JPH09211813A - Multicolor filter array for lcd and photographing method for production of the same array - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a thermally stable color image on a transparent supporting body having high dimensional stability and optical isotropy by forming an org. resin layer containing a specified cyan color image forming coupler and an oil forming agent on a specified supporting body. SOLUTION: A color photographic printing material containing plural spectral sensitive silver halide emulsion layers is exposed, color developed and coated with a hydrophobic org. resin layer which does not permeate water, and then hardened at 100 to 250 deg.C, and further, a transparent electrode layer and an alignment layer are formed thereon. A 2,5-diacylaminophenol coupler expressed by a formula is used as the cyan dye image forming coupler. In the formula, Z is a hydrogen atom, etc., X is a group having an enough bulk size to prevent diffusion of the color coupler in an alkali permeable layer, R<n> is H, an electron withdrawing atom, etc., (n) is an integer of 1 to 5. After the heat treatment, the photosensitive material has >=50% cyan color dye image density to the density before heating. The supporting body is optically transparent with >=80% transmittance for 570nm wavelength and has dimensional stability with <5% shrinkage after heating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multicolor filter array element.
Photographic materials suitable for use in the manufacture of t), such elements and multicolor liquid crystal display devices containing such elements.

[0002]

Liquid crystal display devices are used today in numerous applications such as watches, home appliances, electronic calculators, audio devices and the like. There is an increasing tendency to replace cathode ray tubes by liquid crystal display devices, which are advantageous for their small volume and low power consumption. There is no competition in applications such as laptop computers and liquid crystal display devices for pocket TVs.

High-definition televisions require screen diagonals in excess of 50 inches in their ultimate form (see P. Plezh).
ko, Periodical Information Display 1991 Sep 9
Mon, Vol. 7 no. 9, p. 19). Although not yet present, CRT-based 50-inch screens are considered extremely impractical due to their weight and size. Liquid crystal technology is basically capable of producing high definition television (HDTV) screens of moderate weight and size.

Liquid crystal display devices typically include two spaced apart glasses that define a sealed cavity that is filled with a liquid crystal material. The glass plate is coated with a transparent electrode layer that is patterned in such a way as to create a mosaic of pixels.

By using a color filter array element in the liquid crystal display device, sufficient color expression is possible.

Passive system (passive (intrinsic) s
ystem) or active system (active (extrinsic) sy
stem) and either of the two addressing systems are used to drive the display.

According to a passive system in a liquid crystal device, two electrode layers are patterned with a regular array of stripes. The stripes on one plate are at right angles to that on the other plate.

Application of a voltage across two opposing stripes causes a change in the optical properties of the liquid crystal material located at the intersection of the two stripes, resulting in light passing through the energized pixel called a pixel. It causes a change in transmittance.

According to the active system, which greatly improves the performance of liquid crystal display devices, each pixel has its own individual microelectronic switch, which such microswitch has individual transparent pixel electrodes (the plane size of which is the pixel size). (Which defines the size of). The microswitches are individually addressable and are 3-terminal or 2-terminal switching elements.

The two or more terminal switches are formed by thin film transistors (TFTs). These transistors are arranged in a matrix pattern on a glass plate, which together with the glass plate carrying a transparent uniform (unpatterned) electrode layer forms a gap filled with liquid crystal material.

In a diode or similar two terminal switch device, the transparent electrode layer must be patterned.

A color filter array element is provided on one of the two glass plates in order to provide the liquid crystal display device with a color display capability. Active matrix displays (examples of which are US-P5081004 and 500)
330)), this is the glass plate that faces the glass plate that normally carries the switch element.

A color filter array for full color representation is composed of red, green and blue patches arranged in a predetermined order. For improved contrast, the color spots may be separated by a black contour line pattern depicting individual color pixels (see eg US Pat. No. 4,987,043).

Color filters are preferably avoided from the electrical circuit in order to prevent loss of effective voltage with respect to the liquid crystal material. It means that the transparent electrode is attached on top of the color filter array element.

Several techniques for making color filter array elements have been described in the prior art.

First, the widely used technique operates according to the principles of photolithography (eg published EP-A0138).
459), based on photocuring of polymers (eg gelatin). Photosensitizer-doped dichromate gelatin is coated on glass, exposed through a mask, developed to harden the gelatin in the exposed areas and washed to remove unexposed gelatin. The remaining gelatin is colored in one of the desired colors. A new gelatin layer is coated on the colored relief image, exposed, developed, washed, tinted with the next color, etc. Due to its wash-off and coloring technique, four complete operating cycles are needed to obtain a red, green and blue color filter array with color spots outlined by black contours. Alternatively, it is used to produce a color photoresist overlaid with a tintable or tinted photopolymer. In repeated exposure, the accuracy of alignment is required to obtain color filter spots matching the pixel electrodes.

In a variation of the photoresist technology, organic dyes or pigments are applied by evaporation under reduced pressure (vacuum deposition) to form color patterns corresponding to the openings in the photoresist (see Proceedings of th).
e SID, Vol. 25/4, pp. 281-285, (198
4)). Or mechanical precision stencil screen,
Used for pattern-wise deposition by evaporating the dye onto a selected support (eg Japan Di
splay 86, p. 320-322).

According to the second technique, a curable binder polymer,
The dye is electrodeposited from the dispersion of the dispersant and the color pigment onto the patterned transparent electrode. Separate deposition and curing steps are required for each color.

According to a third technique, the red, green and blue dyes are applied by thermal transfer from a dye donor material to a dye receiving material comprising a transparent support (eg a glass plate) having thereon a dye receiving layer. . Image-wise heating is preferably performed by laser or high intensity light flash. Separate dye transfer steps must be performed for each color.

According to a fourth technique, for example as described in US Pat. No. 4,271,246, a method for producing a multicolor optical filter comprises the following steps: (1) Support and single, ie one black and white silver halide emulsion layer. A photographic material containing a. Is exposed to light through a first pattern; (2) the exposed emulsion layer is developed with a first coupler-containing color developer to form a first dye pattern; and (3) the emulsion layer. Exposing the unexposed portion of the composition to light through a second pattern; (4) developing the exposed area with a second coupler-containing color developing solution to form a second dye pattern; (5) repeating exposure and development to obtain A pattern containing 3 and optionally subsequent color dyes, thereby forming a color pattern of at least two colors; and after the final color development step. Goods are subjected to the silver removal process.

The above techniques require that they have at least three (four if the black contour pattern requires another step) processing steps, some of which are required to reach the desired level of alignment. All of them are common because they require an extremely expensive exposure apparatus.

A large number of manufacturing steps and the required accuracy create new tasks. That is, the percentage of color filter array elements that are factory manufactured to meet quality control standards is unusually low. Filter manufacturing is simplified,
Moreover, if high quality is maintained, extremely expensive investment can be reduced.

When using multi-layer color photographic silver halide materials for the production of multi-color filters comparable to print films used in the motion picture film industry, avoiding the above-mentioned problems with image registration and multiple processing steps. it can. It is possible to produce an unlimited number of color positives on a film at extremely high speed from a single color negative. Only one exposure is needed for each positive. Multiple exposed positives can be chemically processed simultaneously on the same machine. This makes the whole process extremely attractive from a yield and investment standpoint. A method of operating with a negative color image as an original for forming a complementary color pattern on a glass support in this manner has already been described in JP-A-60-133427.

EP-A396824 describes a smectic C in which liquid crystal molecules are arranged in such a way that the liquid crystal layer exhibits an electrically controllable rotation of the plane of polarization of light incident on the display.
(Chiral smectic) Ferroelectric liquid crystal (ferroelectric
liquid crystals) or twisted or super twisted
The present invention relates to a method for manufacturing a multi-color liquid crystal display device including a liquid crystal layer consisting essentially of a nematic crystal having a supertwisted structure. The liquid crystal layer is arranged between front and rear transparent electrodes for changing the electric field on the liquid crystal layer on a pixel basis together with a multi-color filter element,
The electrodes are respectively coupled with front and rear polarizer elements. The method comprises, in sequential order, the following steps: (1) providing a photographic print material containing a number of different spectrally sensitive silver halide emulsion layers on a glass support; (2) providing the print material in a single step. Subject to exposure on a multicolor pixel basis, (3) color-process the exposed print material, thereby creating a different color pixel pattern in each silver halide emulsion layer.
(4) coating the silver halide emulsion layer assembly side of the color treated print material with a hydrophobic water impermeable organic resin layer, and (5) acting as a coating layer for the silver halide emulsion layer assembly. One of the electrodes is deposited on the organic resin layer by vapor deposition.

Prior to the introduction of the multicolor filter into a liquid crystal device, the top emulsion layer of the photographic print material thus treated is coated with a hydrophobic water impermeable organic resin onto which a coating layer of the resin is applied. To form a transparent conductive (electrode) layer by vapor deposition on top of the resin coating thus applied.

The resin layer on top of the color filter array provides good planarity and prevents emission of volatiles from the emulsion layer during vapor deposition (eg by sputtering) of the transparent conductive layer. Baking at a temperature of 150 ° C. or higher is required to give the resin layer good impermeability by hardening.

The so-called twisted nematic (which is the mainstream of active matrix liquid crystal displays)
In a tic (TN)) type liquid crystal display, the transparent, uniformly applied and patterned electrodes are covered with an alignment layer. This layer is usually composed of a thermosetting polyimide resin. By rubbing the cured layer in a predetermined direction with, for example, nylon cloth (for example, GB-A15).
No. 05192), the liquid crystal molecules near the surface of the layer will be aligned in the rubbing direction.

From the above it is clear that the multi-color filter array element is subjected to a rather severe heat treatment during the manufacture of the liquid crystal display device material. These heating steps must not cause filter discoloration or dye fading.

Most of the dyes formed by the reaction based on the coupling of oxidized color developers of the p-phenylenediamine type with color formers have a fairly limited resistance to high temperatures, yellow or Tends to turn brown (blue turns dark gray).

Thermal degradation of a color filter made by a multilayer color photographic silver halide material containing a color coupler is a phenomenon which occurs in two simultaneous ways, namely the decomposition of one or more of the constituent dyes and the residual normal which is still present in the processing layer. It has been experimentally confirmed by us to be due to the coloring of colorless color couplers. This is also mentioned as a problem in JP-A 63-261361, in which the color filter is 120 ° C.
It is described that it is handled at the above temperatures and, for the purpose of the invention, it imparts excellent heat resistance and excellent surface smoothness to a color dye image produced by a simple method.

The main contribution to the coloring (yellow or brown) of color filters produced by silver halide color photography based on color coupling comes from the pyrazolone type magenta-forming color couplers. It represents almost all of the magenta color couplers used in modern color photographic materials. Further, the color couplers can react with magenta dyes derived from them, thereby causing loss of magenta dyes (PW
Vittum and FC Duennebier, J. Am. Chem. Soc.
, 72, 1536 (1950)). Apart from this special phenomenon, the degradation of dyes is mainly determined by their structure.

EP-A No. 95200306 (19
Stability of the dye formed in the coupling reaction between the color coupler and the color developing material in the oxidized form as described in the application represented by the structural formula below. The structure of the color developing material according to the general formula is strongly improved:

Embedded image In the formula, R ¹ , R ² and R ³ each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, or R ¹ and R ² or R ³ and R ² or R ³ and R ¹
Or R ³ and R ⁷ or R ³ and R ⁵ or (R ¹ or R ²
) And R ⁵ or (R ¹ or R ² ) and R ⁷ represent the atoms necessary to form a ring system with the atoms to which they are attached, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently Represents hydrogen, alkyl, aryl, halogen, nitro, cyano, alkoxy, aryloxy, alkylthio, arylthio, acylamino, sulfonylamino, ureido, alkoxycarboxylamino, carbamoyl, sulfamoyl, sulfonyl, amino, alkoxycarbonyl group, or (R ⁴ and R ⁵ ) or (R ⁶ and R ⁷ ) represent the atoms necessary to form a ring system with the atoms to which they are attached.

Further, in a preferred example, R ¹ and R ² are both a lower alkyl group having ¹ to 6 C atoms, more preferably a C ₁ -C ₃ alkyl group, and in a more preferred example, R ⁴ and R ⁵ And R ⁷ is hydrogen, and R ¹ , R
Each of ² , R ³ and R ⁶ is a methyl or ethyl group.

However, for example, CD-1, CD-
The use of the well-known standard p-phenylenediamine used in 2, 2, CD-3 and CD-4 processing developers is described in EP-A No. It is clear that the color development structure described in 95200306 has inferior results to those obtained with the developers used, but is not excluded.

Nevertheless, although the p-phenylene derivative according to the above general formula (I) is utilized from the three dye types (yellow, magenta and cyan) produced by color coupling with a p-phenylenediamine type developer. , Cyan dye is most easily decomposed under heat binding,
Therefore, it can be expected that the thermal stability of the color filter as a whole is greatly improved by the selection of the cyan dye-forming coupler.

The heat treatment of the color filters contained in LCDs is quite rigorous, and there is still a need for stable dyes, ie p-phenylenediamine derivatives which give stable dyes after color development.

There is further a need for dimensional stability of color filters coated on transparent supports, which is to the substrate and the layer on which the color filters are coated, especially the subbing layer coated thereon. To a large extent depending on the presence of certain (polymeric) compounds. The dimensional stability is required when the color filter is present inside an LCD device when the color filter undergoes a whole manufacturing cycle including a "baking" or "heating" cycle. Therefore, the transparent support should not shrink one-dimensionally or two-dimensionally during the process, that it can withstand treatment with a corrosive agent, and its optical transparency and optical isotropy or near Isotropicity is required to be maintained.

[0038]

It is an object of the present invention to include at least three spectrally distinct silver halide emulsion layers sensitive to blue, green and red light, respectively, whereby they are thermally stable. Provide a method for processing a silver halide color photographic material in which three color images are formed on a transparent support having high dimensional stability (minimum shrinkage), high optical isotropy and transparency. Especially.

Another object of the present invention is to manufacture a multi-color liquid crystal display device (multi-color LCD), which includes a high temperature treatment process in the manufacturing process, and the heat treatment does not substantially affect the color quality of the multi-color filter. It is to provide a method for processing preferred photographic materials for the simplified manufacture of useful multicolor filters.

It is a further object of the present invention to provide a multi-color filter array element tightly coupled with a transparent electrode layer in a multi-color liquid crystal display device (eg multi-color active matrix LCD).

Another object of the present invention is to provide a method for manufacturing a multi-color liquid crystal display device including a multi-color filter array element rigidly bonded to a transparent electrode layer.

Other objects and advantages will be apparent from the examples and detailed description which do not limit the scope of the invention.

It is an object of the present invention: (i) a single step multi-color pixel reference exposure to provide multiple spectra on an optically transparent, isotropic or near isotropic, dimensionally stable support. Exposing a silver halide color photographic print material containing sensitive silver halide emulsion layers, each of which is sensitive to a different region of the visible wavelength spectrum, (ii) color processing the exposed print material , Thereby creating separately colored pixel patterns in each silver halide emulsion layer, (iii) applying the color treated print material on the silver halide emulsion layer side, with a hydrophobic water-impermeable organic resin layer Coating, (iv) curing the organic resin layer by heating at a temperature of 100 to 250 ° C., (v) depositing a transparent electrode layer on the organic resin layer, and (vi) the transparent A method of manufacturing a multi-color filter array element having a transparent electrode layer firmly bonded in a multi-color liquid crystal display device, comprising the steps of coating an alignment layer on top of a polar layer. At least one cyan dye image-forming coupler and at least one oilforme in the dye image-forming coupler dispersion;
r) corresponds to the following general formula (I), wherein the cyan dye image forming coupler represents a 2,5-diacylaminophenol type color coupler,

Embedded image (In the formula, Z is a hydrogen atom or a group not coupled (coup
X is a ballasting group of sufficient size that does not diffuse the color coupler in the alkali permeable layer of the photographic material, and R ⁿ
Is H, an electron-withdrawing atom or group, an aliphatic or aromatic substituent,
Or formula -Q-Rf (Q is -O -, - S- or -SO ₂ -
Rf is a short-chain group containing at least one electron-withdrawing group), and at least one of R ⁿ is bound to a short-chain group carrying at least one electron-withdrawing atom or group. Represents an aliphatic or aromatic substituent or bonding group or electron withdrawing atom or group, and n represents an integer having a value of 1 to 5); before carrying out steps (iv), (v) and (vi) Is coated on the optically transparent, isotropic or nearly isotropic, dimensionally stable support and after heat treatment at 200 ° C. for 1 hour, at least 50% of the initial concentration before heating. Cyan dye image density is measured; after application of the above manufacturing method,
The support remains optically transparent for at least 80% at 570 nm, and the isotropic or nearly isotropic support has dimensional stability such that shrinkage after heating is less than 5%. It is achieved by providing a method of manufacturing a multi-color filter array element.

Further disclosed is a silver halide color photographic print material, said material having a modulus of elasticity of less than 1.3 when measured vertically and horizontally as a support, 20
Optically transparent isotropic or nearly isotropic support having dimensional stability such that the shrinkage after heat treatment at 0 ° C. for 1 hour is less than 5%, and a plurality of spectra thereon Sensitive silver halide emulsion layers, each of which is sensitive to a different region of the visible wavelength spectrum, and a red-sensitive emulsion layer comprising at least one cyan dye image-forming coupler present as an oil former dispersion. The cyan dye image forming coupler corresponding to the above-mentioned general formula (I) is present in the oil forming agent dispersion liquid.

[0045]

DETAILED DESCRIPTION OF THE INVENTION In the context of the present invention, printing material means a silver halide color photographic material comparable to the color printing films used in the motion picture film industry.

The multi-layer arrangement of hydrophilic colloid (gelatin-containing) layers of the present multicolor print material must be very tightly attached to a dimensionally stable support. In a particularly preferred example, for example, borax glass, borosilicate glass, lime glass, potash glass, soda glass, crown glass,
Glass such as flint glass, silica-flint glass, chrome glass, zinc-crown glass or quartz glass is used as a support, the glass support being for example 0.
5 to 1.5 mm range, more preferably 0.5 to 1.2
the glass support has a thickness in the range of mm
P-Application No. 94203517 (December 5, 1994)
As described in Japanese Patent Application), it has a fracture stress (under tensile stress) of 1 × 10 ⁷ Pa or more and an elastic modulus (Young's modulus) of 10 × 10 ¹⁰ Pa or less.

The use of so-called subbing layers used today in color print films on resin supports is determined by the nature of the support. In the case of glass supports, the subbing layer cannot be used due to the very different nature of the glass support. In that case the strong adhesion of the hydrophilic colloid multilayer array to the glass support should be realized by a very thin subbing layer containing gelatin, a water-soluble inorganic silicon compound such as sodium silicate (water glass) and a gelatin hardener. You can Evenly strong adhesion can be obtained without subbing by addition to the first layer,
It is in a preferred example a hardener for gelatin and a gelatin containing light absorbing antihalation layer of an organosilicon compound such as epoxysilane.

34-40 of said layer after being newly coated
The adhesion of said subbing layer to gelatin-containing layers such as gelatin-silver halide emulsion layers is greatly improved when processed at temperatures in the range of ° C and relative humidity in the range of 70-85%. Particularly suitable subbing layers based on organosilicon compounds are US-A3661584 and GB-A128646.
7. A method for avoiding the disadvantages of silane coupling agglomerated gel is JP-A 6-198033.
It is described in.

Particularly suitable liquid crystalline polyester supports for use in the process according to the invention are isotropic transparent thermoplastics such as polyethylene terephthalate, polyethylene naphthalate or polyether sulfone supports and especially US Pat. No. 5,385,704, 5188930. , 51
08666 and 5270160 and EP-A06195.
16 and 0651287.

Particularly suitable isotropic supports which are resistant to dimensional changes at elevated temperatures according to the present invention include linear condensation polymers having a glass transition temperature of 190 ° C. or higher, more preferably 220 ° C. or higher. Such as polycarbonate, polycarboxyester, polyamide, polysulfonamide, polyether, polyimide and their copolymers (US Pat. No. 3,640,89,377).
2405, 3725070 and 3793249 and 54
07791 and EP-A 0583787). In addition, RD10119 and 10148 (197)
2nd September); RD10613 (February 1973); RD
11709 (January 1974); RD11833 (19)
1974); RD12046 and 12012 (197).
April 4); RD13455 (June 1975); RD
17643 (December 1978); and RD30811
9 (December 1989). Recent patents are RD36544, Chapter XV, 531-
532, given with an overview in September 1994.

The term "resistance to dimensional stability" is understood to mean less than 5%, more preferably less than 1.5%, even more preferably less than 1% shrinkage at 200 ° C. for 1 hour in all directions. To be done. “Regular support”
Has a shrinkage of about 5-10%. An example of a polyethylene terephthalate film having a shrinkage width of 2 to 20% is EP.
-A0639792. In order to avoid such high shrinkage, the film is briefly (eg about 10
Seconds), heat set at an extremely high temperature (eg 240 ° C),
Research Disclosure 34458 (December 1992)
Should be subjected to mitigation treatment as described in.

It is understood that the term "isotropic or nearly isotropic" should have a modulus of elasticity measured in the vertical and horizontal directions of about 1.0, especially less than 1.3. To be done. For polyethersulfone, this value is about 1.
0.

According to the invention, an undercoat layer which optionally improves the stress resistance properties in order to improve the dimensional stability of the support is, for example, US Pat. No. 5,232,225, 5019494,
4990434, 4977071, 4965180, 5
204219, 5194347, 4994353, 49
54430, 5061611 and EP-A052969.
7 and 0466124.
Suitable additives for improving the dimensional stability of photographic materials coated thereon are synthetic polymers which are water-soluble or almost insoluble in water, such as alkyl (meth) acrylates, alkoxy (meth) acrylates, glycidyl (meth) s. Polymers of acrylates, (meth) acrylamides, vinyl esters, acrylonitriles, olefins and styrenes, or the above with acrylic acid, methacrylic acid,
It is a dispersion liquid of a copolymer of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, and styrenesulfonic acid.

According to the invention said support is at least 1
It has resistance to dimensional change at a high temperature of 100 ° C. for 000 hours, at 150 ° C. for about 10 hours, and at a high temperature of 180-200 ° C. for about 1-2 hours. In order to obtain an allowance time for the support to hold the resistance to dimensional change, 210 ° C.
Should not exceed the temperature. It is clear that the stability required at such high temperatures for over an hour does not correspond to that required from conventional photography, especially from conventional silver halide color materials.

Thermal stability and dark fading (da
rk-fading) Many attempts to reduce instability have been described, both of which are described in US-A 5,094,938,
5200305, 4818668, 5084375, 4
463086, 4617255, 4609618, 45
32202, 4451558, 4463086, 434
Commonly processed as described in 1864 and EP-A0159913.

The thermal stability of the cyan dye formed by the reaction of the cyan dye image-forming coupler and the p-phenylenediamine type developer in the method according to the present invention depends on the cyan dye image-forming coupler in the cyan forming layer according to the general formula (I). It has been found to be enhanced by use.

According to the invention, cyan-forming dyes corresponding to general formula (I) which represent 2,5-diacylaminophenol type color couplers are particularly preferred.

Embedded image In the formula, Z represents a hydrogen atom or a non-coupling group, X represents a bulky group of a sufficient size that does not diffuse the color coupler in the alkali permeable layer of the photographic material,
R ⁿ is H, an electron-withdrawing atom or group, an aliphatic or aromatic substituent, or a formula —Q—Rf (Q is —O—, —S— or —SO).
_2- , Rf is a short-chain group containing at least one electron-withdrawing group), and at least one of R ⁿ is a short-chain group carrying at least one electron-withdrawing atom or group. Represents an aliphatic or aromatic substituent bonded to, or a bonding group, or an electron-withdrawing atom or group, and n represents an integer having a value of 1 to 5.

A preferred example of a withdrawing atom is a halogen atom, of which F is most preferred. Otherwise the most preferred electron withdrawing group is -CN.

Examples of cyan dye image-forming couplers which are very useful in the process of the present invention are described in US-A 4342825 and EP-A 0269766, both of which are incorporated herein by reference. US-P43428
In No. 25, at least one -Q-Rf group (Q is -O-, -S-, or -SO _{2-) in} the benzene nucleus of the benzamide group.
And Rf is a short-chain fluorine-containing group derived from hexafluoro-propylene or trifluorochloroethylene)) and a cyan-forming phenolic color coupler containing a benzamide group at the 2-position of the phenol is described. EP-A0269766 describes a 2,5-diacylaminophenol type color coupler carrying a 3-chloro-2,2,3-trifluoropropionamide group, said coupler being an oxidized aromatic primary amino development. It is possible to form a cyanindoaniline dye by reaction with the main drug, said 3-chloro-
The 2,2,3-trifluoropropionamide group is characterized as forming part of the acylamino substituent at the 5-position of the phenol.

According to the present invention, a totally unexpected effect is the very great influence of the amount and presence of the oil-forming material used in the oil-forming agent dispersion made from the cyan dye image-forming coupler. A useful example of which is the patent document US
-A5026631, 5008179 and 505740
8.

In particular tricresyl phosphate and phthalates (eg dibutyl phthalate) are oil formers which are preferably used in the preparation of oil former dispersions of dye image-forming couplers (especially cyan dye image-forming couplers according to the invention). I knew it was. Examples of other useful oil formers are US-A 5162197 and 4684606 and JP.
-A 0102257, 01017051 and 010
09454.

Particularly preferred according to the invention are dibutyl phthalate and tricresyl phosphate, more preferably 0.3 to 30% by weight, based on the amount of dye image-forming coupler. The molar amount of oil former and dye is 0.2-5 mmol / m ² . These oil formers are used in the preparation of oil former dispersions in which a suitable cyan imaging coupler is dispersed. This is because the dye image-forming coupler is present in the developer rather than in the color-forming layer of the color filter material, eg EP-A0380223.
The opposite of the presence of the coating component of the oil former as described in. Furthermore, no oil formers are used in EP-A 0615161 and the compound C described therein.
1 represents a cyan dye image-forming coupler in which an electron-withdrawing group is present, but it is stated that after heat treatment at 200 ° C. for a maximum of 90 minutes, an improvement is made when maintaining a high density for red light. It is clearly inferior to the improvements in the present invention in which the presence of the oil forming agent dispersion of the cyan image forming coupler is an essential feature.

Pyrazolotriazole compounds are particularly preferred as magenta dye-forming couplers, for example they are represented by M-1 as a further preferred example.

[Chemical 6]

Another example of the pyrazolotriazole magenta dye-forming coupler is described in US Pat. No. 4,710,453,53.
42748, 4665015, 46955533, 506
6575, 5013636 and the like.

Benzoyl acetanilide compounds are particularly useful as yellow dye image forming couplers. The compounds are described, for example, in US-A 4,777,123. Particularly suitable benzoylacetanilide compounds are those having a purine or theophylline derivative in the coupling position.

In a preferred example, the order in which the different spectrally sensitive silver halide emulsion layers are applied on the glass support is the order described in EP-A 615161 (incorporated herein by reference).

The amount of color coupler required to obtain an optical density of 2.5 or less at the maximum of the spectral absorption of the dye formed can be determined by simple tests.

The amount of silver halide present in each color coupler-containing layer is preferably adjusted so that the color coupler is fully converted to dye during color development in the areas of strongest exposure. This means that the equivalent ratio of silver halide to color coupler in the print material should preferably be at least 10% higher than 1.

A ratio of 1 in equivalents means that 4 or 2 moles of silver halide are added for each mole of color coupler present in the layer, depending on whether the color coupler is 4- or 2-equivalent. Means that.

Conversion of 1 mole of 4-equivalent color coupler to 1 mole of dye contains 4 moles of oxidized color developer, which means that 4 moles of silver halide must be reduced. To do. In the case of 2-equivalent color couplers, only 2 moles of silver halide are needed for complete conversion.

In modern color print films, the amount of color coupler and the silver halide / color coupler ratio serve a completely different purpose, ie they are such that an excess of color coupler speeds up color development and a maximum density of 3 or more. For a preferred continuous tone display to obtain a large deviation from the above ratio.

In order to prevent the diffusion of the oxidized developing agent into the adjacent silver halide emulsion layer, said layer is an intermediate water permeable colloid layer, eg gelatin containing a scavenger for the oxidized developing agent. Separated by the containing layer. Suitable scavengers for that purpose are preferably diffusion resistant hydroquinone derivatives containing one or more aliphatic bulky groups having at least 6 carbon atoms. Such scavengers and their uses are described, for example, in DE-A 3545611.

The silver halide emulsion layer may contain any type of light sensitive silver halide emulsions such as emulsions which form a latent image mainly on the surface of silver halide grains or mainly silver halide. An emulsion that forms an internal latent image can be contained inside the grain. The emulsion can be a negative working emulsion (eg a surface sensitive emulsion or an unfogged internal latent image forming emulsion) or a positive working emulsion (eg an unfogged internal latent image forming type direct positive emulsion), the development of which Is carried out in the presence of a nucleating agent or with uniform exposure. Further, a direct positive emulsion of the type which has been previously fogged can be mentioned. It liberates chlorine, bromine and / or iodine during image-wise exposure and destroys imagewise the development centers created during total prefog. Direct positive emulsions (like negative emulsions) require only one development.

The inverted silver halide emulsion is not prefogged. These processes include two development steps and one fogging step. The first development is carried out with a black and white developer, thereby forming a negative black and white silver image. The remaining silver halide can be developed by physical (by exposure) or chemical fog. A positive color image is obtained upon subsequent color development, bleaching and fixing.

Negative action means that the concentration observed after treatment is proportional to the irradiation dose. By positive working is meant that the silver halide emulsion produces a positive image on exposure and development, ie the density is inversely proportional to the irradiation dose.

The silver halide applied can be of the silver chloride, silver chlorobromide, silver bromide, silver bromoiodide, or silver chlorobromoiodide type.

The silver halide can sensitize the surface. The use of noble metals (eg gold), central chalcogens (eg sulfur, selenium or tellurium), and reduction sensitizers, alone or in combination, is particularly contemplated. Typical chemical sensitizer is
Research Disclosure (RD) December 1989, item
308119, section III and RD 1994 9
Moon, listed in item 36544, section IV.

Silver halide is cyanine, merocyanine,
Complex sensitization with various types of dyes including polymethine dyes including oxonol, hemioxonol, styryl, merostyryl, and streptocyanin can be spectrally sensitized. Yes (R above
esearch Disclosure 308119, section IV and 36544, section V).

Suitable vehicles for the emulsion layer and other layers of the print material are RD 3 from Research Disclosure, supra.
08119, section IX and RD 36544, sectio
n II. RD for whitening agents and antifoggants
308119, section V and VI, and RD 365
44, sections VI and VII, respectively. Hardener for gelatin is RD 308119, sec
It is described in tion X.

As already mentioned above, the color filter for a liquid crystal display usually includes a repeating pattern of color spots such as a mosaic pattern, or may form a stripe pattern. The color spots are preferably separated by black contour lines, which according to the invention are formed by overlapping areas of different emulsion layers in which cyan, magenta and yellow dyes respectively are formed during color development.

According to a preferred embodiment, the reflection from the glass plate into the multilayer array is eliminated by the presence of a light absorbing (antihalation) layer between the glass support and the first photographic silver halide emulsion layer. The antihalation layer must lose its light absorbing properties during or after processing and should be as clear as possible. For this purpose one or more dyes are present in the layer in which the dyes are either chemically decomposed in one or more treatment liquids or dissolved in one or more treatment liquids or rinse water and washed. It is advantageous to use non-diffusion type antihalation dyes, i.e. dyes that do not dissolve in water and do not migrate to the adjacent layers during manufacture. This is important when the dye can change the photographic properties of adjacent silver halide emulsion layers by virtue of its spectrum or other properties.

Non-diffusion type yellow dyes useful in decolorizable antihalation layers for use in multicolor print materials according to the present invention are US-A 4,770,984.
It is described in.

Filters or antihalation dyes can be present in one or more layers of the multilayer arrangement to reduce unwanted interlayer reflections and / or to improve the optical properties of the individual layers. This method is for example US
It is well known to the person skilled in the art as described in -A4770984 or EP-A058200.

The pixel-based exposure of the multicolor print material according to the invention can be carried out in various ways.

For example, the exposure may be in a single step via a multi-color master, in multiple steps with light of different colors (blue, green and red) via a pitch-shiftable black-and-white mask, or simultaneously or sequentially. It may also be done with laser beams modulated on a pixel basis of different colors (blue, green and red).

A convenient method for producing a color filter for use in accordance with the present invention is to perform the exposure in a single step through a multi-color master (especially in mass production where many of them are required). That is.

When used in combination with a negative type multilayer silver halide color material, the master must be a color negative master, while the color positive master is a direct positive or reversal type multilayer silver halide color material when included. Needed.

The color negative master predominantly has yellow, magenta and cyan color pixels at locations corresponding to the blue, green and red pixels respectively on the color filter array element.

In said single step exposure using a white light source, the color master is in close contact with or in contact with the multilayer silver halide color material making up the color filter, the gelatin layers of both materials facing each other. The single step exposure simultaneously forms a latent image in three spectrally sensitive silver halide emulsion layers of different photosensitivity.

Deviations from the desired spectral transmission properties of the filter region can be corrected by inserting filters in the white light which alter the proportion of red, green and blue transmitted by the multicolor master.

The negative and positive masters may be made of recording materials other than silver halide emulsion type materials.

For example, a multicolor master may be made by photolithography, vacuum deposition or electrodeposition of dyes, thermal transfer of dyes, electrophotography with color toners or inkjet printing with color inks.

In most examples of color development of exposed print materials containing color couplers, p-phenylenediamine type developing agents are used. EP-A0459
At 210, derivatives of p-phenylenediamine are described that produce dyes with improved lightfastness. Therefore, such developing materials are advantageously used in the manufacture of color filters which are subsequently subjected to radiation and / or heat treatment.

In a preferred example, the developing solution containing the p-phenylenediamine derivative is EP-ANo. 95200030
6 (filed Feb. 8, 1995; incorporated herein by reference), which forms a multicolor filter array useful in the manufacture of multicolor liquid crystal displays (multicolor LCDs). It is used according to the invention for developing the printing material used for.

After processing, the silver halide color filter is coated with a protective resin layer which must be present in the production of the multicolor filter combined with the electrode layer.

Since gelatin is a hydrophilic polymer, it still contains small amounts of water even after undergoing drying.
Even a small amount of water will greatly hinder the operation of the liquid crystal display, so it is necessary to prevent water from entering the liquid crystal cell. Furthermore, during application of the electrode layer by vacuum evaporation, water or other volatiles must not escape from the gelatin-containing layer, and above the color developed silver halide emulsion layer on top of the color filter. It must continue to be blocked by a protective impermeable resin layer. In the manufacture of the liquid crystal display according to the present invention, a thermosetting resin is used to manufacture the impermeable layer.

Examples of thermosetting organic resins and curing agents therefor are Ernest W. Flick “Handbook of Adhesive Raw
Materials ”−Noyens Publications −Park Ridge
, New Jersey, USA (1982). Polyimide resins that can be thermoset are, for example, US-A4
It is the photocurable polyimide resin disclosed in 689295. Further included are epoxy resins that are heat curable with amines that are thermally released from amine precursors (eg ketimines which produce amines upon reaction with water) (see The.
Chemistry of Organic Film Formers, DH S
olomon, John Wiley & Sons, Inc. (1967), 1
Page 90).

The water-impermeable hydrophobic organic resin layer may be coated from a liquid composition containing an evaporable solvent, or
Laminating using, for example, a thermosetting layer that is originally sandwiched between a polyethylene film and a protective cover sheet, similar to the type of material described in J. Photogr. Sci., 18 , 150 (1970). May be applied over the processed multi-color material.

The wet strength of color treated gelatin containing a silver halide emulsion layer assembly prior to coating with an organic resin layer in step (iii) of the text of the present invention contains the following self-crosslinking reaction products. It can be greatly improved as described in EP-A0396824 published by treatment with an aqueous composition: (i) epihalohydrin or α-dihalohydrin, (i
i) a water-soluble polyimide, and (iii) containing at least two nitrogen atoms separated by at least three carbon atoms and optionally at least one oxygen or sulfur atom, and having at least a hydrogen atom bonded to a different nitrogen atom. A water-soluble polyamine with two. The self-crosslinking reaction product may itself form a water-impermeable hydrophobic organic resin layer that acts as a coating layer or as a subbing layer for another outermost water-impermeable organic resin layer.

The method for producing the above self-crosslinking reaction product is GB-
A1269381 and the product is described to improve the wet strength of paper.

The transparent conductive layer forming the electrode layer is applied to the impermeable resin layer by a known technique. For example, a transparent indium tin oxide (ITO) layer is applied by vacuum evaporation.

Although the multicolor filter elements produced according to the invention are very well suited for the production of active matrix liquid crystal displays, their application is not limited to that type of display. It is a passive matrix liquid crystal display, especially super twisted nematic (STN), double super twisted nematic (DST).
N), retardation film super twisted nematic (R
FSTN), ferroelectricity (FLC), guest host (G
H), polymer dispersion (PF), polymer network (PN) liquid crystal display, etc. can be similarly incorporated. They can also be incorporated into electroluminescent displays, light emitting displays such as CRT devices and charge coupled device (CCD) cameras.

[0103]

EXAMPLES The present invention will be described with reference to the following examples, but the present invention is not limited thereto.

Example 1 The following layers were coated in the order given on a polyester support having a thickness of 85 μm to form a color photographic material.

The polyester support has 13 per liter.
It was a colorless machine-direction and cross-direction stretched polyethylene terephthalate film support with one side subbed with a coating amount of 0 m ² . Then film 22 for about 10 seconds
Heat setting was performed while continuing to pull at a temperature of 0 ° C.

The elastic modulus measured in the vertical and horizontal directions was 1.2. After heat setting, the film was cooled.

As a result, the shrinkage after the treatment at 200 ° C. for 1 hour was adjusted to 0.
6% and 1.2% in the width direction.

The polyethylene terephthalate film was subbed to give the following layers per m ² -a latex copolymer of vinylidene chloride (88% by weight), methyl acrylate (10% by weight) and itaconic acid (2% by weight). 170 g, -methyl methacrylate (47.5% by weight), 1,3-
0.06 g of a latex copolymer of butadiene (47.5% by weight) and itaconic acid (2% by weight), 0.001 g of polymethylmethacrylate particles having a mean particle size of 3.5 μm as matting agent.

In another experiment in which polyethylene naphthalate was used, the subbing was carried out as described in EP-A 0583787.

Antihalation Layer YD non-diffusive yellow dye was dispersed in gelatin.
The coating amounts of the yellow dye YD and gelatin are each 0.
5 and 1.5 g / m ² .

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Blue Sensitive Layer A 100% silver chloride emulsion having an average grain size of 0.4 μm was sensitized to blue light with a spectral sensitizer of formula SB. A yellow dye-forming coupler of formula Y1 was added to this emulsion. Silver halide, gelatin and color coupler Y1
Of 0.57, 3.30 and 1.0 g / m ² respectively.
Met.

[0112]

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First Intermediate Layer A material of formula SD capable of scavenging oxidized color developing agent was dispersed in gelatin and coated at a coverage of 0.08 g SD / m ² and 0.77 g gelatin / m ² . .

[0114]

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Green Sensitive Layer A silver chlorobromide (90/10 molar ratio) silver emulsion having an average grain size of 0.12 μm was sensitized to green light with a spectral sensitizer of formula SG. A magenta dye forming coupler of formula M1 was added to this emulsion. The amounts of silver halide, gelatin and color coupler M1 were 0.71, 2.8 and 0.53 g / m ² , respectively.

[0116]

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Second Intermediate Layer This layer has the same composition as the first intermediate layer.

Red Sensitive Layer Silver chlorobromide (90/10 molar ratio) silver emulsion having an average grain size of 0.12 μm was sensitized to red light with a spectral sensitizer of formula SR. A cyan dye-forming coupler of formula C-1 for material MATL1 was added to this emulsion. Material MAT
Formula C-used as a comparative cyan dye-forming coupler for L2, MATLAB3, MATLAB4 and MATLAB5
2, C-3, C-4 and C-5 compounds were added. The amounts of silver halide, gelatin and color coupler were 0.49, 4.5 and 0.95 g / m ² , respectively.

[0119]

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In these formulas, C-1 to C-3 and C-5
Is a 2-equivalent coupler, while C-4 is a 4-equivalent coupler.

Yellow, magenta and cyan water-soluble dyes which act as acutance dyes are present in the blue, green and red sensitive layers, respectively, in suitable coverages,
Hydroxytrichlorotriazine, which acts as a curing agent, was present in the red sensitive layer at a coverage of 0.035 g / m ² .

The equivalent ratio of silver halide to color coupler was about 1.2 for the three light sensitive layers of the material. Coverage of blue, green and red couplers (mmol / m
² ) were 1.4, 0.9 and 1.1, respectively.

Exposure 1. By color processing as described below.
Sufficient white light exposure was applied to the 3 sheet material to produce a black density of 50.

The developing material was treated with 4-amino-3-methyl-N as a developing compound.
It was developed with a developing solution containing -ethyl-N-isopropylaniline hydrochloride. The composition of the developer is as follows.

Sodium sulfite (anhydrous) 4 g 4-Amino-3-methyl-N-ethyl-N-isopropylaniline hydrochloride 3 g Sodium carbonate (anhydrous) 17 g Sodium bromide 1.7 g Sulfuric acid 7N 0.62 ml Ethanol 50 ml Water To 1000 ml.

After development, each sheet material was treated with an acid stop bath prepared by adding up to 1 liter of water in 50 ml of 7N sulfuric acid.

After treatment in the stop bath, rinse with fresh water for 2 minutes and then fix with an aqueous solution having the following composition for 2 minutes: (NH ₄ ) ₂ S ₂ O ₃ 58% aqueous solution 100 ml sodium sulfite (anhydrous) 2 0.5 g sodium bisulfite (anhydrous) 10.3 g Make up to 1000 ml with water.

After treatment with the fixer solution, it was rinsed with fresh water for 2 minutes and then bleached with an aqueous solution having the following composition for 3 minutes: Hexacyanoferrate (III) potassium (anhydrous) 30 g Sodium bromide (anhydrous) 17 g water To 1000 ml.

Each sheet was then treated again with the fixer and rinsed with fresh water for 3 minutes.

Finally, each sheet was treated with an aqueous solution containing 20 ml of 40% aqueous formaldehyde solution acting as a curing agent per liter and having a pH of 9.

The sheet was subjected to a heat treatment at 200 ° C. for 60 minutes. The different concentrations (maximum concentration, concentration D = 1.0 and concentration D) remaining after the heat treatment expressed as a percentage of the starting concentration.
= 0.5) for cyan density is given in Table 1 below.
The originally confirmed total concentrations are also given in the same table 1.

[0132]

[Table 1]

Cyan dye-forming couplers according to general formula I having electron withdrawing atoms such as F at C-1 and Cl at C-5 or -CN at C-4 and C-5 in the structure. It can be seen from the above that the thermal stability of the cyan color generated during color development is significantly better than that of the cyan color having no electron-attracting atoms or groups at all densities. This is consistent with the situation as described in EP-A0615161, except for the special features of the support according to the invention. In this example, the advantages provided by the present invention are not fully explained because the cyan dye image-forming coupler is dispersed in the absence of an oil former (as a result we refer to Table 1 as "Invention"). Described).

Example 2 A material having the same composition was coated as in Example 1 except for the cyan dye forming coupler used in the red sensitive layer. Compound C-1 was added to this emulsion for material MATL6, but the cyan dye-forming coupler was dispersed with dibutyl phthalate (DBP) as the oil former in an amount of 10% by weight. Materials MATL7, MATL8 and MA
Cyan dye forming couplers of formulas C-6, C-7 and C-8 for TL9 were added. Each of the cyan dye-forming coupler dispersions contains dibutyl phthalate as an oil former in an amount of 10% by weight. The cyan dye image forming couplers C-6, C-7 and C-8 all have F atoms in their chemical structure as described below, which are suitable for thermal stability according to the results shown in Table 1. The matl 10 shown as a comparative example is different from matl 6 in which no oil former is used in the dispersion of compound C-1.

[0135]

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[Chemical 21]

C-6, C-7 and C-8 have F as an electron-withdrawing atom. C-6 is 4 equivalents, C-7 and C-8 are 2 equivalent couplers.

The sheet coated on the same support as in Example 1 was subjected to heat treatment at 200 ° C. for 60 minutes in the same manner as in Example 1. The cyan densities for the different densities (maximum density, density D = 1.0 and density D = 0.5) remaining after the heat treatment, expressed as a percentage of the starting density, are given below together with the total cyan density originally measured after the treatment. It is given in Table 2.

[0138]

[Table 2]

The thermal stability of the cyan color generated during color development from a cyan image dye-forming coupler according to general formula I having electron withdrawing atoms in its structure is good but different from the properties of the cyan dye-forming coupler. Confirmed in 2. Furthermore, it can be seen that the presence of an oil former in the coupler dispersion is more favorable for thermal stability.

Example 3 Therefore, in Example 3 the cyan dye-forming coupler C-1 was used.
The effect of the properties of the oil formers on the thermal stability of was investigated.
The following oil formers were used in the preparation of the dispersions of C-1: Oil former 0-12 dibutyl phthalate (coated as described in Example 1, coated on MATL11 C-
1 dispersion); oil former 0-12 (MATL12); oil former 0-13 tricresyl phosphate (MATL1)
3); 0-14 (MATL14); and 0-15 (MA
TL15). The formulas of the oil formers 0-12 to 0-15 are given below. MATLAB 10 was used as a comparative example (no oil former present).

[0141]

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The sheet was heated to 200 ° C. as described in Example 1.
It was subjected to a heat treatment for 60 minutes. The cyan image densities for the different densities (maximum density, density D = 1.0 and density D = 0.5) expressed after the heat treatment, expressed as a percentage of the starting density, were originally calculated after treatment as described in Example 1. The total cyan densities measured are given in Table 3 below.

[0143]

[Table 3]

As can be seen from Table 3, the nature of the oil former used in the dispersion of the cyan dye image forming compound is to determine its thermal stability. From this table it can be deduced that for all concentrations all oil formers produce a substantial improvement. However, tricresyl phosphate and dibutyl phthalate are preferred to achieve the objects of this invention.

Example 4 In Example 4, the effect of developer properties on the thermal stability of the cyan dye image forming coupler C-1 was investigated. Therefore, in the developing solution containing 4-amino-3-methyl-N, N-diethylaniline hydrochloride as a developing compound, 4-amino-3-methyl-N-ethyl-N-isopropylaniline hydrochloride was used instead of 4-amino-3-methyl-N-isopropylaniline hydrochloride. The same material as 3 was developed. The composition of the developer is as follows.

Sodium sulfite (anhydrous) 4 g 4-Amino-3-methyl-N, N-diethyl aniline hydrochloride (CD-2) 3 g Sodium carbonate (anhydrous) 17 g Sodium bromide 1.7 g Sulfuric acid 7N 0.62 ml Ethanol 50 ml Make up to 1000 ml with water.

After development, the sheet material was further processed as in Example 1.

The sheet was placed at 200 ° C. 6 as in Example 1.
It was subjected to a heat treatment for 0 minutes. The cyan dye image densities for the different densities (maximum density, density D = 1.0 and density D = 0.5) expressed after the heat treatment, expressed as a percentage of the initial measured density, were determined as described above in the presence of developing agent. Is given in Table 4 below, along with the total cyan density originally measured after the process characterized by Dmax and% densities remaining after development with the developer used for Example 3 were added to further facilitate the comparison.

[0149]

[Table 4]

As can be seen from Table 4, the nature of the developing agent determines the thermal stability. The known CD-2 developed p-phenylenediamine derivatives work well according to the invention, but E
PA No. The developing agents corresponding to the invention described in 95200306 (filed Feb. 8, 1995) work even better. The differences measured between the materials are exactly the same as those given in Example 3. Therefore, the same conclusion can be drawn.

The light stability was tested apart from the thermal stability of the cyan dye image forming coupler. Therefore CD-2 (Table 5
In "CD2" and a developer called "LCD2" (EP-A No. 95200306).
(MATCH 11-MATL 15 (invention)) developed (inventor described in the application filed Feb. 8, 1995).
And MATT10 (comparative example) "sun test (suntest
) "Has been applied. MAT L12 and MAT L15 were not present here as they failed experimentally.

The so-called solar test is based on the L393-filtered low pressure xenon lamp NXe150.
The material developed with 0 (manufactured by HERAEUS) light is exposed for 100 hours. The light source realized by the xenon lamp was 110 kLux. Total irradiance is 414.5
It was W / m < ² > (when there is no filter in the wavelength range of 300-830 nm).

Different densities (maximum density Dmax, density D =
The cyan density remaining after the irradiation treatment of the developed material, expressed as a percentage of the starting density, for 1.0 and a density D = 0.5) is given in Table 5 below.

[0154]

[Table 5]

As can be seen from Table 5, the color developing agents used for color processing have a strong influence on the photostability of the processed materials. That is, LCD2 is much better than CD2.

The CD-2 developed p-phenylenediamine derivatives work well according to the invention, but under the influence of oil formers as dispersants for cyan dye image-forming couplers EP-Application No. The developing agent corresponding to the invention described in 95200306 (filed Feb. 8, 1995) works well again. The effect on thermal stability is described in E above.
There was a compelling explanation in the P application.

The difference in the original cyan density percentage after development, measured between different materials and retained after the "sun test", is related to the thermal stability and the differences given in Tables 3 and 4. Is exactly the same. Therefore, the same conclusions can be drawn for photostability and thermal stability.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Luk Van Mael in Septerrato, Belgium Mortzeer 27 In Agfa Gewert Namrose Bennachtchap (72) Inventor Erman Van Gort, Septrat 27 Belgium Agfa Gewert Namrose Rose Bennault Chap

Claims (10)

[Claims] 1. (i) A plurality of spectrally sensitive silver halides on an optically transparent, isotropic or nearly isotropic, dimensionally stable support by single step multi-color pixel reference exposure. Exposing a silver halide color photographic print material containing emulsion layers, each of which is sensitive to different regions of the visible wavelength spectrum, (ii)
Color-processing the exposed print material, thereby creating a separately colored pixel pattern in each silver halide emulsion layer, (iii) the color-processed print material on the silver halide emulsion layer side, Coating with a hydrophobic water-impermeable organic resin layer, (iv) 100-
Cured by heating at a temperature of 250 ° C.,
(V) depositing a transparent electrode layer on the organic resin layer, and (vi) covering the upper portion of the transparent electrode layer with an alignment layer, firmly bonding the transparent electrode layer in a multi-color liquid crystal display device. A method of manufacturing a multi-color filter array element according to claim 1, wherein in the printing material, at least one cyan dye image forming coupler and at least one oil forming agent in the cyan dye image forming coupler dispersion are two cyan dye image forming couplers. , 5
-Corresponding to the following general formula (I), which represents a diacylaminophenol type color coupler, (In the formula, Z represents a hydrogen atom or a non-coupling group, X represents a bulky group of a sufficient size that does not diffuse the color coupler in the alkali permeable layer of the photographic material, R ⁿ represents H, an electron withdrawing atom. Or a group, an aliphatic or aromatic substituent, or the formula -Q-Rf (Q is -O-, -S- or -SO).
_2- , Rf is a short-chain group containing at least one electron-withdrawing group), and at least one of R ⁿ is a short-chain group carrying at least one electron-withdrawing atom or group. Represents an aliphatic or aromatic substituent or a bonding group or an electron-withdrawing atom or group bonded to n, and n represents an integer having a value of 1 to 5); steps (iv), (v) and (vi) Before being performed, the optically transparent and isotropic or nearly isotropic,
Coated on a dimensionally stable support, after heat treatment at 200 ° C. for 1 hour, at least 50 relative to the initial concentration before heating.
% Cyan dye image density is measured; after application of the process described above the support remains optically transparent for at least 80% at 570 nm and the isotropic or nearly isotropic support contracts after heating. Has a dimensional stability such that is less than 5%. 2. The method of claim 1 wherein the oil former is dibutyl phthalate, tricresyl phosphate or mixtures thereof. 3. The method according to claim 1, wherein after the heat treatment at 200 ° C. for 1 hour, a cyan dye image density of 70% or more based on the initial density before heating is measured. 4. The support is at least 90% at 570 nm.
The method according to any one of claims 1 to 3, wherein the optical transparency is maintained. 5. The shrinkage is less than 1.5%.
4. The method according to any one of 4 to 4. 6. The method according to claim 1, wherein the isotropic or nearly isotropic support has a modulus of elasticity of less than 1.3 when measured in the vertical and horizontal directions. 7. The method according to claim 1, wherein the support is a glass support or the support is a linear condensation polymer having a glass transition temperature of 190 ° C. or higher. 8. The method according to claim 7, wherein the support comprising the linear condensation polymer is a polyethylene terephthalate, polyethylene naphthalate or polyether sulfone support. 9. An optical material having a modulus of elasticity of less than 1.3 as measured as a support in vertical and horizontal directions and having a dimensional stability such that the shrinkage after heat treatment at 200 ° C. for 1 hour is less than 5%. A transparent, isotropic or nearly isotropic support and thereon a plurality of spectrally sensitive silver halide emulsion layers, each of which is sensitive to a different region of the visible wavelength spectrum, The red-sensitive emulsion layer comprises at least one cyan dye image-forming coupler present as an oil former dispersion, said cyan dye image-forming coupler representing a 2,5-diacylaminophenol type color coupler. Which corresponds to (In the formula, Z represents a hydrogen atom or a non-coupling group, X represents a bulky group of a sufficient size that does not diffuse the color coupler in the alkali permeable layer of the photographic material, R ⁿ represents H, an electron withdrawing atom. Or a group, an aliphatic or aromatic substituent, or the formula -Q-Rf (Q is -O-, -S- or -SO).
_2- , Rf is a short-chain group containing at least one electron-withdrawing group), and at least one of R ⁿ is a short-chain group carrying at least one electron-withdrawing atom or group. Represents an aliphatic or aromatic substituent or a bonding group or an electron-withdrawing atom or a group bonded to n, and n represents an integer having a value of 1 to 5), and the cyan dye image-forming coupler is used as an oil former dispersion. Present, silver halide color photographic print materials. 10. The material according to claim 9, wherein the support is a glass support or the support is composed of a linear condensation polymer having a glass transition temperature of 190 ° C. or higher.