CA2016831A1 - Mixture of yellow and cyan dyes to form a green hue for color filter array element - Google Patents
Mixture of yellow and cyan dyes to form a green hue for color filter array elementInfo
- Publication number
- CA2016831A1 CA2016831A1 CA002016831A CA2016831A CA2016831A1 CA 2016831 A1 CA2016831 A1 CA 2016831A1 CA 002016831 A CA002016831 A CA 002016831A CA 2016831 A CA2016831 A CA 2016831A CA 2016831 A1 CA2016831 A1 CA 2016831A1
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- dye
- substituted
- group
- represents hydrogen
- 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
- B41M5/3858—Mixtures of dyes, at least one being a dye classifiable in one of groups B41M5/385 - B41M5/39
-
- 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
- B41M5/265—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used for the production of optical filters or electrical components
-
- 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
-
- 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
- B41M5/388—Azo dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/146—Laser beam
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/148—Light sensitive titanium compound containing
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
- Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Abstract
-i-MIXTURE OF YELLOW AND CYAN DYES TO FORM
A GREEN HUE FOR COLOR FILTER ARRAY ELEMENT
Abstract of the Disclosure A thermally-transferred color filter array element comprising a transparent support having thereon a thermally-transferred image comprising a repeating mosaic pattern of colorants in a receiving layer, one of the colorants being a mixture of a yellow dye and a cyan dye to form a green hue, said yellow dye having the formula:
I wherein: R1 and R2 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membered ring; or either or both of R1 and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R3 represents hydrogen or halogen;
Y represents hydrogen; halogen; cyano; a substituted or unsubstituted alkyl or alkoxy -ii-group of from 1 to about 6 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms; aryloxy; acylamido, alkylsulfonamido;
or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
II wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms;
R5 may be taken together with R4 to form a 5- or 6-membered ring;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R7 represents hydrogen, a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms, halogen, sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyl, alkylsulfonyl, arylsulfonyl, -iii-acyl, alkoxycarbonyl, carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro, cyano, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8.
A GREEN HUE FOR COLOR FILTER ARRAY ELEMENT
Abstract of the Disclosure A thermally-transferred color filter array element comprising a transparent support having thereon a thermally-transferred image comprising a repeating mosaic pattern of colorants in a receiving layer, one of the colorants being a mixture of a yellow dye and a cyan dye to form a green hue, said yellow dye having the formula:
I wherein: R1 and R2 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membered ring; or either or both of R1 and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R3 represents hydrogen or halogen;
Y represents hydrogen; halogen; cyano; a substituted or unsubstituted alkyl or alkoxy -ii-group of from 1 to about 6 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms; aryloxy; acylamido, alkylsulfonamido;
or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
II wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms;
R5 may be taken together with R4 to form a 5- or 6-membered ring;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R7 represents hydrogen, a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms, halogen, sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyl, alkylsulfonyl, arylsulfonyl, -iii-acyl, alkoxycarbonyl, carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro, cyano, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8.
Description
MIXTURE OF YELLOW AND CYAN DYES TO FORM
A GRE~N HUE EOR COLOR FILTER ARRAY ELEMENT
This invention relates to the use of a mixture of a yellow dye and a cyan dye to form a green hue for a thermally-transferred color ilter array element which is used in various applications such as a liquid crystal display device.
In recent years, thermal transfer systems have been developed to obtain prints from pictures which have been generated electronically from a color video camera. According to one way of obtaining such prints, an electronic picture is ~irst æubjected to color separation by color filters. The respective color-separated images are then converted into elec-trical signals. These signals are then operated onto produce cyan, magenta and yellow electrical sig-nals. These si~nals are then transmitted to a ther-mal printer. To obtain the print, a cyan, magenta or yellow dye-donor element is placed face-to-face with a dye-receiving element. The two are then inserted between a thermal printing head and a platen roller.
A line-type thermal printing head is used to apply heat from the back of the dye-donor sheet. The thermal printing head has many heating elements and is heated up sequentially in res~onse to the cyan, magenta and yellow signals. The process is then repeated for the other two colors. A color hard copy is thus obtained which corresponds to the original picture viewed on a screen. Further details of this process and an apparatus for carrying it out are contained in U.S. Patent No. 4,621,271 by Brownstein entitled "Apparatus and Method For Controlling A
Thermal Printer Apparatus," issued November 4, 1986.
Another way to thermally obtain a print using the electronic signals described above is to ~ ~,F ~ 3~,~
--2~
use a laser instead of a thermal printing head. In such a system, the donor sheet includes a material which strongly absorbs at the wavelength o~ the laser. When the donor is irradiated, this absorbing material converts light energy to thermal energy and transfers the heat to the dye in the immediate vicinityl thereby heating the dye to its vaporization temperature for transfer to the receiver. The absorbing material may be present in a layer beneath the dye and/or it may be admi~ed with thc dye. The laser beam is modulated by electronic signals which are representative of the shape and color of the original image, so that each dye is heated to cause volatilization only in tho~e areas in which its presence is required on the receiver to reconstruct the color of the original object. Further details of this process are found in GB 2,083,726A.
Liquid crystal display devices are known for digital display in electronic calculators, clocks, household appliances, audio equipment, etc. There has been a need to incorporate a color display capability into such monochrome display devices, particularly in such applications as peripheral terminals using various kinds of equipment involving phototube display, mounted electronic display, or TV-image display. Various attempts have been made to incorporate a color display usin~ a color filter array into these devices. Eowever, none of the color array systems for liquid crystal display devices so far proposed have been successful in meeting all the users needs.
One commercially-available type of color filter array which has been used in liquid crystal display devices for color display capability is a transparent support having a gelatin layer thereon .
~fL~
which contains dyes having the additive primary colors red, green and blue in a mosaic pattern obtained by using a photolithographic technigue. To prepare such a color filter array element, a gelatin layer is sensitized, exposed to a mask for one of the colors of the mosaic pattern, developed to harden the gelatin in the exposed are s, and washed to remove the unexposed (uncrosslinked) gelatin, thus producing a pattern of gelatin which is then dyed with dye of the desired color. The element is then recoated and the above steps are repeated to obtain the other two colors. This method contains many labor-intensive steps, requires careful alignment, is time-consuming and very costly. Further details of this process are disclosed in U.S. Patent 4,081,277.
In addition, a color filter array element to be used in a liguid cry3tal display device may have to undergo rather severe heating and treatment steps during manufacture. For example, a transparent ~0 electrode layer, such as indium tin oxide, is usually vacuum sputtered onto the color ~ilter array element. This may take place at temperatures elevated as high as 200C for times which may be one hour or more. This is followed by coating with a thin alignment layer for the liquid crystals, such as a polyimide. Regardless o the alignment layer used, the surface finish of this layer in contact with the liguid crystals is very important and may require rubbing or may re~uire curing for several hours at an elevated temperature. These treatment steps can be very harmful to many color filter array elements, especially those with a gelatin matrix.
It is thus apparent that dyes used in color filter arrays for liquid crystal displays must have a high degree of heat and light stability above the requirements desired for dyes used in conventional thermal dye transfer imaging.
While a green dye may be formed from a mixture of one or more cyan and one or more yellow dyes, not all such combinations will produce a dye mixture with the correct hue for a color filter array. Further, when a dye mixture with the correct hue is found, it may not have the requisite stability to light. An additional requirement is that no single dye of the mixture can have an adverse effect on the stability to light or crystallinity of any of the other dye components.
U.S. Patent 4,701,439 describes yellow dyes useful in thermal printing. There is no disclosure in that patent, however, that such dyes may be mixed with a particular cyan dye to form a green dye useful in a color filter array.
EP 235,939, JP 61/227,092, JP 60/031,565, JP 61/268,494, JP 62/099,195 and JP 62/132,684 relate to the use of various arylazoaniline cyan dyes for thermal dye transfer. However, none of these references describe the use of these dyes for color filter array elements.
It would be desirable to provide a color filter array element having high quality, good sharpness and which could be obtained easily and at a ~S lower price than those of the prior art. It would also be desirable to provide such a color filter array element having a green dye of the correct hue and which would have good stability to heat and light.
