US2633422A - Process for making integral color correction masks - Google Patents
Process for making integral color correction masks Download PDFInfo
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- US2633422A US2633422A US22300A US2230048A US2633422A US 2633422 A US2633422 A US 2633422A US 22300 A US22300 A US 22300A US 2230048 A US2230048 A US 2230048A US 2633422 A US2633422 A US 2633422A
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- silver
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- 238000000034 method Methods 0.000 title claims description 37
- 230000008569 process Effects 0.000 title claims description 24
- 238000012937 correction Methods 0.000 title description 6
- -1 AMINO Chemical class 0.000 claims description 21
- 150000001989 diazonium salts Chemical class 0.000 claims description 18
- 230000000873 masking effect Effects 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 239000012954 diazonium Substances 0.000 claims description 13
- 239000000839 emulsion Substances 0.000 claims description 12
- 150000001241 acetals Chemical class 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001228 spectrum Methods 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- XLKGMMIGYSYARU-UHFFFAOYSA-N N-(3-formylphenyl)-2-hydroxy-3-methylbenzamide Chemical compound CC1=C(C(C(=O)NC=2C=C(C=O)C=CC2)=CC=C1)O XLKGMMIGYSYARU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000001429 visible spectrum Methods 0.000 claims description 2
- UBAOEYGRGUWZPT-UHFFFAOYSA-N n-(3-formylphenyl)-3-oxo-3-phenylpropanamide Chemical compound O=CC1=CC=CC(NC(=O)CC(=O)C=2C=CC=CC=2)=C1 UBAOEYGRGUWZPT-UHFFFAOYSA-N 0.000 claims 1
- 239000000975 dye Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 230000009102 absorption Effects 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000003086 colorant Substances 0.000 description 15
- 238000005859 coupling reaction Methods 0.000 description 15
- 238000010168 coupling process Methods 0.000 description 14
- 230000008878 coupling Effects 0.000 description 12
- 238000011161 development Methods 0.000 description 11
- 230000033458 reproduction Effects 0.000 description 10
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 150000008049 diazo compounds Chemical class 0.000 description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- UEUIKXVPXLWUDU-UHFFFAOYSA-N 4-diazoniobenzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=C([N+]#N)C=C1 UEUIKXVPXLWUDU-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002429 hydrazines Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 229950000244 sulfanilic acid Drugs 0.000 description 4
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006149 azo coupling reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 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
- 238000012545 processing Methods 0.000 description 3
- 150000004060 quinone imines Chemical class 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000001043 yellow dye Substances 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- PFRYFZZSECNQOL-UHFFFAOYSA-N 2-methyl-4-[(2-methylphenyl)diazenyl]aniline Chemical compound C1=C(N)C(C)=CC(N=NC=2C(=CC=CC=2)C)=C1 PFRYFZZSECNQOL-UHFFFAOYSA-N 0.000 description 2
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 2
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 2
- PNPCRKVUWYDDST-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1 PNPCRKVUWYDDST-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- PBGKNXWGYQPUJK-UHFFFAOYSA-N 4-chloro-2-nitroaniline Chemical compound NC1=CC=C(Cl)C=C1[N+]([O-])=O PBGKNXWGYQPUJK-UHFFFAOYSA-N 0.000 description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 2
- CMOLPZZVECHXKN-UHFFFAOYSA-N 7-aminonaphthalene-1,3-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=CC(N)=CC=C21 CMOLPZZVECHXKN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 235000021384 green leafy vegetables Nutrition 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- NRZRRZAVMCAKEP-UHFFFAOYSA-N naphthionic acid Chemical compound C1=CC=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 NRZRRZAVMCAKEP-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 1
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- GVBHRNIWBGTNQA-UHFFFAOYSA-N 2-methoxy-4-nitroaniline Chemical compound COC1=CC([N+]([O-])=O)=CC=C1N GVBHRNIWBGTNQA-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- QFMJFXFXQAFGBO-UHFFFAOYSA-N 4-methoxy-2-nitroaniline Chemical compound COC1=CC=C(N)C([N+]([O-])=O)=C1 QFMJFXFXQAFGBO-UHFFFAOYSA-N 0.000 description 1
- XTBFKMDOQMQYPP-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine;hydron;chloride Chemical compound Cl.CCN(CC)C1=CC=C(N)C=C1 XTBFKMDOQMQYPP-UHFFFAOYSA-N 0.000 description 1
- WBSMIPLNPSCJFS-UHFFFAOYSA-N 5-chloro-2-methoxyaniline Chemical compound COC1=CC=C(Cl)C=C1N WBSMIPLNPSCJFS-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 125000000043 benzamido group Chemical group [H]N([*])C(=O)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
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- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
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- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical class ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JLXXLCJERIYMQG-UHFFFAOYSA-N phenylcyanamide Chemical class N#CNC1=CC=CC=C1 JLXXLCJERIYMQG-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001008 quinone-imine dye Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 239000001060 yellow colorant Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
- G03C7/18—Processes for the correction of the colour image in subtractive colour photography
Definitions
- This invention relates to processes of color photography. More particularly it relates to processes of duplicating subtractive color reproductions of an original scene. Still more particularly it relates to such processes wherein color correction of subtractive colors is accomplished by a novel integral masking procedure.
- subtractive three-color reproduction processes utilize three colorants which are complementary in color, respectively, to three primary analysis colors.
- the analysis colors are red, green, and blue, and the colorants, cyan (blue-green), magenta, and yellow. Facsimile reproduction of a colored subject is never achieved because no set of three subtractive colorants, e. g., dyes, pigments, etc., with ideal spectral absorption are known.
- Cyan colorants for example, absorb in both the blue and green region of the spectrum.
- Magenta colorants absorb in the blue and red regions of the spectrum, and yellow colorants ab-; sorb in the green region of the spectrum.
- the present invention avoids all of these disadvantages and provides a method of great flexibility for controlling color reproduction as is shown in subsequent paragraphs.
- An object of this invention is to improve the duplication of subtractive color reproductions. Another object is to provide a practical manner of correcting the undesirable absorption of subtractive color formers. A further object is to provide a practical method of correcting the undesirable absorption of subtractive color formers by the generation of colored masks in the layers containing color-developed dye images. Still l 2 other objects will be apparent from the following description of the invention.
- the invention is especially useful in the treatment of multilayer monopack film elements:
- the film element is first exposed in a camera or from separation records, or from a positive subtractive color transparency,
- cyan, magenta, and yellow dye im- The element is then subjected to a dye-generation such that the residual cyan (minus-red) color former ages in situ with metallic silver images.
- the colored masks which are produced are of a contrast opposite in sign to that of the primary images since the density of masking dye in any area is inversely proportional to the density of the color-developed dye image in that area.
- contrast and density of the mask images may .be
- the quinoneimine dyes which may be obtained from these dye intermediates by interaction with oxidized p-amino diethylaniline may be represented in the form of a composite plot of their spectrophotometric curves as shown in Figure I of the accompanying drawing.
- the densities orv the individual components have been chosen to yield the closest approximation to composite neutral.
- the total density of the three components at each wave length is represented by the irregular black line in the vicinity of the horizontal axis corresponding to density 1.0.
- True neutral, as represented by the straight line at density 1.0 will never be achieved with any mixture of three real subtractive printing colors, but it should be recognized that the irregular black line represents a visually acceptable neutral.
- This mask should have selective absorption for blue. In other words, it may be yellow.
- the blue absorption of the magenta subtractive primary may be compensated for by means of a mask of opposite gamma which absorbs blue light.
- the numerical value of the gamma of the mask is dependent upon the amount of undesired blue absorption by the magenta component.
- the cyan component of the figure exhibits undesirable absorption in both the blue and green portions of the spectrum.
- a correcting mask which absorbs in both regions, to avoid contamination of blue and green primary analysis records, should be orange-red in color and the com trast of the mask may be determined, as above, in accordance with the relative absorption of green and blue by the cyan component.
- the yelq' low subtractive primary of the figure is reasonably satisfactory and requires no correction.
- Multilayer monopack films which contain the integral masks described above in the magenta and cyan dye image layers can be used in several ways, e. g.,
- dupe color negative serving as an intermediate step in reproducing from a positive (reversal) monopack original or from primary analysis black and white separation records.
- the preferred method of forming the color masks in the image-bearing layers as described above is by azo coupling. This may be carried out by means of diazonium salt solutions, stabilized diazo compounds, or by means of the ac-,-
- Preferred diazo compounds for use in the production of the required orange and yellow masks from color coupling components of the conventional type are those derived from aromatic amines with electrophyllic substituents such as COOI-I, SOaH. -NO2, halogen, CN, and CFa.
- a self-masking color duplicate negative may be used to print multiple copies of color corrected positive prints.
- magenta component in the outermost layer of a monopack structure as described in copending application Serial Number 634,255 filed December 11, 1945, now U. S. Patent No. 2,551,086. Such an arrangement may be readily achieved with the present process, while maintaining the automatic masking.
- Suitable specific compounds are those derived from metanilic acid, sulfanilic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-chloroaniline, p-chloroaniline, cyano-anilines or m-aminobenzotrifluoride, naphthionic acid, m-xylidine, 2-naphthylamine-6,8-disulfonic acid, and l-chloro-Z-aminotoluene.
- any other diazo compounds may be employed, those listed are well suited to producin colorless or nearly colorless reaction products from conventional yellow color formers while yielding the desired orange and yellow masks from the cyan and magenta components, respectively.
- the useful stabilized diazo salts are the zinc chloride complexes and organic stabilized diazos.
- diazo compounds from which diazo compounds can be generated, e. g., diazoiminos, triazines and nitrosoamines and anti-diazotates.
- Different diazo salts may be employed, for example, by treating the outermost layer of a monopack structure with a diazo salt solution of such composition as to retard the penetration of the diazonium compound, thereby limiting or restricting its action to an upper layer in the monopack structure. Subsequently, a diiferent diazonium compound may be caused to react upon the second, third, or lowermost layer either in separate stages or simultaneously. Such a procedure may be particularly advantageous in order to completely couple the coupling component in the outermost layer with a diazonium compound which yields thereby a substantially colorless or extremely pale yellow azo dye. This procedure may be employed when no integral mask is required to be introduced into the outermost layer, i. e., that carrying the yellow subtractive component. Following the complete coupling of this layer a different diazonium compound may be utilized to yield the desired mask for the remaining subtractive component.
- diazonium compounds A large number of other diazonium compounds is available for use in the alternative procedure just described.
- stabilized salts which may be employed are the diazo salts from the following amines: meta-chloroaniline, meta-nitropara-anisidine, ortho-aminoazotoluene, l-aminoanthraquinone, 5-nitro-2-aminoanisole, metanitro-para-toluidine, 4-chloro-2-nitroaniline, 4- chloro-2-aminoanisole, 2,5-dichloroaniline, 4- nitro-Z-aminoanisole, 4-chloro-2-nitroaniline and the tetrazo salt from o-dianisidine.
- the zinc chloride and other stabilized salts can be used.
- Dye coupling reactions other than azo coupling similarly may be employed in order to produce one or more integral masks by reaction with residual or unused color formers.
- Other reducing agents which are capable of undergoing coupling in their oxidized form may be employed; 1. e., 1,4- naphthalene diamine-Y-sulfonic acid is a color coupling developer and yields a yellow color upon reaction with l-phenyl-3-methyl-pyrazolone-5 and thereby may be utilized to produce a mask for correction of the undesired blue absorption films is the preferred basis of rawstocks to be used in the masking processing since such stocks will withstand wide variations in processing, including temperature.
- the process itself is particularly advantageous for the production of intermediate color dupes in motion picture production whereby final release prints may be prepared in unlimited quantity without the necessity for registration printing and without attendant color degradation.
- Multilayer films containing non-diffusing com pounds in conventional colloid silver halide emulsions may be utilized for masking procedures of similar type, although their use does not afford the latitude in processing that is possible with the hydrophilic color-former polymer structures.
- Many combinations of steps may be employed in processes of color reproduction for still and motion pictures in which the masking procedure may occur as an initial or as an intermediate step in the complete process. More than one masking step may be included in the complete process if several subtractive stages are involved.
- Example I A photographic element comprising a trans-- parent support and a light-sensitive silver halide layer utilizing as the colloid binding medium a hydrophilic polyvinyl acetal color former containing several naphthol sulfonamide groupings of the structure:
- Example II 1 A photographic element characterized by colorcoupling groupings of the structure:
- Example III Elements in which the light-sensitive layers were the same as those described in Example I were processed by color-coupling development, followed by a second color generating reaction employing a solution of diazotized-p-aminobenzoic acid.
- a second color generating reaction employing a solution of diazotized-p-aminobenzoic acid.
- an orange 8. mask was obtained from the element yielding a cyan image from color-coupling development, a yellow mask from the magenta element, and a substantially colorless reaction product from the yellow element.
- Example IV A photographic element of a type similar to that described in Example I, but characterized by color-former nuclei of the structure:
- Example V A photographic element of a m-(3-methylsalicylamido) -benzaldehyde polyvinyl acetal similar to that employed in Example IV was exposed and color-developed in the usual manner and several samples were then treated at room temperature with .5% solutions of stabilized diazo compounds as follows to give masks of the color shown in the table:
- Example VII A result similar to that of Example VI was obtained by bathing the color-developed sample, after fixing and washing, in the solution of the aniline-diazoamino derivative. Hydrolysis and sample in an atmosphere of about 100% relative humidity at a temperature of about 90 to 100 C.
- Example VIII A multilayer film element having the following strata, in order, on a transparent support:
- a thin colorless separator layer of a hydrophilic hydrolyzed ethylene vinyl acetate interpolymer is a hydrophilic hydrolyzed ethylene vinyl acetate interpolymer.
- An emulsion layer for color development of magenta like that of Example I and containing a yellow filter dye, e. g., Tartrazine (Colour Index No. 640) was exposed to a graduated step tablet and through three red, green and blue primary filters.
- a yellow filter dye e. g., Tartrazine (Colour Index No. 640)
- the element was processed as in Example I by color developing with p-amino-diethylaniline, bleaching, fixing, washing, and treating with diazotized sulfanilic acid of the same strength. A multicolor negative image with superimposed orange and yellow masks was obtained.
- Example IX A photographic element characterized by pyrazolone nuclei of the type used in Example I was exposed and processed by color coupling development to yield a magenta dye image. Without fixing, the element was washed thoroughly, re-exposed and redeveloped in a developer like that employed in Example I, but containing in place of the p-amino-diethylaniline, 2 grams of 1,4-naphthylenediamine-'I-sulfonic acid. After washing, the element was bleached, fixed and rewashed whereby a primary magenta image and a superposed yellow mask image were produced.
- the second development step is carried out with an aromatic hydrazine or hydrazine derivative
- superposed masks may be generated under conditions of control which may be regulated by variation in second exposure, duration of treatment, and other conditions.
- the second colorgenerating step of this example which is used for formation of the masking image by exposure and development, can be modified by using a developer solution of a hydrazine as described in United States Patent 2,220,929 (Example I).
- hydrazine derivatives such as N- acyl-N-arylhydrazines (French Patent 925,609) or sulfonhydrazides (disclosed in United States Patent 2,424,256) may be employed for developing the secondary masking images by reduction of exposed silver salts and coupling with residual color-former nuclei.
- Example X Photographic elements of the three types described in Examples I, II, and III above were bathed in a fixer to dissolve silver halides, then washed and dried. Samples of each of the elements so prepared were then bathed in solutions of diazonium salts of the amines listed in the table below. These solutions were prepared by diazotization of the several amines, adjustment (with sodium acetate) of the pH of the resulting diazonium salt solutions to neutrality, and dilution of the solutions with water to yield concentrations of 0.05% based on the weights of the amines used.
- Heading columns 2, 3, and 4 are the colors which the three respective photographic elements yielded when exposed and developed as in Examples I, II, and III above. Also in these columns are listed the dye colors which the respective elements yielded when treated in diazonium salt solutions as in the preceding paragraph.
- Example XII A photographic element like that of Example I was prepared by substituting for the hydrophilic color former 4-methoxy-3-(benzoylacetamido) benzaldehyde polyvinyl acetal.
- the latter compound can be made after the manner taught in United States Patent 2,310,943 by acetalizing polyvinyl alcohol with i-methoxy-B-(benzoylacetamido benzaldehyde or its ethylene glycol acetal.
- the element was then exposed and developed in a developer similar to that in Example I.
- the developed color resulting from coupling (with the p-amino-diethylaniline hydrochloride of the developer) was yellow.
- the element was bathed for five minutes in a diazonium salt solution prepared by diazotizing sulfanilic acid, adjusting to neutral pH with sodium acetate, and diluting to 0.05% concentration (based on the weight of sulfanilic acid). No coloration of the 11 element was produced by the treatment in the diazonium salt solution.
- this element exhibits properties ideal for theyellow polymer layer of a film described earlier as a negative employing integral masking.
- the invention has the additional advantage that it provides a practical and effective process for correcting the undesirable absorption of quinoneimine and azomethine dye images in the reproduction of subtractive originals.
- a further advantage is that the process provides a full neutral scale, and saturated orange, red and yellow colors are produced.
- a still further advantage is that good control of color densities is achieved and their relative proportions in the grays are the same as if no masking had been employed,
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Description
March 31, 1953 A. B. JENNINGS 2,633,422
pnocass FOR' MAKING INTEGRAL 001.01: CORRECTION MASKS Filed April 21, 1948 (D z .40 I I m TOTALDENSV '7 .20 LOO ,a-TRUE' NIEUTRAL .80 gusrrv v /CYAN .60
.4 MAGENTA 400 I Y 500 e00. 700
WAVELENGTH mmvroa.
ANDREW BRADSHAW JENNINGS ATTORNEY Patented Mar. 31, 1953 PROCESS FOR MAKING INTEGRAL COLOR CORRECTION MASKS Andrew Bradshaw Jennings, New Brunswick,
N. J., assignor to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware Application April 21, 1948, Serial No. 22,300
4 Claims.
This invention relates to processes of color photography. More particularly it relates to processes of duplicating subtractive color reproductions of an original scene. Still more particularly it relates to such processes wherein color correction of subtractive colors is accomplished by a novel integral masking procedure.
subtractive three-color reproduction processes utilize three colorants which are complementary in color, respectively, to three primary analysis colors. The analysis colors are red, green, and blue, and the colorants, cyan (blue-green), magenta, and yellow. Facsimile reproduction of a colored subject is never achieved because no set of three subtractive colorants, e. g., dyes, pigments, etc., with ideal spectral absorption are known. Cyan colorants, for example, absorb in both the blue and green region of the spectrum. Magenta colorants absorb in the blue and red regions of the spectrum, and yellow colorants ab-; sorb in the green region of the spectrum.
It has been previously proposed to employ colored couplers for masking but it was difficult, if not impossible, to find such compounds capable of yielding correct density and contrast values for both the primary color component image and the, masking images. In order to overcome this difficulty it has been proposed to utilize mixtures of colored and colorless coupler which yield dyes of the same hue on color development. Even this method, however, suffers from the difficulty of finding such combinations in which the colored and uncolored couplers are capable of coupling at the proper rate in relation to each other. Moreover, the use of colored substances in the lightsensitive layers of a photographic element introduces filtering effects, thereby reducing the eliective sensitivity of the element. The use of colored couplers in a photographic element imposes severe limitations on the choice of layer arrangements and precludes the use of such elements for any other purpose.
The present invention avoids all of these disadvantages and provides a method of great flexibility for controlling color reproduction as is shown in subsequent paragraphs.
An object of this invention is to improve the duplication of subtractive color reproductions. Another object is to provide a practical manner of correcting the undesirable absorption of subtractive color formers. A further object is to provide a practical method of correcting the undesirable absorption of subtractive color formers by the generation of colored masks in the layers containing color-developed dye images. Still l 2 other objects will be apparent from the following description of the invention.
It has been found that the deficiencies of cyan and magenta color-developed quinoneimine. or azomethine dye images, whereby they absorb in the blue and green and blue regions, respectively, of the spectrum, can be compensated for by superimposing on the cyan and magenta image components colored masks which absorb in the regions of undesired absorptions, which they are intended to correct, by a dye coupling and preferably an azo coupling procedure in which the residual color formers in the image areas and reverse areas couple whereby a dye. e. g., an azo dye of spectral properties difiering from those of the quinoneimine or azomethine dye images, is formed. The silver and silver salts are removed, leaving the dye images and integral color mask. When the resulting image-bearing layer is printed onto a light-sensitive photographic element,
the undesirable absorption characteristics of the dye images are automatically compensated for.
The invention is especially useful in the treatment of multilayer monopack film elements:
which contain light-sensitive silver halide layers and subtractive cyan, magenta, and yellow color formers in the appropriate layers.
gion of the spectrum. The film element is first exposed in a camera or from separation records, or from a positive subtractive color transparency,
then developed in an aqueous developer solution containing a primary aromatic amino developing agent to yield cyan, magenta, and yellow dye im- The element is then subjected to a dye-generation such that the residual cyan (minus-red) color former ages in situ with metallic silver images.
is converted into an orange dye and the residual magenta (minus-green) color former is converted into a yellow dye in the respective layers. The colored masks which are produced are of a contrast opposite in sign to that of the primary images since the density of masking dye in any area is inversely proportional to the density of the color-developed dye image in that area. The
contrast and density of the mask images may .be
varied, thus making the process one of great ver- The yellow color formers need not be compensated for because of their slight absorption in the green remoans-Q H (l H:
Ha I The quinoneimine dyes which may be obtained from these dye intermediates by interaction with oxidized p-amino diethylaniline may be represented in the form of a composite plot of their spectrophotometric curves as shown in Figure I of the accompanying drawing. In this figure, the densities orv the individual components have been chosen to yield the closest approximation to composite neutral. The total density of the three components at each wave length is represented by the irregular black line in the vicinity of the horizontal axis corresponding to density 1.0. True neutral, as represented by the straight line at density 1.0 will never be achieved with any mixture of three real subtractive printing colors, but it should be recognized that the irregular black line represents a visually acceptable neutral. This selection of neutral density 1.0 has been made because it will be apparent that the densities of the individual color components are proportional to their relative contrasts. The term density in this specification, as referred to a color component, is the maximum density as read from the spectrophotometric curve.
In making a tricolor analysis of the film represented in the figure, three monochromatic bands of wave lengths 440, 540, and 660 millimicrons are used. It will be noted that at each of these wave lengths, density is contributed by all three components. Specifically, these densities may be tabulated as follows:
Table I 440 mu I 540 Inn 660 mu .64 .04 .00 .39 1.02 .06 Cyan l2 l0 96 Consider now the function of the magenta image component: ideally it should modulate only the green analysis primary; yet, it exhibits a small amount of density in the red region which, in fact, can be ignored, but a very appreciable absorption of blue light is evident which cannot be ignored. If, however, a mask derived from the magenta image component be superimposed upon the monopack, cancellation of the efiective absorption of blue light by the magenta component will have been realized provided that the contrast of the mask is opposite in sign and proportional to the ratio of blue to green densities of the magenta component. This mask should have selective absorption for blue. In other words, it may be yellow. Thus it is seen that the blue absorption of the magenta subtractive primary may be compensated for by means of a mask of opposite gamma which absorbs blue light. The numerical value of the gamma of the mask is dependent upon the amount of undesired blue absorption by the magenta component.
The cyan component of the figure exhibits undesirable absorption in both the blue and green portions of the spectrum. A correcting mask which absorbs in both regions, to avoid contamination of blue and green primary analysis records, should be orange-red in color and the com trast of the mask may be determined, as above, in accordance with the relative absorption of green and blue by the cyan component. The yelq' low subtractive primary of the figure is reasonably satisfactory and requires no correction.
Multilayer monopack films which contain the integral masks described above in the magenta and cyan dye image layers can be used in several ways, e. g.,
1. As a color negative camera film for original recording.
2. As a color reversal positive camera film for original recording.
As a dupe color negative serving as an intermediate step in reproducing from a positive (reversal) monopack original or from primary analysis black and white separation records.
The preferred method of forming the color masks in the image-bearing layers as described above is by azo coupling. This may be carried out by means of diazonium salt solutions, stabilized diazo compounds, or by means of the ac-,-
tion of hydrazines and derivatives of hydrazines' together with exposed silver salts. Preferred diazo compounds for use in the production of the required orange and yellow masks from color coupling components of the conventional type are those derived from aromatic amines with electrophyllic substituents such as COOI-I, SOaH. -NO2, halogen, CN, and CFa.
In processes of automatic integral masking which have been proposed heretofore, it is usually necessary to maintain a normal" arrangement of layer sensitivity and respective color generating capacity for those layers. This normal arrangement involves the use of an outermost blue-sensitive layer which is subsequently converted into a yellow image component. The remaining layers are usually green and red-sensitive in that order, each layer being responsible for an image component in its complementary color.
In a preferred form of the present invention, a self-masking color duplicate negative may be used to print multiple copies of color corrected positive prints. For processes of color cinematography which require an accompanying sound record, it has been shown to be advantageous to provide the magenta component in the outermost layer of a monopack structure as described in copending application Serial Number 634,255 filed December 11, 1945, now U. S. Patent No. 2,551,086. Such an arrangement may be readily achieved with the present process, while maintaining the automatic masking.
In practice, moreover, the deviations from ideal maskingwhich may be actually obtainable, can be readily adjusted so as to place emphasis on superior reproduction of reds, blues, or greens in accordance with the requirements at hand. Controls of this type may be exercised in the present process since it is possible to use any combination of layer sensitivity and distribution of color generating elements, thus making the process possess great flexibility and versatility not found in previously proposed methods.
Suitable specific compounds are those derived from metanilic acid, sulfanilic acid, anthranilic acid, m-aminobenzoic acid, p-aminobenzoic acid, o-chloroaniline, p-chloroaniline, cyano-anilines or m-aminobenzotrifluoride, naphthionic acid, m-xylidine, 2-naphthylamine-6,8-disulfonic acid, and l-chloro-Z-aminotoluene. Although any other diazo compounds may be employed, those listed are well suited to producin colorless or nearly colorless reaction products from conventional yellow color formers while yielding the desired orange and yellow masks from the cyan and magenta components, respectively.
Among the useful stabilized diazo salts are the zinc chloride complexes and organic stabilized diazos. There can also be used derivatives of diazo compounds from which diazo compounds can be generated, e. g., diazoiminos, triazines and nitrosoamines and anti-diazotates.
Different diazo salts may be employed, for example, by treating the outermost layer of a monopack structure with a diazo salt solution of such composition as to retard the penetration of the diazonium compound, thereby limiting or restricting its action to an upper layer in the monopack structure. Subsequently, a diiferent diazonium compound may be caused to react upon the second, third, or lowermost layer either in separate stages or simultaneously. Such a procedure may be particularly advantageous in order to completely couple the coupling component in the outermost layer with a diazonium compound which yields thereby a substantially colorless or extremely pale yellow azo dye. This procedure may be employed when no integral mask is required to be introduced into the outermost layer, i. e., that carrying the yellow subtractive component. Following the complete coupling of this layer a different diazonium compound may be utilized to yield the desired mask for the remaining subtractive component.
A large number of other diazonium compounds is available for use in the alternative procedure just described. Among such stabilized salts which may be employed are the diazo salts from the following amines: meta-chloroaniline, meta-nitropara-anisidine, ortho-aminoazotoluene, l-aminoanthraquinone, 5-nitro-2-aminoanisole, metanitro-para-toluidine, 4-chloro-2-nitroaniline, 4- chloro-2-aminoanisole, 2,5-dichloroaniline, 4- nitro-Z-aminoanisole, 4-chloro-2-nitroaniline and the tetrazo salt from o-dianisidine. As stated above, the zinc chloride and other stabilized salts can be used.
Dye coupling reactions other than azo coupling similarly may be employed in order to produce one or more integral masks by reaction with residual or unused color formers. Other reducing agents which are capable of undergoing coupling in their oxidized form may be employed; 1. e., 1,4- naphthalene diamine-Y-sulfonic acid is a color coupling developer and yields a yellow color upon reaction with l-phenyl-3-methyl-pyrazolone-5 and thereby may be utilized to produce a mask for correction of the undesired blue absorption films is the preferred basis of rawstocks to be used in the masking processing since such stocks will withstand wide variations in processing, including temperature. The process itself is particularly advantageous for the production of intermediate color dupes in motion picture production whereby final release prints may be prepared in unlimited quantity without the necessity for registration printing and without attendant color degradation.
Multilayer films containing non-diffusing com pounds in conventional colloid silver halide emulsions may be utilized for masking procedures of similar type, although their use does not afford the latitude in processing that is possible with the hydrophilic color-former polymer structures. Many combinations of steps may be employed in processes of color reproduction for still and motion pictures in which the masking procedure may occur as an initial or as an intermediate step in the complete process. More than one masking step may be included in the complete process if several subtractive stages are involved.
In order to control the rate or extent of the supplementary dye generating reactions so as to yield the exact density and contrast which is required in the individual masks, it may be desirable to employ surface active agents which have the efiect of limiting or retarding the rate of consumption of dye-formingagent in the same manner that such agents are employed in textile dyeing to control rate of exhaustion of dye baths thereby producing level dyeing.
The invention will be further illustrated but is not intended to be limited by the following examples.
Example I A photographic element comprising a trans-- parent support and a light-sensitive silver halide layer utilizing as the colloid binding medium a hydrophilic polyvinyl acetal color former containing several naphthol sulfonamide groupings of the structure:
momnQ H obtained as described in United States Patent 2,423,572, was exposed and developed for ten minutes in a color developer of the composition:
p-Amino-N-diethylaniline hydrochloride V2.5 orange.
T again, the element was bathed for five minutes in a diazonium salt solution prepared as follows:
-To 20 cc. of 10% aqueous sodium hydroxide, 8.7 grams of sulfanilic acid were added. The mixture was stirred until solution was complete and then cooled to 5 C. and acidified with 13.5 cc. of concentrated hydrochloric acid. Stirring was maintained in order to secure fine particles of the amine hydrochloride. Cracked ice was added to the mixture so as to maintain a temperature of to C. and a solution of 3.5 grams of sodium nitrite in cc. of water was added with continued stirring. After standing one-half hour, water and cracked ice were added to make up the total volume to about 500 cc. Solid sodium acetate was added until disappearance of a positive test for hydrochloric acid with Congo red test paper. The pH of the solution was about 5.0. The entire solution was filtered and diluted to 1 liter.
To generate a colored mask the washed film strip was bathed for five minutes in a 12.5 cc. portion of the diaz-o solution which had been diluted to 100 cc. After shaking off the surface liquid, the strip was immersed in a solution of 1% ammonia for three minutes, washed thoroughly, and dried. The steps of a graduated exposure on the strip had substantially uniform density to blue and green light and good contrast to red light. The color of the dye mask Example II 1 A photographic element characterized by colorcoupling groupings of the structure:
OONH H 0 O as described in United States application Serial Number 9330 now U. S. Patent No. 2,513,190 filed February 18, 1948, produces a yellow color upon coupling development and a substantially colorless reaction product upon treatment with diazotized sulfanilic acid.
Example III Elements in which the light-sensitive layers were the same as those described in Example I were processed by color-coupling development, followed by a second color generating reaction employing a solution of diazotized-p-aminobenzoic acid. As in the first example, an orange 8. mask was obtained from the element yielding a cyan image from color-coupling development, a yellow mask from the magenta element, and a substantially colorless reaction product from the yellow element.
Example IV A photographic element of a type similar to that described in Example I, but characterized by color-former nuclei of the structure:
CH: --0 ONHQ H dlsclosed in application Serial No. 19,155 filed April 5, 1948 now U. S. Patent No. 2,489,655, was processed in two stages; first, by color development with a p-amino-N-diethylaniline developer solution as described in Example I, and then by coupling with diazotized sulfanilic acid. A minus-red dye image with a superimposed blue and green absorbing mask was obtained.
If the completely processed film element of this example is bathed before drying in a dilute solution of acetic acid or in a buffer solution of about pH 5.0, the color of the mask image is altered to a deeper shade of orange. This treatment has no eifect on the color-developed image or upon the mask image of the magenta and yellow elements of Example I.
Example V A photographic element of a m-(3-methylsalicylamido) -benzaldehyde polyvinyl acetal similar to that employed in Example IV was exposed and color-developed in the usual manner and several samples were then treated at room temperature with .5% solutions of stabilized diazo compounds as follows to give masks of the color shown in the table:
Color of Dye Diazo Salt of Amino Mask m-chloroaniline Orange. m-nitro-p-anisidine. Do. o-amino-azotoluene. Light Red. laminoanthmquinone. -1 Red.
E-nitro-Z-aminoanisola. Magenta.
m-nitro-p-toluidine Orange. 4-chloro-2-nitroaniline Dark Orange. -chloro-2-aminoanisole. range. 2,5-dichloroaniline Yellow 4-nitro-2-aminoanisole.. Orange o-dianisidine Bed.
Ewample VI Example VII A result similar to that of Example VI was obtained by bathing the color-developed sample, after fixing and washing, in the solution of the aniline-diazoamino derivative. Hydrolysis and sample in an atmosphere of about 100% relative humidity at a temperature of about 90 to 100 C.
Example VIII A multilayer film element having the following strata, in order, on a transparent support:
1. An emulsion layer for color-development of a cyan image like that of Example I and sensitized for red light.
' 2. A thin colorless separator layer of a hydrophilic hydrolyzed ethylene vinyl acetate interpolymer.
3. An emulsion layer for color-development or" a yellow image like that of Example I and sensitized for green light.
4. A separator like layer 2.
5. An emulsion layer for color development of magenta like that of Example I and containing a yellow filter dye, e. g., Tartrazine (Colour Index No. 640) was exposed to a graduated step tablet and through three red, green and blue primary filters.
The element was processed as in Example I by color developing with p-amino-diethylaniline, bleaching, fixing, washing, and treating with diazotized sulfanilic acid of the same strength. A multicolor negative image with superimposed orange and yellow masks was obtained.
A similar element was color-developed, washed, U
bleached, fixed, washed and dried to yield a multicolor image without masks. The two processed samples were then printed directly onto a multilayer element of the same construction. The color temperature of the printing source and the duration of the printing exposure were adjusted in each case so as to produce equal, neutral densities, from corresponding highlight areas, in the two reproductions. Marked improvement in the reproduction of the red, green and blue primary colors is apparent in the case of the print from the masked negative as compared to the unmasked print.
Example IX A photographic element characterized by pyrazolone nuclei of the type used in Example I was exposed and processed by color coupling development to yield a magenta dye image. Without fixing, the element was washed thoroughly, re-exposed and redeveloped in a developer like that employed in Example I, but containing in place of the p-amino-diethylaniline, 2 grams of 1,4-naphthylenediamine-'I-sulfonic acid. After washing, the element was bleached, fixed and rewashed whereby a primary magenta image and a superposed yellow mask image were produced.
If in the procedure of this example, the second development step is carried out with an aromatic hydrazine or hydrazine derivative, superposed masks may be generated under conditions of control which may be regulated by variation in second exposure, duration of treatment, and other conditions. For example, the second colorgenerating step of this example, which is used for formation of the masking image by exposure and development, can be modified by using a developer solution of a hydrazine as described in United States Patent 2,220,929 (Example I). Alternatively, hydrazine derivatives such as N- acyl-N-arylhydrazines (French Patent 925,609) or sulfonhydrazides (disclosed in United States Patent 2,424,256) may be employed for developing the secondary masking images by reduction of exposed silver salts and coupling with residual color-former nuclei.
:10 Example X Photographic elements of the three types described in Examples I, II, and III above were bathed in a fixer to dissolve silver halides, then washed and dried. Samples of each of the elements so prepared were then bathed in solutions of diazonium salts of the amines listed in the table below. These solutions were prepared by diazotization of the several amines, adjustment (with sodium acetate) of the pH of the resulting diazonium salt solutions to neutrality, and dilution of the solutions with water to yield concentrations of 0.05% based on the weights of the amines used.
Column 1 of the table lists the amines from 'which the diazonium salt solutions were prepared.
Heading columns 2, 3, and 4 are the colors which the three respective photographic elements yielded when exposed and developed as in Examples I, II, and III above. Also in these columns are listed the dye colors which the respective elements yielded when treated in diazonium salt solutions as in the preceding paragraph.
Amine cal) Comparison of the dye colors listed in the above table with those described in Examples I, II, and III reveals that these colors are proper for use as integral masks to cancel all or part of the undesirable light absorptions of subtractive color dyes as described earlier.
Exampl XI Samples of a photographic element of the type described in Examples IV and V were prepared and treated in diazonium salt solutions as in Example X above. A yellow dye color resulted from such treatment in solutions of the diazonium salts of o-chloro-aniline, p-chloro-aniline, 2-naphthylamine-6,8-disulfonic acid, m-amino-benzotrifluoride, naphthionic acid, and metanilic acid.
Example XII A photographic element like that of Example I was prepared by substituting for the hydrophilic color former 4-methoxy-3-(benzoylacetamido) benzaldehyde polyvinyl acetal. The latter compound can be made after the manner taught in United States Patent 2,310,943 by acetalizing polyvinyl alcohol with i-methoxy-B-(benzoylacetamido benzaldehyde or its ethylene glycol acetal.
The element was then exposed and developed in a developer similar to that in Example I. The developed color resulting from coupling (with the p-amino-diethylaniline hydrochloride of the developer) was yellow. After washing, bleaching, fixing, and washing again, the element was bathed for five minutes in a diazonium salt solution prepared by diazotizing sulfanilic acid, adjusting to neutral pH with sodium acetate, and diluting to 0.05% concentration (based on the weight of sulfanilic acid). No coloration of the 11 element was produced by the treatment in the diazonium salt solution. Thus this element exhibits properties ideal for theyellow polymer layer of a film described earlier as a negative employing integral masking.
Similar effects may be observed when the original primary color exposures are made from an original colored scene or from color separation positives of the original scene by means of red, green and blue primary color filter exposures.
The invention has the additional advantage that it provides a practical and effective process for correcting the undesirable absorption of quinoneimine and azomethine dye images in the reproduction of subtractive originals. A further advantage is that the process provides a full neutral scale, and saturated orange, red and yellow colors are produced. .A still further advantage is that good control of color densities is achieved and their relative proportions in the grays are the same as if no masking had been employed,
but are altered in areas corresponding to strong blues, greens, reds, and yellows.
As many widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.
What is claimed is:
1. The process of making integral color masking images in a multicolor picture made up of subtractive color images which comprises developing with a primary aromatic amino color developing agent, an exposed multilayer photographic film bearing a colloid silver halide emulsion layer initially sensitized to light from one primary color region of the spectrum and including as a cyan color former a m-(3-methylsalicylamido)benzaldehyde polyvinyl acetal, a colloid silver halide emulsion layer initially sensitized to light of a second primary color region of the spectrum including as a magenta color former a m- [p- (3-methy1'1-pyrazolyl) benzamido] -benzaldehyde polyvinyl acetal and a colloid silver halide emulsion layer initially sensitized to a third primary color region of the visible spectrum including as a yellow color former a m-ben zoylacetamidobenzaldehyde polyvinyl acetal, said film initially bearing a stratum containing a yellow filter dye and being arranged so that blue light will not expose two of such emulsion layers, treating the developed element in at least one aqueous solution containing a diazonium salt and removing the silver and silver salts from the resulting film.
2. A process as set forth in claim 1 wherein said polyvinyl acetals are the sole binding agents for the silver halides in the respective layers.
3. A process as set forth in claim 2 wherein a single diazonium salt solution is used.
4. A process as set forth in claim 8 wherein said salt is diazotized sulfanilic acid.
ANDREW BRADSHAW JENNINGS.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,193,931 Michaelis Mar. 19, 1940 2,297,732 Woodward Oct. 6, 1942 2,306,410 Schinzel Dec. 29, 1942 2,449,966 Hanson Sept. 21, 1948 2,431,996 Duerr et al Dec. 2, 1947 2,518,739 Young Aug. 15, 1950
Claims (2)
1. THE PROCESS OF MAKING INTEGRAL COLOR MASKING IMAGES IN A MULTICOLOR PICTURE MADE UP OF SUBTRACTIVE COLOR IMAGES WHICH COMPRISES DEVELOPING WITH A PRIMARY AROMATIC AMINO COLOR DEVELOPING AGENT, AN EXPOSED MULTILAYER PHOTOGRAPHIC FILM BEARING A COLLOIC SILVER HALIDE EMULSION LAYER INITIALLY SENSITIZED TO LIGHT FROM ONE PRIMARY COLOR REGION OF THE SPECTRUM AND INCLUDING AS A CYAN COLOR FORMER A M-(3-METHYLSALICYLAMIDO) BENZALDEHYDE POLYVINYL ACETAL, A COLLOID SILVER HALIDE EMULSION LAYER INITIALLY SENSITIZED TO LIGHT OF A SECOND PRIMARY COLOR REGION OF THE SPECTRUM INCLUDING AS A MAGENTA COLOR FORMER A M-(P-(3-METHYL-L-PYRAZOLY) BENZAMIDO)-BENZALDEHYDE POLYVINYL ACETAL AND A COLLOID SILVER HALIDE EMULSION LAYER INITIALLY SENSITIZED TO A THIRD PRIMARY COLOR REGION OF THE VISIBLE SPECTRUM INCLUDING AS A YELLOW COLOR FORMER A M-BENZOYLACETAMIDOBENZALDEHYDE POLYVINYL ACETAL, SAID FILM INITIALLY BEARING A STRATUM CONTAINING A YELLOW FILTER DYE AND BEING ARRANGED SO THAT BLUE LIGHT WILL NOT EXPOSE TWO OF SUCH EMULSION LAYERS, TREATING THE DEVELOPED ELEMENT IN AT LEAST ONE AQUEOUS SOLUTION CONTAINING A DIAZONIUM SALT AND REMOVING THE SILVER AND SILVER SALTS FROM THE RESULTING FILM.
2. A PROCESS AS SET FORTH IN CLAIM 1 WHEREIN SAID POLYVINYL ACETALS ARE THE SOLE BINDING AGENTS FOR THE SILVER HALIDES IN THE RESPECTIVE LAYERS.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US22300A US2633422A (en) | 1948-04-21 | 1948-04-21 | Process for making integral color correction masks |
GB10064/49A GB665657A (en) | 1948-04-21 | 1949-04-13 | Improvements in or relating to colour photography |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US22300A US2633422A (en) | 1948-04-21 | 1948-04-21 | Process for making integral color correction masks |
Publications (1)
Publication Number | Publication Date |
---|---|
US2633422A true US2633422A (en) | 1953-03-31 |
Family
ID=21808881
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US22300A Expired - Lifetime US2633422A (en) | 1948-04-21 | 1948-04-21 | Process for making integral color correction masks |
Country Status (2)
Country | Link |
---|---|
US (1) | US2633422A (en) |
GB (1) | GB665657A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2704709A (en) * | 1949-07-16 | 1955-03-22 | Gen Aniline & Film Corp | Masking process for multilayer photographic color film |
US2994607A (en) * | 1956-11-20 | 1961-08-01 | Agfa Ag | Process for the production of color-corrected color photographic images |
US3338711A (en) * | 1962-11-15 | 1967-08-29 | Du Pont | Process for forming azo dye photographic images |
US4557998A (en) * | 1985-01-02 | 1985-12-10 | Eastman Kodak Company | Colorless ligand-releasing monomers and polymers and their use to provide dyes with metal ions |
US4680356A (en) * | 1985-01-02 | 1987-07-14 | Eastman Kodak Company | Colorless ligand-releasing monomers and polymers and their use to provide dyes with metal ions |
US5695914A (en) * | 1995-09-15 | 1997-12-09 | Eastman Kodak Company | Process of forming a dye image |
US6279300B1 (en) | 1999-02-12 | 2001-08-28 | Ebrahim Simhaee | Method of manufacturing air cell dunnage |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2193931A (en) * | 1936-03-24 | 1940-03-19 | Bela Gaspar | Process for producing multicolored photographic images |
US2297732A (en) * | 1940-05-15 | 1942-10-06 | Du Pont | Photographic color process involving the formation of azo dye images |
US2306410A (en) * | 1936-07-07 | 1942-12-29 | Eastman Kodak Co | Color development |
US2431996A (en) * | 1944-05-03 | 1947-12-02 | Gen Aniline & Film Corp | Production of color negative film containing integral masking images for color correction |
US2449966A (en) * | 1944-05-03 | 1948-09-21 | Eastman Kodak Co | Integral mask for color film |
US2518739A (en) * | 1947-07-03 | 1950-08-15 | Eastman Kodak Co | Method of masking photographic color images |
-
1948
- 1948-04-21 US US22300A patent/US2633422A/en not_active Expired - Lifetime
-
1949
- 1949-04-13 GB GB10064/49A patent/GB665657A/en not_active Expired
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2193931A (en) * | 1936-03-24 | 1940-03-19 | Bela Gaspar | Process for producing multicolored photographic images |
US2306410A (en) * | 1936-07-07 | 1942-12-29 | Eastman Kodak Co | Color development |
US2297732A (en) * | 1940-05-15 | 1942-10-06 | Du Pont | Photographic color process involving the formation of azo dye images |
US2431996A (en) * | 1944-05-03 | 1947-12-02 | Gen Aniline & Film Corp | Production of color negative film containing integral masking images for color correction |
US2449966A (en) * | 1944-05-03 | 1948-09-21 | Eastman Kodak Co | Integral mask for color film |
US2518739A (en) * | 1947-07-03 | 1950-08-15 | Eastman Kodak Co | Method of masking photographic color images |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2704709A (en) * | 1949-07-16 | 1955-03-22 | Gen Aniline & Film Corp | Masking process for multilayer photographic color film |
US2994607A (en) * | 1956-11-20 | 1961-08-01 | Agfa Ag | Process for the production of color-corrected color photographic images |
US3338711A (en) * | 1962-11-15 | 1967-08-29 | Du Pont | Process for forming azo dye photographic images |
US4557998A (en) * | 1985-01-02 | 1985-12-10 | Eastman Kodak Company | Colorless ligand-releasing monomers and polymers and their use to provide dyes with metal ions |
US4680356A (en) * | 1985-01-02 | 1987-07-14 | Eastman Kodak Company | Colorless ligand-releasing monomers and polymers and their use to provide dyes with metal ions |
US5695914A (en) * | 1995-09-15 | 1997-12-09 | Eastman Kodak Company | Process of forming a dye image |
US6279300B1 (en) | 1999-02-12 | 2001-08-28 | Ebrahim Simhaee | Method of manufacturing air cell dunnage |
Also Published As
Publication number | Publication date |
---|---|
GB665657A (en) | 1952-01-30 |
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