Methods for Preparing Color Filter Elements Using Laser Induced Transfer of Colorants With Associated Liquid Crystal Display Device

1. Field of the Invention

This invention relates to methods for using laser induced transfer of colorant layers to prepare color filter elements for use in color displays. In particular, this invention relates to a method for preparing a color filter element for use in liquid crystal display devices.

2. Background of the Art

One method of making colored images upon a non-photosensitive base uses laser induced colorant transfer or laser induced mask production. A donor element is induced (as by ablative levels of radiation) to transfer donor color material to a receptor surface. The donor may contain radiation or thermally sensitive materials to enhance the efficiency of transfer, or the donor material may be ablated without additional materials. Examples of this type of imaging process includes U.S. Pat. Nos. 5,156,938, 5,171,650, 5,256,506, and 5,089,372. The first three patents generally refer to producing a pattern of intelligence.

U.S. Pat. No. 5,171,650 discloses methods and materials for thermal imaging using an "ablation-transfer" technique. The donor element for that imaging process comprises a support, an intermediate dynamic release layer, and an ablative carrier topcoat. The topcoat carries the colorant. The dynamic release layer may also contain infrared-absorbing (light to heat conversion) dyes or pigments. The pigments also include black copper as an additive. Nitrocellulose is disclosed as a possible binder.

Copending U.S. application Ser. No. 07/855,799 filed on Mar. 23, 1992 discloses ablative imaging elements comprising a substrate coated on a portion thereof with an energy sensitive layer comprising a glycidyl azide polymer in combination with a radiation absorber. Demonstrated imaging sources included infrared, visible, and ultraviolet lasers. Solid state lasers were disclosed as exposure sources, although laser diodes were not specifically mentioned. This application is primarily concerned with the formation of relief printing plates and lithographic plates by ablation of the energy sensitive layer. No specific mention of utility for thermal mass transfer was made.

U.S. Pat. No. 5,308,737 discloses the use of black metal layers on polymeric substrates with gas-producing polymer layers which generate relatively high volumes of gas when irradiated. The black aluminum absorbs the radiation efficiently and converts it to heat for the gas-generating materials. It is observed in the examples that in some cases the black metal was eliminated from the substrate, leaving a positive image on the substrate.

U.S. Pat. No. 5,278,023 discloses laser-addressable thermal transfer materials for producing color proofs, printing plates, films, printed circuit boards, and other media. The materials contain a substrate coated thereon with a propellant layer wherein the propellant layer contains a material capable of producing nitrogen (N.sub.2) gas at a temperature of preferably less than about 300 degree C.; a radiation absorber; and a thermal mass transfer material. The thermal mass transfer material may be incorporated into the propellant layer or in an additional layer coated onto the propellant layer. The radiation absorber may be employed in one of the above-disclosed layers or in a separate layer in order to achieve localized heating with an electromagnetic energy source, such as a laser. Upon laser induced heating, the transfer material is propelled to the receptor by the rapid expansion of gas. The thermal mass transfer material may contain, for example, pigments, toner particles, resins, metal particles, monomers, polymers, dyes, or combinations thereof. Also disclosed is a process for forming an image as well as an imaged article made thereby.

None of these patents teach the use of laser induced transfer of colorant layers to produce color filter elements.

A series of patents (U.S. Pat. Nos. 4,965,242, 4,962,081, 4,975,410, 4,923,860, 5,073,534, and 5,166,126) have been assigned to Kodak disclosing the use of thermal dye diffusion transfer to make filter elements and color filter constructions. U.S. Pat. Nos. 4,965,242 and 5,073,534 teach the use of high T.sub.g polycarbonate and polyester receiving layers to accept the thermally transferred dye. With both receiving layers, a vaporous solvent treatment is required to drive the dye into the receiving layer.

This invention involves the preparation of a color filter element via laser induced thermal imaging. In particular, this invention involves the preparation of color filter elements for use in liquid crystal display devices.

In one embodiment, a transparent substrate is provided as a receptor and a color filter element is formed by laser induced thermal transfer of colorant to the surface of the substrate and subsequent association (e.g., overlay, bonding, framing, etc.) with a liquid crystal display device.. The transparent substrate can be flexible (i.e., polymeric film), or rigid (i.e., glass) and may be treated with an adhesive to promote the transfer of the imaged colorant. The optical transmission characteristics of the elements in the display are controlled by electronic addressing of the liquid crystal cells. Color patterns are obtained by aligning the color filter array with the liquid crystal. array and the light source.

In an alternative embodiment, a black matrix is provided on one surface of the transparent substrate and a color filter element is formed within that matrix by laser induced thermal transfer of colorant material within window areas of the matrix. A black coated substrate may first be imaged to create a black matrix containing windows. Colorants may then be successively transferred in registration to window areas of the matrix from a color donor element through high power laser exposure in a patternwise fashion. The liquid crystal filtering device is then associated with the color filter created. The color filter provides specific images which are desired to be displayed, including graphics designs such as squares, rectangles, triangles, arrows, stars, diamonds, etc. Upon electrical addressing of the liquid crystal display in desired areas, the optical transmission is controlled, allowing light to be transmitted in selected areas through the color filter and then through the liquid crystal (or depending upon the ordering of layers, through the liquid crystal and then through the color filter).

In yet another embodiment, a black matrix having window areas is formed on the surface of the transparent substrate by laser induced thermal transfer of black colorant, and a color filter element is formed within that matrix by laser induced thermal transfer of colorant material within window areas of the matrix. Colorants can be successively transferred in registration to window areas of the matrix from a color donor element through high power laser exposure in a patternwise fashion.

In still another embodiment, a pigment layer is directly transferred to a glass substrate, without a receiving layer, and no further treatment is required. This invention has the distinct advantage of being capable of using pigments as colorants which are less prone to migration and are considerably more lightfast than dyes.

The method of this invention allows the production of color filters having color patches with lateral dimensions of about 5 or 10 microns or greater. This invention has the distinct advantage of being capable of using pigments as colorants which are less prone to migration, more thermally stable, and considerably more lightfast than dyes. This invention enables a direct, dry transfer to either a flexible (e.g., polymeric) or solid substrate (i.e., glass) in far fewer steps than conventional processes. In addition, registration of the windows with the color filter elements is possible to a high degree of precision using a mechanically simple system.

The present invention involves the preparation of a color filter element via laser induced thermal imaging. In particular, this invention involves the preparation of color filter elements for use in liquid crystal display devices.

In one embodiment, a transparent substrate is provided as a receptor and a color filter element is formed by laser induced thermal transfer of colorant to the surface of the substrate and subsequent association (e.g., overlay, bonding, framing, etc.) with a liquid crystal display device.. The transparent substrate can be flexible (i.e., polymeric film), or rigid (i.e., glass) and may be treated with an adhesive to promote the transfer of the imaged colorant. Upon electrical addressing of a liquid crystal element overlaying the patterns of color images in the filter, light corresponding to the colors in the patterns is allowed to pass through the selected areas of the display to provide a visual signal.

In an alternative embodiment, a black matrix is provided on one surface of the transparent substrate and a color filter element is formed within that matrix by laser induced thermal transfer of colorant material within window areas of the matrix. A black coated substrate may first be imaged to create a black matrix containing windows. Colorants may then be successively transferred in registration to window areas of the matrix from a color donor element through high power laser exposure in a patternwise fashion. The liquid crystal filtering device is then associated with the color filter created. The color filter provides specific images which are desired to be displayed, including graphics designs such as squares, rectangles, triangles, arrows, stars, diamonds, etc. Upon electrical addressing of a liquid crystal element overlaying the patterns of color images in the filter, light corresponding to the colors in the patterns is allowed to pass through the selected areas of the display to provide a visual signal.

In yet another embodiment, a black matrix having window areas is formed on the surface of the transparent substrate by laser induced thermal transfer of black colorant, and a color filter element is formed within that matrix by laser induced thermal transfer of colorant material within window areas of the matrix. Colorants can be successively transferred in registration to window areas of the matrix from a color donor element through high power laser exposure in a patternwise fashion.

In still another embodiment, a pigment layer is directly transferred to a glass substrate, without a receiving layer, and no further treatment is required. This invention has the distinct advantage of being capable of using pigments as colorants which are less prone to migration and are considerably more lightfast than dyes.

For a color filter element to be useful as a component of certain types of liquid crystal displays, the color filter array is preferably coated with a planarizing layer. This is usually followed by a coating of a transparent conductor, commonly indium tin oxide (ITO). The conductive layer may or may not be patterned. Finally, an alignment layer, typically a polyamide, is applied onto the conductive layer. The alignment layer is typically patterned (e.g., by brushing) to control the alignment of the liquid crystal material in the functioning display.

When a matrix is used in the practice of the present invention, it may be formed by any convenient method available. For example, a black matrix may be formed by lithographic etching of a black substrate, wherein a solid black surface is etched away to leave a pattern of window frames within which the colorant can be deposited. It is also possible to lay down a photoresist, etch the pattern of the matrix into the photoresist, and deposit black material into the etched areas to form the matrix windows. A preferred method, disclosed in copending U.S. patent application Ser. No. 08/273,419, filed on Jul. 11, 1994 is to transparentize a black metal surface by laser induced thermal imaging techniques to leave the matrix. It would be equally useful to form the matrix by thermally induced laser transfer of a black coating layer or composition onto the carrier surface for the color filter in the form of a matrix of windows.

The substrate may be any substance upon which a color filter or the like is desired to be formed. Preferably the substrate is a transparent (at least light transmissive) substrate, such as glass, polymer film, and the like. When glass is the substrate, the use of glass treated with silane coupling agents (e.g., 3-aminopropyltriethoxysilane) may be useful to increase adhesion of the colorant layer. Possible substrates include glass, polyester base (e.g., polyethylene terephthalate, polyethylene naphthalate), polycarbonate resins, polyolefin resins, polyvinyl resins (e.g., polyvinyl chloride, polyvinylidene chloride, polyvinyl acetals, etc.), cellulose ester bases (e.g., cellulose triacetate, cellulose acetate), and other conventional polymeic films used as supports in various imaging arts. Transparent polymeric film base of 2 to 100 mils (e.g., 0.05 to 2.54 mm) is preferred. If the substrate is a polymeric film, it is preferred that the film be non-birefringent so as not to interfere with the operation of the display in which it is to be integrated. When polymeric films are chosen as the substrate, it is sometimes desirable to have an adhesive layer on the substrate to maximize the transfer of the colorant layer. Preferred examples of non-birefringent substrates are polyesters that are solvent cast. Typical examples of these are those derived from polymers consisting or consisting essentially of repeating, interpolymerized units derived from 9,9-bis-(4-hydroxyphenyl)-fluorene and isophthalic acid, terephthalic acid or mixtures thereof, the polymer being sufficiently low in oligomer (i.e., chemical species having molecular weights of about 8000 or less) content to allow formation of a uniform film. This polymer has been disclosed as one component in a thermal transfer receiving element in U.S. Pat. No. 5,318,938. Another class of non-birefringent substrates are amorphous polyolefins (e.g., Zeonex.TM. from Nippon Zeon Co., Ltd.). The most preferred substrate is glass. It is preferred that this glass be 0.5 to 2.0 mm thick. Especially preferred thicknesses are 0.7 and 1.1

The colors to be deposited on the substrate sheet may comprise any color material which can be deposited with adherence to the substrate. In a preferred embodiment, the colorant is in a suitable binder system and is solvent coated.

When pigments are used as the color material, they are preferably transparent. Examples of transparent pigments that can be used in this invention include Sun RS Magenta 234-007.TM., Hoechst GS Yellow GG 11-1200.TM., Sun GS Cyan 249-0592.TM., Sun RS Cyan 248-061, Ciba-Geigy BS Magenta RT-333D.TM., Ciba-Geigy Microlith Yellow 3G-WA.TM., Ciba-Geigy Microlith Yellow 2R-WA.TM., Ciba-Geigy Microlith Blue YG-WA.TM., Ciba-Geigy Microlith Black C-WA.TM., Ciba-Geigy Microlith Violet RL-WA.TM., Ciba-Geigy Microlith Red RBS-WA.TM., any of the Heucotech Aquis II.TM. series, any of the Heucosperse Aquis III.TM. series, and the like.

A preferred method of inserting or depositing the colors on the matrix is by laser induced mass transfer, including both a "melt stick" or an ablative transfer process in which a donor sheet having the colors thereon is used to transfer colors onto the substrate. "Ablative transfer" refers to a process in which a medium is ablated in thermal imaging processes by the action of a thermal source, through the rapid removal of material from the surface, but without sublimation of the material. Such donor sheets are known in the art for direct image forming, but are not believed to have been shown for use in the formation of color filters.

An example of a suitable color donor element would be a coating of dye or pigment (with or without a binder) on a substrate. A laser or other focused radiation source is used to heat the color material in an imagewise manner to transfer the color to the matrix bearing receptor sheet. It is often desirable in such constructions to assist in the absorption intensity of the imaging radiation since the dye or pigment (and the substrate) may not necessarily be highly absorptive of the imaging radiation. An imaging radiation absorbent material may be included within the dye/pigment layer (e.g., where an infrared emitting imaging radiation source is used, an infrared absorbing dye with little or no visible absorbance may be used). A separate imaging radiation layer may also be used, normally adjacent to the color containing donor layer. The colors of the donor layer may be selected as needed by the user from amongst the many available colors normally or specially used in filter elements, such as cyan, yellow, magenta, red, blue, green, white and other colors and tones of the spectrum as contemplated. The dyes are preferably transmissive of preselected specific wavelengths when transferred to the matrix bearing receptor layer. For many applications, highly transmissive dyes, e.g., dyes having an optical density of less than 0.5 optical density units within a narrow wavelength distribution of 10 nanometers or less when those dyes are present on the matrix, are preferred. Dyes with even lower absorption characteristics within those narrow wavelength bands are more preferred.

A typical color donor element is comprised of a substrate layer, a light-to-heat-conversion layer (LTHC), a colorant layer, and optionally a The substrate layer is typically a polyester film. However, any film that has sufficient transparency at the imaging wavelength and sufficient mechanical stability can be used. The LTHC layer can be a black body absorber, an organic pigment, or dye such that the LTHC layer has an optical density between 0.2-3.0. A preferred LTHC layer is a metal/metal oxide layer (e.g. black aluminum). The colorant layer is comprised of at least one organic or inorganic colorant or pigment and optionally an organic polymer or binder. The colorant layer may also contain a variety of additives including but not limited to dyes, plasticizers, UV stabilizers, film forming additives, and adhesives. When a dye is used as an additive, it is generally preferable that the dye absorbs light of the same frequency as the imaging light source. The optional adhesive layer may also contain a dye that absorbs light of the same frequency as the imaging laser or light source.

Substantially any metal capable of forming an oxide or sulfide can be used in the practice of this invention for the black metal layer. In particular aluminum, tin, chromium, nickel, titanium, cobalt, zinc, iron, lead, manganese, copper and mixtures thereof can be used. Not all of these metals when converted to metal oxides according to this process will form materials having all of the specifically desirable properties (e.g., optical density, light transmissivity, etc.). However, all of these metal oxide containing layers formed according to the practice of the present invention will be useful and contain many of the benefits of the present process including bondability to polymeric materials. The metal vapors in the chamber may be supplied by any of the various known techniques suitable for the particular metals, e.g., electron beam vaporization, resistance heaters, etc. Reference is made to Vacuum Deposition Of Thin Films, L. Holland, 1970, Chapman and Hall, London, England with regard to the many available means of providing metal vapors and vapor coating techniques, in general.

Metal oxide or metal sulfide containing layers, exemplary of the black metal layers according to the present invention, may be deposited as thin as layers of molecular dimensions up through dimensions in micrometers. The composition of the layer throughout its thickness may be readily controlled as herein described. Preferably the metal/metal oxide or sulfide layer will be between 50 and 5000 .ANG. in its imaging utilities, but may contribute bonding properties when 15.ANG., 25.ANG. or smaller and structural properties when 5.times.10.sup.4 .ANG. or higher.

The conversion to graded metal oxide or metal sulfide is effected by the introduction of oxygen, sulfur, water vapor or hydrogen sulfide at points along the metal vapor stream. By thus introducing these gases or vapors at specific points along the vapor stream in the vapor deposition chamber, a coating of a continuous or graded composition (throughout either thickness of the layer) may be obtained. By selectively maintaining a gradation of the concentration of these reactive gases or vapors across the length of the vapor deposition chamber through which the substrate to be coated is being moved, an incremental gradation of the composition of the coating layer (throughout its thickness) is obtained because of the different compositions (i.e., different ratios of oxides or sulfides to metals) being deposited in different regions of the vapor deposition chamber. One can in fact deposit a layer comprising 100% metal at one surface (the top or bottom of the coating layer) and 100% metal oxide or sulfide at the other surface. This kind of construction is a particularly desirable one because it provides a strong coherent coating layer with excellent adhesion to the substrate.

A substrate which is to be coated continuously moves along the length of the chamber from an inlet area of the vapor deposition chamber to an outlet area. Metal vapor is deposited over a substantial length of the chamber, and the proportion of metal oxide or sulfide being codeposited with the metal at any point along the length of the chamber (or deposited as 100% oxide or sulfide) depends upon the amount of reactive gas or vapor which has entered that portion of the metal vapor stream which is being deposited at that point along the length of the chamber. Assuming, for purposes of illustration, that an equal number of metal atoms (as metal or oxides or sulfides) are being deposited at any time at any point along the length of the chamber, gradation in the deposited coating is expected by varying the amount of oxygen or sulfur containing reactive gas or vapor which contacts the metal vapor at various points or areas along the length of the chamber. By having a gradation of increasing amounts of reactive gas along the length of the chamber, one gets a corresponding gradation in the increased proportions of oxide or sulfide deposited. Deposition of metal vapor is seldom as uniform as that assumed, but in actual practice it is no more difficult according to the procedures of the present invention to locally vary the amount of oxygen, water, sulfur or hydrogen sulfide introduced into different regions of said metal vapor along the length of the surface of the substrate to be coated as the substrate is moved so as to coat the surface with a layer having varying ratios of metal/(metal oxide or sulfide) through its thickness. It is desirable that the reactive gas or vapor enter the stream itself and not just diffuse into the stream. The latter tends to cause a less controllable distribution of oxides within the stream. By injecting or focussing the entrance of the reactive gas or vapor into the stream itself, a more consistent mixing in that part of the stream is effected.

Transitional characteristics bear an important relationship to some of the properties of the black metal products. The coating has dispersed phases of materials therein, one the metal and the other the metal oxide or sulfide. The latter materials are often transparent or translucent, while the former are opaque. By controlling the amount of particulate metal which remains dispersed in the transparent oxide or sulfide phase, the optical properties of the coating can be dramatically varied. Translucent coatings of yellowish, tan, and gray tones may be provided, and substantially opaque black film may be provided from a single metal by varying the percentage of conversion of the metal to oxide during deposition of the coating layer.

Thermal mass transfer of colorant onto a support is a significant improvement over dye (e.g., sublimation) transfer in forming color filter elements. The colors are more durable with respect to both abrasion and color fading(when pigments are used). The transferred mass material carries its own binder and can be applied to a greater range of substrate materials. No post-treatment of the transferred mass colorant is needed as may be required for dye transferred materials used in color filters of the prior art (e.g., U.S. Pat. Nos. 4,965,242 and 5,073,534).

In a preferred embodiment, the colorant layer refers to a layer containing a pigment, surfactant, binder, and possibly other additives. Any pigment may be used, but preferred are those listed as having good color permanency and transparency in the NPIRI Raw Materials Data Handbook, Volume 4 (Pigments). Either non-aqueous or aqueous dispersions of pigment in binder may be used. In the non-aqueous case, solvent based pigment dispersions may be used along with an appropriate solvent based binder (i.e. Elvacite.TM. acrylic resins available from DuPont). However, it is often preferred to use an aqueous dispersion of pigment in binder. In this case, the most preferred pigments are in the form of binderless aqueous dispersions (i.e. Aquis II.TM. supplied by Heucotech) and the most preferred binders are those specifically designed for pigment wetting (i.e. Neocryl BT.TM. acrylic resins from Zeneca Resins). The use of appropriate binders promotes the formation of sharp, well defined lines during transfer. When the colorant transfer is induced by a high powered light source (i.e., xenon flash lamp), it is usually necessary to include as binder an energetic or gas producing polymer such as disclosed in U.S. Pat. Nos. 5,308,737 and 5,278,023.

The pigment/binder ratio is typically 1:1 but may range from 0.25:1 to 4:1. A Mayer bar may be used to coat the colorant layer. Typically, a #4 bar is used to coat the dispersion which contains approximately 10 wt. % solids to give a dry coating thickness of about 1 micron. Other combinations of dispersion % solids and Mayer bar number are used to achieve different coating thicknesses. In general, a dry coating thickness of 0.1 to 10 microns is desired.

Transfer assist layer refers to a layer of adhesive coated as the outermost layer of the donor or receptor. The adhesive serves to promote complete transfer of colorant during the separation of the donor from the receptor after imaging. Preferred are colorless, transparent materials with a slight tack or no tack at room temperature, such as Daratak.TM. adhesive emulsion from Hampshire Chemical Corporation.

A general description of color filters for liquid crystal displays is given in C. C. O Mara, Liquid Crystal Flat Panel Display: Manufacturing Science and Technology, Van Norstrand Reinhold, 1993 p. 70. Several fabrication methods are disclosed. The most common method for preparing color filters is using photolithographic techniques. One photolithographic process is detailed in an article entitled "Color Filters from Dyed Polyimides" W. J. Latham and D. W. Hawley, Solid State Technology, May 1988. This paper shows the complex, multi-step nature of the photolithographic process. By comparison, this invention provides a much simpler process for making a color filter array.

The shapes of the color elements may be simple geometric objects such as rectangles, squares or triangles. Alternatively, for some configurations of color filters, the color elements may be created as stripes. Another common configuration for a color filter array is when the color elements in one row are displaced by one element in the second row and by two elements in the third row such that the color elements are diagonally aligned.

The dimensions of the elements can range from 5-1000 microns. More typically the dimensions are on the order of 50-300 microns. These dimensions are easily produced by photolithographic and laser imaging techniques.

The colors used to form the color filter are generally the primary additive colors, i.e. red, green, and blue. Each of these primary colors preferably has high color purity and transmittance, and, when combined, an appropriate white balance. The color filters preferably have spectral characteristics of red, green, and blue that show chromaticity close to the National Television Standards Committee (NTSC) standard colors indicated by the Commission International de l'Eclairage (CIE) chromaticity diagram. Although red, green, and blue are the most common colors for the filters, other color combinations may be used for specialty applications. In some cases, the repeat sequence in a row is red:green:blue. For other applications the repeat sequence in a row is red:green:green:blue.

The process of the present invention may be performed by fairly simple steps, which is one of the major advantages of the present invention. A laser may be used to induce mass transfer of the colorant to the substrate.

During laser exposure it may be desirable to minimize formation of interference patterns due to multiple reflections from the imaged material. This can be accomplished by various methods. The most common method is to effectively roughen the surface of the donor material on the scale of the incident radiation as described in U.S. Pat. No. 5,089,372. This has the effect of disrupting the spatial coherence of the incident radiation, thus minimizing self interference. An alternate method is to employ the use of an antireflection coating on the second interface that the incident illumination encounters. The use of anti-reflection coatings is well known in the art, and may consist of quarter-wave thicknesses of a coating such as magnesium fluoride, as described in U.S. Pat No. 5,171,650. Due to cost and manufacturing constraints, the surface roughening approach is preferred in many applications.

One embodiment of the present invention is to prepare a black matrix by transfer of black colorant, leaving transparent windows.

A specific method of practicing this aspect of the present invention would be to retain the original data defining the window areas of a matrix formed on a black coated receptor sheet, assigning specific location values to each window. In providing colors within the windows, each window having an assigned location value can be provided with a predetermined color assigned to each location value. A modification of the assigned values (e.g., increase the image area for each color window by specified percentages of the matrix line widths, or an increase of specific dimensions in each direction [length and width]) can be programmed into the imaging data for the colors or be used to automatically or selectively modify the image values to change the location values for one or more colors, or even provide variations of colors in different areas of the windows, as where different color intensities might be desirable in different areas on the filter.

These and other aspects of the present invention can be seen in the following, non-limiting examples of the present invention.

Materials

A sample of a Toshiba DTI LCD filter was examined under a microscope in order to determine the approximate dimensions of the black matrix and color filter elements. A data file was generated to create images with these dimensions. A source of color donor sheets was obtained from GTI , Laser Proof 3-M (Product Code 3257).

Black aluminum (AlO.sub.x) coated polyester (4 mil) was prepared using an ebeam evaporation technique as described above with respect to U.S. Pat. No. 4,364,995.

The Black Matrix Precursor/Pigment Receiving Element

Daratac 90L adhesive (Hampshire Chemical Corporation) was diluted with distilled water to a 10% solid solution and coated with a #4 wire-wrapped rod onto either a) the non-aluminized side or b) the aluminized side of the black aluminum coated polyester and dried in an oven at 60.degree. C. for 2 minutes.

Preparation of 5% Solution of Energetic Polymer-5% Poly BAMO/10AD

PolyBAMO{poly[bis(azidomethyl)oxetane]}, molecular weight of 4500 daltons as determined by gel permeation chromatography, was obtained from Aerojet Corp. A suspension of 90 g of BAMO in 300 g of methylethylketone (MEK) was warmed to about 60.degree. C., at which point a homogeneous solution resulted. To the this solution was added 10 g of acetylene dicarboxylic acid. The mixture was heated for 3 hrs at 60.degree. C. and then cooled to room temperature. Analysis by .sup.13 C NMR indicated triazole formation. The MEK was evaporated to yield a viscous liquid which was then redissolved in a mixture at 50.degree. C. of 2.4 g ethanolamine, 66 g isopropanol, and 160 g water. The mixture was analyzed to determine the percent solids whereupon it was further diluted with 350 g of water to result in a solution containing 5% solids.

Preparation of Pigment Stock Solutions

Blue dispersion A preparation: a pint jar, was charged with 66 g deionized water, 26.4 g isopropanol, and 39.6 g Microlith blue 4G-WA (Ciba-Geigy). This mixture was agitated on a high speed shear mixer for 2 minutes at slow speed, then 8.8 g of triethanolamine was added and the speed was increased to 1/2 speed for 20 minutes. To this mixture was added 22 g of deionized water and 8.8 g of isopropanol and stirring was continued for an additional 5 minutes.

The above procedure was repeated to give the dispersions with the following pigments used in place of Microlith blue 4G-WA: yellow dispersion A, Microlith yellow 2R-WA; yellow dispersion B, Microlith yellow 3G-WA; black dispersion A, Microlith black C-WA; violet dispersion A, Microlith violet RL-WA; red dispersion A, Microlith red RBS-WA.

Preparation of Binderless Pigment Stock Solutions

Binderless aqueous red, green, and blue pigment dispersions were obtained under the trade name Aquis II from Heucotech, Ltd. (QA magenta RW-3116, phthalo green GW-3450, and phthalo blue G/BW-3570, respectively). The dispersions were diluted to 10 wt % solids with distilled water and were agitated on a shaker table for ten minutes to obtain stock solutions.

Preparation of Energetic Polymer Stock Solution

A stock solution was prepared containing the ingredients: 0.9 g deionized water, 0.15 g 5% Fluorad.TM. FC 170Cin 1:1 (propanol:water), 13 g of 5% BAMO/10AD, 2.0 g Hycar 26106 dispersion (B. F. Goodrich).

Preparation of Vancryl Stock Solution

A stock solution was prepared containing the ingredients: 14 g water, 0.15 g 5% Fluorad.TM. to FC 170Cin 1:1 (propanol:water), 2.0 g Vancryl 600 (an aqueous latex vinyl chloride-ethylene adhesive from Air Products).

Preparation of Neocryl Stock Solution

Neocryl BT-24 (45 wt % solids, emulsion in water, Zeneca Resins) was diluted to 20 wt % solids with distilled water and then was neutralized with aqueous ammonia to pH 8.0.

Preparation of Surfactant Solution

3M FC-170C surfactant was diluted to 5 wt % solids with water/isopropanol 1:1.

Preparation of Pigment/Energetic Polymer Coating Solutions

The pigment/energetic polymer coating solutions were prepared according to the following formulations:

Blue coating solution: The energetic polymer stock solution (3 g), 0.55 g of blue dispersion A, 0.55 g of yellow dispersion A, 1 g of water, and 5 drops of a 10% aqueous ammonium nitrate solution.

Green coating solution: The energetic polymer stock solution (3 g), 0.31 g of violet dispersion A, 0.8 g of blue dispersion A, mad 4 drops of a 10% aqueous ammonium nitrate solution.

Red coating solution: The energetic polymer stock solution (3 g), 0.83 g of red dispersion A, 0.27 g of yellow dispersion A, and 4 drops of a 10% aqueous ammonium nitrate solution.

Black coating solution: The energetic polymer stock solution (4 g), 1.1 g of black dispersion A, and 4 drops of a 10% aqueous ammonium nitrate solution.

Cyan coating solution: The energetic polymer stock solution (4 g), 1.1 g of blue dispersion A, and 4 drops of a 10% aqueous ammonium nitrate solution.

Magenta coating solution: The energetic polymer stock solution (4 g), 0.83 g of red dispersion A, and 4 drops of a 10% aqueous ammonium nitrate solution.

Yellow coating solution: The energetic polymer stock solution (4 g), 0.55 g of yellow dispersion A, 0.55 g of yellow dispersion B, and 4 drops of a 10% aqueous ammonium nitrate solution.

Preparation of Pigment/Vancryl Coating Solutions

The pigment/Vancryl coating solutions were prepared according to the following formulations:

Blue coating solution: The Vancryl stock solution (3 g), 300 mg of violet dispersion A, 800 mg of blue dispersion A, and 1 g of water.

Green coating solution: The Vancryl stock solution (3 g), 550 mg of blue dispersion A, and 550 mg of yellow dispersion A.

Red coating solution: The Vancryl stock solution (3 g), 550 mg of yellow dispersion B, and 800 mg of red dispersion A.

Black coating solution: The Vancryl stock solution (3 g), 1 g of black dispersion A, and 1 g of water.

Preparation of Pigment/Neocryl Coating Solutions

Each of the coating solutions was prepared by mixing the listed ingredients, followed by agitation on a shaker table for ten minutes:

Red coating solution: The Neocryl stock solution (0.5 g), 1 g of binderless red pigment stock solution, 220 mg surfactant solution, and 2.5 g of water.

Green coating solution: The Neocryl stock solution (0.75 g), 2 g of binderless green pigment stock solution, 220 mg surfactant solution, and 1.25 g of water.

Blue coating solution: The Neocryl stock solution (0.5 g), 1 g of binderless blue pigment stock solution, 220 mg surfactant solution, and 2.5 g of water.

Preparation of Color Donor Elements (or Sheets)

The above coating solutions were coated on top of the black aluminum layer (TOD=1.0) of a black aluminum coated polyester. Coating solutions containing energetic polymer were coated with a #5 wire-wound Mayer bar except for the blue coating solution which was coated with a #4 wire-wound Mayer bar. All of the Vancryl and Neocryl based coating solutions were coated with a #4 wire-wound Mayer bar. The coating's were dried at 60.degree. C. for 2 minutes.

Best results were achieved when an antireflection layer was coated onto the non-aluminized side of the polyester coating. This coating diminished an optical interference effect leading to an irregular "wood-grain" pattern. Suitable antireflection layers (described as roughening coatings of silica in U.S. Pat. No. 5,089,372, example 1) were coated onto the non-aluminized side of the polyester substrate.

Daratak/PET Receptor Preparation

Daratak 90L (Hampshire Chemical Company) was diluted to 10 wt % solids by the slow addition of distilled water. Large particles were removed by centrifugation (30 see at 10,000 rpm). The solution was coated onto plain 4 mil PET using a #4 Mayer Rod and then dried for 2 rain at 60 .degree. C.

Two types of laser scanners were used, namely an internal drum type scanner, useful for imaging flexible substrates and a flat field system suitable for both flexible and rigid substrates.

Internal Drum System

Imaging was performed using a Nd:YAG laser, operating at 1.06 microns in TEM.sub.OO mode and focused to a 26 micron spot (1/e.sup.2) with 3.4 W of incident radiation at the image plane. The laser scan rate was 128 m/s. Image data was transferred from a mass-memory system and supplied to an acousto-optic modulator which performed the image-wise modulation of the laser. The image plane consisted of a 135.degree. wrap drum which was translated synchronously perpendicular to the laser scan direction.

The substrate was firmly attached to the drum during the imaging of the window elements and the color filter elements. The required resolution of the final black matrix/color filter element was obtained via accurate placement of the scanned laser spots. The donor and the receptor were translated in a direction perpendicular to the laser scan at a constant velocity, using a precision translation stage.

Flat Field System

A flat-field galvonometric scanner was used to scan a focussed laser beam from a Nd:YAG laser (1064 nm) across an image plane. A vacuum stage was located at the image plane and was mounted in a motorized stage so that the material could be translated in the cross-scan direction. The laser power on the film plane was 3 W and the spot size was.about.100 microns (1/e.sup.2 width). The linear scan speed for the examples cited here was 600 cm/s. Polished glass (Corning #7059F) was mounted on the vacuum stage and was used as the receiving substrate. A donor sheet was placed in vacuum contact with the glass and was imaged with the laser. In the imaged areas, colored stripes of equivalent dimensions (.about.100 microns) were transferred to the glass.

Examples 1-3 demonstrate the formation of an integral black matrix/color filter array.

The black matrix precursor/color receiving sheet (a-construction) was placed in a curved focal plane surface (internal drum) with the black aluminum layer side contacting the drum. This film was imaged to create a series of windows resulting in a black matrix/color receiving element. Without moving the receiving element relative to the drum, an energetic polymer/color donor sheet, described above, was then placed over the black matrix/color receiving sheet such that the color receiving sheet and the color donor sheet were in intimate contact. This contact was promoted by application of a vacuum. The construction was imaged and then the color donor sheet was peeled from the black matrix/color receiving sheet in the direction of the laser scan without moving the receiving sheet relative to the drum. This procedure was then repeated for the other colors to form a black matrix/color filter element. The best results were obtained by rubbing WD-40 (WD-40 Company), a penetrating lubricant, on the black aluminum side of the filter to remove any residual metal from the laser-exposed window elements. This debris removal method is disclosed in copending U.S. patent application Ser. No. 08/217,358 filed on Mar. 24, 1994 , now abandoned.

A film of black aluminum coated polyester without an adhesive layer, was placed in a curved focal plane surface (internal drum) with the black aluminum layer side away from the drum. This film was imaged to create a series of windows resulting in a black matrix/color receiving element. An energetic polymer/color donor sheet, described above, was then placed over the black matrix/color receiving sheet such that the color receiving sheet and the color donor sheet were in intimate contact. This contact was promoted by application of a vacuum. The construction was imaged and then the color donor sheet was peeled from the black matrix/color receiving sheet in the direction of the laser scan. This procedure was then repeated for the other colors to form a black matrix/color filter element.

A film of black aluminum coated polyester without an adhesive layer, was placed in a curved focal plane surface (internal drum) with the black aluminum layer side away from the drum. This film was imaged to create a series of windows resulting in a black matrix/color receiving element. A GTI color donor sheet, was then placed over the black matrix/color receiving sheet such that the color receiving sheet and the color donor sheet were in intimate contact. This contact was promoted by application of a vacuum. The construction was imaged and then the color donor sheet was peeled from the black matrix/color receiving sheet in the direction of the laser scan. This procedure was then repeated for the other colors to form a black matrix/color filter element. The GTI color donor sheet was believed to differ in two key respects from the energetic polymer color donor elements of the previous examples. The GII color layer appeared to have a thin metallic aluminum layer, instead of a black aluminum layer, and 2) the GTI colorant layer was believed to contain an infrared absorbing dye.

Examples 4-6 demonstrate the formation of color filter elements without a black matrix. In these cases, the receiving substrate was not black aluminum coated polyester, but a polyester with an adhesive coating (Daratak 90L). In a similar manner, a black matrix could be used as the receiving element. Example 6 demonstrates the transfer of colorant without energetic polymer binders.

Same as Example 3, except that GTI donor sheets were used with a Daratak 90L coated polyester color receiving sheet instead of a black matrix/color receiving sheet to form a color filter element.

Same as Example 4, except that the energetic polymer/color donor sheets were used in place of the GTI donor sheets to form a color filter element.

Same as Example 4 except that the Vancryl/color donor sheets (red, green, and blue) were used in place of the GTI donor sheets to form a color filter element.

Examples 7-13 demonstrate the use of glass as the receiving substrate. These experiments were done using the flat field laser system. Although these examples demonstrate the formation of color filter elements without a black matrix, in a similar manner a black matrix could be used as the receiving element. An important aspect of these examples is the direct transfer to the glass substrate without the need for a receiving layer such as the Daratak.

The GTI color donors (yellow, cyan) were sequentially transferred to glass to form colored stripes,and then the GTI color donor (black) was transferred to form the black matrix, resulting in a black matrix/color filter element.

The GTI color donor (black) was transferred to glass to form a black matrix. Energetic polymer donor sheets (cyan and yellow) were then sequentially transferred on the black matrix to form a black matrix/color filter element.

An energetic polymer/black donor sheet was transferred to glass to form a black matrix. Energetic polymer donor sheets (red, green, and blue) were sequentially transferred as stripes to the black matrix to form a black matrix/color filter element.

Examples 10-13 are examples of colorant transfer without energetic polymer binders. These experiments were done using the flat field laser system.

The Vancryl/color donor sheet (red) was transferred directly to glass to form colored stripes.

The Vancryl/color donor sheet (green) was transferred directly to glass to form colored stripes.

The Vancryl/color donor sheet (black) was transferred directly to glass to form colored stripes.

The Vancryl/color donor sheet (blue) was transferred directly to glass to form colored stripes.

The Neocryl/color donor sheets (red, green, and blue) were sequentially transferred to a Daratak/PET receptor sheet using the internal drum laser system to form approximately 100.times.300 micron color patches of a color filter element.

The black matrix precursor/color receiving sheet (b-construction) was placed in a curved focal plane surface (internal drum) with the Daratak/black aluminum side away from the drum. This film was imaged to create a series of windows by transparentizing the black aluminum while leaving the Daratak layer intact, resulting in a black matrix/color receiving element. Without moving the receiving element relative to the drum, a Neocryl color donor sheet (red) was placed over the black matrix/color receiving sheet such that the color receiving sheet and the color donor sheet were in intimate contact. This contact was promoted by application of a vacuum. The construction was imaged and then the color donor sheet was peeled from the black matrix/color receiving sheet in the direction of the laser scan without moving the receiving sheet relative to the drum. This procedure was then repeated for the other colors (green and blue) to form a black matrix/color filter element.

Solvent based coating solutions were prepared according to the formulations listed in Table 1. A 10 wt % solution of dye was prepared by dissolving 4-tricyanovinyl-N,N-dibutylaniline (prepared by proced detailed in McKusick, et. al., J. Amer. Chem. Soc., 80, 1958, 2806-15) in MEK. A 10 wt % solution of binder was prepared by dissolving PMMA (75,000 MW polymethylmethacrylate available from Polysciences) in MEK. The solutions were coated onto the black aluminum substrate (TOD=0.9) using a #5 Mayer bar. The coatings were dried for 5 rain at 55.degree. C. and then imaged. The magenta dye crystallized in the coated film at a dye/binder ratio of 1 or greater (40D-H) as was evidenced by a decrease in transparency and observable birefringence (using cross polarizers in an optical microscope). The crystalline magenta dye had a much redder hue than the dispersed dye.

Imaging was performed on a flat field Nd: YAG (TEM.sub.OO mode) imaging device using a linear galvanometer. The parameters were 85 micron spot size, 7.2 W on the film plane, 6 m/sec linear scan speed). The receptor was an uncoated glass microscope slide.

The state of the dye on the corresponding imaged glass receptor was the same as that of the donor. Coatings with dye/binder ratios less than 1 were imaged to produce uniform films with dissolved dye. Those with ratios greater than or equal to 1 produced films with crystalline dye. The adhesion of all colorants to the glass surface was good to excellent--even those without binder.

All of the transferred samples appeared to be "overheated" in that the binders had a bubbled, thermally shocked look. In some cases such as 40A, a small portion of the dye appeared to be heated beyond the melting point, flowed, and recrystallized outside of the binder boundary. This indicated a post image heating and a scan speed that was lower than optimum and was likely an effect that was independent of the LITI transfer process.

Aqueous coating solutions were prepared according to the formulations listed in Table 2. A 10 wt % solution of dye was prepared by dissolving copper(II) phthalocyanine tetrasulfonic acid tetrasodium salt (Kodak) in water. A 10 wt % solution of binder was prepared by dissolving Neocryl BT-8.TM. (Zeneca Resins) in water, followed by neutralization with aqueous ammonia to pH 8. The solutions were coated onto the black aluminum substrate (TOD=0.9) using a #5 Mayer bar. The coatings were dried for 5 rain at 55.degree. C. and then imaged. The dye crystallized in the coated film at a dye/binder ratio of 1 or greater (40N-S) as was evidenced by a decrease in transparency and observable birefringence (using cross polarizers in an optical microscope).

Imaging was performed as described in Example 16. The state of the dye on the corresponding imaged glass receptor was the same as that of the donor. Coatings with dye/binder ratios less than 1 were imaged to produce uniform films with dissolved dye. Those with ratios greater than or equal to 1 produced films with crystalline dye. The adhesion of all colorants to the glass surface was good to excellent. This example demonstrates the efficient transfer of an ionic dye in an ionic binder in the formation of color filter elements.

A sacrificial layer was prepared as follows. A 10 wt % mixture in water of the ingredients listed in Table 3 was prepared at .about.70.degree. C.

A small amount (2-5% to the solid content of the solution) of charging agent, OLOA 1200 (Chevron Chemical Co,., Rolling Meadows, Ill.), was added to the mixture. The solution was then brought back to room temperature under high speed agitation and a stable emulsion was obtained.

The emulsion was coated on 6 micron PET using a #10 Meyer bar and dried in an oven at 80.degree. C. for 1 minute to form a non-ir absorbing thermoplastic coating. The film was then laminated to black aluminum at 230.degree. F. A reflective mask was placed in contact with the substrate and imaged as described earlier. After laser exposure and removal of the mask, the 6 micron PET with the thermoplastic coating was peeled away from the black aluminum film. An exact replica of the original image was obtained and no debris was observable on the surface.

Solvent based pigment millbases were prepared according to the formulations (in grams) listed in Table 4:

The pigments used in the GS Yel, RS Mag, BS Mag, GS Cyan, and RS Cyan millbases were Hoechst Celanese GG-1100, Sun 234-0077, Hoechst Celanese 13-7019, Sun 249-0592 and Sun 248-0165, respectively. Joncryl was Joncryl 690 by Johnson Wax; Butvar was Butvar B-98 by Monsanto; and Dis. 161 was Disperbyk 161 by Byk Chemie. All were 25% solids in MEK/1-methoxy-2-propanol 1:3.

The blue, green, and red color donor coatings were formulated from the above millbases as follows:

Blue: 1.6 g RS Cyan, 0.4 g BS Magenta, 0.75 g MEK;

Green: 0.4 g GS Cyan, 0.7 g GS Yellow, 0.5 g MEK;

Red: 1.7 g RS Magenta, 0.3 g GS Yellow, 1.0 g MEK.

The above ingredients were combined and were placed on a shaker table for 10 minutes. The formulations were coated onto black aluminum with a #4 Mayer Rod and were dried for 2 minutes at 60.degree. C.

A receptor coating solution was prepared by adding 9.0 g water slowly with stirring to 2.0 g Daratak 90L (W. R. Grace Co.) and stirring for ten minutes. The solution was coated onto clear PET and was dried as described above to give a receptor sheet.

The blue, green, and red color donors were imaged against the receptor sheet on the internal drum system at 64 m/sec to give patches of colors to form a color filter matrix.

A binderless red pigment stock solution was prepared by diluting a 1:1 mixture by weight of Aquis II binderless aqueous red pigment dispersions (PR-224 and PR-179 from Heucotech, Ltd) with distilled water to 10 wt % solids, followed by agitation on a shaker table for ten minutes. Binderless green and blue pigment stock solutions were prepared as described previously.

Neocryl BT-8 (40 wt % solids acrylate polymer emulsion in water, Zeneca Resins) was diluted to 20 wt % solids with distilled water and then was neutralized with aqueous ammonia to pH 8.0.

Pigment/Neocryl coating solutions were prepared by mixing the listed ingredients, followed by agitation on a shaker table for ten minutes. Red coating solution: The Neocryl stock solution (0.75 g), 1.5 g of binderless red pigment stock solution, 5 drops surfactant solution, and 1.5 g of water. Green coating solution: The Neocryl stock solution (0.75 g), 2 g of binderless green pigment stock solution, 5 drops surfactant solution, and 1.0 g of water. Blue coating solution: The Neocryl stock solution (1.0 g), 2 g of binderless blue pigment stock solution, 10 drops surfactant solution, and 4.0 g of water.

Color donor elements were prepared by using a #4 wire-wound Mayer bar to coat the above Pigment/Neocryl coating solutions on top of the black aluminum layer (TOD=1.0) of black aluminum coated polyester. The coatings were dried at 60.degree. C. for 2 minutes. Daratak 90L (Hampshire Chemical Company) was diluted to 10 wt % solids by the slow addition of distilled water. Large particles were removed by centrifugation (30 sec at 10,000 rpm). The solution was coated onto the color donor element using a #4 Mayer Rod and then dried for 2 min at 60 .degree. C.

An indium-tin-oxide (ITO)-coated surface of a 50-micron polyester film (Altair-0-80-B-G-2 mil, Southwall Technologies, Palo Alto, Calif.) was used as the receptor.

The blue, green, and red color donors were imaged against the receptor sheet on the internal drum system at 64 m/sec to give 100.times.300 micron patches of colors forming a color filter matrix on the ITO coated receptor.

The preparation of polymer-dispersed liquid crystal films are described in copending U.S. patent application Ser. No. 08/235,561 filed Apr. 29, 1994 and U.S. patent application Ser. No. 08/121,964 filed Sep. 15, 1993 now abandoned) , both incorporated herein by reference. A polymer-dispersed liquid crystal (PDLC) film was prepared by placing approximately 1 gram of a solution containing 55 wt % of the liquid crystal material BL036 (EM Industries, Inc., Hawthorne, N.Y.) and 45 wt % of a solution containing 2.5 wt % Esacure KB1 (Sartomer, Exton, Pa.), 45.0 wt % isooctyl acrylate, 20.0 wt % allyl aliphatic urethane 9460 (Monomer Polymer and Dajac, Trevose, Pa.), 20.0 wt % 2-phenoxyethyl acrylate (Sartomer, Exton, Pa.) and 12.5 wt % Uralac 3004-102 (DSM Resin, Inc., Elgin, Ill.) onto the moving indium-tin-oxide (ITO)-coated surface of a 50-micron polyester film (Altair-0-80-B-G-2 mil, Southwall Technologies, Palo Alto, Calif.) just prior to the nip gap of a coater similar to that described in the above referenced U.S. patent application Ser. No. 08/12 1,964, (now abandoned) but modified to allow 27.degree. C. cooling fluid to be circulated through the nip rolls. At the nip rolls which were set to produce a PDLC layer approximately 17 microns thick, a second ITOcoated 50-micron polyester film entered to form a laminate with the ITO-coated surfaces facing each other. The laminate was then transported into a cure zone where it was irradiated for approximately 3 minutes at approximately 24 .degree. C. with long wavelength ultraviolet light at intensity of approximately 1.5 mW/cm.sup.2 as measured with a UVIBRITE meter model number UBM365MO from Electronics Instrumentation and Technology, Inc., Sterling, Va. specially calibrated to read absolute intensity.

One of the ITO coated PET sheets was delaminated from the above construction, leaving a PET/ITO/PDLC sheet. The PDLC side of this sheet was pressed against the color filter element which was prepared on the ITO coated PET base. This resulted in an operational liquid crystal display device incorporating the color filter element. When a potential of from 20 to 30 volts was applied across the liquid crystal display device by connecting leads to the two ITO layers, the liquid crystal device became transparent and light from backside illumination provided by an overhead projector was transmitted through the red, green, and blue patches of the color filter element. When the applied potential was removed, the liquid crystal device became opaque, and light was not transmitted through the color filter element.

A transparent electrically conductive layer is a continuous or patterned layer possessing an average optical density in the 400-700 nm region of the elctromagnetic spectrum of less than 0.2, preferably less than 0.1, and more preferably less than 0.05 and a resistivity of less than 1000 ohms/square, preferably less than 100 ohms/square, and more preferably less than 15 ohms/square. Conductive polymers and thin metal layers can provide this function.