Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/04—Additive processes using colour screens; Materials therefor; Preparing or processing such materials
  • G03C7/06—Manufacture of colour screens
  • G03C7/10—Manufacture of colour screens with regular areas of colour, e.g. bands, lines, dots
  • G03C7/12—Manufacture of colour screens with regular areas of colour, e.g. bands, lines, dots by photo-exposure
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/407—Development processes or agents therefor
  • G03C7/413—Developers
  • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

• This invention relates to a photographic material suitable for use in the production of a multicolour filter array element, to such element and a multicolour liquid crystal display device incorporating such element.
• Liquid crystal display devices are used nowadays in numerous applications such as clocks, household appliances, electronic calculators, audio equipment, etc. There is a growing tendency to replace cathode ray tubes by liquid crystal display devices being favoured for their smaller volume and lower power consumption. In some applications like e.g. laptop computers and pocket TV's liquid crystal display devices are even without competition.
• High definition television in its ultimate version will require screen diagonals exceeding 50 inch (see P. Plezhko in the periodical Information Display September 1991, Vol. 7 no. 9, p. 19 a.f.) Although not yet in existence CRT-based 50 inch screens can be expected to be very impractical because of their weight and size. Liquid crystal technology is basically able to produce high definition television (HDTV) screens with moderate weight and size.
• Liquid crystal display devices generally include two spaced glass panels, which define a sealed cavity, which is filled with a liquid crystal material.
• the glass plates are covered with a transparent electrode layer which may be patterned in such a way that a mosaic of picture elements (pixels) is created.
• Two addressing systems are used to drive the display : either a passive system or an active system.
• the two electrode layers are patterned in a regular array of stripes.
• the stripes on one plate are perpendicular to those on the other plate.
• each pixel has its own individual microelectronic switch, which means that such a microswitch is connected to an individual transparent pixel electrode, the planar size of which defines the size of the pixel.
• the microswitches are individually addressable and are three-terminal or two-terminal switching elements.
• TFT thin film transistors
• the transparent electrode layer must be patterned.
• a colour filter array element is provided on one of the two glass plates.
• this is usually the glass plate opposite the glass plate carrying the switching elements.
• a colour filter array for full colour reproduction consists of red, green and blue patches arranged in a given order.
• the colour patches may be separated by a black contour line pattern delineating the individual colour pixels (ref. e.g. US-P 4,987,043).
• the colour filter is preferably kept out of the electrical circuit which means that the transparent electrode is deposited on top of the colour filter array element.
• a first widely used technique operates according to the principles of photolithography (ref. e.g. published EP-A 0 138 459) and is based on photohardening of polymers e.g. gelatin.
• Dichromated gelatin, doped with a photosensitizer is coated on glass, exposed through a mask, developed to harden the gelatin in the exposed areas and washed to remove the unexposed gelatin. The remaining gelatin is dyed in one of the desired colours.
• a new gelatin layer is coated on the dyed relief image, exposed, developed, washed and dyed in the next colour, and so on.
• wash-off and dying technique four complete operation cycles are needed to obtain a red, green and blue colour filter array having the colour patches delineated with a black contour line.
• dyeable or coloured photopolymers are used for producing superposed coloured photoresists. In the repeated exposures a great registration accuracy is required in order to obtain colour filter patches matching the pixel-electrodes.
• organic dyes or pigments are applied by evaporation under reduced pressure (vacuum evaporation) to form a coloured pattern in correspondence with photoresist openings [ref. Proceedings of the SID, vol. 25/4, p. 281-285, (1984)].
• a mechanical precision stencil screen has been used for patternwise deposition by evaporation of dyes onto a selected substrate (ref. e.g. Japan Display 86, p. 320-322.
• dyes are electrodeposited on patterned transparent electrodes from a dispersion of curable binder polymers, dispersing agents and coloured pigments. For each colour a separate deposition and curing step is needed.
• red, green and blue dyes are deposited by thermal transfer from a dye donor element to a dye-receiving element, comprising a transparent support, e.g. glass plate, having thereon a dye-receiving layer.
• Image-wise heating is preferably done by means of a laser or a high intensity light flash. For each colour a separate dye transfer step must be carried out.
• a method of producing a multicolour optical filter comprises the steps of
• the manufacturing yields i.e. the percentage of the colour filter array elements made in the factory which meet quality control standards are exceptionally low.
• the very costly investments could be brought down when the filter production could be simplified and yet high quality maintained.
• EP-A 396 824 relates to a process for the production of a multicolour liquid crystal display device comprising a liquid crystal layer essentially consisting of nematic crystals in twisted or supertwisted configuration or smectic C (chiral smectic) ferroelectric liquid crystals wherein the liquid crystal molecules are aligned in such a way that said layer shows an electrically controllable rotation of the polarization plane of the light incident on the display.
• Said liquid crystal layer together with a multicolour filter element is arranged between front and rear transparent electrodes for altering pixelwise the electric field over the liquid crystal layer and said electrodes are associated respectively with a front and rear light polarizer element.
• Said process comprises in consecutive order the steps of :
• the uppermost emulsion layer of the thus processed photographic print material is coated with a hydrophobic water-impermeable organic resin to form a covering layer of said resin thereon, and by vacuum-deposition on top of the thus-applied resin coating a transparent electrically conducting (electrode) layer is formed.
• Said resin layer on top of the colour filter array provides a good planarity and prevents the release of volatile substances from the emulsion layer during vacuum-deposition, e.g. by sputtering, of the transparent conducting layer. Usually a bake at 150 °C or even higher is needed to impart by curing a good impermeability to the resin layer.
• liquid crystal displays of the so-called twisted nematic (TN) type (as are the majority of active matrix liquid crystal displays) the transparent uniformly applied electrode and also the patterned electrode are covered with an alignment layer.
• This layer usually consists of a heat-cured polyimide resin. Rubbing this cured layer with e.g. a nylon cloth (ref. e.g. GB-P 1,505,192) in a given direction causes an orientation of the liquid crystal molecules near the surface of the layer in the rubbing direction.
• a nylon cloth ref. e.g. GB-P 1,505,192
• the multicolour filter array element is subjected to rather severe heat treatment steps during the manufacture of the liquid crystal display element. These heating steps may not give rise to discolouration of the filter and dye fading.
• the photographic print material comprises (i) a silver halide emulsion layer sensitive to blue light and containing a yellow dye forming colour coupler, (ii) a silver halide emulsion layer sensitive to green light and containing a magenta dye forming colour coupler, (iii) a silver halide emulsion layer sensitive to red light and containing a cyan dye forming colour coupler, wherein said layer (iii) is most remote from said support and in each silver halide emulsion layer the equivalent ratio of silver hal
• the structure of the colour developing substance is decisive also for the dye-stability.
• p-phenylenediamine type developing agents are used. Paraphenylenediamine developers are well known in the art. In e.g.
• JP-A 3-002 745 it is closed that p-phenylenediamine derivatives wherein one of the amine functions is di-substituted by alkyl, aryl or heterocyclic groups, are very well suited for the development of direct positive emulsions, giving low fog, high maximum density and a steep slope in the low density parts of the sensitometric curve. No particular derivative is selected as being extra well suited, and the thermal stability of the dyes is not mentioned.
• DE-OS 26 12 120 it is disclosed to use in a colour developer for silver halide colour materials, p-phenylenediamine derivatives that comprise on one of the nitrogen atoms an alkyl group carrying hydroxy-, methoxy-, sulphophenoxy- or sulpho- groups and an isopropyl group.
• the advantage of using such developers is, according to that disclosure, that the fog is diminished, especially in silver halide materials coated on paper. From this disclosure it seems that the specified developing substance brings no advantage when used to develop colour materials on coated on film or on glass.
• FR-A 2,300,356 it is disclosed to use in a developer for silver halide colour materials, a p-phenylenediamine derivative whereof one of the amino groups is substituted by an alkyl group and by an alkylether group. It is said that, when using such developers, the dyes, formed upon development, are less sensitive to the action of heat, light and humidity, but except for the stability against light fading, no indication of heat stability is given.
• EP-A 459 210 derivatives of p-phenylenediamine yielding dyestuffs with improved fastness to light are described.
• Such colour developing substances are therefore advantageously used in the production of colour filters subjected lateron to radiation and/or thermal treatment.
• JP-A 62-063901 a process for preparing colour filters for use in LCD's is disclosed.
• a three-colour photographic material is used to produce the filter by exposing the photographic material with white light through an appropriate mask and by developing the photgraphic material in a p-phenylenediamine developer.
• No preference for a special type of p-phenylenendiamine developing compound is given.
• JP-A 63-261361 a colour photographic photosensitive material for preparing colour filters for LCD's is disclosed.
• the disclosure is particularly concerned with the use of two colour couplers, yielding a different hue of the same colour, in the same emulsion layer. It is disclosed that several p-phenylenediamine derivatives are useful as developing agent for the material, but no preference for specific compounds has been disclosed.
• the objects of the present invention are realized by providing a method for manufacturing a multicolour filter array element, firmly associated with a transparent electrode layer in a multicolour liquid crystal display device, comprising the steps of :
• both R 1 and R 2 are lower alkyl groups, having between 1 and 6 C-atoms, more preferably C 1 to C 3 - alkyl groups.
• R 4 , R 5 and R 7 are hydrogen, and each of R 1 , R 2 , R 3 and R 6 is either a methyl or an ethyl group.
• the developer solution comprising a p-phenylene diamine derivative comprises further a lower aliphatic alcohol, most preferably ethanol or methanol or a mixture of both.
• the p-phenylene diamine derivatives, according to the present invention can be used as developing substance for developing any silver halide colour photographic material, i.e. negative working materials, reversal materials, etc.
• a colour developer solution comprising a p-phenylene diamine derivative according to the above general formula, is used in accordance with the present invention to develop a print material that is used to form a multicolour filter array useful in the production of multicolour Liquid Crystal Displays (multicolour LCD's).
• print material is meant a silver halide colour photographic material that is comparable to the colour print film used in the motion picture film industry.
• the sequence wherein the differently spectrally sensitive silver halide emulsion layers are applied on a glass support is the sequence that is described in EP-A 615 161, which is incorporated herein by reference.
• the amount of colour coupler needed to obtain an optical density not higher than 2.5 at the maximum of spectral absorption of the dye formed can be determined by simple tests.
• each colour coupler containing layer is adjusted preferably in such a way that in the strongest exposed regions the colour coupler is completely converted to dye during the colour development.
• the equivalent ratio of silver halide to colour coupler in the print material should be preferably at least 10 % higher than 1.
• a ratio of 1 in equivalent amounts means that for each mole of colour coupler present in the layer 4 or 2 moles of silver halide are added, depending on whether the colour coupler is of the 4- or the 2-equivalent type.
• scavenging agents for that purpose are diffusion-resistant hydroquinone derivatives, preferably containing one or more aliphatic ballast groups having at least 6 carbon atoms. Such scavenging agents and their use are described e.g. in DE-P 3 545 611.
• the silver halide emulsion layer may contain any type of light-sensitive silver halide emulsion, e.g. an emulsion that forms a latent image primarily on the surfaces of the silver halide grains, or that forms an internal latent image predominantly in the interior of the silver halide grains.
• the emulsions can be negative-working emulsions, e.g. surface-sensitive emulsions or unfogged internal latent image-forming emulsions, or positive-working emulsions e.g. direct-positive emulsions of the unfogged, internal latent image-forming type, the development of which is conducted with uniform light exposure or in the presence of a nucleating agent.
• Direct-positive emulsions of the pre-fogged type wherein during image-wise exposure chlorine, bromine and/or iodine is liberated which image-wise destroys the developable centres created during overall prefogging.
• Direct-positive emulsions need only one development (as do negative emulsions).
• Reversal silver halide emulsions are not prefogged. Their processing includes 2 development steps and a fogging step.
• the first development is carried out with a black-and-white developer whereby a negative black-and-white silver image is formed.
• the remaining silver halide is made developable by fogging, either physically (by exposure to light) or chemically.
• bleaching and fixing a positive colour image is obtained.
• negative-working is meant that the density observed after processing is proportional to the exposure.
• positive-working is meant that the silver halide emulsions yield upon exposure and development positive images, i.e. the density is inversely proportional to the exposure.
• the applied silver halide can be of the silver chloride, the silver chloride-bromide, the silver bromide, the silver bromide-iodide or the silver chloride-bromide-iodide type.
• the silver halide can be surface sensitized.
• Noble metal e.g. gold
• middle chalcogen e.g. sulfur, selenium or tellurium
• reduction sensitizers employed individually or in combination, are specifically contemplated.
• Typical chemical sensitizers are listed in Research Disclosure December 1989, item 308119, section III.
• the silver halide can be spectrally sensitized with dyes from a variety of classes, including the polymethine dye class, which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e. tri-, tetra-, and polynuclear cyanines and merocyanines) oxonols, hemioxonols, styryls, merostyryls, and streptocyanines; see said Research Disclosure, section IV.
• the polymethine dye class which includes the cyanines, merocyanines, complex cyanines and merocyanines (i.e. tri-, tetra-, and polynuclear cyanines and merocyanines) oxonols, hemioxonols, styryls, merostyryls, and streptocyanines; see said Research Disclosure, section IV.
• Suitable vehicles for the emulsion layers and other layers of the print material are described in section IX of said Research Disclosure and brighteners and antifoggants are described respectively in sections V and VI, and hardeners for gelatin in section X.
• colour filters for liquid crystal displays normally comprise a repeating pattern of coloured patches as in a mosaic pattern or may form a pattern of stripes.
• the coloured patches are preferably separated by a black contour line, which according to the present invention is formed by superposed area of the different emulsion layers wherein on colour-development cyan, magenta and yellow dye is formed respectively.
• the reflections from the glass plate back into the multilayer arrangement are eliminated by the presence of a light-absorbing (anti-halation) layer between the glass substrate and the first photographic silver halide emulsion layer.
• This anti-halation layer must lose its light-absorbing properties during or after processing and become as clear as possible.
• one or more dyes are present in said layer which dyes should be destroyed chemically in one or more processing liquids or simply be soluble in one or more of the processing liquids or in the rinse water and be washed out.
• anti-halation dyes of the non-diffusing type i.e. dyes that are insoluble in water and do not migrate to adjacent layers during manufacture. Such is important when the dyes, due to their spectral or other properties, can change the photographic properties of the adjacent silver halide emulsion layers.
• Filter or anti-halation dyes may be present in one or more layers of the multilayer arrangement to decrease unwanted interlayer reflections and/or to improve the optical characteristics of individual layers. This practice is well known to those skilled in the art.
• the multilayer arrangement of hydrophillic colloid (gelatin containing) layers of the present multicolour print material must stick very firmly to the glass substrate.
• the glass used for the substrate is e.g. borax glass, borosilicate glass, lime glass, potash glass, soda glass, crown glass, flint glass, silica-flint glass, chromium glass, zinc-crown glass or quartz glass.
• the glass support has e.g. a thickness in the range of 0.5 to 1.5 mm.
• subbing layers currently used in colour print film on a resin support cannot be used due to the very different nature of the glass substrates.
• a strong adhesion of the hydrophillic colloid multilayer arrangement to the glass support can be realized by means of a very thin subbing layer containing gelatin, a water-soluble inorganic silicon compound like e.g. sodium silicate (water glass) and a gelatin hardening agent.
• a very thin subbing layer containing gelatin e.g. sodium silicate (water glass) and a gelatin hardening agent.
• an equally strong adhesion can be obtained without a subbing layer by the addition to the first layer, which in a preferred embodiment is a gelatin-containing light-absorbing anti-halation layer, of an organic silicon compound such as an epoxysilane and a hardening agent for gelatin.
• the first layer which in a preferred embodiment is a gelatin-containing light-absorbing anti-halation layer, of an organic silicon compound such as an epoxysilane and a hardening agent for gelatin.
• the pixelwise exposure of the multicolour print material according to the present invention can be performed in several ways.
• the exposure may proceed in a single step through a multicolour master, in a plurality of steps with light of different colour (blue, green and red) through a pitchwise shiftable black-and-white mask or simultaneously or subsequently by means of pixelwise modulated laser beams of different colour, blue, green and red.
• a multicolour master in a plurality of steps with light of different colour (blue, green and red) through a pitchwise shiftable black-and-white mask or simultaneously or subsequently by means of pixelwise modulated laser beams of different colour, blue, green and red.
• a convenient method for manufacturing the colour filters for use according to the present invention, especially in mass-production when a great number of them is needed, is to carry out the exposure in a single step through a multicolour master.
• the master When used in conjunction with a negative type multilayer silver halide colour material the master must be a coloured negative master, whereas a coloured positive master is needed when a direct positive or reversals type multilayer silver halide colour material is involved.
• a coloured negative master has predominantly yellow-, magenta-and cyan coloured pixels at the places corresponding respectively with the blue, green and red pixels on the colour filter array element.
• the coloured master is in close or near contact with the multilayer silver halide colour material from which a colour filter is to be made, the gelatin layers of both materials facing each other.
• said single step exposure simultaneously latent images in the 3 light-sensitive differently spectrally sensitive silver halide emulsion layers are formed.
• Deviation from the desired spectral transmission characteristics of the filter area may be corrected by inserting in the white light beam filters changing the proportion of red, green and blue transmitted by the multicolour master.
• the negative and positive masters may be made by means of other recording materials than silver halide emulsion type materials.
• the multicolour master may be made by photolithography, vacuum-deposition or electrodeposition of dyes, thermal transfer of dyes, electro(photo)graphy with coloured toner or inkjet printing with coloured inks.
• the silver halide colour filter After processing the silver halide colour filter is covered with a protective resin layer which in the production of a multicolour filter associated with an electrode layer has to be present.
• gelatin is a hydrophillic polymer it contains still a small amount of water even after thorough drying. Minor quantities of water may not enter the liquid crystal cell since they profoundly disturb the operation of the liquid crystal display. Moreover, during the application of the electrode layer by vacuum-deposition water or other volatile substance may not escape from the gelatin-containing layers and has to be kept blocked by a protective impermeable resin layer on top of the uppermost colour-developed silver halide emulsion layer of the colour filter. In the manufacture of a liquid crystal display according to the present invention heat-curable resins are used for producing said impermeable layer.
• the water-impermeable hydrophobic organic resin layer may be coated from a liquid composition containing (an) evaporatable solvent(s) or may be applied onto the processed multicolour material by lamination using e.g. a heat-curable layer sandwiched originally between a polyethylene film and a protective cover sheet analogously to the type of material described in J. photogr. Sci., 18 , 150 (1970).
• a transparent conductive layer forming the electrode layer is applied to the impermeable resin layer by known techniques, e.g. a transparent indium tinoxyde (ITO) layer is applied by vacuum-deposition.
• ITO transparent indium tinoxyde
• the multicolour filter array elements prepared according to the present invention are very well suited for the production of active matrix liquid crystal displays there use is not restricted to that type of displays. They can be incorporated likewise in passive matrix liquid crystal displays, especially in supertwisted nematic (STN), double supertwisted nematic (DSTN), retardation film supertwisted nematic (RFSTN), in ferroelectric (FLC), guest host (GH), polymerdispersed (PF), polymer network (PN) liquid crystal displays, and so on. They can further be incorporated in emissive displays like electroluminescent displays, CRT devices and in charge coupled device (CCD) cameras.
• STN supertwisted nematic
• DSTN double supertwisted nematic
• RFSTN retardation film supertwisted nematic
• FLC ferroelectric
• GH guest host
• PF polymerdispersed
• PN polymer network
• emissive displays like electroluminescent displays, CRT devices and in charge coupled device (CCD) cameras.
• a non-diffusing yellow dye of formula YD was dispersed in gelatin.
• epoxysilane E (structure defined hereinafter) acting as an adhesion promoter was added.
• the coverages of yellow dye YD, gelatin and epoxysilane E were 0.5, 1.5 and 0.1 g/m 2 respectively.
• a 100 % silverchloride emulsion with an average grain size of 0.4 ⁇ m was sensitized to blue light with a spectral sensitizing agent of formula SB.
• a yellow dye forming coupler of formula Y1 was added to this emulsion.
• the amounts of silverhalide, gelatine and colour coupler Y1 were 0.57, 3.30 and 1.0 g/m 2 respectively.
• a substance of formula SD capable of scavenging oxidized colour developing agent was dispersed in gelatin and coated at a coverage of 0.08 g SD/m 2 and of 0.77 g gelatine/m 2 .
• a silver chloride-bromide (90/10 molar ratio) emulsion with an average grain size of 0.12 ⁇ m was sensitized to green light with a spectral sensitizing agent of formula SG.
• a magenta dye forming coupler of formula M1 was added to this emulsion.
• the amounts of silver halide, gelatin and colour coupler M1 were 0.71, 2.8 and 0.53 g/m 2 respectively.
• This layer has the same composition as the first intermediate layer.
• a silver chloride-bromide (90/10 molar ratio) emulsion with an average grain size of 0.12 ⁇ m was sensitized to red light with a spectral sensitizing agent of formula SR.
• a cyan dye forming coupler of formula C1 was added to this emulsion.
• the amounts of silver halide, gelatin and colour coupler C1 were 0.49, 4.5 and 0.95 g/m 2 respectively.
• Is equal to INDEV1, with 100 ml of ethanol instead of 50 ml ethanol per litre.
• each sheet was treated in an acid stop bath prepared by adding water up to 1 l to 50 ml of sulphuric acid 7 N.
• the treatment with stop bath was followed by 2 minutes rinsing in plain water followed by a 2 minutes fixing in an aqueous solution having the following composition : 58 % aqueous solution of (NH 4 ) 2 S 2 O 3 100 ml sodium sulphite (anhydrous) 2.5 g sodium-hydrogen sulphite (anhydrous) 10.3 g water up to 1000 ml
• the treatment with fixing liquid was followed by a 2 minutes rinsing in plain water followed by a 3 minutes bleaching in an aqueous solution having the following composition : potassium hexacyanoferrate (III) (anhydrous) 30 g sodium bromide (anhydrous) 17 g water up to 1000 ml Thereupon each sheet was

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  • 1996-01-18 EP EP96200114A patent/EP0726492A1/fr not_active Withdrawn

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