US20010038956A1 - Method of making a random color filter array - Google Patents
Method of making a random color filter array Download PDFInfo
- Publication number
- US20010038956A1 US20010038956A1 US09/808,844 US80884401A US2001038956A1 US 20010038956 A1 US20010038956 A1 US 20010038956A1 US 80884401 A US80884401 A US 80884401A US 2001038956 A1 US2001038956 A1 US 2001038956A1
- Authority
- US
- United States
- Prior art keywords
- color filter
- filter array
- layer
- dispersed
- film
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000000049 pigment Substances 0.000 claims abstract description 36
- 239000006185 dispersion Substances 0.000 claims abstract description 27
- 239000000975 dye Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 9
- 239000003086 colorant Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000839 emulsion Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 108010010803 Gelatin Proteins 0.000 claims description 17
- 229920000159 gelatin Polymers 0.000 claims description 17
- 239000008273 gelatin Substances 0.000 claims description 17
- 235000019322 gelatine Nutrition 0.000 claims description 17
- 235000011852 gelatine desserts Nutrition 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 239000008119 colloidal silica Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 64
- 238000012545 processing Methods 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000003491 array Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 229940116335 lauramide Drugs 0.000 description 4
- ILRSCQWREDREME-UHFFFAOYSA-N lauric acid amide propyl betaine Natural products CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000003232 water-soluble binding agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- -1 silver halide Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 2
- RHGBRYSELHPAFL-UHFFFAOYSA-N 1,4-bis(pentylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCCC)=CC=C2NCCCCC RHGBRYSELHPAFL-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- IJHIIHORMWQZRQ-UHFFFAOYSA-N 1-(ethenylsulfonylmethylsulfonyl)ethene Chemical compound C=CS(=O)(=O)CS(=O)(=O)C=C IJHIIHORMWQZRQ-UHFFFAOYSA-N 0.000 description 1
- GBAJQXFGDKEDBM-UHFFFAOYSA-N 1-(methylamino)-4-(3-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC(C)=C1 GBAJQXFGDKEDBM-UHFFFAOYSA-N 0.000 description 1
- QAMCXJOYXRSXDU-UHFFFAOYSA-N 2,4-dimethoxy-n-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].COC1=CC(OC)=CC=C1NC=CC1=[N+](C)C2=CC=CC=C2C1(C)C QAMCXJOYXRSXDU-UHFFFAOYSA-N 0.000 description 1
- QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 description 1
- BPTKLSBRRJFNHJ-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=CC=C1 BPTKLSBRRJFNHJ-UHFFFAOYSA-N 0.000 description 1
- REPMZEQSQQAHJR-UHFFFAOYSA-N 7-(diethylamino)-3,4-dioxo-10H-phenoxazine-1-carboxamide hydrochloride Chemical compound [Cl-].OC(=[NH2+])C1=CC(=O)C(=O)C2=C1NC1=CC=C(N(CC)CC)C=C1O2 REPMZEQSQQAHJR-UHFFFAOYSA-N 0.000 description 1
- JUQPZRLQQYSMEQ-UHFFFAOYSA-N CI Basic red 9 Chemical compound [Cl-].C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)=C1C=CC(=[NH2+])C=C1 JUQPZRLQQYSMEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- CWNSVVHTTQBGQB-UHFFFAOYSA-N N,N-Diethyldodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CC)CC CWNSVVHTTQBGQB-UHFFFAOYSA-N 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 101150082840 SM30 gene Proteins 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 235000012544 Viola sororia Nutrition 0.000 description 1
- 241001106476 Violaceae Species 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- PXOZAFXVEWKXED-UHFFFAOYSA-N chembl1590721 Chemical compound C1=CC(NC(=O)C)=CC=C1N=NC1=CC(C)=CC=C1O PXOZAFXVEWKXED-UHFFFAOYSA-N 0.000 description 1
- IPHJYJHJDIGARM-UHFFFAOYSA-M copper phthalocyaninesulfonic acid, dioctadecyldimethylammonium salt Chemical compound [Cu+2].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC.C=1C(S(=O)(=O)[O-])=CC=C(C(=NC2=NC(C3=CC=CC=C32)=N2)[N-]3)C=1C3=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 IPHJYJHJDIGARM-UHFFFAOYSA-M 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000019233 fast yellow AB Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019239 indanthrene blue RS Nutrition 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AFCCDDWKHLHPDF-UHFFFAOYSA-M metam-sodium Chemical group [Na+].CNC([S-])=S AFCCDDWKHLHPDF-UHFFFAOYSA-M 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- VKWNTWQXVLKCSG-UHFFFAOYSA-N n-ethyl-1-[(4-phenyldiazenylphenyl)diazenyl]naphthalen-2-amine Chemical compound CCNC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 VKWNTWQXVLKCSG-UHFFFAOYSA-N 0.000 description 1
- VXLFYNFOITWQPM-UHFFFAOYSA-N n-phenyl-4-phenyldiazenylaniline Chemical compound C=1C=C(N=NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 VXLFYNFOITWQPM-UHFFFAOYSA-N 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GVKCHTBDSMQENH-UHFFFAOYSA-L phloxine B Chemical compound [Na+].[Na+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 GVKCHTBDSMQENH-UHFFFAOYSA-L 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RCTGMCJBQGBLKT-PAMTUDGESA-N scarlet red Chemical compound CC1=CC=CC=C1\N=N\C(C=C1C)=CC=C1\N=N\C1=C(O)C=CC2=CC=CC=C12 RCTGMCJBQGBLKT-PAMTUDGESA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- XRFRTDKENRGSSX-UHFFFAOYSA-J tetrasodium;3-[[4-[[4-[(4,8-disulfonatonaphthalen-2-yl)diazenyl]-3-methylphenyl]carbamoylamino]-2-methylphenyl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N=NC3=CC=C(NC(=O)NC=4C=C(C)C(N=NC=5C=C6C(=CC=CC6=C(C=5)S([O-])(=O)=O)S([O-])(=O)=O)=CC=4)C=C3C)=CC(S([O-])(=O)=O)=C21 XRFRTDKENRGSSX-UHFFFAOYSA-J 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- AMMPRZCMKXDUNE-UHFFFAOYSA-N trihexyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCOC(=O)CC(O)(C(=O)OCCCCCC)CC(=O)OCCCCCC AMMPRZCMKXDUNE-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Images
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
- G03C7/08—Manufacture of colour screens from diversely-coloured grains irregularly distributed
Definitions
- the invention relates to color film and in particular to a method of making a random color filter array film.
- the Dufaycolor process (initially the Dioptichrome plate, L.Dufay, 1909) used a regular array of red, green and blue dyed patches and lines printed on a gelatin layer in conjunction with a reversal-processed black-and-white emulsion system, which similarly gave a colored image of the scene when viewed by transmitted light.
- Polavision (Edwin Land and the Polaroid Corporation, 1977) was a color movie system employing a rapid and convenient reversal processing method on a black-and-white emulsion system coated above an array of red, green and blue stripes, which gave a colored projected image. It was marketed as a still color transparency system called Polachrome in 1983.
- U.S. Pat. No. 4,971,869 discloses a film with a regular repeating filter array which claims to be less susceptible to aliasing problems.
- the film disclosed comprises a panchromatic photographic emulsion and a repetitive pattern of a unit of adjacent colored cells wherein at least one of the cells is of a subtractive primary color (e.g. yellow, magenta or cyan) or of a pastel color.
- Scene information can be extracted from the developed film by opto-electronic scanning methods.
- European Patent Application 935 168 discloses a light sensitive material comprising a transparent support having thereon a silver halide emulsion layer and a randomly arranged color filter layer comprising colored resin particles. Also disclosed is exposing, processing and elecro-optically scanning the resultant image in such a film and reconstructing the image by digital image processing.
- Color photographic films which comprise a color filter array and a single image recording layer or layer pack have the advantage of rapid and convenient photographic processing, as the single image recording layer or layer pack can be processed rapidly without the problem of mismatching different color records if small variations occur in the process. A small change in extent of development for example will affect all color records equally. Exceptionally rapid processing is possible using simple negative black-and-white development, and if suitable developing agents are included in the coating, the photographic response can be remarkably robust or tolerant towards inadvertent variations in processing time or temperature. Developing agents suitable for including in the coating, and a preferred way of incorporating them, are disclosed in U.S. Pat. No. 5,804,359.
- the method of manufacturing the color filter array be of comparatively low cost.
- Known methods of making regular filter arrays such as those used for Dufaycolor or Polachrome films, are complex and costly, involving several sequential applications of materials to the film.
- Known methods of making random filter arrays such as those used for Autochrome film and that described in EP 935 168 also involve complex operations, including separating and grading or sizing the colored particles of starch or resin respectively, dispersing them in a coating medium, coating and drying and then calendaring the coated layer to flatten the particles.
- any pigment particles dispersed within the water immiscible oily liquid have a mean length of less than 0.5 micrometers.
- the method of the invention uses existing photographic manufacturing methods such as oil-in-water dispersion and photographic coating. Thus no new equipment is required. Furthermore there is no need to separate or isolate the color elements. Little or no volatile organic solvents need to be evaporated or recovered and the only drying step is the normal drying of a coated photographic film. No calendaring step needed as the fluid filter elements become flatter as the coating dries.
- the method of the invention also allows convenient manufacture of films having a preferred film structure in which the CFA is located between the emulsion layers and the top coated surface of the film, that is located further from the support than the emulsion layers.
- This film structure is preferred because it allows the film to be exposed in the camera with the support towards the back of the camera and the emulsion side toward the lens, which is the orientation for which films and cameras are normally designed.
- Such a film structure is preferred in the case of Advanced Photographic System films because the magnetic recording layer functions most effectively when coated on the back of the support and has to be in contact with the magnetic heads in the back of the camera.
- the filter array preparation methods of the prior art would entail complex operations on top of an already-coated emulsion layer, which would need to be done under safelight conditions and would risk harming the very sensitive coated emulsion layers for instance by causing fog or desensitization.
- Heat calendaring operations, as used in the method described in EP 935 168 could very probably cause heat and pressure fog in the already-coated emulsion layer(s).
- the method of the invention provides a low cost means of manufacturing color filter arrays, and the random nature of the array will give reduced color fringing at edges and with fine geometric structures in the scene, relative to a regular color array.
- FIG. 1 is a schematic view of a filter layer in a wet, swollen state
- FIG. 2 is a schematic view of a filter layer in a dried state
- FIG. 3 is a schematic view of an embodiment of a film having a color filter array prepared according to the invention.
- FIG. 4 is a schematic view of a second embodiment of a film having a color filter array prepared according to the invention.
- FIG. 1 is a schematic view of a wet filter layer in which colored elements 1 are mixed together within a binder 2 .
- FIG. 2 is a schematic view of the filter layer in its dried state, the thickness of the binder 2 being similar to the thickness of the elements 1 .
- the colored elements 1 of the color filter array may comprise various colored fluid or liquid substances, including droplets of water-immiscible organic solvents. These may be so-called coupler solvents as used in the photographic industry, in which are incorporated dyes or pigments.
- Suitable water-immiscible organic solvents are in general of low volatility, and include for example tricresyl phosphate, di-n-butyl phthalate, diundecyl phthalate, N,N-diethyl lauramide, N,N-di-n-butyl lauramide, triethyl citrate and trihexyl citrate.
- Other solvents which may be partially water-soluble, such as ethyl acetate and cyclohexanone, may be used in addition during the preparation of the dispersions, and they may be removed from the final dispersion or coating either by washing or by evaporation.
- Suitable dyes may be oil-soluble in nature, and can be chosen for example from the classes of solvent dyes and disperse dyes listed in the Color Index, 3 rd Edition, published by The Society of Dyers and Colorists, Bradford, England. Specific examples are listed under their Color Index (CI) names, and include CI Solvent Blue 14, CI Solvent Blue 35, CI Solvent Blue 63, CI Solvent Blue 79, CI Solvent Yellow 174, CI Solvent Orange 1, CI Solvent Red 19, CI Solvent Red 24, CI Disperse Yellow 3, and 4-phenylazodiphenylamine.
- CI Color Index
- Suitable pigments are chosen for their properties of hue, fastness, and dispersibility, and can include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15:3, CI Pigment Blue 60, CI Pigment Violet 23, CI Pigment Red 122, CI Pigment Red 177, CI Pigment Red 194, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 110, and CI Pigment Yellow 139.
- pigment particles When pigment particles are incorporated in the colored elements, they should be of a fine particle size, preferably substantially less than one micrometer.
- Various substances including polymeric and particulate substances may be incorporated within the colored elements, and these may include dispersing agents such as those used in the pigment and paint industries.
- dispersing agents examples include the SolsperseTM range of dispersants marketed by Avecia Limited, such as Solsperse 5000, Solsperse 17,000, Solsperse 22,000, and Solsperse 24,000. Further Solsperse dispersing agents are numbered 13650, 13940, and 34750.
- Another suitable dispersing agent is Carbam 111TM, marketed by AAA (Applied Analytics and Automation, M. H. Mathews Additive & Messgerate, Bad Nauheim, Germany).
- Polymeric additives to modify the rheology or other properties of the fluid droplets include oil soluble polymers such as polyvinyl butyral, styrene polymers and copolymers, vinyl polymers and copolymers, and acrylate polymers and copolymers.
- the coloring agents are dyes, then these are dissolved in the water-immiscible organic solvent in the quantity required to give the required depth of color in the color elements when coated. Combinations of dyes may be used to give the desired spectral properties.
- the coloring agents are pigments
- the appropriate quantity of pigment or pigments are mixed with the water-immiscible organic solvent, together with dispersing agents if required, and the mixture milled to reduce the pigment particles to a suitable size, which in general should be less than half a micrometer in length or diameter, and preferably less than 0.3 micrometers.
- a suitable size which in general should be less than half a micrometer in length or diameter, and preferably less than 0.3 micrometers.
- Various milling methods and devices known in the art of pigment preparation may be used, and these include ball mills, media mills and sand mills.
- the resulting colored water-immiscible organic solvent or oil is then dispersed in an aqueous medium so as to form colored droplets of the desired size.
- Dispersing methods known in the photographic art may be used. These include rotor-stator devices, homogenisers and emulsifiers which force the liquid at high shear through orifices or channels, and ultrasonic devices such as horns and probes.
- the oil/water interface may be stabilized by addition to the aqueous phase of surfactants, polymers including natural polymers such as gelatin, and particulate species such as colloidal silica. Surface stabilization by particulate species such as colloidal silica is particularly preferred as it can give a narrow size distribution of the resultant colored droplets and the size of the droplets may be controlled by the concentration of the particulate species employed.
- a water-soluble film former or binder such as gelatin.
- the water-soluble film former or binder may be colorless, or colored by means of dyes or pigments which are incorporated in the aqueous phase. If dyes are used, they must be bound within the aqueous layer for instance by incorporating a mordant which binds the dye or dyes within the layer, or by using reactive dyes which chemically react with a polymeric species within the layer.
- pigment particles are used, they must be milled to a sufficiently fine particle size, for example less than 0.5 micrometers, and it may be necessary to incorporate dispersing agents to prevent aggregation or clumping of the dispersed particles.
- Pigments used to color the water-permeable polymeric binder can include those listed above.
- Dyes used to color the water-permeable polymeric binder are water-soluble dyes, and may be anionic dyes such as acid dyes, direct dyes and mordant dyes, for example CI Acid Yellows 40, 42, 65 and 99; CI Acid Orange 63; CI Acid Red 92; CI Acid Violets 7, 9 and 17; CI Acid Blues 7, 92, and 249; CI Direct Yellow 50; CI Direct Red 75; and CI Mordant Red 3.
- Anionic dyes may be bound in the layer by means of a cationic polymeric mordant, or by interaction with large cationic molecules or with metal salts.
- cationic dyes may be used, and bound in the layer by means of an anionic polymeric mordant, or by interaction with large anionic molecules including surfactant molecules.
- anionic polymeric mordant or by interaction with large anionic molecules including surfactant molecules.
- cationic dyes which may be used include CI Basic Yellow 11, CI Basic Red 9, CI Basic Blues 3 and 66, and CI Mordant Blue 14.
- Various combinations of colors may be used, for instance red, green and blue droplets coated in a colorless gelatin binder, or red and blue droplets coated in a green-colored gelatin binder.
- the colored droplets may contain more than one coloring agent, for instance a blue droplet may contain a mixture of magenta and cyan pigments or dyes. Cyan, magenta and yellow droplets may be used, or other combinations such as cyan, magenta and green droplets in a yellow-colored binder.
- the combined mixture of dispersed colored droplets and the solution of optionally colored water-soluble binder is then coated on the film. It may be coated simultaneously with other layers, and/or on top of already-coated layers such as emulsion layers. Alternatively, it may be dried and further layers then coated on top of the coated color filter array.
- the coated laydown of colored droplets should be adjusted to give the desired closeness of packing in the dried layer without excessive overlapping of droplets.
- the water-soluble binder is colored, it is desirable to adjust the coated laydown of water-soluble binder so that the dried thickness of the colored binder is similar to the thickness of the dried-down droplets themselves, as depicted schematically in FIG. 2.
- a hardening agent will be added to one or more layers of the film so that the binder(s) in the film, including the water-soluble binder in the filter layer, becomes hardened or cross-linked to make the array physically robust, and, in the case of a photographic film, so that the film can swell but not dissolve in the developer and other processing solutions.
- FIG. 3 shows one embodiment of a film having a color filter array prepared according to the invention.
- the film 3 comprises a support 4 , a color filter array 5 , emulsion layers 6 and a supercoat 7 .
- the film 3 is coated with a color filter array 5 nearest to the support 4 .
- an underlayer (not shown) may be coated between the support 4 and the color filter array 5 . Chemicals which are useful during chemical processing may be coated in the underlayer.
- An emulsion layer unit 6 is provided above the color filter array 5 .
- the top layer of the film is provided by a supercoat 7 with antihalation means.
- the emulsion layer unit 6 may comprise one or more layers.
- the unit is sensitive to light which has passed through each or all of the different color elements of the array 5 .
- the image information for each color record is recorded in the emulsion layer unit.
- the emulsions may be of different speeds.
- Photographic addenda known in the art such as antifoggants and speed-increasing agents may be present in or adjacent to the emulsion layers.
- Substances such as developing agents, blocked developing agents, color couplers and other materials which take part in the processing step may be in or adjacent to the emulsion layer unit 6 .
- Developing agents suitable for including in the coating, and a preferred way of incorporating them, are disclosed in U.S. Pat. No. 5,804,359.
- FIG. 4 shows a second embodiment of the film prepared in accordance with the invention.
- the color filter array 5 is further from the support 4 than the emulsion layer unit 6 .
- An antihalation layer 8 is provided between the support 4 and the emulsion layer unit 6 . Chemicals which are useful during chemical processing may also be coated in this antihalation layer.
- the light-sensitive emulsion layer 6 prefferably be a heat-developable layer, so that the development and processing of the film is achieved by overall heating of the exposed film.
- the random color filter array prepared according to the invention comprises colored elements or patches whose individual linear dimensions (diameter in the case of a circular element) in the plane of the film may be between 1 and 50 micrometers. In a preferred embodiment of the invention the elements will be between 3 and 10 micrometers in diameter. Three or more color channels are generally required. These can be provided by, for example, two color classes of color element spaced irregularly in the plane of the film with the spaces between them, viewed from a direction normal to the film plane, either colorless (clear or white), or of a third color. Alternatively, three or more color classes of discrete color elements may be provided, and the spaces between them may be colorless (clear or white), or dark or black, or colored.
- the emulsion layers 6 When a film prepared according to the invention is used, it is necessary for the emulsion layers 6 to be exposed by light which has passed through the color filter array 5 .
- the support 4 With the film structure depicted in FIG. 3, the support 4 will be closer to the camera lens during exposure than the coated layers.
- the coated layers With the film structure depicted in FIG. 4, the coated layers will be closer to the camera lens during exposure than the film support 4 .
- the emulsion layers may be developed and fixed by known methods of photographic processing so as to give an image which modulates light passing through each of the spectrally distinguishable types of filter element.
- a simple technique for scanning is to scan the photographically processed element point-by-point along a series of laterally offset parallel scan paths.
- the intensity of light received from or passing through the photographic element at a scanning point is noted by a sensor which converts radiation received into an electrical signal.
- the electrical signal is processed and sent to memory in a digital computer together with locant information required for pixel location within the image.
- a convenient form of scanner can consist of a single multicolor image sensor or a single set of color sensors, with a light source placed on the opposite side of the film. Light transmitted through the film can give information on the image pattern in the emulsion layer(s) modulated by the color filter array.
- Various methods of image processing may be employed.
- a relatively simple method is to represent the image data in a color model which has a luminance or lightness component and two chromatic or color components, such as the CIE L*a*b model.
- the chromatic components are then blurred with a suitable image filter to remove the higher frequency color information which arises largely from the color filter array, and the blurred chromatic information recombined with the original luminance information.
- the color saturation of the image may be varied by altering the contrast of the chromatic components.
- the resulting representation of the scene recorded by the method of the invention may be viewed on a screen or printed by suitable means to give a printed photographic image.
- the array comprised droplets of a non-volatile oily liquid colored with dyes and pigment particles, dispersed in an aqueous phase using colloidal silica as a surface-stabilizing and size-controlling substance, and then coated with gelatin as a binder and dried.
- the dispersion was then added to 150 g of 12.5% w/v aqueous gelatin solution containing 0.17% w/v Alkanol XC surfactant.
- Layer 1 gelatin, 1.0 g/m2
- Layer 2 gelatin, 2.2 g/m2, red oil phase, 0.70 g/m2, green oil phase, 0.75 g/m2, blue oil phase, 0.60 g/m2
- Layer 3 gelatin, 0.72 g/m2.
- a length of the coated color filter array was then coated with photographic emulsion layers so that the emulsion layers were immediately above the layers of the array.
- Emulsion Layer A is a first layer
- Emulsion Layer B is a first layer
- Mid speed silver bromoiodide panchromatically sensitized emulsion (tabular grain, average diameter approx. 1.1 ⁇ m, thickness 0.12 ⁇ m, 4.5 mol % iodide), coated at 1.5 g/m2
- slow silver bromoiodide panchromatically sensitized emulsion (tabular grain, average diameter approx. 0.7 ⁇ m, thickness 0.11 ⁇ m, 3 mol % iodide), coated at 1.0 g/m2 together with gelatin, 2.0 g/m2.
- 4-hydroxy-6-methyl-1,3,3A,7-tetraazindene, sodium salt was also present at 1.5 g per mole of silver.
- Gelatin 1.6 g/m2, hardener bis(vinylsulphonyl)methane, 0.072 g/m2, and an antihalation dye whose color was dischargeable in the developer solution, coated as a particulate dispersion, 0.1 g/m2.
- a length of the film was slit to 35 mm width, the edges were perforated, the film was put in a standard 35 mm cassette, and the cassette loaded into a single lens reflex camera.
- the film was oriented so that light from the camera lens passed first through the film base, then through the coated color filter array, and then onto the emulsion layers.
- the camera was adjusted to give an exposure at a speed setting of 200 ISO, and a photograph taken of an outdoor scene.
- the exposed film was developed for 2 minutes at 25 C in the following developer solution: sodium carbonate (anh.) 9 g/l ascorbic acid 7.5 sodium sulphite (anh.) 2.5 sodium bromide 0.5 4-hydroxymethyl-4-methyl- 0.35 -1-phenyl-3-pyrazolidone pH adjusted to 10.0 with dilute sodium hydroxide solution.
- the image was then scanned with a Kodak RFS 2035 scanner and the resulting image file imported into Adobe PhotoshopTM image manipulation software.
- the “Autolevels” command was used to correct overall brightness, contrast and color balance, then the image was converted to L*a*b* color space.
- the a and b channels were treated with a blurring filter (Gaussian blur, 12 pixels radius) then their contrast increased using a numerical value of 75, which resulted in a strong increase in color saturation.
- the image was converted back to R,G,B space and color saturation and color balance adjusted to give a pleasing colored image of the original scene.
- the invention uses existing photographic manufacturing methods such as oil-in-water dispersion and photographic coating which means that no new equipment is required.
- the invention results in a simplified and economical process when compared with the known prior art.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optical Filters (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
- The invention relates to color film and in particular to a method of making a random color filter array film.
- The great majority of color photographs today are taken using chromogenic color film, in which color-forming couplers, which may be incorporated in the film or present in the processing solution, form cyan, magenta and yellow dyes by reaction with oxidized developing agent which is formed where silver halide is developed in an imagewise pattern. Such films require a development process which is carefully controlled in respect of time and temperature, which is usually followed by a silver bleaching and a fixing step, and the whole process typically takes several minutes and needs complex equipment.
- Color photography by exposing a black-and-white photographic emulsion through a color filter array which is an integral part of the film or plate on which the photographic emulsion is coated, has long been known to offer certain advantages of simplicity or convenience in color photography. Thus the Autochrome process, disclosed by the Lumiere brothers in 1906 (U.S. Pat. No. 822,532) exposed the emulsion through a randomly disposed layer of red, green and blue-colored potato starch grains, and the emulsion was reversal processed to give a positive image of the scene which appeared colored when viewed by light transmitted through the plate. The process allowed the formation of a colored photograph without the chemical complexity of later photographic methods.
- The Dufaycolor process (initially the Dioptichrome plate, L.Dufay, 1909) used a regular array of red, green and blue dyed patches and lines printed on a gelatin layer in conjunction with a reversal-processed black-and-white emulsion system, which similarly gave a colored image of the scene when viewed by transmitted light.
- Polavision (Edwin Land and the Polaroid Corporation, 1977) was a color movie system employing a rapid and convenient reversal processing method on a black-and-white emulsion system coated above an array of red, green and blue stripes, which gave a colored projected image. It was marketed as a still color transparency system called Polachrome in 1983.
- These methods suffered a number of disadvantages. The images were best viewed by passing light through the processed film or plate, and the image quality was not sufficient to allow high quality prints to be prepared from them, due to the coarse nature of the Autochrome and Dufaycolor filter arrays, and the coarse nature of the positive silver image in the Polavision and Polacolor systems. The regular array patterns were complicated and expensive to manufacture. In addition, the films which used regular or repeating filter arrays were susceptible to color aliasing when used to photograph scenes with geometrically repeating features.
- U.S. Pat. No. 4,971,869 discloses a film with a regular repeating filter array which claims to be less susceptible to aliasing problems. The film disclosed comprises a panchromatic photographic emulsion and a repetitive pattern of a unit of adjacent colored cells wherein at least one of the cells is of a subtractive primary color (e.g. yellow, magenta or cyan) or of a pastel color. Scene information can be extracted from the developed film by opto-electronic scanning methods.
- European Patent Application 935 168 discloses a light sensitive material comprising a transparent support having thereon a silver halide emulsion layer and a randomly arranged color filter layer comprising colored resin particles. Also disclosed is exposing, processing and elecro-optically scanning the resultant image in such a film and reconstructing the image by digital image processing.
- Color photographic films which comprise a color filter array and a single image recording layer or layer pack have the advantage of rapid and convenient photographic processing, as the single image recording layer or layer pack can be processed rapidly without the problem of mismatching different color records if small variations occur in the process. A small change in extent of development for example will affect all color records equally. Exceptionally rapid processing is possible using simple negative black-and-white development, and if suitable developing agents are included in the coating, the photographic response can be remarkably robust or tolerant towards inadvertent variations in processing time or temperature. Developing agents suitable for including in the coating, and a preferred way of incorporating them, are disclosed in U.S. Pat. No. 5,804,359.
- It is desirable that the method of manufacturing the color filter array be of comparatively low cost. Known methods of making regular filter arrays, such as those used for Dufaycolor or Polachrome films, are complex and costly, involving several sequential applications of materials to the film. Known methods of making random filter arrays, such as those used for Autochrome film and that described in EP 935 168 also involve complex operations, including separating and grading or sizing the colored particles of starch or resin respectively, dispersing them in a coating medium, coating and drying and then calendaring the coated layer to flatten the particles.
- It is an object of the invention to provide a method of making a color filter array film which is simpler and of comparatively low cost as compared to methods known in the prior art.
- According to the invention there is provided a method of making a random color filter array comprising the steps of:
- dispersing in an aqueous medium a water immiscible oily liquid having dyes and/or pigment particles dissolved and/or dispersed therein to form colored droplets,
- mixing the resulting dispersion with one or more other dispersions of different colors in a continuous aqueous phase having a film forming polymer dissolved therein and
- coating the resulting mixture onto a support layer.
- Preferably any pigment particles dispersed within the water immiscible oily liquid have a mean length of less than 0.5 micrometers.
- The method of the invention uses existing photographic manufacturing methods such as oil-in-water dispersion and photographic coating. Thus no new equipment is required. Furthermore there is no need to separate or isolate the color elements. Little or no volatile organic solvents need to be evaporated or recovered and the only drying step is the normal drying of a coated photographic film. No calendaring step needed as the fluid filter elements become flatter as the coating dries.
- The method of the invention also allows convenient manufacture of films having a preferred film structure in which the CFA is located between the emulsion layers and the top coated surface of the film, that is located further from the support than the emulsion layers. This film structure is preferred because it allows the film to be exposed in the camera with the support towards the back of the camera and the emulsion side toward the lens, which is the orientation for which films and cameras are normally designed. Such a film structure is preferred in the case of Advanced Photographic System films because the magnetic recording layer functions most effectively when coated on the back of the support and has to be in contact with the magnetic heads in the back of the camera. The filter array preparation methods of the prior art would entail complex operations on top of an already-coated emulsion layer, which would need to be done under safelight conditions and would risk harming the very sensitive coated emulsion layers for instance by causing fog or desensitization. Heat calendaring operations, as used in the method described in EP 935 168 could very probably cause heat and pressure fog in the already-coated emulsion layer(s).
- In the case of digital image capture devices such as digital cameras and scanners, the method of the invention provides a low cost means of manufacturing color filter arrays, and the random nature of the array will give reduced color fringing at edges and with fine geometric structures in the scene, relative to a regular color array.
- Reference is made to related commonly owned co-pending applications entitled Film with Random Color Filter Array, (reference 11575) and Random Color Filter Array, (reference 11576), both filed concurrently herewith, the entire contents of which are incorporated herein.
- The method of the invention will now be described, by way of example, with reference to the accompanying drawings, in which:
- FIG. 1 is a schematic view of a filter layer in a wet, swollen state;
- FIG. 2 is a schematic view of a filter layer in a dried state;
- FIG. 3 is a schematic view of an embodiment of a film having a color filter array prepared according to the invention; and
- FIG. 4 is a schematic view of a second embodiment of a film having a color filter array prepared according to the invention.
- FIG. 1 is a schematic view of a wet filter layer in which
colored elements 1 are mixed together within abinder 2. FIG. 2 is a schematic view of the filter layer in its dried state, the thickness of thebinder 2 being similar to the thickness of theelements 1. - The
colored elements 1 of the color filter array may comprise various colored fluid or liquid substances, including droplets of water-immiscible organic solvents. These may be so-called coupler solvents as used in the photographic industry, in which are incorporated dyes or pigments. - Suitable water-immiscible organic solvents are in general of low volatility, and include for example tricresyl phosphate, di-n-butyl phthalate, diundecyl phthalate, N,N-diethyl lauramide, N,N-di-n-butyl lauramide, triethyl citrate and trihexyl citrate. Other solvents, which may be partially water-soluble, such as ethyl acetate and cyclohexanone, may be used in addition during the preparation of the dispersions, and they may be removed from the final dispersion or coating either by washing or by evaporation.
- Suitable dyes may be oil-soluble in nature, and can be chosen for example from the classes of solvent dyes and disperse dyes listed in the Color Index, 3 rd Edition, published by The Society of Dyers and Colorists, Bradford, England. Specific examples are listed under their Color Index (CI) names, and include CI Solvent Blue 14, CI Solvent Blue 35, CI Solvent Blue 63, CI Solvent Blue 79, CI Solvent Yellow 174,
CI Solvent Orange 1, CI Solvent Red 19, CI Solvent Red 24, CI Disperse Yellow 3, and 4-phenylazodiphenylamine. - Suitable pigments are chosen for their properties of hue, fastness, and dispersibility, and can include
CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15:3, CI Pigment Blue 60, CI Pigment Violet 23, CI Pigment Red 122, CI Pigment Red 177, CI Pigment Red 194, CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 110, and CI Pigment Yellow 139. - When pigment particles are incorporated in the colored elements, they should be of a fine particle size, preferably substantially less than one micrometer. Various substances including polymeric and particulate substances may be incorporated within the colored elements, and these may include dispersing agents such as those used in the pigment and paint industries.
- Examples of dispersing agents include the Solsperse™ range of dispersants marketed by Avecia Limited, such as Solsperse 5000, Solsperse 17,000, Solsperse 22,000, and Solsperse 24,000. Further Solsperse dispersing agents are numbered 13650, 13940, and 34750. Another suitable dispersing agent is Carbam 111™, marketed by AAA (Applied Analytics and Automation, M. H. Mathews Additive & Messgerate, Bad Nauheim, Germany).
- Polymeric additives to modify the rheology or other properties of the fluid droplets include oil soluble polymers such as polyvinyl butyral, styrene polymers and copolymers, vinyl polymers and copolymers, and acrylate polymers and copolymers.
- If the coloring agents are dyes, then these are dissolved in the water-immiscible organic solvent in the quantity required to give the required depth of color in the color elements when coated. Combinations of dyes may be used to give the desired spectral properties.
- If the coloring agents are pigments, then the appropriate quantity of pigment or pigments are mixed with the water-immiscible organic solvent, together with dispersing agents if required, and the mixture milled to reduce the pigment particles to a suitable size, which in general should be less than half a micrometer in length or diameter, and preferably less than 0.3 micrometers. Various milling methods and devices known in the art of pigment preparation may be used, and these include ball mills, media mills and sand mills.
- The resulting colored water-immiscible organic solvent or oil is then dispersed in an aqueous medium so as to form colored droplets of the desired size. Dispersing methods known in the photographic art may be used. These include rotor-stator devices, homogenisers and emulsifiers which force the liquid at high shear through orifices or channels, and ultrasonic devices such as horns and probes. The oil/water interface may be stabilized by addition to the aqueous phase of surfactants, polymers including natural polymers such as gelatin, and particulate species such as colloidal silica. Surface stabilization by particulate species such as colloidal silica is particularly preferred as it can give a narrow size distribution of the resultant colored droplets and the size of the droplets may be controlled by the concentration of the particulate species employed.
- To form the color filter array, dispersions of colored water-immiscible organic solvent or oil of two or more color classes are mixed together in the presence of a water-soluble film former or binder such as gelatin. The water-soluble film former or binder may be colorless, or colored by means of dyes or pigments which are incorporated in the aqueous phase. If dyes are used, they must be bound within the aqueous layer for instance by incorporating a mordant which binds the dye or dyes within the layer, or by using reactive dyes which chemically react with a polymeric species within the layer. If pigment particles are used, they must be milled to a sufficiently fine particle size, for example less than 0.5 micrometers, and it may be necessary to incorporate dispersing agents to prevent aggregation or clumping of the dispersed particles. Pigments used to color the water-permeable polymeric binder can include those listed above. Dyes used to color the water-permeable polymeric binder are water-soluble dyes, and may be anionic dyes such as acid dyes, direct dyes and mordant dyes, for example CI Acid Yellows 40, 42, 65 and 99; CI Acid Orange 63; CI Acid Red 92;
CI Acid Violets 7, 9 and 17;CI Acid Blues 7, 92, and 249; CI Direct Yellow 50; CI Direct Red 75; andCI Mordant Red 3. Anionic dyes may be bound in the layer by means of a cationic polymeric mordant, or by interaction with large cationic molecules or with metal salts. Alternatively, cationic dyes may be used, and bound in the layer by means of an anionic polymeric mordant, or by interaction with large anionic molecules including surfactant molecules. Examples of cationic dyes which may be used include CI Basic Yellow 11, CI Basic Red 9,CI Basic Blues 3 and 66, and CI Mordant Blue 14. - Various combinations of colors may be used, for instance red, green and blue droplets coated in a colorless gelatin binder, or red and blue droplets coated in a green-colored gelatin binder. The colored droplets may contain more than one coloring agent, for instance a blue droplet may contain a mixture of magenta and cyan pigments or dyes. Cyan, magenta and yellow droplets may be used, or other combinations such as cyan, magenta and green droplets in a yellow-colored binder.
- The combined mixture of dispersed colored droplets and the solution of optionally colored water-soluble binder is then coated on the film. It may be coated simultaneously with other layers, and/or on top of already-coated layers such as emulsion layers. Alternatively, it may be dried and further layers then coated on top of the coated color filter array. The coated laydown of colored droplets should be adjusted to give the desired closeness of packing in the dried layer without excessive overlapping of droplets. In the case that the water-soluble binder is colored, it is desirable to adjust the coated laydown of water-soluble binder so that the dried thickness of the colored binder is similar to the thickness of the dried-down droplets themselves, as depicted schematically in FIG. 2.
- Normally, a hardening agent will be added to one or more layers of the film so that the binder(s) in the film, including the water-soluble binder in the filter layer, becomes hardened or cross-linked to make the array physically robust, and, in the case of a photographic film, so that the film can swell but not dissolve in the developer and other processing solutions.
- FIG. 3 shows one embodiment of a film having a color filter array prepared according to the invention. The
film 3 comprises asupport 4, acolor filter array 5,emulsion layers 6 and asupercoat 7. In this embodiment thefilm 3 is coated with acolor filter array 5 nearest to thesupport 4. Optionally, an underlayer (not shown) may be coated between thesupport 4 and thecolor filter array 5. Chemicals which are useful during chemical processing may be coated in the underlayer. Anemulsion layer unit 6 is provided above thecolor filter array 5. - The top layer of the film is provided by a
supercoat 7 with antihalation means. - The
emulsion layer unit 6 may comprise one or more layers. The unit is sensitive to light which has passed through each or all of the different color elements of thearray 5. Thus the image information for each color record is recorded in the emulsion layer unit. The emulsions may be of different speeds. Photographic addenda known in the art, such as antifoggants and speed-increasing agents may be present in or adjacent to the emulsion layers. Substances such as developing agents, blocked developing agents, color couplers and other materials which take part in the processing step may be in or adjacent to theemulsion layer unit 6. Developing agents suitable for including in the coating, and a preferred way of incorporating them, are disclosed in U.S. Pat. No. 5,804,359. - FIG. 4 shows a second embodiment of the film prepared in accordance with the invention. In this
film 3 thecolor filter array 5 is further from thesupport 4 than theemulsion layer unit 6. Anantihalation layer 8 is provided between thesupport 4 and theemulsion layer unit 6. Chemicals which are useful during chemical processing may also be coated in this antihalation layer. - It is possible in both embodiments for the light-
sensitive emulsion layer 6 to be a heat-developable layer, so that the development and processing of the film is achieved by overall heating of the exposed film. - The random color filter array prepared according to the invention comprises colored elements or patches whose individual linear dimensions (diameter in the case of a circular element) in the plane of the film may be between 1 and 50 micrometers. In a preferred embodiment of the invention the elements will be between 3 and 10 micrometers in diameter. Three or more color channels are generally required. These can be provided by, for example, two color classes of color element spaced irregularly in the plane of the film with the spaces between them, viewed from a direction normal to the film plane, either colorless (clear or white), or of a third color. Alternatively, three or more color classes of discrete color elements may be provided, and the spaces between them may be colorless (clear or white), or dark or black, or colored.
- When a film prepared according to the invention is used, it is necessary for the emulsion layers 6 to be exposed by light which has passed through the
color filter array 5. Thus with the film structure depicted in FIG. 3, thesupport 4 will be closer to the camera lens during exposure than the coated layers. With the film structure depicted in FIG. 4, the coated layers will be closer to the camera lens during exposure than thefilm support 4. - After exposure, the emulsion layers may be developed and fixed by known methods of photographic processing so as to give an image which modulates light passing through each of the spectrally distinguishable types of filter element. Conventional black-and-white development, using developing agents contained in the solution and/or coated in the film, followed by fixing and washing, is a suitable form of photographic processing.
- Conventional scanning techniques can be employed, including point-by-point, line-by-line and area scanning, and require no detailed description. A simple technique for scanning is to scan the photographically processed element point-by-point along a series of laterally offset parallel scan paths. The intensity of light received from or passing through the photographic element at a scanning point is noted by a sensor which converts radiation received into an electrical signal. The electrical signal is processed and sent to memory in a digital computer together with locant information required for pixel location within the image.
- A convenient form of scanner can consist of a single multicolor image sensor or a single set of color sensors, with a light source placed on the opposite side of the film. Light transmitted through the film can give information on the image pattern in the emulsion layer(s) modulated by the color filter array. Various methods of image processing may be employed. A relatively simple method is to represent the image data in a color model which has a luminance or lightness component and two chromatic or color components, such as the CIE L*a*b model. The chromatic components are then blurred with a suitable image filter to remove the higher frequency color information which arises largely from the color filter array, and the blurred chromatic information recombined with the original luminance information. The color saturation of the image may be varied by altering the contrast of the chromatic components.
- Other methods of image processing may be employed.
- Another method of image processing is disclosed in co-pending UK application no GB 0002481.0, entitled Method of Image Processing, which is here incorporated by reference.
- After image processing the resulting representation of the scene recorded by the method of the invention may be viewed on a screen or printed by suitable means to give a printed photographic image.
- Preparation of a Random Color Filter Array
- The array comprised droplets of a non-volatile oily liquid colored with dyes and pigment particles, dispersed in an aqueous phase using colloidal silica as a surface-stabilizing and size-controlling substance, and then coated with gelatin as a binder and dried.
- Two silica dispersions were prepared:
- Silica Dispersion A:
- To 320 g of water was added 12 g of Ludox (trade mark) SM30 colloidal silica suspension and 1.2 g of a 10% w/v aqueous solution of a copolymer of methylaminoethanol and adipic acid. The mixture was stirred and its pH adjusted from its initial value of 4.86 to 4.00 by addition of 4M sulphuric acid.
- Silica Dispersion B:
- To 312 g of water was added 20 g of Ludox AM30 colloidal silica suspension and 1.0 g of a 10% w/v aqueous solution of a copolymer of methylaminoethanol and adipic acid. The mixture was stirred and its pH adjusted from its initial value of 4.48 to 4.00 by addition of 4M sulphuric acid.
- Dispersions of Colored Oil Droplets were Prepared:
- Red Dispersion:
- The following were mixed together to form a colored oil phase:
Sudan M Red 462 Liquid Dye (supplied by BASF) 3.5 g Sudan Yellow 172 Liquid Dye (supplied by BASF) 2.7 Tricresyl phosphate 8.0 di-n-butyl lauramide 8.0 - To this was added the following aqueous phase:
Silica dispersion A 24 g Silica dispersion B 12 g Water 64 - and the combined mixture was agitated for 5 minutes with a “Soniprobe” ultrasonic probe (supplied by Lucas Dawe Ultrasonics) to form an oil-in-water dispersion. The probe used had a tip diameter of half an inch (1.3 cm), and the power setting employed was 5 or 50%. The dispersion was then added to 120 g of 12.5% w/v aqueous gelatin solution containing 0.17% w/v Alkanol XC surfactant.
- Blue Oil Phase:
- The following mixture was ball-milled for 3 days using 1 mm diameter zirconia beads as the grinding media:
CI Pigment Violet 23 6.0 g CI Solvent Blue 14 3.2 CI Solvent Blue 35 1.6 Tricresyl phosphate 30 di-n-butyl lauramide 30 - Blue Dispersion:
- To 20 g of the blue oil phase was added the following aqueous phase:
Silica dispersion A 22.5 g Silica dispersion B 10.0 Water 92.5 - and the combined mixture was agitated for 5 minutes with a “Soniprobe” ultrasonic probe (supplied by Lucas Dawe Ultrasonics) to form an oil-in-water dispersion. The probe used had a tip diameter of half an inch (1.3 cm) and the power setting employed was 5 or 50%.
- The dispersion was then added to 150 g of 12.5% w/v aqueous gelatin solution containing 0.17% w/v Alkanol XC surfactant.
- Green Oil Phase:
- The following mixture was ball-milled for 3 days using 1 mm diameter zirconia beads as the grinding media:
CI Pigment Green 79.0 g CI Pigment Yellow 92 6.0 tricresyl phosphate 30.0 di-n-butyl lauramide 30.0 ethanol 30.0 - Green Dispersion:
- To 28 g of the green oil phase was added the following aqueous phase:
Silica dispersion A 30.0 g Silica dispersion B 15.0 - Water 72.5
- and the combined mixture was agitated for 5 minutes with a “Soniprobe” ultrasonic probe (supplied by Lucas Dawe Ultrasonics) to form an oil-in-water dispersion. The probe used had a tip diameter of half an inch (1.3 cm) and the power setting employed was 5 or 50%.
- The dispersion was then added to 150 g of 12.5% w/v aqueous gelatin solution containing 0. 17% w/v Alkanol XC surfactant.
- Coating of Color Filter Array:
- Portions of the above dispersions were mixed together:
Red dispersion 82 g Green dispersion 123 Blue dispersion 95 Water 48 - and the resulting mixture was coated on photographic film base at a wet coverage of 35 ml per square meter. At the same time, aqueous gelatin layers were coated above and below the filter array layer, to give the following coated laydowns:
- Layer 1: gelatin, 1.0 g/m2
- Layer 2: gelatin, 2.2 g/m2, red oil phase, 0.70 g/m2, green oil phase, 0.75 g/m2, blue oil phase, 0.60 g/m2
- Layer 3: gelatin, 0.72 g/m2.
- On examining the coated layer under a microscope, it was seen that it had dried to give an array of closely packed red, green and blue color elements, approximately circular in shape and having diameters between 5 and 10 micrometers. They were in a single layer, with little overlap between adjacent elements, and about 12% of the total area comprised colorless areas between the colored elements.
- Coating of Light Sensitive Layers:
- A length of the coated color filter array was then coated with photographic emulsion layers so that the emulsion layers were immediately above the layers of the array.
- Emulsion Layer A:
- Fast silver bromoiodide panchromatically sensitized emulsion (tabular grain, average diameter approx. 1.7 μm, thickness 0.13 μm, 4.5 mol % iodide), coated at 0.7 g/m2, together with gelatin, 1.3 g/m2. 4-hydroxy-6-methyl-1,3,3A, 7-tetraazindene, sodium salt, was also present at 1.5 g per mole of silver.
- Emulsion Layer B:
- Mid speed silver bromoiodide panchromatically sensitized emulsion (tabular grain, average diameter approx. 1.1 μm, thickness 0.12 μm, 4.5 mol % iodide), coated at 1.5 g/m2, slow silver bromoiodide panchromatically sensitized emulsion (tabular grain, average diameter approx. 0.7 μm, thickness 0.11 μm, 3 mol % iodide), coated at 1.0 g/m2 together with gelatin, 2.0 g/m2. 4-hydroxy-6-methyl-1,3,3A,7-tetraazindene, sodium salt, was also present at 1.5 g per mole of silver.
- Supercoat:
- Gelatin, 1.6 g/m2, hardener bis(vinylsulphonyl)methane, 0.072 g/m2, and an antihalation dye whose color was dischargeable in the developer solution, coated as a particulate dispersion, 0.1 g/m2.
- Surfactants used to aid the coating operation are not listed in this example.
- Recording a Scene with the Film:
- A length of the film was slit to 35 mm width, the edges were perforated, the film was put in a standard 35 mm cassette, and the cassette loaded into a single lens reflex camera. The film was oriented so that light from the camera lens passed first through the film base, then through the coated color filter array, and then onto the emulsion layers.
- The camera was adjusted to give an exposure at a speed setting of 200 ISO, and a photograph taken of an outdoor scene.
- The exposed film was developed for 2 minutes at 25 C in the following developer solution:
sodium carbonate (anh.) 9 g/l ascorbic acid 7.5 sodium sulphite (anh.) 2.5 sodium bromide 0.5 4-hydroxymethyl-4-methyl- 0.35 -1-phenyl-3-pyrazolidone pH adjusted to 10.0 with dilute sodium hydroxide solution. - It was treated for 15 s with a stop bath (1% acetic acid aqueous solution) and fixed for 1 minute in Kodak “3000” Fixer Solution diluted 1+3 with water, then washed for 3 minutes and dried. A colored negative image of the scene was visible.
- The image was then scanned with a Kodak RFS 2035 scanner and the resulting image file imported into Adobe Photoshop™ image manipulation software. The “Autolevels” command was used to correct overall brightness, contrast and color balance, then the image was converted to L*a*b* color space. The a and b channels were treated with a blurring filter (Gaussian blur, 12 pixels radius) then their contrast increased using a numerical value of 75, which resulted in a strong increase in color saturation. The image was converted back to R,G,B space and color saturation and color balance adjusted to give a pleasing colored image of the original scene.
- As stated earlier the invention uses existing photographic manufacturing methods such as oil-in-water dispersion and photographic coating which means that no new equipment is required. The invention results in a simplified and economical process when compared with the known prior art.
- The invention has been described with particular reference to one example. It will be understood by those skilled in the art that variations and modifications may be effected within the spirit and scope of the invention as defined in the appended claims.
- 1. colored elements
- 2. binder
- 3. film
- 4. support
- 5. color filter array
- 6. emulsion layer
- 7. supercoat
- 8. antihalation layer
Claims (11)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB0006940.1A GB0006940D0 (en) | 2000-03-23 | 2000-03-23 | Method of making a random colour filter array |
| GB0006940 | 2000-03-23 | ||
| GB0006940.1 | 2000-03-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20010038956A1 true US20010038956A1 (en) | 2001-11-08 |
| US6365304B2 US6365304B2 (en) | 2002-04-02 |
Family
ID=9888193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US09/808,844 Expired - Fee Related US6365304B2 (en) | 2000-03-23 | 2001-03-15 | Method of making a random color filter array |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6365304B2 (en) |
| EP (1) | EP1136882A3 (en) |
| JP (1) | JP2001271036A (en) |
| GB (1) | GB0006940D0 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11467483B1 (en) * | 2020-01-22 | 2022-10-11 | Penumbra Foundation | Photographic color image using black and while emulsion |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8989516B2 (en) | 2007-09-18 | 2015-03-24 | Fotonation Limited | Image processing method and apparatus |
| US8417055B2 (en) * | 2007-03-05 | 2013-04-09 | DigitalOptics Corporation Europe Limited | Image processing method and apparatus |
| US8264576B2 (en) * | 2007-03-05 | 2012-09-11 | DigitalOptics Corporation Europe Limited | RGBW sensor array |
| US9160897B2 (en) * | 2007-06-14 | 2015-10-13 | Fotonation Limited | Fast motion estimation method |
| US7639889B2 (en) * | 2004-11-10 | 2009-12-29 | Fotonation Ireland Ltd. | Method of notifying users regarding motion artifacts based on image analysis |
| US7636486B2 (en) | 2004-11-10 | 2009-12-22 | Fotonation Ireland Ltd. | Method of determining PSF using multiple instances of a nominally similar scene |
| US8698924B2 (en) | 2007-03-05 | 2014-04-15 | DigitalOptics Corporation Europe Limited | Tone mapping for low-light video frame enhancement |
| US8180173B2 (en) * | 2007-09-21 | 2012-05-15 | DigitalOptics Corporation Europe Limited | Flash artifact eye defect correction in blurred images using anisotropic blurring |
| US8199222B2 (en) * | 2007-03-05 | 2012-06-12 | DigitalOptics Corporation Europe Limited | Low-light video frame enhancement |
| US7639888B2 (en) * | 2004-11-10 | 2009-12-29 | Fotonation Ireland Ltd. | Method and apparatus for initiating subsequent exposures based on determination of motion blurring artifacts |
| EP1812782A4 (en) * | 2004-11-16 | 2010-04-07 | Datacolor Holding Ag | Method for designing a colorimeter having integral cie color-matching filters |
| EP1812781A4 (en) * | 2004-11-17 | 2010-04-07 | Datacolor Holding Ag | Tristimulus colorimeter having integral dye filters |
| US7580130B2 (en) * | 2005-03-23 | 2009-08-25 | Datacolor Holding Ag | Method for designing a colorimeter having integral illuminant-weighted CIE color-matching filters |
| US7474402B2 (en) * | 2005-03-23 | 2009-01-06 | Datacolor Holding Ag | Reflectance sensor for integral illuminant-weighted CIE color matching filters |
| JP4684029B2 (en) * | 2005-07-06 | 2011-05-18 | パナソニック株式会社 | Solid-state imaging device and manufacturing method thereof |
| IES20070229A2 (en) * | 2006-06-05 | 2007-10-03 | Fotonation Vision Ltd | Image acquisition method and apparatus |
| US7773118B2 (en) * | 2007-03-25 | 2010-08-10 | Fotonation Vision Limited | Handheld article with movement discrimination |
| US20080309770A1 (en) * | 2007-06-18 | 2008-12-18 | Fotonation Vision Limited | Method and apparatus for simulating a camera panning effect |
| US20090086064A1 (en) * | 2007-09-27 | 2009-04-02 | Micron Technology, Inc. | Dynamic adaptive color filter array |
| US20100208266A1 (en) * | 2009-02-17 | 2010-08-19 | Colman Shannon | Tristimulus colorimeter having integral dye filters |
| TWI463193B (en) | 2011-11-17 | 2014-12-01 | Au Optronics Corp | Color filter and liquid crystal display |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US822532A (en) * | 1904-11-22 | 1906-06-05 | Auguste Lumiere | Photographic plate for color photography. |
| US3728116A (en) * | 1971-06-15 | 1973-04-17 | Gaf Corp | Instant access one-layer color photography |
| US4971869A (en) | 1989-06-19 | 1990-11-20 | Polaroid Corporation | Color encoding photographic film |
| GB9512364D0 (en) | 1995-06-17 | 1995-08-16 | Kodak Ltd | Photographic silver halide materials |
| JPH11223721A (en) * | 1998-02-06 | 1999-08-17 | Konica Corp | Color filter, silver halide photographic sensitive material, image forming method, treatment of silver halide photographic sensitive material, exposing method of silver halide photographic sensitive material and recovering method of resource |
-
2000
- 2000-03-23 GB GBGB0006940.1A patent/GB0006940D0/en not_active Ceased
-
2001
- 2001-03-15 EP EP01200965A patent/EP1136882A3/en not_active Withdrawn
- 2001-03-15 US US09/808,844 patent/US6365304B2/en not_active Expired - Fee Related
- 2001-03-21 JP JP2001080170A patent/JP2001271036A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11467483B1 (en) * | 2020-01-22 | 2022-10-11 | Penumbra Foundation | Photographic color image using black and while emulsion |
| US12468215B2 (en) | 2020-01-22 | 2025-11-11 | Penumbra Foundation | Photographic color image using black and white emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1136882A3 (en) | 2002-05-08 |
| GB0006940D0 (en) | 2000-05-10 |
| US6365304B2 (en) | 2002-04-02 |
| EP1136882A2 (en) | 2001-09-26 |
| JP2001271036A (en) | 2001-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6365304B2 (en) | Method of making a random color filter array | |
| US6326108B2 (en) | Random color filter array | |
| US6387577B2 (en) | Film with random color filter array | |
| US6599668B2 (en) | Process for forming color filter array | |
| JPH06266065A (en) | Method for obtaining of individual imagelike exposure records and photographic element for it | |
| DE69407203T2 (en) | Photographic elements for producing blue, green and red exposure pictures with the same shade of color and method for the recovery and differentiation of exposure pictures | |
| US6607873B2 (en) | Film with color filter array | |
| JPS6235352A (en) | Method and device for forming image | |
| US6555278B1 (en) | Color filter array film | |
| US6602656B1 (en) | Silver halide imaging element with random color filter array | |
| DE69033875T2 (en) | COLOR IMAGE PROCESS | |
| EP0935168B1 (en) | Silver halide light sensitive photographic material | |
| US12468215B2 (en) | Photographic color image using black and white emulsion | |
| JPS6325651A (en) | Multi-color laser recording | |
| DE69419870T2 (en) | Spatially fixed absorber dyes in less sensitive layers | |
| DE60119243T2 (en) | Motion picture film element | |
| GB2294777A (en) | Photographic colour material | |
| JPS63202739A (en) | Silver halide color photographic sensitive material having good reproducibility | |
| JPH04285950A (en) | Image forming method | |
| JP2005165175A (en) | 3-dimensional image display method, 3-dimensional image display material, and forgery-proof layered product, forgery-proof card and forgery-proof printed matter using the same | |
| JP2000221638A (en) | Silver halide color photographic sensitive material and manufacture of color proof | |
| JPH01112238A (en) | Formation of silver halide color photographic image | |
| JPH05113633A (en) | Color image forming method | |
| JP2003202655A (en) | Dye fixing element for color diffusion transfer process and image forming method using the same | |
| WO1994001803A1 (en) | Method of constructing light-sensitive materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: EASTMAN KODAK COMPANY, NEW YORK Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:SIMONS, MICHAEL J.;REEL/FRAME:011664/0398 Effective date: 20010226 |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| AS | Assignment |
Owner name: OMNIVISION TECHNOLOGIES, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:EASTMAN KODAK COMPANY;REEL/FRAME:026227/0213 Effective date: 20110415 |
|
| FEPP | Fee payment procedure |
Free format text: PAYER NUMBER DE-ASSIGNED (ORIGINAL EVENT CODE: RMPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| REMI | Maintenance fee reminder mailed | ||
| LAPS | Lapse for failure to pay maintenance fees | ||
| STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
|
| FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20140402 |