These and other objects are achieved in accordance with this invention which comprises a thermally-transferred color filter array element comprising a transparent support having thereon a thermally-transferred image comprising a repeating mosaic pattern of colorants in a receiving layer, one of the colorants being a mixture of a yellow dye and a cyan dye to form a green hue, said yellow dye having the formula:
CN
I Yn_l wherein: Rl and R2 each independently represents hydrogen, a substituted or unsubstituted alkyl group o~ from 1 to about 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl or such alkyl groups substituted with hydroxy, acyloxy, alkoxy, aryl, cyano, acylamido, halogen, etc.; a cycloalkyl group of from about 5 to about 7 carbon atoms such as cyclopentyl, cyclohexyl, p-methylcyclohexyl, etc.; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms such as phenyl, p-tolyl, : m-chlorophenyl, p-metho~yphenyl, m-bromophenyl, o-tolyl, etc.; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membe~ed ring such as morpholine, pyrrolidine, piperidine, oxazoline, pyrazoline, etc.; or either or both of and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a S - or 6 - membered sing, thus forming a polycyclic system such as 1,2,3,4-tetrahydrQquinoline, julolidine, 2,3-dihydroindole, benzomorpholine, etc.;
R3 represents hydrogen or halogen such as chloro, bromo or fluoro;
~ f~
Y represents hydrogen; halogen such as chloro, bromo or fluoro; cyano; a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 6 carbon atoms, such as those listed above for Rl, methoxy, ethoxy, etc.; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms, such as those listed above for Rl; aryloxy;
acylamido; alkylsulfonamido; or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
/R8 ~ 4 ~ :
II R9-- \ ~D N=N ~ R5 wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atom~ such as methyl, et;hyl, propyl, isopropyl, butyl, pentyl, hexyl or such alkyl groups substitutecl ~ith hydroxy, acyloxy~ alkoxy, aryl, aryloxy, cyano, ~:
acylamido, alkoxycarbonyl, --alkoxycarbonyloxy, phthalimido, succinimido, sulfonamido, halogen, etc.; a cycloalkyl group of from about 5 to about 7 carbon atoms such as cyclopentyl, cyclohexyl, p-methylcyclohexyl, etc~; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atom~ such as phenyl, p-tolyl, m-chlorophenyl, p-methoxyphenyl, m-bromophenyl, o-tolyl, .
' ~ ,?~
naphthyl, 3-pyridyl, o-ethoxyphenyl, etc., or such groups substituted as above;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl~
hexyl, methoxy, ethoxy, isopropoxy, etc., or such alkyl or al~oxy groups substituted with hydroxy, acyloxy, alkoxy, aryl, aryloxy, cyano, acylamido, alkoxycarbonyl, alkoxycarbonyloxy, phthalimido, succinimido, sulfonamido, halogen, etc.;
R5 may be taken together with R4 to form a 5- or 6-membered ring such as morpholine, pyrrolidine, piperidine, oxazoline, pyrazoline, etc.;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring, thus forming a polycyclic system such as 1,2,3,4-tetrahydroquinoline, julolidine, 2,3-dihydroindole, benzomorpholine, etc.;
R7 reprcsents hydrogen; a substituted or unsubstituted alkyl or alkoxy group of ~rom 1 to about 10 carbon atoms such as ~hose listed above for R6; halogen such as chlorine, bromine, fluorine, etc.;
sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyI, alkylsulfonyl, arylsulfonyl, acyl, alkoxycarbonyl~ carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro, cyano, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8-.
$~
Yellow dyes according to formula I useful in the invention are described in U.S. Patent 4,701,439.
In a preferred embodiment of the invention, R and R in structural formula I represents the - 5 atoms which are taken together to form, along with the nitrogen to which they are attached, a 6-membered ring. In another preferred embodiment of the invention, R3 in formula I is hydrogen.
The compounds according to formula I of the invention may be prepared by any of the processes disclosed in U.S. Patents 3,917,604, 4,180,663 and 3,247,211.
Specific yellow dyes useful in the invention include the following: :
, ~ .
; ~ , .
Yellow Dves ~C--CH--I `O' ` I
R Rl 10Cmpd.R9 R4 R5 R6 R7 R8 Rl B CH3 CH3CH3 H H HC~H40CNHC6H5 O . ,:
25 E CH3 CH3 CH3 H CH3 ~ HCE2fHOCNHC6H5 O
F CH3 CH3C~3 H CH3H:CH2fHCH20CCH3 ~ :
: OCCH3 O
O ::
G CH3 CH3CH3 H CH3 Hc~2l~CE20CNHC2H5 .
':
-10~
Cmpd. 9 4 R5 R6 R7 R8Rl C~3 CH3 CH3 H CH3 HCH2~H2CH2NHeNHC6H5 I CH3CH:3 CH3 H CH3 HCH2CH2CH2NHeOC2H5 I~ ,0 K H H CH3 H Cl HCH2CH20 - I~ ,0 Cl : ~ L H H CH3 H CH3 HCH2CHCH20COC2~I5 ~ 1COC2H5 : ~ 30 O
M H X CH3 H CH3 HCH2CH2NHe I O : ~
~, ~:
.;
.
5y ~./ \ ~ ~5 CH2 CH2--X , Compound No. _ R7_ R4 R5 Y X
N CX3 CH3 CH3 3-CH3 -OCO-N~(C6H5) P CH3 CH3 CE3 -OCO-N~[C6H3-3,5 (OC~3)2]
Q CH3 CH3 CH3 -OCo-(c6H4-4-co2cH3) R CH3 CH3 CH3 -N( CH3)(-so2c6~5) -NH
O
.
,; ' :
-.
-12- :
C~3 CH / ~-/ \N/ \C~ 3~' C~C~2-0CO-N~(C6~5) I
1 o u C `C=CH--t ` ~
CH2CH2--OCO--NH~C6H5 ) CN\
V ~C=CCl-o\ ~--NHC2H5 W /\C=CH-~ 2 6 5 ~ COC2H5 In another preferred embodiment of the invention, R4 and R5 in the above formula II ~or cyan dyes are each independently hydrogen, ethyl, n-propyl, benzyl, cyclohexyl, -(C2H40)2C~H2, or may be taken together to form a morpholino group. In another preferred embodiment of the invention, R6 is hydrogen or methoxy and R7 is -NHCoCH3. In yet another preferred embodiment of the invention, R is cyano or trifluoromethyl and R9 is nitro or cyano. In yet still another preferred embodiment of the invention, J is S or -CH=CR8- wherein R8 is nitro or cyano.
Specific cyan dyes useful in the invention include the following:
,. , - . , ~ , ~:
~ : , , ~ .. '' ' ' : ` ' : : .. ' . , .
E ~i ~D ~ u~ oo cr~
r~ ~ ) ~ I~
C~
o Z Z
~; ~
s~
~o; Zo; `~ Zo; ~o; o o z z p~ o ~` O o ~ o o o p:
~
o o o o o o o , u~ u~
Q
U ~ U~
~ ~ P~ ~ P~ ~ ~ ~ ~ a~
~ ~ v~ ~
Cyan ~max*
(nm) ~CN ~COCH3 8 02N-~ -N=N-~ 2 5 623 4=-~ ~ _ ~ (CH3~2 c~3 *In acetone The dye-receiving layer of the color filter array element of the invention may comprise, for example, sucrose acetate or polymers such as a polycarbonate, a polyurethane, a polyester, a polyvinyl chloride, a polyamide, a polystyrene, an acrylonitrile, a polycaprolactone or mixîures thereof. The dye-receiving layer may be present in any amount which is effective fo:c the intended purpose. In general, good results have been obtained at a concentration of from about 0.25 to about 5 glm .
In a preferred embodiment of the invention, the receiving layer comprises a polycarbonate binder having a Tg greater than about 200C. as described in Application Serial No. 334,269 of ~arrison et al., fi~ed April 6, 1989. The term "polycarbonatel' as used herein means a polyester of carbonic acid and one or more glycols or dihydric phenols. In another preferred embodiment, the polycarbonate is derived from a bisphenol component comprising a diphenyl methane moiety. Examples of such polycarbonates include those derived ~rom 4,4'-(hexahydro-4,7-methanoindene-5-ylidene~bisphenol, 2,2l,6,6~-tetrachlorobisphenol-A and 4,4'-(2-norbornyli-dene)bisphenol.
In another preferred embodiment of the invention, the mosaic pattern which is obtained by ~ !
' '~
' the thermal transfer process consists of a set of red, green and blue additive primaries.
In another preferred embodiment of the invention, each area of primary color and each set of - 5 primary colors are separated from each other by an opaque area, e.g., black grid lines. This has been found to give improved color reproduction and reduce ~lare in the displayed image.
The size of the mosaic set is normally not critical since it depends on the viewing distance.
In general, the individual pixelæ of the set are from about 50 to about 300 ~m. They do not have to be of the same size.
In a preferred embodiment of the invention, the repeating mosaic pattern of dye to form the color filter array consiæts of uniform, square, linear repeating areas, with one color diagonal displacement as follows:
~ G~ \R G
B ~ G B R
G B ~ G~ \
In another preferred embodiment, the above squares are approximately 100 ~m.
As noted above, the color filter array elements of the invention are used in various display devices such as a liquid crystal display device.
Such liquid crystal display devices are described, for example, in UK Patents 2,154,355; 2,130,781;
30 2,162,674 and 2,161,971.
A process of forming a color filter array element according to the invention comprises a) imagewise-heating a dye-donor element comprising a support having thereon a dye layer as deæcribed a~ove, and 3 ~!~
b) transferring portions of the dye layer to a dye-receiving element comprising a transparent support having thereon a dye-receiving layer, - 5 the imagewise-heating being done in such a way as to produce a repeating mosaic pattern of dyes to form the color filter array element.
Various methods can be used to supply energy to transfer dye from the dye donor to the transparent support to form the color filter array of the invention. There may be used, for example, a thermal print head. A high intensity light flash technique with a dye-donor containing an energy absorptive material such as carbon black or a non-subliming light-absorbing dye may also be used. This method is described more fully in U.K. Application No.
8824366.2 by Simons filed October 18, 1988.
Another method of transferring dye from the dye-donor to the transparent support to form the color filter array of the inventlon is to use a heated embossed roller as described more fully in U.K. Application No. 8824365.4 by Simons filed October 18, 1988.
In a preferred embodiment of the invention, a laser is used to supply energy to transfer dye from the dye-donor to the recei~er as described more fully in U.S. Serial Number 259,080, filed October 18, 1988 of DeBoer entitled ~Color Filter Array Element Obtained by Laser-induced Thermal Dye Transfer~.
If a laser or high-intensity light ~la~h is used to transfer dye from the dye-donor to the -17- ~ ]
receiver, then an additional absorptive but non-volatile material is used in the dye-donor. Any material that absorbs the laser or light energy may be used such as carbon black or non-volatile infrared-absorbing dyes or pigments which are well known to those skilled in the art. Cyanine infrared absorbing dyes may also be employed with infrared diode lasers as described in DeBoer Application Serial Number 221,163 filed July 19, 1988.
A dye-donor element that is used to form the color filter array element of the invention comprises a support having thereon a mixture of dyes to form a green hue as described above along with other colorants such as imaging dyes or pigments to form the red and blue areas. Other imaging dyes can be used in such a layer provided they are transferable to the dye-receiving layer of the color array element of the invention by the action of heat. Especially good results have been obtained with sublimable dyes. Examples of additive subllmable dyes include anthraquinone dyes, e.g., Sumikalon Violet RSTM
(Sumitomo Chemical Co., Ltd.), Dlanix Fast Violet 3R-FSTM (Mitsubishi Chemical Industries, Ltd.), and Kayalon Polyol Brilliant Blue N-BGMTM and KST Black 146TM (Nippon Kayaku Co., Ltd.); azo dyes such as Kayalon Polyol Brilliant Blue BMrM, Kayalon Polyol Dark Blue 2BMTM, and KST Black KRTM (Nippon Kayaku Co., Ltd.), Sumickaron Diazo Black 5GTM
(Sumitomo Chemical Co., Ltd.), and Miktazol Black 5GHTM (Mitsui Toatsu Chemicals, Inc.); direct dyes such as Direct Brown MTM and Direct Fast Black DTM (Nippon Kayaku Co. Ltd.); acid dyes such as Kayanol Milling Cyanine 5RTM ~Nippon Kayaku Co.
Ltd.); basic dyes such as Sumicacryl Blue 6GTM
(Sumitomo Chemical Co., Ltd.). Examples of subtractive dyes useful in the invention include the following:
5N~5~ N-N ~ N(C2E5~CH2C6H5) (magenta) ~H3\ /CH3 0 oI~ ~ ~ J=CH-CH=./ l C6H5 (yellow) CX N(CH3)2 o ~ \ ~!~ ,CONXCH3 I -O O (cyan) O D
--N(C2~5)2 or any of the dyes disclosed in U.S. Patent 4,541,830. The above cyan, magenta, and yellow subtractive dyes may be employed in various combinations, either in the dye-donor itself or by being sequentially transferred to the dye image-receiving element, to obtain the other desired blue and red additive primary colors. The dyes may be mixed within the dye layer or transferred sequentially if coated in separate dye layers. The dyes may be used at a coverage of from about 0.05 to about 1 g/m2.
The imaging dye, and an infrared- or visible light-absorbing material if one is present, are dispersed in the dye-donor element in a polymeric binder such as a cellulose derivative, e.g., cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate, a polycarbonate; poly(styrene-co-acrylonitrile), a poly(sulfone) or a poly(phenylene oxide). The binder may be used at a coverage of from about 0.1 to about 5 glm2.
The dye layer of the dye-donor element may be coated on the support or printed thereon by a printing technique such as a gravure process.
Any material can be used as the support ~or the dye-donor element provided it is dimensionally stable and can withstand the heat generated by the thermal transfer device such as a laser beam. Such materials include polyesters such as poly(ethylene terephthalate); polyamides; polycarbonates; glassine paper; condenser paper; cellulose esters; fluorine polymers; polyethers; polyacetals; polyolefins; and polyimides. The support general:Ly has a thickness of from about 2 to about 250 ~m. It may also be ?0 coated with a subbing layer, if desired.
The support for the dye image-receiving element or color filter array element of the invention may be any transparent material such as polycarbonate, poly(ethylene terephthalate), cellulo~e acetate, polystyrene, etc. In a preferred embodiment, the support is glass.
After the dyes are transferred to the receiver, the image may be treated to further diffuse the dye into the dye-receiving layer in order stabilize the image. This may be done by radiant heating, solvent vapor, or by contact with heated rollers. The fusing step aids in preventing fading upon e~posure to light and surface abrasion of the image and also tends to prevent crystallization of the dyes. Solvent vapor fusing may also be used instead of thermal fusing.
~20-Several different kinds of lasers could be used to effect the thermal transfer of dye from a donor sheet to the dye-receiving element to form a color filter array element, such as ion gas lasers - 5 like argon and krypton; metal vapor lasers such as copper, gold, and cadmium; solid state lasers such as ruby or YAG; or diode lasers such as gallium arsenide emitting in the infrared region from 750 to 870 nm.
However, in practice, the diode lasers are prefexred because they offer substantial advantages in terms of their small size, low cost, stability, reliability, ruggedness, and ease of modulation. In practice, before any laser can be used to heat a dye-donor element, the laser radiation must be absorbed into the dye layer and converted to heat by a molecular process known as internal conversion. Thus, the construction of a useful dye layer will depend not only on the hue, sublimability and intensity of the image dye, but also on the ability of the dye layer to absorb the radiation and convert it to heat.
Lasers which can be used to transfer dye from the dye-donor element to the dye image-receiving element to form the color filter array element in a preferred embodiment of the invention are available commercially. There can be employed, for example, Laser Model SDL-2420-~2TM from Spectrodiode Labs, or Laser Model SLD 304 V/WTM from Sony Corp.
The following example is provlded to illustrate the invention.
Example A green dye-donor was prepared by coating on a gelatin subbed transparent 175 ~m poly(ethylene terephthalate) support a dye layer containing cyan dye 5 illustrated above (0.21 g/m2) and yellow dye A illustrated above (0.23 g/m ) in a cellulose acetate propionate (2.5% acetyl, 46% propionyl) binder (0.26 g/m2) coated from a l-propanol, 2-butanone, toluene and cyclopentanone solvent mixture. The dye layer also contained Raven Black No. 1255TM (Columbia Carbon Co.) (0.21 g/m2) ball-milled to submicron particle size, FC-431TM
dispersing agent (3M Company) (0.01 g/m2) and SolsperseT~ 2400 dispersing agent (ICI Corp.) (0.03 glm ).
A control green dye-donor was prepared as described above except that it contained the following indoaniline cyan dye (0.64 g/m2~ as described in U.S. Patent 4,695,287 instead of cyan dye 5:
~ ~ ,!~ ,CONHCH3 I~ ,0~ ,5 Z0 N-o\ /--N(c2H5)~
A dye-receiver was prepared by spin-coating the following layers on a 53 ~ thick flat-surfaced borosilicate glass:
l) Subbing layer of duPont VM-651 Adhesion Promoter as a 1% solution in a methanol-water solvent mixture (0.5 ym thick layer equivalent to 0.54 g/m ), and 2~ Receiver layer of a polycarbonate of 4,4'-(hexahydro-4,7-methanoindene-S-ylidene)bisphenol, as described in U.S.
Application Serial No. 334,269, of Marrison et al. referred to above, from methylene chloride solvent (2.5 g/m2).
The dye-donor was placed ~ace down upon the dye-receiver. A MecablitzTM Model 45 (Metz AG
Company> electronic flash unit was used as a thermal energy source. It was placed 40 mm above the dye-donor using a 45-degree mirror box to concentrate the energy from the flash unit to a 25x50 mm area.
The dye transfer area was masked to 12x42 mm. The flash unit was flashed once to produce a transferred transmission density of 1.9 at the maximum absorption of the dye mixture.
The same flash transfer procedure was used for the control coating producing a transferred transmission density of 2.0 at the maximum density of the dye mixture.
Each transferred area was placed under a PyropanelTM no. 4083 (Research Inc., Minneapolis Mn.~ in~rared heat panel at 230OC for 45 sec. to diffuse the dyes into the dye-receiving layer.
The Red and ~lue Status A densities o~ the transferred area were read. Each transferred area was then placed in an oven at 180C, 25% RH for one hour and the densities were re-read to determlne the % dye loss. Each transferred area was also subjected to exposure for 4 days, 50 kLux, 5400K, approximately 25% RH. The densities were then re-read to determine the percent dye loss due to light fade. The following results were obtained:
Red Status A Densitv Blue Status A Density Receiver Init. Heated % Loss Ini~ ~eated % Loss Control 2.00 0.81 60 1.06 0.96 9 Invention 1.89 1.81 4 1.80 1.74 3 Red $tatus A Density Blue Status A Densitv Receiver Init. Faded % Loss Init. Faded /0 Loss Control 1.76 0.98 h4 1.01 0.96 11 Invention 1.77 1.49 16 1.57 1.57 6 ~ç~
The above results indicate that the receiver containing the dyes according to the invention had better stability to heat and light than the control receiver containing an indoaniline cyan dye.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
' .
-.
, . .
A GRE~N HUE EOR COLOR FILTER ARRAY ELEMENT
This invention relates to the use of a mixture of a yellow dye and a cyan dye to form a green hue for a thermally-transferred color ilter array element which is used in various applications such as a liquid crystal display device.
In recent years, thermal transfer systems have been developed to obtain prints from pictures which have been generated electronically from a color video camera. According to one way of obtaining such prints, an electronic picture is ~irst æubjected to color separation by color filters. The respective color-separated images are then converted into elec-trical signals. These signals are then operated onto produce cyan, magenta and yellow electrical sig-nals. These si~nals are then transmitted to a ther-mal printer. To obtain the print, a cyan, magenta or yellow dye-donor element is placed face-to-face with a dye-receiving element. The two are then inserted between a thermal printing head and a platen roller.
A line-type thermal printing head is used to apply heat from the back of the dye-donor sheet. The thermal printing head has many heating elements and is heated up sequentially in res~onse to the cyan, magenta and yellow signals. The process is then repeated for the other two colors. A color hard copy is thus obtained which corresponds to the original picture viewed on a screen. Further details of this process and an apparatus for carrying it out are contained in U.S. Patent No. 4,621,271 by Brownstein entitled "Apparatus and Method For Controlling A
Thermal Printer Apparatus," issued November 4, 1986.
Another way to thermally obtain a print using the electronic signals described above is to ~ ~,F ~ 3~,~
--2~
use a laser instead of a thermal printing head. In such a system, the donor sheet includes a material which strongly absorbs at the wavelength o~ the laser. When the donor is irradiated, this absorbing material converts light energy to thermal energy and transfers the heat to the dye in the immediate vicinityl thereby heating the dye to its vaporization temperature for transfer to the receiver. The absorbing material may be present in a layer beneath the dye and/or it may be admi~ed with thc dye. The laser beam is modulated by electronic signals which are representative of the shape and color of the original image, so that each dye is heated to cause volatilization only in tho~e areas in which its presence is required on the receiver to reconstruct the color of the original object. Further details of this process are found in GB 2,083,726A.
Liquid crystal display devices are known for digital display in electronic calculators, clocks, household appliances, audio equipment, etc. There has been a need to incorporate a color display capability into such monochrome display devices, particularly in such applications as peripheral terminals using various kinds of equipment involving phototube display, mounted electronic display, or TV-image display. Various attempts have been made to incorporate a color display usin~ a color filter array into these devices. Eowever, none of the color array systems for liquid crystal display devices so far proposed have been successful in meeting all the users needs.
One commercially-available type of color filter array which has been used in liquid crystal display devices for color display capability is a transparent support having a gelatin layer thereon .
~fL~
which contains dyes having the additive primary colors red, green and blue in a mosaic pattern obtained by using a photolithographic technigue. To prepare such a color filter array element, a gelatin layer is sensitized, exposed to a mask for one of the colors of the mosaic pattern, developed to harden the gelatin in the exposed are s, and washed to remove the unexposed (uncrosslinked) gelatin, thus producing a pattern of gelatin which is then dyed with dye of the desired color. The element is then recoated and the above steps are repeated to obtain the other two colors. This method contains many labor-intensive steps, requires careful alignment, is time-consuming and very costly. Further details of this process are disclosed in U.S. Patent 4,081,277.
In addition, a color filter array element to be used in a liguid cry3tal display device may have to undergo rather severe heating and treatment steps during manufacture. For example, a transparent ~0 electrode layer, such as indium tin oxide, is usually vacuum sputtered onto the color ~ilter array element. This may take place at temperatures elevated as high as 200C for times which may be one hour or more. This is followed by coating with a thin alignment layer for the liquid crystals, such as a polyimide. Regardless o the alignment layer used, the surface finish of this layer in contact with the liguid crystals is very important and may require rubbing or may re~uire curing for several hours at an elevated temperature. These treatment steps can be very harmful to many color filter array elements, especially those with a gelatin matrix.
It is thus apparent that dyes used in color filter arrays for liquid crystal displays must have a high degree of heat and light stability above the requirements desired for dyes used in conventional thermal dye transfer imaging.
While a green dye may be formed from a mixture of one or more cyan and one or more yellow dyes, not all such combinations will produce a dye mixture with the correct hue for a color filter array. Further, when a dye mixture with the correct hue is found, it may not have the requisite stability to light. An additional requirement is that no single dye of the mixture can have an adverse effect on the stability to light or crystallinity of any of the other dye components.
U.S. Patent 4,701,439 describes yellow dyes useful in thermal printing. There is no disclosure in that patent, however, that such dyes may be mixed with a particular cyan dye to form a green dye useful in a color filter array.
EP 235,939, JP 61/227,092, JP 60/031,565, JP 61/268,494, JP 62/099,195 and JP 62/132,684 relate to the use of various arylazoaniline cyan dyes for thermal dye transfer. However, none of these references describe the use of these dyes for color filter array elements.
It would be desirable to provide a color filter array element having high quality, good sharpness and which could be obtained easily and at a ~S lower price than those of the prior art. It would also be desirable to provide such a color filter array element having a green dye of the correct hue and which would have good stability to heat and light.
These and other objects are achieved in accordance with this invention which comprises a thermally-transferred color filter array element comprising a transparent support having thereon a thermally-transferred image comprising a repeating mosaic pattern of colorants in a receiving layer, one of the colorants being a mixture of a yellow dye and a cyan dye to form a green hue, said yellow dye having the formula:
CN
I Yn_l wherein: Rl and R2 each independently represents hydrogen, a substituted or unsubstituted alkyl group o~ from 1 to about 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl or such alkyl groups substituted with hydroxy, acyloxy, alkoxy, aryl, cyano, acylamido, halogen, etc.; a cycloalkyl group of from about 5 to about 7 carbon atoms such as cyclopentyl, cyclohexyl, p-methylcyclohexyl, etc.; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms such as phenyl, p-tolyl, : m-chlorophenyl, p-metho~yphenyl, m-bromophenyl, o-tolyl, etc.; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membe~ed ring such as morpholine, pyrrolidine, piperidine, oxazoline, pyrazoline, etc.; or either or both of and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a S - or 6 - membered sing, thus forming a polycyclic system such as 1,2,3,4-tetrahydrQquinoline, julolidine, 2,3-dihydroindole, benzomorpholine, etc.;
R3 represents hydrogen or halogen such as chloro, bromo or fluoro;
~ f~
Y represents hydrogen; halogen such as chloro, bromo or fluoro; cyano; a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 6 carbon atoms, such as those listed above for Rl, methoxy, ethoxy, etc.; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms, such as those listed above for Rl; aryloxy;
acylamido; alkylsulfonamido; or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
/R8 ~ 4 ~ :
II R9-- \ ~D N=N ~ R5 wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atom~ such as methyl, et;hyl, propyl, isopropyl, butyl, pentyl, hexyl or such alkyl groups substitutecl ~ith hydroxy, acyloxy~ alkoxy, aryl, aryloxy, cyano, ~:
acylamido, alkoxycarbonyl, --alkoxycarbonyloxy, phthalimido, succinimido, sulfonamido, halogen, etc.; a cycloalkyl group of from about 5 to about 7 carbon atoms such as cyclopentyl, cyclohexyl, p-methylcyclohexyl, etc~; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atom~ such as phenyl, p-tolyl, m-chlorophenyl, p-methoxyphenyl, m-bromophenyl, o-tolyl, .
' ~ ,?~
naphthyl, 3-pyridyl, o-ethoxyphenyl, etc., or such groups substituted as above;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, pentyl~
hexyl, methoxy, ethoxy, isopropoxy, etc., or such alkyl or al~oxy groups substituted with hydroxy, acyloxy, alkoxy, aryl, aryloxy, cyano, acylamido, alkoxycarbonyl, alkoxycarbonyloxy, phthalimido, succinimido, sulfonamido, halogen, etc.;
R5 may be taken together with R4 to form a 5- or 6-membered ring such as morpholine, pyrrolidine, piperidine, oxazoline, pyrazoline, etc.;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring, thus forming a polycyclic system such as 1,2,3,4-tetrahydroquinoline, julolidine, 2,3-dihydroindole, benzomorpholine, etc.;
R7 reprcsents hydrogen; a substituted or unsubstituted alkyl or alkoxy group of ~rom 1 to about 10 carbon atoms such as ~hose listed above for R6; halogen such as chlorine, bromine, fluorine, etc.;
sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyI, alkylsulfonyl, arylsulfonyl, acyl, alkoxycarbonyl~ carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro, cyano, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8-.
$~
Yellow dyes according to formula I useful in the invention are described in U.S. Patent 4,701,439.
In a preferred embodiment of the invention, R and R in structural formula I represents the - 5 atoms which are taken together to form, along with the nitrogen to which they are attached, a 6-membered ring. In another preferred embodiment of the invention, R3 in formula I is hydrogen.
The compounds according to formula I of the invention may be prepared by any of the processes disclosed in U.S. Patents 3,917,604, 4,180,663 and 3,247,211.
Specific yellow dyes useful in the invention include the following: :
, ~ .
; ~ , .
Yellow Dves ~C--CH--I `O' ` I
R Rl 10Cmpd.R9 R4 R5 R6 R7 R8 Rl B CH3 CH3CH3 H H HC~H40CNHC6H5 O . ,:
25 E CH3 CH3 CH3 H CH3 ~ HCE2fHOCNHC6H5 O
F CH3 CH3C~3 H CH3H:CH2fHCH20CCH3 ~ :
: OCCH3 O
O ::
G CH3 CH3CH3 H CH3 Hc~2l~CE20CNHC2H5 .
':
-10~
Cmpd. 9 4 R5 R6 R7 R8Rl C~3 CH3 CH3 H CH3 HCH2~H2CH2NHeNHC6H5 I CH3CH:3 CH3 H CH3 HCH2CH2CH2NHeOC2H5 I~ ,0 K H H CH3 H Cl HCH2CH20 - I~ ,0 Cl : ~ L H H CH3 H CH3 HCH2CHCH20COC2~I5 ~ 1COC2H5 : ~ 30 O
M H X CH3 H CH3 HCH2CH2NHe I O : ~
~, ~:
.;
.
5y ~./ \ ~ ~5 CH2 CH2--X , Compound No. _ R7_ R4 R5 Y X
N CX3 CH3 CH3 3-CH3 -OCO-N~(C6H5) P CH3 CH3 CE3 -OCO-N~[C6H3-3,5 (OC~3)2]
Q CH3 CH3 CH3 -OCo-(c6H4-4-co2cH3) R CH3 CH3 CH3 -N( CH3)(-so2c6~5) -NH
O
.
,; ' :
-.
-12- :
C~3 CH / ~-/ \N/ \C~ 3~' C~C~2-0CO-N~(C6~5) I
1 o u C `C=CH--t ` ~
CH2CH2--OCO--NH~C6H5 ) CN\
V ~C=CCl-o\ ~--NHC2H5 W /\C=CH-~ 2 6 5 ~ COC2H5 In another preferred embodiment of the invention, R4 and R5 in the above formula II ~or cyan dyes are each independently hydrogen, ethyl, n-propyl, benzyl, cyclohexyl, -(C2H40)2C~H2, or may be taken together to form a morpholino group. In another preferred embodiment of the invention, R6 is hydrogen or methoxy and R7 is -NHCoCH3. In yet another preferred embodiment of the invention, R is cyano or trifluoromethyl and R9 is nitro or cyano. In yet still another preferred embodiment of the invention, J is S or -CH=CR8- wherein R8 is nitro or cyano.
Specific cyan dyes useful in the invention include the following:
,. , - . , ~ , ~:
~ : , , ~ .. '' ' ' : ` ' : : .. ' . , .
E ~i ~D ~ u~ oo cr~
r~ ~ ) ~ I~
C~
o Z Z
~; ~
s~
~o; Zo; `~ Zo; ~o; o o z z p~ o ~` O o ~ o o o p:
~
o o o o o o o , u~ u~
Q
U ~ U~
~ ~ P~ ~ P~ ~ ~ ~ ~ a~
~ ~ v~ ~
Cyan ~max*
(nm) ~CN ~COCH3 8 02N-~ -N=N-~ 2 5 623 4=-~ ~ _ ~ (CH3~2 c~3 *In acetone The dye-receiving layer of the color filter array element of the invention may comprise, for example, sucrose acetate or polymers such as a polycarbonate, a polyurethane, a polyester, a polyvinyl chloride, a polyamide, a polystyrene, an acrylonitrile, a polycaprolactone or mixîures thereof. The dye-receiving layer may be present in any amount which is effective fo:c the intended purpose. In general, good results have been obtained at a concentration of from about 0.25 to about 5 glm .
In a preferred embodiment of the invention, the receiving layer comprises a polycarbonate binder having a Tg greater than about 200C. as described in Application Serial No. 334,269 of ~arrison et al., fi~ed April 6, 1989. The term "polycarbonatel' as used herein means a polyester of carbonic acid and one or more glycols or dihydric phenols. In another preferred embodiment, the polycarbonate is derived from a bisphenol component comprising a diphenyl methane moiety. Examples of such polycarbonates include those derived ~rom 4,4'-(hexahydro-4,7-methanoindene-5-ylidene~bisphenol, 2,2l,6,6~-tetrachlorobisphenol-A and 4,4'-(2-norbornyli-dene)bisphenol.
In another preferred embodiment of the invention, the mosaic pattern which is obtained by ~ !
' '~
' the thermal transfer process consists of a set of red, green and blue additive primaries.
In another preferred embodiment of the invention, each area of primary color and each set of - 5 primary colors are separated from each other by an opaque area, e.g., black grid lines. This has been found to give improved color reproduction and reduce ~lare in the displayed image.
The size of the mosaic set is normally not critical since it depends on the viewing distance.
In general, the individual pixelæ of the set are from about 50 to about 300 ~m. They do not have to be of the same size.
In a preferred embodiment of the invention, the repeating mosaic pattern of dye to form the color filter array consiæts of uniform, square, linear repeating areas, with one color diagonal displacement as follows:
~ G~ \R G
B ~ G B R
G B ~ G~ \
In another preferred embodiment, the above squares are approximately 100 ~m.
As noted above, the color filter array elements of the invention are used in various display devices such as a liquid crystal display device.
Such liquid crystal display devices are described, for example, in UK Patents 2,154,355; 2,130,781;
30 2,162,674 and 2,161,971.
A process of forming a color filter array element according to the invention comprises a) imagewise-heating a dye-donor element comprising a support having thereon a dye layer as deæcribed a~ove, and 3 ~!~
b) transferring portions of the dye layer to a dye-receiving element comprising a transparent support having thereon a dye-receiving layer, - 5 the imagewise-heating being done in such a way as to produce a repeating mosaic pattern of dyes to form the color filter array element.
Various methods can be used to supply energy to transfer dye from the dye donor to the transparent support to form the color filter array of the invention. There may be used, for example, a thermal print head. A high intensity light flash technique with a dye-donor containing an energy absorptive material such as carbon black or a non-subliming light-absorbing dye may also be used. This method is described more fully in U.K. Application No.
8824366.2 by Simons filed October 18, 1988.
Another method of transferring dye from the dye-donor to the transparent support to form the color filter array of the inventlon is to use a heated embossed roller as described more fully in U.K. Application No. 8824365.4 by Simons filed October 18, 1988.
In a preferred embodiment of the invention, a laser is used to supply energy to transfer dye from the dye-donor to the recei~er as described more fully in U.S. Serial Number 259,080, filed October 18, 1988 of DeBoer entitled ~Color Filter Array Element Obtained by Laser-induced Thermal Dye Transfer~.
If a laser or high-intensity light ~la~h is used to transfer dye from the dye-donor to the -17- ~ ]
receiver, then an additional absorptive but non-volatile material is used in the dye-donor. Any material that absorbs the laser or light energy may be used such as carbon black or non-volatile infrared-absorbing dyes or pigments which are well known to those skilled in the art. Cyanine infrared absorbing dyes may also be employed with infrared diode lasers as described in DeBoer Application Serial Number 221,163 filed July 19, 1988.
A dye-donor element that is used to form the color filter array element of the invention comprises a support having thereon a mixture of dyes to form a green hue as described above along with other colorants such as imaging dyes or pigments to form the red and blue areas. Other imaging dyes can be used in such a layer provided they are transferable to the dye-receiving layer of the color array element of the invention by the action of heat. Especially good results have been obtained with sublimable dyes. Examples of additive subllmable dyes include anthraquinone dyes, e.g., Sumikalon Violet RSTM
(Sumitomo Chemical Co., Ltd.), Dlanix Fast Violet 3R-FSTM (Mitsubishi Chemical Industries, Ltd.), and Kayalon Polyol Brilliant Blue N-BGMTM and KST Black 146TM (Nippon Kayaku Co., Ltd.); azo dyes such as Kayalon Polyol Brilliant Blue BMrM, Kayalon Polyol Dark Blue 2BMTM, and KST Black KRTM (Nippon Kayaku Co., Ltd.), Sumickaron Diazo Black 5GTM
(Sumitomo Chemical Co., Ltd.), and Miktazol Black 5GHTM (Mitsui Toatsu Chemicals, Inc.); direct dyes such as Direct Brown MTM and Direct Fast Black DTM (Nippon Kayaku Co. Ltd.); acid dyes such as Kayanol Milling Cyanine 5RTM ~Nippon Kayaku Co.
Ltd.); basic dyes such as Sumicacryl Blue 6GTM
(Sumitomo Chemical Co., Ltd.). Examples of subtractive dyes useful in the invention include the following:
5N~5~ N-N ~ N(C2E5~CH2C6H5) (magenta) ~H3\ /CH3 0 oI~ ~ ~ J=CH-CH=./ l C6H5 (yellow) CX N(CH3)2 o ~ \ ~!~ ,CONXCH3 I -O O (cyan) O D
--N(C2~5)2 or any of the dyes disclosed in U.S. Patent 4,541,830. The above cyan, magenta, and yellow subtractive dyes may be employed in various combinations, either in the dye-donor itself or by being sequentially transferred to the dye image-receiving element, to obtain the other desired blue and red additive primary colors. The dyes may be mixed within the dye layer or transferred sequentially if coated in separate dye layers. The dyes may be used at a coverage of from about 0.05 to about 1 g/m2.
The imaging dye, and an infrared- or visible light-absorbing material if one is present, are dispersed in the dye-donor element in a polymeric binder such as a cellulose derivative, e.g., cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate, a polycarbonate; poly(styrene-co-acrylonitrile), a poly(sulfone) or a poly(phenylene oxide). The binder may be used at a coverage of from about 0.1 to about 5 glm2.
The dye layer of the dye-donor element may be coated on the support or printed thereon by a printing technique such as a gravure process.
Any material can be used as the support ~or the dye-donor element provided it is dimensionally stable and can withstand the heat generated by the thermal transfer device such as a laser beam. Such materials include polyesters such as poly(ethylene terephthalate); polyamides; polycarbonates; glassine paper; condenser paper; cellulose esters; fluorine polymers; polyethers; polyacetals; polyolefins; and polyimides. The support general:Ly has a thickness of from about 2 to about 250 ~m. It may also be ?0 coated with a subbing layer, if desired.
The support for the dye image-receiving element or color filter array element of the invention may be any transparent material such as polycarbonate, poly(ethylene terephthalate), cellulo~e acetate, polystyrene, etc. In a preferred embodiment, the support is glass.
After the dyes are transferred to the receiver, the image may be treated to further diffuse the dye into the dye-receiving layer in order stabilize the image. This may be done by radiant heating, solvent vapor, or by contact with heated rollers. The fusing step aids in preventing fading upon e~posure to light and surface abrasion of the image and also tends to prevent crystallization of the dyes. Solvent vapor fusing may also be used instead of thermal fusing.
~20-Several different kinds of lasers could be used to effect the thermal transfer of dye from a donor sheet to the dye-receiving element to form a color filter array element, such as ion gas lasers - 5 like argon and krypton; metal vapor lasers such as copper, gold, and cadmium; solid state lasers such as ruby or YAG; or diode lasers such as gallium arsenide emitting in the infrared region from 750 to 870 nm.
However, in practice, the diode lasers are prefexred because they offer substantial advantages in terms of their small size, low cost, stability, reliability, ruggedness, and ease of modulation. In practice, before any laser can be used to heat a dye-donor element, the laser radiation must be absorbed into the dye layer and converted to heat by a molecular process known as internal conversion. Thus, the construction of a useful dye layer will depend not only on the hue, sublimability and intensity of the image dye, but also on the ability of the dye layer to absorb the radiation and convert it to heat.
Lasers which can be used to transfer dye from the dye-donor element to the dye image-receiving element to form the color filter array element in a preferred embodiment of the invention are available commercially. There can be employed, for example, Laser Model SDL-2420-~2TM from Spectrodiode Labs, or Laser Model SLD 304 V/WTM from Sony Corp.
The following example is provlded to illustrate the invention.
Example A green dye-donor was prepared by coating on a gelatin subbed transparent 175 ~m poly(ethylene terephthalate) support a dye layer containing cyan dye 5 illustrated above (0.21 g/m2) and yellow dye A illustrated above (0.23 g/m ) in a cellulose acetate propionate (2.5% acetyl, 46% propionyl) binder (0.26 g/m2) coated from a l-propanol, 2-butanone, toluene and cyclopentanone solvent mixture. The dye layer also contained Raven Black No. 1255TM (Columbia Carbon Co.) (0.21 g/m2) ball-milled to submicron particle size, FC-431TM
dispersing agent (3M Company) (0.01 g/m2) and SolsperseT~ 2400 dispersing agent (ICI Corp.) (0.03 glm ).
A control green dye-donor was prepared as described above except that it contained the following indoaniline cyan dye (0.64 g/m2~ as described in U.S. Patent 4,695,287 instead of cyan dye 5:
~ ~ ,!~ ,CONHCH3 I~ ,0~ ,5 Z0 N-o\ /--N(c2H5)~
A dye-receiver was prepared by spin-coating the following layers on a 53 ~ thick flat-surfaced borosilicate glass:
l) Subbing layer of duPont VM-651 Adhesion Promoter as a 1% solution in a methanol-water solvent mixture (0.5 ym thick layer equivalent to 0.54 g/m ), and 2~ Receiver layer of a polycarbonate of 4,4'-(hexahydro-4,7-methanoindene-S-ylidene)bisphenol, as described in U.S.
Application Serial No. 334,269, of Marrison et al. referred to above, from methylene chloride solvent (2.5 g/m2).
The dye-donor was placed ~ace down upon the dye-receiver. A MecablitzTM Model 45 (Metz AG
Company> electronic flash unit was used as a thermal energy source. It was placed 40 mm above the dye-donor using a 45-degree mirror box to concentrate the energy from the flash unit to a 25x50 mm area.
The dye transfer area was masked to 12x42 mm. The flash unit was flashed once to produce a transferred transmission density of 1.9 at the maximum absorption of the dye mixture.
The same flash transfer procedure was used for the control coating producing a transferred transmission density of 2.0 at the maximum density of the dye mixture.
Each transferred area was placed under a PyropanelTM no. 4083 (Research Inc., Minneapolis Mn.~ in~rared heat panel at 230OC for 45 sec. to diffuse the dyes into the dye-receiving layer.
The Red and ~lue Status A densities o~ the transferred area were read. Each transferred area was then placed in an oven at 180C, 25% RH for one hour and the densities were re-read to determlne the % dye loss. Each transferred area was also subjected to exposure for 4 days, 50 kLux, 5400K, approximately 25% RH. The densities were then re-read to determine the percent dye loss due to light fade. The following results were obtained:
Red Status A Densitv Blue Status A Density Receiver Init. Heated % Loss Ini~ ~eated % Loss Control 2.00 0.81 60 1.06 0.96 9 Invention 1.89 1.81 4 1.80 1.74 3 Red $tatus A Density Blue Status A Densitv Receiver Init. Faded % Loss Init. Faded /0 Loss Control 1.76 0.98 h4 1.01 0.96 11 Invention 1.77 1.49 16 1.57 1.57 6 ~ç~
The above results indicate that the receiver containing the dyes according to the invention had better stability to heat and light than the control receiver containing an indoaniline cyan dye.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
' .
-.
, . .
Claims (20)
1. A thermally-transferred color filter array element comprising a transparent support having thereon a thermally-transferred image comprising a repeating mosaic pattern of colorants in a receiving layer, one of said colorants being a mixture of a yellow dye and a cyan dye to form a green hue, said yellow dye having the formula:
wherein: R1 and R2 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membered ring; or either or both of R1 and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R3 represents hydrogen or halogen;
Y represents hydrogen; halogen; cyano; a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 6 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms; aryloxy; acylamido, alkylsulfonamido;
or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
II wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms;
R5 may be taken together with R4 to form a 5- or 6-membered ring;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R represents hydrogen, a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms, halogen, sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyl, alkylsulfonyl, arylsulfonyl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro; cyano:, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8-.
wherein: R1 and R2 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membered ring; or either or both of R1 and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R3 represents hydrogen or halogen;
Y represents hydrogen; halogen; cyano; a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 6 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms; aryloxy; acylamido, alkylsulfonamido;
or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
II wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms;
R5 may be taken together with R4 to form a 5- or 6-membered ring;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R represents hydrogen, a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms, halogen, sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyl, alkylsulfonyl, arylsulfonyl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro; cyano:, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8-.
2. The element of Claim 1 wherein said receiving layer comprises a polycarbonate binder having a Tg greater than about 200°C.
3. The element of Claim 2 wherein said polycarbonate is derived from a bisphenol component comprising a diphenyl methane moiety.
4. The element of Claim 1 wherein said and said R2 in said structural formula I represents the atoms which are taken together to form, along with the nitrogen to which they are attached, a 6-membered ring.
5. The element of Claim 1 wherein said R4 and said R5 in said structural formula II are each independently hydrogen, ethyl, n-propyl, benzyl, cyclohexyl, -(C2H4O)2C2H2, or may be taken together to form a morpholino group.
6. The element of Claim 1 wherein said pattern consists of a set of red, green and blue additive primaries.
7. The element of Claim 6 wherein each area of said primary color and each said set of primary colors are separated from each other by an opaque area.
8. The element of Claim 1 wherein said thermally-transferred image is obtained using laser induction.
9. The element of Claim 1 wherein said thermally transferred image is obtained using a high intensity light flash.
10. The element of Claim 1 wherein said support is glass.
11. A process of forming a color filter array element comprising a) imagewise-heating a dye-donor element comprising a support having thereon a dye layer, and b) transferring portions of said dye layer to a dye-receiving element comprising a transparent support having thereon a dye-receiving layer, said imagewise-heating being done in such a way as to produce a repeating mosaic pattern of dyes to form said color filter array element, one of said dyes being a mixture of a yellow dye and a cyan dye to form a green hue, said yellow dye having the formula:
wherein: R1 and R2 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membered ring; or either or both of R1 and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R3 represents hydrogen or halogen;
Y represents hydrogen; halogen; cyano; a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 6 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms; aryloxy; acylamido, alkylsulfonamido;
or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
II wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms;
R5 may be taken together with R4 to form a 5- or 6-membered ring;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R7 represents hydrogen, a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms, halogen, sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyl, alkylsulfonyl, arylsulfonyl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro, cyano, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8-.
wherein: R1 and R2 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of about 6 to about 10 carbon atoms; or can be taken together to form, along with the nitrogen to which they are attached, a 5- or 6-membered ring; or either or both of R1 and R2 can be joined to a carbon atom of the aromatic ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R3 represents hydrogen or halogen;
Y represents hydrogen; halogen; cyano; a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 6 carbon atoms; a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms; aryloxy; acylamido, alkylsulfonamido;
or arylsulfonamido; and n is a positive integer from 1 to 5; and said cyan dye having the formula:
II wherein R4 and R5 each independently represents hydrogen; a substituted or unsubstituted alkyl group of from 1 to about 6 carbon atoms; a cycloalkyl group of from about 5 to about 7 carbon atoms; or a substituted or unsubstituted aryl or hetaryl group of from about 6 to about 10 carbon atoms;
R6 represents hydrogen or a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms;
R5 may be taken together with R4 to form a 5- or 6-membered ring;
R4 or R5 may be combined with R6 or may be joined to the carbon atom of the benzene ring at a position ortho to the position of attachment of the anilino nitrogen to form a 5- or 6-membered ring;
R7 represents hydrogen, a substituted or unsubstituted alkyl or alkoxy group of from 1 to about 10 carbon atoms, halogen, sulfonamido or acylamido;
R8 represents nitro, cyano, fluorosulfonyl, alkylsulfonyl, arylsulfonyl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl, trifluoromethyl or halogen;
R9 represents nitro, cyano, acyl, trifluoroacetyl, dicyanovinyl or tricyanovinyl; and J represents -S- or -CH=CR8-.
12. The process of Claim 11 wherein said receiving layer comprises a polycarbonate binder having a Tg greater than about 200°C.
13. The process of Claim 12 wherein said polycarbonate is derived from a bisphenol component comprising a diphenyl methane moiety.
14. The process of Claim 11 wherein said R1 and said R2 in said structural formula I
represents the atoms which are taken together to form, along with the nitrogen to which they are attached, a 6-membered ring.
represents the atoms which are taken together to form, along with the nitrogen to which they are attached, a 6-membered ring.
15. The process of Claim 11 wherein said R4 and said R5 in said structural formula II are each independently hydrogen, ethyl, n-propyl, benzyl, cyclohexyl, -(C2H4O)2C2H2, or may be taken together to form a morpholino group.
16. The process of Claim 11 wherein said dye-donor element contains an additional light-absorbing non-volatile material.
17. The process of Claim 16 wherein a laser is used to supply energy in said imagewise-heating step.
18. The process of Claim 16 wherein a high intensity light flash is used to supply energy in said imagewise-heating step.
19. The process of Claim 11 which includes a further step of heating the transferred image to further diffuse the dye into said dye-receiving layer.
