.9 g/m2) in place of the polycarbonate binder.
A donor e~ement strip approximately 3 cm x 15 cm in area was placed in contact wi~h the coupler-binder layer side of a receiving element of the same area. This assemblage was clamped to a motor driven 14 mm diameter rubber roller. A TDK Thermal Head L-133 (No. 6-2R16-1) was pressed with a force of 3.6 kg against thc donor element side of the contacted , ; . , ', ~ ,:
.
~tt~3~6 pair pushing it against the rubber roller.
The imaging electronics were activated causing the donor/receiver a~semblage to be drawn between the printing head and roller at 3.1 mm/sec.
Coincidentally the reæistive elements in the thermal print head were pulsed for discrete sequential intervals at per~pixel pulse widths ~rom 0 up to 8 msec ~o generate a ~tepped density image. The vol~age supplied to the print-head was approximately 21 volts representing approximately 1.4 watts/dot ~12. mjoules/dot) for maximum power.
The receiver element was separated from the donor element and the Status A blue, green and red reflection densities of each single color generated image consisting of a series of eight graduated density steps one cm square were read after 1 hour.
Dye generation was observed to be instantaneous in most instances, however, some dyes required ~everal minutes to form completely.
The following ma~imum density, D-max, and minimum density, D-min, data were obtained. Status A
reflection densities are tabulated for the predomi-nate hue only; Rt G, or B. Spectral absorption curves were also obtained to determine the ~-max of each in situ generated dye.
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-~3-Ex~mple 2 This example is 8 imilar to Example 1 but illustrates dye-generatiorl imaging with the coupler in the donor and the electrophile in the receiver.
Donor elements were prepared as in Egample 1, but in place of the electrophile, the indicated coupler (0.22 g/m2) was coated in a cellulose acetate propionate ~inder (0.32 g/m2) from ethyl acetate.
Receiving elements were prepared similar to R-l of Example l, but in place of the coupler, the electrophile (EL-2~ ~0.23 g/m ) was coated in the polycarbonate binder (2.9 g/m2) from methylene chloride.
The evaluation procedure was as described in Example 1, and the data below ~how that good image discrimination is also obtained with this format with change in location of electrophile and coupler as compared to Example 1.
~ ~Eormed~Pye Electro~hile Coupler ~-max Status A
in Re~elver in Donor U!Q nm D-min/D~max E-31 EL-2 C-19 Magenta 518 1.2/0.18 (G~
E-32 EL-2 5-30 Cyan 612 1.6/0.16 (R) ~0 Example_3 This example illustrates the power re~uire-ments for thermal imaglng with in situ dye generation and for preformed dyes.
Two dye~ were evaluated for compari~on, E-3 and E-4. A dye image was formed as in Examples 1 and 2 using dye generation and compared to the same dye preformed and coated in the donor for transfer.
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Thermal transfer receiver~ were prepared with the coupler in a polycarbonate bi~der 9 R-l, as described in Example 1. Donor~ containing the electrophile were prepared ~imilar to Example 1 except the electrophile, EL-l, for the magenta dye forma~ion was at 0.055 g/m2 (0.36 mmoles/m2) in cellulo~e acetate propionate binder (0.14 g/m2) and the electrophile EL-2 ~or the cyan dye ~ormation was at 0.16 ~/m2 (o 77 mmoles/m2) in cellulose acetate propionate binder (0.28 g/m~).
For preformed-dye thermal transfer, do~ors were prepared as in Example l with the above de-Rcribed e~ternally ~ormed magenta and cyan dye~ at 0.11 g/m ~0.36 mmoles/m2) in cellulose ace*ate propionate binder (0.~7 g/m2) for the magenta and at 0.27 g/m2 ~0,77 ~moles/m2) for the cyan. The mmoles of dye were kept cons~ant for the generated and preformed dyes 80 tbat comparisons ~ere more meaningful. The receiver used with these donors containing preformed dye ~as like the R-l poly-carbonate receiver of Example l Pxcept ~o coupler waæ
added.
The transfer o~ the mag~enta and cyan dyes both preformed and using dye genleration was as de~cribed below. Graduated density 11 ~tep ima~es were each generated at 15, 19, and 23.5 volts. In this manner plots of dye-den~ity ver~u~ a given step number ~or each ~oltage were obtained and compared.
The dye-~ide of a donor element ~trip approximately 10 cm x 13 cm in area wa~ placed in contaet with the polymeric receiver layer ~ide o~ a receiver element of the ~ame area. This assemblage was clamped to a stepper-motor driven 60 mm diameter rubber roller. A TDK Thermal ~ead L-231 (thermo-~tatted at 260C) was pressed with a force ~f 3.6 kgagainst the dye-donor eleme~t side of the contac~ed pair pushing it against the rubber roller.
57~
-2~-The imaging el~ctronic~ were activated eausing the donor-receiver assemblage to be drawn through the printing head/roller nip at 6.9 mm/sec.
Coincidentally the resistive elements in the thermal print head were pulsed for 29 usec/pulse at 128 usec intervals during the 33 msec/dot printing time. A
stepped density image was generated by incrementally increasing the number of pulses/dot from 0 to 255.
The voltage supplied to the printing head was either 15, 19, or 23.5 volts, resulting in an instantaneous peak ~ower of 1.3 watts/dot and maximum total energy of 9.6 mJoules/dot at the maximum voltage of 23.5.
The resulting stepped images were read to Statu~ A
green or red reflection density.
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From the volta~e versus density plot~, the voltage required to reach a ma~imum density of 1.0 was estima~ed. The~e values are:
s Magent.a Dye ~y~n Dye Preformed Gener~Q~ Preform~d Genera~ed Volta~e ~o D=l.0 23v l9v * 18v lû
*Not feasible -highe3t density tsansPerred was only 0.3, even at 23.5 volts.
At a given step (~iven energy) at a specified 15 voltage, higher den~itie~ are obtained when the dyes are generated in-situ. The preformed cyan dye in particular was incapable of producing a denæity greater than 0.3. The preformed magenta dye could produce a d~nsity of about 1.0 by trans$er. Den~ities 20 of 2.0 or more were obtained with generation of the same two dyes. Virtually no meaningful density wa~
tran~ferred with the pre~ormed cyan dye unless a head voltage of 23.5 was u~ed.
~5 ~ El~ 4 This example illustrate~ thermal dye-generation imaging with two di~ferent electrophilesl EL-l and EL-2, and a ~ingle coupler, C-1, in the donor used with a "non reagent7' receiver. EL-1, EL-2, and 30 C-l are as illu trated above.
Donors were prepared by coating on a first ~ide of a 6 ~m polyethylene terephthalate support:
(1) a subbing layer as in E~ample 1, and (2) a layer of either the magenta electrophile, EL-l ~0.14 g/m2), the cyan electrophile, EL-2 (0.32 g/m ), or the coupler compound, C-l, (1.3 g/m2) in a cellulo~e acetate propionate binder 35~
(2.5% acetyl, 45% propionyl) (at 0.14, 0.28t or 0.57 g/m2, respecti~ely) from ethyl acetate, 9n the rever~e ~ide of the ~upport~, ~ubbing and ~lipping layerg were coated a~ in ~xample 1. The recei~er used with these donor~ was like the R-l polycarbonate receiver of Example l e~cept no coupler was added.
The dye-3ide of an electrophile donor element approximately 3 cm ~ 15 cm in area was placed in contact with a receiver element of the ~ame area.
This assemblage was elamped to a 6tepper-motor driven 60 mm diameter rubber roller. A TDK Thermal Head L-231 (thermostatted at 26OC) was pre~sed with a force of 3.~ kg agai~st the dye-donor element eide of the contacted pair pushing it against the rubber roller.
The imaging electronic3 were activated causing the donor-receiver assemblage to be drawn through the printing head/roller nip at 6.9 ~m/sec.
Coincidentally the resi~tive elements in the thermal print head were pulsed for 29 usec/pul~e at 128 usee intervals during the 33 msecldot printing time. A
stepped density image was generated by incrementally increasing the number of pulses/dot from 0 to 255.
The voltage supplied to the printing head wa~ 18 volts, resulting in an instantaneous peak power of 1.3 watt8/dot and maximum total energy of 7.8 mJouleg/dot.
After either the magenta or cyan electro-phile-donor was printed, the complete area of the coupler-donor was overprinted non-imagewise on the receiver at 18. volt~. As 800n as this overprinting was done, magenta and cyan dye were observed to form.
For comparison, the magenta and eyan e~ectrophiles were transferred under the ~ame conditions to a receiver already containing the coupler compound (at 0.23 g/m2) coated in the polycarbonate layer a~ in Example 1.
Each receiver ~as separated from the donor and the Statu6 A green (G~ and red (R) reflection ~357~t densities of each ~ingle color ~rans~erred ima~e consisting of a ~eries of eleven ~raduated density ~teps one cm square were read within one hour.
~tatuS A Den~ity QIu~ler Coupler Coated Transferr in ~ceiver ~rom Donor Magent~ Cyan ~g~ Cyan Step (P~lses/~ot2 (G~ (R~ (G2 (R~
100 (Dmin) 0 0.10 0.06 0.12 0.07 4 92 0.12 0.07 0.13 0.09 7 161 0.63 0.2S 0.59 0.37 11 ~Dmax) 255 1.37 Q.87 1.64 1.3 The above data ~hows that high densities can be obtained by delivery of both the coupler compound and the electrophile ~rom a donor elemen~.
The invention has been clescribed in detail with particular reference to preferred embodiments thereof, but it will be under~tood that variations and modif ications can be effected wit;hin the ~pirit and scope of the invention.
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Claims (26)
1. A dye image recording element comprising a support bearing an electrophile capable of reacting with a coupler compound to form an arylidene dye, said electrophile having the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety o E1;
and n is zero or one.
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety o E1;
and n is zero or one.
2. The element of Claim 1, wherein n is zero and E1 and E2 together form -C(O)NR1C(O)- where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
3. The element of Claim 2, wherein the electrophile is:
.
.
4. The element of Claim 1, wherein the electrophile is:
where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
5. The element of Claim 1, wherein the electrophile is:
.
.
6. The element of Claim 1, wherein said support bears sequential repeating areas of plural distinct electrophiles, each electrophile being capable of reacting with a coupler compound to form dyes of different hues.
7. The element of Claim 1, wherein said support bears said electrophile is a first area, and wherein said element further comprises a second, separate adjacent area of said support bearing said coupler compound.
8. The element of Claim 7, wherein said support bears sequential repeating areas of plural distinct electrophiles, each electrophile being capable of reacting with said coupler compound to form dyes of different hues.
9. The element of Claim 7, wherein said support bears sequential repeating areas of plural distinct coupler compounds, each coupler compound being capable of reacting with said electrophile to form dyes of different hues.
10. The element of Claim 7, wherein the coupler compound is an aromatic amine, an aromatic hydroxyl compound, a compound comprising a five-member unsaturated hetero-ring having at least one N, O, or S
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
11. A dye image recording assemblage comprising:
(a) a first element comprising a first support bearing on one surface of the first support a coupler compound capable of reacting with an electrophile to form an arylidene dye, and (b) a second element comprising a second support bearing on one surface of the second support said electrophile, said electrophile having the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstitutcd arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six member ring with a carbonyl moiety of El;
and n is zero or one, wherein said first element and said second element are in superposed relationship with each other so that the surface of the first support bearing the coupler compound faces the surface of the second support bearing the electrophile.
(a) a first element comprising a first support bearing on one surface of the first support a coupler compound capable of reacting with an electrophile to form an arylidene dye, and (b) a second element comprising a second support bearing on one surface of the second support said electrophile, said electrophile having the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstitutcd arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six member ring with a carbonyl moiety of El;
and n is zero or one, wherein said first element and said second element are in superposed relationship with each other so that the surface of the first support bearing the coupler compound faces the surface of the second support bearing the electrophile.
12. The assemblage of Claim 11, wherein the coupler compound is an aromatic amine, an aromatic hydroxyl compound, a compound comprising a five-member unsaturated hetero-ring having at least one N, O, or S
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R and R are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R and R are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
13. The assemblage of Claim 12, wherein the coupler is an aromatic amine and the electrophile is:
, , or where R1 is hydrogen, or substituted or unsub-stituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
, , or where R1 is hydrogen, or substituted or unsub-stituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
14. A process for forming a dye image comprising imagewise transferring an electrophile prom a donor element comprising a support bearing said electrophile to a receiver element comprising a support bearing a coupler compound capable of reacting with said electrophile to form an arylidene dye, and reacting said electrophile with said coupler compound to form said dye image, wherein said electrophile has the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
15. The process of Claim 14, wherein the coupler compound is an aromatic amine, an aromatic hydroxyl compound, a compound comprising a five-member unsaturated hetero-ring having at least one N, Q, or S
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
16. The process of Claim 15, wherein the coupler is an aromatic amine and the electrophile is:
, , or where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
, , or where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
17. A process for forming a dye image comprising imagewise transferring a coupler compound from a donor element comprising a support bearing said coupler compound to a receiver element comprising a support bearing an electrophile capable of reacting with said coupler compound to form an arylidene dye, and reacting said electrophile with said coupler compound to form said dye image, wherein said electrophile has the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and 82 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and 82 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
18. The process of Claim 17, wherein the coupler compound is an aromatic amine, an aromatic hydroxyl compound, a compound comprising a five-member unsaturated hetero-ring having at least one N, O, or S
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R3 are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
19. The process of Claim 18, wherein the coupler is an aromatic amine and the electrophile is:
, or where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
, or where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
20. A process for forming a dye image on a receiving element comprising:
(a) transferring an electrophile from a donor element comprising a support bearing said electrophile to said receiving element;
(b) transferring a coupler compound capable of reacting with said electrophile to form an arylidene dye from a donor element comprising a support bearing said coupler compound to said receiving element; and (c) reacting said electrophile with said coupler compound to form said dye image;
wherein at least one of said electrophile and said coupler compound is transferred imagewise and wherein said electrophile has the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
(a) transferring an electrophile from a donor element comprising a support bearing said electrophile to said receiving element;
(b) transferring a coupler compound capable of reacting with said electrophile to form an arylidene dye from a donor element comprising a support bearing said coupler compound to said receiving element; and (c) reacting said electrophile with said coupler compound to form said dye image;
wherein at least one of said electrophile and said coupler compound is transferred imagewise and wherein said electrophile has the following structure:
wherein X is halogen, substituted or unsubstituted alkylsulfonyloxy, substituted or unsubstituted arylsulfonyloxy, or substituted or unsubstituted acyloxy;
E1, E2, E3, and E4 are each independently hydrogen, substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, substituted or unsubstituted aryl having up to about ten carbon atoms, halogen, cyano, benzoxazolyl, nitro, -CO2R, -COR, -CONH2, -CONHR, -CONRR, or -SO2R, wherein each R is independently substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms, or substituted or unsubstituted aryl having up to about ten carbon atoms, with the proviso that at least two of the E groups are other than hydrogen, alkyl, alkenyl, aryl or halogen;
B1 and B2 represent the atoms necessary to complete optional five- or six-member rings formed with carbonyl moieties of E1, E2 or E3;
B3 represents hydrogen or the atoms necessary to complete an optional five- or six-member ring with a carbonyl moiety of E1;
and n is zero or one.
21. The process of Claim 20, wherein the coupler compound is an aromatic amine, an aromatic hydroxyl compound, a compound comprising a five-member unsaturated hetero-ring having at least one N, O, or S
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
atom, or a compound of the formula G1-CH2-G2 wherein G1 and G2 are each independently:
cyano, substituted or unsubstituted aryl, five- or six-member N, O, or S containing unsaturated hetero-ring, -CO2R2, -COR2, or -CONR2R3, where R2 and R are each independently hydrogen or substituted or unsubstituted alkyl, alkenyl, or aryl having up to about ten carbon atoms, and wherein G1 and G2 may be optionally joined to form a carbocyclic ring.
22. The process of Claim 21, wherein the coupler is an aromatic amine and the electrophile is:
, or , where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
, or , where R1 is hydrogen, or substituted or unsubstituted alkyl or alkenyl having up to about six carbon atoms or aryl having up to about ten carbon atoms.
23. The process of Claim 20, wherein step (a) further comprises sequentially individually imagewise transferring plural distinct electrophiles, each electrophile being capable of reacting with said coupler compound to form dyes of different hues.
24. The process of Claim 23, wherein the coupler compound is transferred imagewise corresponding to the total density of the plural electrophiles individually transferred.
25. The process of Claim 23, wherein the coupler compound is transferred uniformly.
26. The process of Claim 20, wherein step (b) further comprises sequentially individually imagewise transferring plural distinct coupler compounds, each coupler compound being capable of reacting with said electrophile to form dyes of different hues.
7. The process of Claim 26, wherein the electrophile is transferred imagewise corresponding to the total density of the plural coupler compounds individually transferred.
28, The process of Claim 26, wherein the electrophile is transferred uniformly.
7. The process of Claim 26, wherein the electrophile is transferred imagewise corresponding to the total density of the plural coupler compounds individually transferred.
28, The process of Claim 26, wherein the electrophile is transferred uniformly.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/490,116 US5011811A (en) | 1990-03-07 | 1990-03-07 | In situ dye generation for thermal transfer printing |
| US490,116 | 1990-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2035760A1 true CA2035760A1 (en) | 1991-09-08 |
Family
ID=23946694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002035760A Abandoned CA2035760A1 (en) | 1990-03-07 | 1991-02-06 | In situ dye generation for thermal transfer printing |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5011811A (en) |
| EP (1) | EP0445761B1 (en) |
| JP (1) | JPH0615268B2 (en) |
| CA (1) | CA2035760A1 (en) |
| DE (1) | DE69102453T2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5194571A (en) * | 1991-08-19 | 1993-03-16 | Eastman Kodak Company | Colored polyester compositions |
| US5283165A (en) * | 1992-12-23 | 1994-02-01 | Eastman Kodak Company | Pyrrolinone dyes |
| US5424268A (en) * | 1994-05-13 | 1995-06-13 | Polaroid Corporation | Imaging medium and process |
| US5683956A (en) * | 1995-08-30 | 1997-11-04 | Eastman Kodak Company | Thermal dye transfer system with receiver containing amino groups |
| US6334676B1 (en) * | 1997-09-29 | 2002-01-01 | Eastman Kodak Company | Using colorant precursors and reactants in microfluidic printing |
| US6109746A (en) * | 1998-05-26 | 2000-08-29 | Eastman Kodak Company | Delivering mixed inks to an intermediate transfer roller |
| US6097406A (en) * | 1998-05-26 | 2000-08-01 | Eastman Kodak Company | Apparatus for mixing and ejecting mixed colorant drops |
| US7307173B1 (en) | 2004-02-19 | 2007-12-11 | University Of Washington | Pyrroline chromophores |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US28956A (en) * | 1860-07-03 | Mode of polishing varnish | ||
| US3013013A (en) * | 1959-04-24 | 1961-12-12 | Du Pont | 5-cyanomethylene-2-oxo-3-pyrrolines |
| USRE28956E (en) | 1959-09-28 | 1976-09-07 | Horizons Research Incorporated | Latent image photographic system |
| US3332557A (en) * | 1964-05-26 | 1967-07-25 | Pall Corp | Wire mesh filter element with anchoring rim |
| JPS5243566B2 (en) * | 1972-08-03 | 1977-10-31 | ||
| JPS5677189A (en) * | 1979-11-30 | 1981-06-25 | Fuji Photo Film Co Ltd | Recording material |
| JPS5769091A (en) * | 1980-10-17 | 1982-04-27 | Ricoh Co Ltd | Peel-off type heatsensitive recording paper |
| US4500896A (en) * | 1983-01-25 | 1985-02-19 | Ricoh Company, Ltd. | Heat-sensitive recording medium affording patterns with different colors |
| JPS60101078A (en) * | 1983-11-09 | 1985-06-05 | Ricoh Co Ltd | Image recording method |
| JPS60156760A (en) * | 1984-01-26 | 1985-08-16 | Sumitomo Chem Co Ltd | Heterocyclic compound, dyeing and coloring using it |
| JPS60158262A (en) * | 1984-01-27 | 1985-08-19 | Sumitomo Chem Co Ltd | Heterocyclic compound and dyeing or colorig method using the same |
| JPS60161190A (en) * | 1984-02-01 | 1985-08-22 | Ricoh Co Ltd | Multicolor image recording method |
| US4614521A (en) * | 1984-06-06 | 1986-09-30 | Mitsubishi Chemical Industries Limited | Transfer recording method using reactive sublimable dyes |
| JPS6131293A (en) * | 1984-07-24 | 1986-02-13 | Sharp Corp | Thermal recording method |
| DE3601525A1 (en) * | 1985-01-21 | 1986-07-24 | Mitsubishi Paper Mills, Ltd., Tokio/Tokyo | HEAT SENSITIVE AND HEAT TRANSFERABLE RECORD SHEET |
| JPS61173987A (en) * | 1985-01-30 | 1986-08-05 | Sugai Kagaku Kogyo Kk | Thermal transfer recording material |
| US4745046A (en) * | 1985-06-03 | 1988-05-17 | Polaroid Corporation | Thermal imaging method |
| JPH0649835B2 (en) * | 1986-03-24 | 1994-06-29 | 日本化薬株式会社 | Pyrrole compound, method for producing the same, and dyeing or coloring method using the same |
| JPH0639573B2 (en) * | 1986-07-07 | 1994-05-25 | 日本化薬株式会社 | Pyrrole compound and dyeing or coloring method using the same |
-
1990
- 1990-03-07 US US07/490,116 patent/US5011811A/en not_active Expired - Lifetime
-
1991
- 1991-02-06 CA CA002035760A patent/CA2035760A1/en not_active Abandoned
- 1991-03-06 EP EP91103388A patent/EP0445761B1/en not_active Expired - Lifetime
- 1991-03-06 DE DE69102453T patent/DE69102453T2/en not_active Expired - Fee Related
- 1991-03-07 JP JP3041675A patent/JPH0615268B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0615268B2 (en) | 1994-03-02 |
| EP0445761A1 (en) | 1991-09-11 |
| US5011811A (en) | 1991-04-30 |
| EP0445761B1 (en) | 1994-06-15 |
| DE69102453D1 (en) | 1994-07-21 |
| JPH04219288A (en) | 1992-08-10 |
| DE69102453T2 (en) | 1995-01-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |