EP0802453A1 - Farbphotographisches Silberhalogenidmaterial mit einer spezifischen Zwischenschicht - Google Patents
Farbphotographisches Silberhalogenidmaterial mit einer spezifischen Zwischenschicht Download PDFInfo
- Publication number
- EP0802453A1 EP0802453A1 EP96201046A EP96201046A EP0802453A1 EP 0802453 A1 EP0802453 A1 EP 0802453A1 EP 96201046 A EP96201046 A EP 96201046A EP 96201046 A EP96201046 A EP 96201046A EP 0802453 A1 EP0802453 A1 EP 0802453A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- colour
- group
- silver halide
- cyan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 57
- -1 silver halide Chemical class 0.000 title claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 55
- 239000004332 silver Substances 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 239000000839 emulsion Substances 0.000 claims abstract description 63
- 230000008878 coupling Effects 0.000 claims abstract description 36
- 238000010168 coupling process Methods 0.000 claims abstract description 36
- 238000005859 coupling reaction Methods 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000002516 radical scavenger Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 9
- 125000003226 pyrazolyl group Chemical group 0.000 claims abstract description 7
- 238000009792 diffusion process Methods 0.000 claims abstract description 6
- 150000005204 hydroxybenzenes Chemical class 0.000 claims abstract description 6
- 229920000159 gelatin Polymers 0.000 claims description 37
- 235000019322 gelatine Nutrition 0.000 claims description 37
- 108010010803 Gelatin Proteins 0.000 claims description 30
- 239000008273 gelatin Substances 0.000 claims description 30
- 235000011852 gelatine desserts Nutrition 0.000 claims description 30
- 238000011161 development Methods 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000004973 liquid crystal related substance Substances 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 195
- 239000000203 mixture Substances 0.000 description 22
- 230000006866 deterioration Effects 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001828 Gelatine Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000005331 crown glasses (windows) Substances 0.000 description 2
- 239000005308 flint glass Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- XBYRMPXUBGMOJC-UHFFFAOYSA-N 1,2-dihydropyrazol-3-one Chemical compound OC=1C=CNN=1 XBYRMPXUBGMOJC-UHFFFAOYSA-N 0.000 description 1
- JWXVMAPCVCDLEW-UHFFFAOYSA-N 4,5,6-trichloro-1-hydroxy-2h-triazine Chemical compound ON1NN=C(Cl)C(Cl)=C1Cl JWXVMAPCVCDLEW-UHFFFAOYSA-N 0.000 description 1
- WNRVXVWPXKDOEB-UHFFFAOYSA-N 4-methylpyrazol-3-one Chemical compound CC1=CN=NC1=O WNRVXVWPXKDOEB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- MPLZNPZPPXERDA-UHFFFAOYSA-N [4-(diethylamino)-2-methylphenyl]azanium;chloride Chemical compound [Cl-].CC[NH+](CC)C1=CC=C(N)C(C)=C1 MPLZNPZPPXERDA-UHFFFAOYSA-N 0.000 description 1
- IEIREBQISNYNTN-UHFFFAOYSA-K [Ag](I)(Br)Cl Chemical compound [Ag](I)(Br)Cl IEIREBQISNYNTN-UHFFFAOYSA-K 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OIPQUBBCOVJSNS-UHFFFAOYSA-L bromo(iodo)silver Chemical compound Br[Ag]I OIPQUBBCOVJSNS-UHFFFAOYSA-L 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
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
- G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
-
- 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
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
- G03C2007/3024—Ratio silver to coupler
-
- 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
- G03C2200/00—Details
- G03C2200/27—Gelatine content
-
- 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
- G03C2200/00—Details
- G03C2200/35—Intermediate layer
-
- 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
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
-
- 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
- G03C7/32—Colour coupling substances
Definitions
- This invention relates to a silver halide colour photographic material.
- this invention relates to such a material suitable for use in the production of a multicolour filter array element that can be used in LCD's (Liquid Crystal Displays).
- a method for producing such a filter array element is also disclosed.
- JP-A 62-063901 it is disclosed that a multicolour mask (a colour filter) for LCD's, being water resistant and with light stable colours could be formed in a silver halide colour material comprising additional layers comprising UV absorbers and comprising a water repellent protective layer.
- 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 silver halide emulsion layers that are exemplified comprise gelatin and colour coupler in a weight ratio between 0.90 and 2.15, depending on the disclosure and the type of colour coupler present.
- EP-A 615 161 it is disclosed that the heat stability of a processed print material, as exemplified in EP-A 396 824, was not sufficient. It was shown that the heat stability of, especially, the cyan colour could largely be increased by coating the cyan forming layer (the red sensitive layer) most remote from the support. It was also shown in EP-A 615 161 that the heat stability could still further be increased when not only the cyan forming (red sensitive) layer was coated most remote from the support, but when the gelatin to coupler ratio of all three the layers was largely increased. Exemplified values of said ratio range from 3.30 to 5.28, depending on the type of colour coupler.
- Colour deterioration means that the colour separation between the layers carrying a yellow, magenta and cyan image respectively is bad.
- the exposure to light was such that only in the magenta forming layer an image should been formed, some development can also take place in the cyan and yellow forming layer, in such a way that the magenta image tends to become dull.
- a scavenger for oxidized developer is present.
- a material comprising such an intermediate layer has been described in, e.g., EP-A 396 824 and European Application 95200306.9 filed on february 8, 1995.
- JP-A 03/039902 it is disclosed to introduce a colourless coupling compound, being a pyrazolinone, in at least one emulsion layer in order to diminish colour deterioration.
- JP-A 04/004291 it is disclosed to introduce a colourless coupling compound, being a pyrazoloazole precursor compound, in at least one emulsion layer in order to diminish colour deterioration.
- the colour deterioration is indeed lowered; but when the gelatin/coupler ratio becomes low (lower than e.g. 5, often lower than 3), the colour deterioration is not brought to the level of materials wherein the gelatin to coupler ratio is larger than 5.
- the objects of the present invention are realized by providing a silver halide photographic material comprising
- said colourless coupling compound is of the group of methylpyrazolone couplers and said scavenger corresponds to the following general formula SD : wherein X is either an OH group or a leaving group, e.g. Cl and wherein R 1 and R 2 may be the same or different, and represent an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic group, an substituted or unsubstituted amino group or an amidegroup.
- X is either an OH group or a leaving group, e.g. Cl
- R 1 and R 2 may be the same or different, and represent an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted heterocyclic group, an substituted or unsubstituted amino group or an amidegroup.
- R 1 and R 2 are the same and each individually represents an alkyl group having between 6 and 20 carbon atoms.
- said cyan layer is farthest from said support, said yellow layer is closest to said support, said magenta layer is in between said yellow and cyan layer and said at least one intermediate layer is present between said cyan layer and said magenta layer.
- the weight ratio of gelatine to colour coupler (GEL/COUP) in the various layers of a colour photographic material could be decreased to a factor of 5 and lower, even to a factor 3 or lower, when between at least the colour forming silver halide layers with low gelatin/coupler ratio, an intermediate layer was present and said intermediate layer comprised a combination of a scavenger for oxidized colour developer and a coupling compound giving no colour, i.e. a colourless coupling compound.
- the lower gelatin/coupler ratio did in that case not deteriorate the correct colour rendering nor did it enhance the colour deterioration.
- scavenger compounds are, e.g., SD1, SD2 and SD3.
- the colourless coupling compound is preferably a coupling compound comprising a pyrazole ring with general formula WK1 : wherein R 3 and R 4 are equal or different and each individually represents an alkyl group, an aryl group or hydrogen, and Z represents the non-metallic atoms required to form a 5 or 6 membered ring structure.
- the colourless coupling compound is a pyrazolone coupling compound with general formula WK2 : wherein R 5 represents hydrogen, an alkyl group or an aryl group, R 6 represents a C1 to C5 alkylgroup or an aryl group and R 7 represents hydrogen, an alkyl group, an aryl group, an heterocyclic group, a substituted or unsubstituted amino group, an amino group and an ether group.
- R 6 is a methyl group.
- the colourless coupling pyrazolone compound can be in a polymeric latex form, wherein, in the polymer forming said polymeric latex, pyrazolone comprising moieties are present.
- very useful examples of colourless coupling compounds for use in the present invention are described in e.g. US 3,912,513.
- a typical example of a very useful colourless coupling compound for use in a silver halide material according to this invention is This is an example of a polymeric colourless coupling compound comprising moieties with pyrazolone groups and moieties of an acrylic acid ester.
- said intermediate layer comprising both a colourless coupling compound, comprising pyrazole ring, and a diffusion-resistant hydroxybenzene derivative is present between the cyan layer and the magenta layer and the cyan layer comprises gelatin and colour coupling compound in a weight ratio equal to or smaller than 3.
- An important advantage of the higher degree of freedom created by the use of an intermediate layer according to the present invention is that it brings the opportunity to use in the magenta layer 2-equivalent coupling compounds, instead of 4-equivalent coupling compounds.
- Most of the 2-equivalent magenta coupling compounds are slow reacting and give rather low maximum density. It was found that in a material comprising an intermediate layer according to the present invention, a very acceptable maximum density could be achieved by using a 2-equivalent coupling compound instead of a 4-equivalent one, while the thermal stability of the magenta colour formed remained the same, but the light stability was greatly enhanced.
- Preferred 2-equivalent magenta coupling compounds are :
- 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.
- the photographic material according to the present invention can comprise any support known in the art, e.g. transparent or dyed plastic (polymeric) films.
- the plastic films may be, e.g. cellulosic esters, polyesters as e.g. polyethyleneterephthalate, polyethylenenaphthalate etc.
- opaque supports may be used, e.g. paper, polyethylene coated paper, opacified polymeric films, etc.
- the glass used as support 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 0.3 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.
- an organic silicon compound such as an epoxysilane and a hardening agent for gelatin.
- subbing layers on the basis of organic silicon compounds are described in US-P 3,661,584 and GB-P 1,286,467.
- the reflections of light from the support 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. Therefore 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. 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 silver halide photographic material according to the present invention is especially well suited for use in the production of colour filters for liquid crystal displays. Therefore this invention comprises also 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 :
- 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 reversal 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 silver halide colour filter After processing the silver halide colour filter is covered with a protective resin, impermeable, layer which in the production of a multicolour filter associated with an electrode layer has to be present.
- a protective resin, impermeable, layer which in the production of a multicolour filter associated with an electrode layer has to be present.
- 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 % silver chloride 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 silver halide, gelatine and colour coupler Y1 were 0.57, 3.30 and 1.0 g/m 2 respectively.
- a substance of formula SD1 capable of scavenging oxidized colour developing agent was dispersed in gelatin and coated at a coverage of 0.08 g SD1/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.
- the comparative example was repeated, except for the gelatin/coupler ratio in the blue, green en red sensitive layers and for the composition of the second intermediate layer.
- the blue sensitive layer 1.15 g/m 2 of gelatine and 1.0 g/m 2 of coupler were present, in the green sensitive layer these amounts were 1.4 and 0.53 g/m 2 respectively and in the red sensitive layer these amounts were 3 and 0.95 g/m 2 respectively.
- the second intermediate layers comprised NO compound SD1.
- Example 1 was repeated, except for the composition of the second intermediate layer. Instead of NO compound SD1, 0.04 g compound SD1 per m 2 were present.
- Example 2 was repeated, except for the composition of the second intermediate layer. Instead of 0.04 g of compound SD1 per m 2 , 0.08 g were present.
- Example 3 was repeated, except for the composition of the second intermediate layer. Instead of 0.08 g of compound SD1 per m 2 , 0.16 g were present.
- Example 3 was repeated, except for the composition of the second intermediate layer. Instead of 0.08 g of compound SD1 per m 2 , no compound SD1 was present, but 0.174 g/m 2 of compound WK3 was present.
- Example 5 was repeated, except for the composition of the second intermediate layer. Instead of 0.174 g/m 2 of compound WK3, 0.347 g/m 2 of compound WK3 was present.
- Example 5 was repeated, except for the composition of the second intermediate layer. Instead of 0.174 g/m 2 of compound WK3, 0.521 g/m 2 of compound WK3 was present.
- Example 3 was repeated, except for the composition of the second intermediate layer. Instead of 0.08 g of compound SD1 per m 2 , 0.04 g/m 2 of compound SD1 and 0.174 g/m 2 of compound WK3 were present.
- Example 8 was repeated, except for the composition of the first and the second intermediate layer. Instead 0.174 g/m 2 of compound WK3, 0.347 g of compound WK3 were present.
- Example 8 was repeated, except for the composition of the first and the second intermediate layer. Instead of 0.04 g/m 2 of compound SD1 and 0.174 g/m 2 of compound WK3, 0.08 g/m 2 of compound SD1 and 0.174 g/m 2 of compound WK3 were present.
- Example 8 was repeated, except for the composition of the first and the second intermediate layer. Instead of 0.04 g/m 2 of compound SD1 and 0.174 g/m 2 of compound WK3, 0.16 g/m 2 of compound SD1 and 0.174 g/m 2 of compound WK3 were present.
- Table 1 the composition of the second intermediate layer of the various examples, regarding the amounts of SD1 and WK3, is summarized.
- Comparative example 1 was repeated except for the magenta coupler in the green sensitive layer, which now was 2-equivalent coupler M21 and for the cyan coupler which was coupler C2.
- Comparative example 2 was repeated, except for the gelatin/coupler ratio in the blue, green en red sensitive layers and for the composition of the second intermediate layer.
- the blue sensitive layer 1.15 g/m 2 of gelatine and 1.0 g/m 2 of coupler were present, in the green sensitive layer these amounts were 1.4 and 0.53 g/m 2 respectively and in the red sensitive layer these amounts were 3 and 0.95 g/m 2 respectively.
- the second intermediate layer 0.04 g/m 2 of compound SD1 was present.
- Example 12 was repeated, except for the composition of the second intermediate layer. Instead of 0.04 g of compound SD1 per m 2 , 0.08 g were present.
- Example 12 was repeated, except for the composition of the second intermediate layer. In that layer 0.04 g of compound SD1 per m 2 and 0.174 g/m 2 of compound WK3 were present.
- Example 14 was repeated, except for the composition of the second intermediate layer. Instead of 0.04 g/m 2 of compound SD1, 0.08 g/m 2 were present.
- table 2 the composition of the second intermediate layer of the various examples, regarding the amounts of SD1 and WK3, is summarized. TABLE 2 Ex # Amounts SD1 and WK3 in the second intermediate layer SD1 in g/m 2 WK3 in g/m 2 CE2 0.080 0 E12 0.040 0 E13 0.080 0 E14 0.040 0.174 E15 0.080 0.174
- 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
- each sheet was treated with the fixing liquid again and rinsed for 3 minutes with plain water.
- each sheet was treated with an aqueous solution having a pH of 9 and containing per litre 20 ml of a 40 % aqueous solution of formaldehyde serving as harden
- the density of the yellow, magenta and cyan images were measured behind a blue, green and red filter.
- the densities measured in the yellow layer after green and red filter are a measure of the colour deterioration in the yellow image, the density measured behind the blue filter is maximum density.
- the densities measured in the magenta layer behind the blue and red filter are a measure of the colour deterioration in the magenta image, the density measured behind the green filter is maximum density.
- the densities measured in the cyan layer behind the blue and green filter are a measure of the colour deterioration in the cyan image, the density measured behind the red filter is maximum density.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96201046A EP0802453A1 (de) | 1996-04-18 | 1996-04-18 | Farbphotographisches Silberhalogenidmaterial mit einer spezifischen Zwischenschicht |
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| Application Number | Priority Date | Filing Date | Title |
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| EP96201046A EP0802453A1 (de) | 1996-04-18 | 1996-04-18 | Farbphotographisches Silberhalogenidmaterial mit einer spezifischen Zwischenschicht |
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| EP0802453A1 true EP0802453A1 (de) | 1997-10-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| EP96201046A Withdrawn EP0802453A1 (de) | 1996-04-18 | 1996-04-18 | Farbphotographisches Silberhalogenidmaterial mit einer spezifischen Zwischenschicht |
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| EP (1) | EP0802453A1 (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0866644A3 (de) * | 1997-03-19 | 1999-03-31 | Fuji Photo Film Co., Ltd. | Elektrolumineszente Vorrichtung |
| JP4773617B2 (ja) * | 1997-10-24 | 2011-09-14 | 奇美電子股▲ふん▼有限公司 | ガラス積層体を基質とする半導体装置の製造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0339902A (ja) * | 1989-04-07 | 1991-02-20 | Konica Corp | カラーフィルターの製造方法 |
| EP0546416A1 (de) * | 1991-12-12 | 1993-06-16 | Agfa-Gevaert AG | Farbfotografisches Aufzeichnungsmaterial |
| EP0615161A1 (de) * | 1993-03-11 | 1994-09-14 | Agfa-Gevaert N.V. | Mehrfarben-Flüssigkristallanzeige und deren Herstellung |
-
1996
- 1996-04-18 EP EP96201046A patent/EP0802453A1/de not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0339902A (ja) * | 1989-04-07 | 1991-02-20 | Konica Corp | カラーフィルターの製造方法 |
| EP0546416A1 (de) * | 1991-12-12 | 1993-06-16 | Agfa-Gevaert AG | Farbfotografisches Aufzeichnungsmaterial |
| EP0615161A1 (de) * | 1993-03-11 | 1994-09-14 | Agfa-Gevaert N.V. | Mehrfarben-Flüssigkristallanzeige und deren Herstellung |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 015, no. 180 (P - 1199) 9 May 1991 (1991-05-09) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0866644A3 (de) * | 1997-03-19 | 1999-03-31 | Fuji Photo Film Co., Ltd. | Elektrolumineszente Vorrichtung |
| JP4773617B2 (ja) * | 1997-10-24 | 2011-09-14 | 奇美電子股▲ふん▼有限公司 | ガラス積層体を基質とする半導体装置の製造方法 |
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