20. The process of Claim 11 which includes a further step of subjecting the transferred image to solvent vapor to further diffuse the dye into said dye-receiving layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US358,976 | 1989-05-26 | ||
| US07/358,976 US4975410A (en) | 1989-05-26 | 1989-05-26 | Thermally-transferred color filter array element and process for preparing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2016831A1 true CA2016831A1 (en) | 1990-11-26 |
Family
ID=23411801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002016831A Abandoned CA2016831A1 (en) | 1989-05-26 | 1990-05-15 | Mixture of yellow and cyan dyes to form a green hue for color filter array element |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4975410A (en) |
| EP (1) | EP0399473B1 (en) |
| JP (1) | JPH0816724B2 (en) |
| CA (1) | CA2016831A1 (en) |
| DE (1) | DE69003008T2 (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5168094A (en) * | 1991-04-30 | 1992-12-01 | Eastman Kodak Company | Mixture of yellow and cyan dyes to form green hue for color filter array element |
| US5147844A (en) * | 1991-06-14 | 1992-09-15 | Eastman Kodak Company | Mixture on cyan and yellow dyes to form a green hue for color filter array element |
| US5175069A (en) * | 1991-06-14 | 1992-12-29 | Eastman Kodak Company | Maleimide blue dyes for color filter array element |
| DE4215536A1 (en) * | 1992-05-12 | 1993-11-18 | Basf Ag | Cyan mixtures for dye transfer |
| DE4215535A1 (en) * | 1992-05-12 | 1993-11-18 | Basf Ag | Dye mixtures for dye transfer |
| US5352651A (en) * | 1992-12-23 | 1994-10-04 | Minnesota Mining And Manufacturing Company | Nanostructured imaging transfer element |
| US5521035A (en) * | 1994-07-11 | 1996-05-28 | Minnesota Mining And Manufacturing Company | Methods for preparing color filter elements using laser induced transfer of colorants with associated liquid crystal display device |
| US6057067A (en) * | 1994-07-11 | 2000-05-02 | 3M Innovative Properties Company | Method for preparing integral black matrix/color filter elements |
| DE4426023A1 (en) * | 1994-07-22 | 1996-01-25 | Basf Ag | Azo dyes with a coupling component from the aminothiazole series |
| DE4437166A1 (en) * | 1994-10-18 | 1996-04-25 | Basf Ag | Dye mixtures containing methine and azo dyes |
| DE4440066A1 (en) * | 1994-11-10 | 1996-05-15 | Basf Ag | Methine and azamethine dyes based on trifluoromethylpyridones |
| DE4440486A1 (en) * | 1994-11-12 | 1996-05-15 | Basf Ag | Azamethine dyes |
| DE4443567A1 (en) * | 1994-12-07 | 1996-06-13 | Basf Ag | Azamethine dyes based on formylaminopyridones |
| DE19504943A1 (en) * | 1995-02-15 | 1996-08-22 | Basf Ag | Triazolopyridine dyes and their intermediates |
| DE19512398A1 (en) * | 1995-04-03 | 1996-10-10 | Basf Ag | Azamethine dyes with heterocyclic side groups |
| US5576265A (en) * | 1995-04-26 | 1996-11-19 | Eastman Kodak Company | Color filter arrays by stencil printing |
| GB9515175D0 (en) * | 1995-07-24 | 1995-09-20 | Zeneca Ltd | Azothiophenes |
| DE19533026A1 (en) * | 1995-09-07 | 1997-03-13 | Basf Ag | Dye mixtures containing methine and anthraquinone dyes |
| US5599766A (en) | 1995-11-01 | 1997-02-04 | Eastman Kodak Company | Method of making a color filter array element |
| US5683836A (en) * | 1996-01-16 | 1997-11-04 | Eastman Kodak Company | Method of making black matrix grid lines for a color filter array |
| EP0792757B1 (en) | 1996-02-27 | 2001-06-06 | Agfa-Gevaert N.V. | Dye donor element for use in thermal transfer printing |
| DE19621026A1 (en) * | 1996-05-24 | 1997-11-27 | Basf Ag | Pyridone dyes |
| GB9612567D0 (en) * | 1996-06-15 | 1996-08-21 | Kodak Ltd | Scanning of images |
| US5614465A (en) * | 1996-06-25 | 1997-03-25 | Eastman Kodak Company | Method of making a color filter array by thermal transfer |
| US6013409A (en) * | 1996-09-10 | 2000-01-11 | 3M Innovative Properties Company | Dry peel-apart imaging process |
| US5856064A (en) * | 1996-09-10 | 1999-01-05 | Minnesota Mining And Manufacturing Company | Dry peel-apart imaging or proofing system |
| US5897727A (en) * | 1996-09-20 | 1999-04-27 | Minnesota Mining And Manufacturing Company | Method for assembling layers with a transfer process using a crosslinkable adhesive layer |
| US5858624A (en) * | 1996-09-20 | 1999-01-12 | Minnesota Mining And Manufacturing Company | Method for assembling planarization and indium-tin-oxide layer on a liquid crystal display color filter with a transfer process |
| US5902769A (en) * | 1996-11-05 | 1999-05-11 | Eastman Kodak Company | Thermal image stabilization by a reactive plastisizer |
| AU5551898A (en) * | 1996-11-23 | 1998-06-22 | Basf Aktiengesellschaft | Trifluormethylpyridone based indolenine methine dyes |
| DE19730168A1 (en) * | 1997-07-15 | 1999-01-28 | Basf Ag | Phenylazoanilines |
| US6097416A (en) * | 1997-11-10 | 2000-08-01 | Eastman Kodak Company | Method for reducing donor utilization for radiation-induced colorant transfer |
| US6031586A (en) * | 1997-12-09 | 2000-02-29 | Eastman Kodak Company | Liquid crystal printing apparatus for radiation thermal transfer of colorant from a donor to a receiver |
| DE19920808A1 (en) * | 1998-05-16 | 1999-11-18 | Basf Ag | Methine and azamethine dyes based on trifluoromethyl-substituted 5-membered heterocycles |
| US6221543B1 (en) | 1999-05-14 | 2001-04-24 | 3M Innovatives Properties | Process for making active substrates for color displays |
| DE10028686A1 (en) | 2000-06-09 | 2001-12-13 | Dystar Textilfarben Gmbh & Co | New hydroxypyridone methide azo dyes, useful in e.g. dyeing and printing hydrophobic fibers, ink-jet printing and color filters |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4081277A (en) * | 1976-10-08 | 1978-03-28 | Eastman Kodak Company | Method for making a solid-state color imaging device having an integral color filter and the device |
| JPS55166607A (en) * | 1979-06-15 | 1980-12-25 | Canon Inc | Color filter |
| JPS5648604A (en) * | 1979-09-28 | 1981-05-01 | Canon Inc | Production of color filter |
| JPS60239291A (en) * | 1984-05-11 | 1985-11-28 | Mitsubishi Chem Ind Ltd | Coloring matter for thermal recording |
| JPS60254001A (en) * | 1984-05-14 | 1985-12-14 | Nissha Printing Co Ltd | Color filter |
| JPS61102602A (en) * | 1984-10-25 | 1986-05-21 | Nec Corp | Color filter and its preparation |
| JPS61227092A (en) * | 1985-04-01 | 1986-10-09 | Mitsubishi Chem Ind Ltd | Azo dyestuff for thermal transfer recording |
| JPH0764123B2 (en) * | 1985-05-23 | 1995-07-12 | 大日本印刷株式会社 | Thermal transfer sheet |
| JPS61268761A (en) * | 1985-05-24 | 1986-11-28 | Mitsui Toatsu Chem Inc | Naphthoquinone-based green dyestuff and its preparation |
| GB8521327D0 (en) * | 1985-08-27 | 1985-10-02 | Ici Plc | Thermal transfer printing |
| JPS6299195A (en) * | 1985-10-28 | 1987-05-08 | Mitsui Toatsu Chem Inc | Magenta coloring matter for thermal sublimation transfer recording |
| JPH0667673B2 (en) * | 1985-12-05 | 1994-08-31 | 三井東圧化学株式会社 | Cyan dye for thermal sublimation transfer recording |
| US4701439A (en) * | 1985-12-24 | 1987-10-20 | Eastman Kodak Company | Yellow dye-donor element used in thermal dye transfer |
| EP0235939B2 (en) * | 1986-02-28 | 1996-10-09 | Zeneca Limited | Thermal transfer printing |
| JPS62276505A (en) * | 1986-05-23 | 1987-12-01 | Mitsubishi Electric Corp | Production of color filter |
-
1989
- 1989-05-26 US US07/358,976 patent/US4975410A/en not_active Expired - Lifetime
-
1990
- 1990-05-15 CA CA002016831A patent/CA2016831A1/en not_active Abandoned
- 1990-05-22 EP EP90109720A patent/EP0399473B1/en not_active Expired - Lifetime
- 1990-05-22 DE DE90109720T patent/DE69003008T2/en not_active Expired - Fee Related
- 1990-05-25 JP JP13688390A patent/JPH0816724B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0317602A (en) | 1991-01-25 |
| EP0399473B1 (en) | 1993-09-01 |
| JPH0816724B2 (en) | 1996-02-21 |
| US4975410A (en) | 1990-12-04 |
| EP0399473A1 (en) | 1990-11-28 |
| DE69003008D1 (en) | 1993-10-07 |
| DE69003008T2 (en) | 1994-04-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |