US2269481A - Production of colored photographic images - Google Patents
Production of colored photographic images Download PDFInfo
- Publication number
- US2269481A US2269481A US286281A US28628139A US2269481A US 2269481 A US2269481 A US 2269481A US 286281 A US286281 A US 286281A US 28628139 A US28628139 A US 28628139A US 2269481 A US2269481 A US 2269481A
- Authority
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- United States
- Prior art keywords
- mono
- malonic acid
- color
- photographic
- groups
- 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.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000004332 silver Substances 0.000 description 32
- 229910052709 silver Inorganic materials 0.000 description 32
- -1 silver halide Chemical class 0.000 description 27
- 239000000839 emulsion Substances 0.000 description 22
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- HGINADPHJQTSKN-UHFFFAOYSA-N Monoethyl malonic acid Chemical compound CCOC(=O)CC(O)=O HGINADPHJQTSKN-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000011161 development Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000000659 freezing mixture Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OIWIYLWZIIJNHU-UHFFFAOYSA-N 1-sulfanylpyrazole Chemical group SN1C=CC=N1 OIWIYLWZIIJNHU-UHFFFAOYSA-N 0.000 description 1
- SJYXMGNEGVJCCD-UHFFFAOYSA-N 2-(4-amino-n-butylanilino)ethanol Chemical compound CCCCN(CCO)C1=CC=C(N)C=C1 SJYXMGNEGVJCCD-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- POEULUASRUJPFD-UHFFFAOYSA-N 2-[4-(methylamino)anilino]ethanol Chemical compound CNC1=CC=C(NCCO)C=C1 POEULUASRUJPFD-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- MVVFUAACPKXXKJ-UHFFFAOYSA-N 4,5-dihydro-1,3-selenazole Chemical compound C1CN=C[Se]1 MVVFUAACPKXXKJ-UHFFFAOYSA-N 0.000 description 1
- ARKYDGLMGXZGFC-UHFFFAOYSA-N 4-n,4-n-dibutylbenzene-1,4-diamine Chemical compound CCCCN(CCCC)C1=CC=C(N)C=C1 ARKYDGLMGXZGFC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- YOJKEVXNAVNUGW-UHFFFAOYSA-N 4-n-chlorobenzene-1,4-diamine Chemical compound NC1=CC=C(NCl)C=C1 YOJKEVXNAVNUGW-UHFFFAOYSA-N 0.000 description 1
- SKIBELYSXFYZPS-UHFFFAOYSA-N 4-n-ethylbenzene-1,4-diamine Chemical compound CCNC1=CC=C(N)C=C1 SKIBELYSXFYZPS-UHFFFAOYSA-N 0.000 description 1
- VVYWUQOTMZEJRJ-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N)C=C1 VVYWUQOTMZEJRJ-UHFFFAOYSA-N 0.000 description 1
- TVOSOIXYPHKEAR-UHFFFAOYSA-N 4-piperidin-1-ylaniline Chemical compound C1=CC(N)=CC=C1N1CCCCC1 TVOSOIXYPHKEAR-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- CBDQSOGUPDQFEY-UHFFFAOYSA-N N[S+]1C2=CC=CC=C2N=C1 Chemical compound N[S+]1C2=CC=CC=C2N=C1 CBDQSOGUPDQFEY-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FHZUMJAAGNDUKE-UHFFFAOYSA-N naphtho[2,3-e][1,3]benzothiazole Chemical group C1=CC=C2C=C3C(N=CS4)=C4C=CC3=CC2=C1 FHZUMJAAGNDUKE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
Definitions
- This invention relates to the production of colored photographic images by color development.
- a colored image may be formed simultaneously with the silver image obtained by developing a silver halide emulsion with an aromatic amino developing agent if a substance known as a color former is present, for example, in the developing solution or in the silver halideemulsion.
- the colored image may be revealed by bleaching out the silver image with Farmer's Reducer or other photographic bleaching agent.
- a further object of the invention is to provide a methodof producing color photographic images with the aid of such color formers and a still further object is to provide light sensitive silver halide photographic materials containing 1 the new color formers.
- the color-former employed is a malonic acid mono-ester mono-amide i. e. an organic compound of the general formula:
- R1 and R2 represent hydrogen atoms or alkyl, aryl, aralkyl or heterocyclic groups (although they do not necessarily represent the same atoms or groups) or they represent groups linked together as a single cyclic grouping
- R3 represents an alkyl, aryl or aralkyl group.
- R1 may be a hydrogen atom, a methyl, ethyl, propyl or other alkyl group, a phenyl or other aryl group, a benzyl or other aralkyl group, a thiazole, thiazoline, oxazole, oxazoline, slenazole, selenazoline, pyridine, quincline, indolenine, diazine (e. g.
- R2 may also be a hydrogen atom or any of the above mentioned groups although in any one compound it is not necessarily the same as 131'. Further, R1 and R1. may together form a single cyclic grouping, for example, a
- R3 may be, for example, a methyl ethyl, propyl or butyl group, a phenyl group or a benzyl group.
- the groups R1, R2 and R3 may themselves be substituted, e. g. by halogen atoms, by alkyl, aryl, aralkyl and other hydrocarbon groups, or by nitro groups, hydroxy groups, amino groups,'substi-- tuted amino groups, alkoxy groups or carbethoxy alkyl groups. Those compounds which contain substituted alkoxy groups yield, in general, colors of especial brilliance.
- the preferred compounds for use according to the present invention are compounds of the type described above where R1 is a hydrogen atom and R2 is a substituted or unsubstituted phenyl group, suitable substituents in the phenyl group being halogen atoms or nitro, hydroxy, alkoxy or amino groups.
- Typical compounds of this type are malonis acid mono ethyl ester mono-oanisidide and malonic acid mono ethyl .ester mono-o-chloranilide.
- the compounds to be used as color formers in accordance with the invention. may be prepared by any suitable method.
- a convenient method is to condense a compound of the type XCOCH2--COOR3 where R3 has the meaning assigned to it above and X is a halogen atom or an alkoxy group with a compound of the type Nil R. where R1 and R2 have the meanings assigned to them above.
- malonic acid mono ethyl ester mono-'o-anisidide may be prepared by condensing malonic acid monoethylester mono acid chloride or malonic acid diethyl ester with o-anisidine.
- Malonic acid mono ethyl ester mono-o-chloranilide may be prepared by a similar condensation using o-chloraniline instead of o-anisidine.
- the color-formers of the invention may be "incorporated in the developing solution or in the photographic silver halide emulsion. In general, they are very insoluble in water and have little tendency to diffuse from one layer to another when incorporated in the emulsion layers of a multi-layer film or to diffuse into processing baths. Moreover, the compounds show a good resistance to the bleaching action of the sulphites frequently included in developing compositions.
- Suitable aromatic amino compounds which may be employed as the developers in conjunction with the color-formers of this invention are derivatives of p-phenylene diamines and particularly of the asymmetric dialkyl-p-phenylene diamines, e. g. p-aminodimethylaniline, p-aminodiethylaniline and p-aminodibutylaniline.
- developing agents which may be used include pphenylene-diamine itself, p-methylaminoaniline, p-ethylaminoaniline and p-aminophenol, N.N-diethyl-o-phenylene-diamine, chloro-p-phenylene diamine, 1.2.5-toluylenediamine, -2-amino-5-.diethyl-aminotoluene, N-p-aminophenylpiperidine, N methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylenediamine, 2- amino 5 (N-p-hydroxyethyl-Nbutyl) aminotoluene and its dihydrochloride and u-vdihydroxypropyl-p-phenylene diamine.
- aromatic amino-developing agents may be used in the form of their salts, which may be either in organic or organic.
- the salts are in general more stable than the free bases.
- suitable salts mention is made of the hydrochlorides, sulfates and acetates.
- a suitable development time, using this solution, is two minutes, at a temperature of 65 F.
- Developing solution A when including this compound and used for the development of photographic silver halide images, produces a brilliant yellow image together with the silver image.
- EXAMPLE 6 This example illustrates the incorporation of the color-formers of this invention in emulsion layers. 20 cos. of 1% solution in ethylene glycol mono-methyl ether of malonic acid mono ethyl ester mono-o-anisidide were added to 25 cos. of aqueous solution of gelatin and the mixture added to 50 cos. of a melted photographiMGa'slight emulsion containing approximately gms. of silver halide, principally silver chloride, per
- emulsion thus prepared-was coated on'a paper support and dried.
- the emulsion coated paper was exposed under a negative and was then developed with a developing solution of the constitution of Developing solution A excluding the color former but including an equivalent quantity'of the water miscible liquid such as ethyl alcohol or ethylene glycol mono methyl ether.
- a brilliant yellow image was produced together with the silver image.
- the dye image may be revealed by bleaching out the silver image with Farmer's Reducer or other known photo'- graphic bleaching agent.
- color formers which may be prepared and used according to this invention:
- the mono-p-cara camera or behind a photographic negative image may be applied to the residual silver halide left when an initial reduced silver image has been dissolved away as in the reversal process of development; or it may be applied to a developed photographic image in metallic silver which has been fixed by the removal of unchanged silver halide, and subsequently converted to a developable silver salt by means of known photographic bleaching agents.
- the residual silver halide and the silver salt respectively may be made developable by the action of light or in any other way, e. g. by treatment with sodium arsenite.
- the production of colored images by means of the color formers of this invention may be applied to colloid layers sensitised by bichromate.
- the color formers may be incorporated in colloid layers (e. g. gelatin, gum arabic or albumin), the layers exposed, the unexposed colloid removed, e. g. by treatment with hot water, and the color developed in the exposed portions by treatment with p-nitro'so-dialkyl-aniline or its derivatives.
- a photographic color forming developer which comprises an aromatic amino developing compound and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
- a photographic color forming developer which comprises an aromatic amino developing compound and a color former of the general formula:
- R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups
- R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
- a photographic color forming developer which comprises an asymmetric di-alkyl-p-phenylene diamine and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
- a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with an aromatic amino developing agent in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
- a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion withan aromatic amino developing agent in the presence of a color former of the general formula:
- R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups
- R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
- a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with .an asymmetrical dialkyl-p-phenylene diamine in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
- a method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with a developing solution which contains an aromatic amino developing agent and a malonic acid mono-ester monoamide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
- R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups
- R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
- R is an aromatic hydrocarbon radical containing an alkoxy group
- R" is a lower alkyl group
- a photographic color forming developer comprising an aromatic amino developing compound and the mono-o-anis-idicle of malonic acid ethyl ester.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Jan. 13, 1942 PRODUCTION O FCOLORED PHOTOGRAPHIC WAGES John Hubert Reindorp, Ilford, England, assignor to Ilford Limited, Ilford, Essex, England, a
British company No Drawing. Application July 24, 1939, Serial No. 286,281. In Great Britain August 3, 1938 13 Claims.
This invention relates to the production of colored photographic images by color development.
It is known that a colored image may be formed simultaneously with the silver image obtained by developing a silver halide emulsion with an aromatic amino developing agent if a substance known as a color former is present, for example, in the developing solution or in the silver halideemulsion. The colored image may be revealed by bleaching out the silver image with Farmer's Reducer or other photographic bleaching agent.
It is an object of this invention to provide a new range of color formers. A further object of the invention is to provide a methodof producing color photographic images with the aid of such color formers and a still further object is to provide light sensitive silver halide photographic materials containing 1 the new color formers. 1
Other objects of the invention will appear hereinafter.
According (to the present invention in a process of color development in which a silver halide photographic emulsion is developed with an aromatic amino compound as a developer in the presence of a color-former, the color-former employed is a malonic acid mono-ester mono-amide i. e. an organic compound of the general formula:
where R1 and R2 represent hydrogen atoms or alkyl, aryl, aralkyl or heterocyclic groups (although they do not necessarily represent the same atoms or groups) or they represent groups linked together as a single cyclic grouping, and R3 represents an alkyl, aryl or aralkyl group. Thus, for example, R1 may be a hydrogen atom, a methyl, ethyl, propyl or other alkyl group, a phenyl or other aryl group, a benzyl or other aralkyl group, a thiazole, thiazoline, oxazole, oxazoline, slenazole, selenazoline, pyridine, quincline, indolenine, diazine (e. g. pyrimidine, and quinazoline) thiodiazole group, or a substituted or unsubstituded polycyclic group such as the benzthiazole, naphthathiazole and anthrathiazole groups, R2 may also be a hydrogen atom or any of the above mentioned groups although in any one compound it is not necessarily the same as 131'. Further, R1 and R1. may together form a single cyclic grouping, for example, a
' dolegroup. R3 may be, for example, a methyl ethyl, propyl or butyl group, a phenyl group or a benzyl group.
The groups R1, R2 and R3 may themselves be substituted, e. g. by halogen atoms, by alkyl, aryl, aralkyl and other hydrocarbon groups, or by nitro groups, hydroxy groups, amino groups,'substi-- tuted amino groups, alkoxy groups or carbethoxy alkyl groups. Those compounds which contain substituted alkoxy groups yield, in general, colors of especial brilliance.
The preferred compounds for use according to the present invention are compounds of the type described above where R1 is a hydrogen atom and R2 is a substituted or unsubstituted phenyl group, suitable substituents in the phenyl group being halogen atoms or nitro, hydroxy, alkoxy or amino groups. Typical compounds of this type are malonis acid mono ethyl ester mono-oanisidide and malonic acid mono ethyl .ester mono-o-chloranilide.
The compounds to be used as color formers in accordance with the invention. may be prepared by any suitable method. A convenient method is to condense a compound of the type XCOCH2--COOR3 where R3 has the meaning assigned to it above and X is a halogen atom or an alkoxy group with a compound of the type Nil R. where R1 and R2 have the meanings assigned to them above. Thus, for example, malonic acid mono ethyl ester mono-'o-anisididemay be prepared by condensing malonic acid monoethylester mono acid chloride or malonic acid diethyl ester with o-anisidine. Malonic acid mono ethyl ester mono-o-chloranilide may be prepared by a similar condensation using o-chloraniline instead of o-anisidine.
The color-formers of the invention may be "incorporated in the developing solution or in the photographic silver halide emulsion. In general, they are very insoluble in water and have little tendency to diffuse from one layer to another when incorporated in the emulsion layers of a multi-layer film or to diffuse into processing baths. Moreover, the compounds show a good resistance to the bleaching action of the sulphites frequently included in developing compositions.
Suitable aromatic amino compounds which may be employed as the developers in conjunction with the color-formers of this invention are derivatives of p-phenylene diamines and particularly of the asymmetric dialkyl-p-phenylene diamines, e. g. p-aminodimethylaniline, p-aminodiethylaniline and p-aminodibutylaniline. Other developing agents which may be used include pphenylene-diamine itself, p-methylaminoaniline, p-ethylaminoaniline and p-aminophenol, N.N-diethyl-o-phenylene-diamine, chloro-p-phenylene diamine, 1.2.5-toluylenediamine, -2-amino-5-.diethyl-aminotoluene, N-p-aminophenylpiperidine, N methyl-N-hydroxyethyl-p-phenylenediamine, N-butyl-N-hydroxyethyl-p-phenylenediamine, 2- amino 5 (N-p-hydroxyethyl-Nbutyl) aminotoluene and its dihydrochloride and u-vdihydroxypropyl-p-phenylene diamine. These aromatic amino-developing agents may be used in the form of their salts, which may be either in organic or organic. The salts are in general more stable than the free bases. As examples of suitable salts mention is made of the hydrochlorides, sulfates and acetates.
In the succeeding examples, the following solution is given by way of example as illustrating the nature of developing solutions which may be employed embodying a color former in accordance with the invention.
Developing solution A Diethyl-p-phenylenediaminehydrochloride grams 1 Sodium carbonate (crystals) NazCOslOI-IzO 80 Sodium sulphite (crystals) Na2SO37H2O dO 12.5 Color former solution (1% or saturated solution, whichever is weaker) ccs 100 Water to make 1itre 1 The color former is dissolved in a suitable water-miscible solvent such as ethyl alcohol or ethylene glycol mono-methyl ether. The sodium sulphite may be omitted if desired.
A suitable development time, using this solution, is two minutes, at a temperature of 65 F.
Th following specific examples illustrate the method of production of the new color formers, and their use:
EXAMPLE 1 Malom'c acid mono ethyl ester mono-o-anisidide cooled solution was filtered.
The filtrate was then diluted to four times its volume with petroleum ether and cooled in a freezing mixture, whereupon the malonic acid mono ethyl ester mono-o-anisidide separated out. M. P. 63-65 C.
Developing solution A, when including this compound and used for the development of photographic silver halide images, produces a brilliant yellow image together with the silver image.
EXAMPLE 2 Melanie acid mono ethyl ester mono-flnaphthalidc EXAMPLE 3 Melanie acid mono ethyl ester mono-m- Y nitram'lide 10 cos. of diethylmalonate and 4.08 gms. of mnitraniline were heated together in an oil bath for three hours at 130-140 C.
The excess diethylmalonate was then distilled off in vacuo and the residue was warmed with 60 ccs. of dry ethyl alcohol. The mixture was then cooled in a freezing mixture and filtered. The filtrate was evaporated on a water bath to remove the ethyl alcohol and Water was added. The mixture was then cooled in ice and filtered. The residue was then boiled up with benzene and filtered hot; the filtrate was evaporated to 10 ccs. and allowed to cool, whereupon yellow crys tals of malonic acid mono ethyl ester mono-mnitranilide separated. M. P. 48 C.
Developing solution A when including this compound and used for the development of photographic silver h-alide images produces a bright yellow image together with the silver ima e.
EXAMPLE 4 Malonz'c acid mono ethyl ester monoo-hydroxyanilide Q- NH- 00- cm 00- 002m 5.45 gms. of o-amino-phenol and 40 gms. of diethylmalonate were heated in an oil bath, for three hours, at C. On cooling, a brown solid, M. P. 106 C. separated and this was recrystallised from benzene. Developing solution A, when including this compound and used for the development of photographic silver halide images produces a deep green image together with the silver image.
EXAMPLE 5 1-w-carbethoryacetylamino benzthiazole o- Nllc 0 cmo o (,n,
4.5 gms. of l-amino-benzthiazole were dissolved by warming in 200 ccs. of xylene and the solution was slowly added to a solution of 9.6 gms. of diethylmalonate in 15 ccs. of xylene and contain ing two drops of pyridine, the addition of the 1- amino-benzthiazole being effected over a period of about thirty minutes.
During this process the solutions were maintained at boiling and about 100 cos. of the xylene was removed. On cooling the products, a yellow solid separated, which on recrystallisation from ethyl alcohol had a melting point of 180 C. Developing solution A when including this compound and used for the development of photographic silver halide images produces an orangebrown image together with the silverimage.
EXAMPLE 6 This example illustrates the incorporation of the color-formers of this invention in emulsion layers. 20 cos. of 1% solution in ethylene glycol mono-methyl ether of malonic acid mono ethyl ester mono-o-anisidide were added to 25 cos. of aqueous solution of gelatin and the mixture added to 50 cos. of a melted photographiMGa'slight emulsion containing approximately gms. of silver halide, principally silver chloride, per
pound weight of emulsion. The emulsion thus prepared-was coated on'a paper support and dried. The emulsion coated paper was exposed under a negative and was then developed with a developing solution of the constitution of Developing solution A excluding the color former but including an equivalent quantity'of the water miscible liquid such as ethyl alcohol or ethylene glycol mono methyl ether. A brilliant yellow image was produced together with the silver image.
In each of the above examples the dye image may be revealed by bleaching out the silver image with Farmer's Reducer or other known photo'- graphic bleaching agent.
In addition to the specific color formers described above, the following are examples of color formers which may be prepared and used according to this invention:
Malonic acid mono ethyl ester mono-p-anisidide Malonic acid mono ethyl ester mono-p-nitroanilide Malonic acid mono ethyl ester mono-anaphthalide l-w-carbethoxy acetylamino-S ethoxy benzthiazole Malonic acid mono ethyl ester mono anilide Malonic acid mono ethyl ester mono-o-nitroanilide Malonic acid mono ethyl ester bethoxy-anilide N.N'-di-carbethoxyacetyl benzidine 1-w-carbethoxyacetylamino-2-hydroxy 4:5 dimethylbenzene Malonic acid di-o-hydroxy-p-nitroanilide Malonic acid mono ethyl ester mono-o-chloranilide The process of development employing the color formers in accordance with the present invention may be applied either to a latent image in an emulsion of a silver halide which has been exposed to the action of light, for example, in
mono-p-cara camera or behind a photographic negative image; or it may be applied to the residual silver halide left when an initial reduced silver image has been dissolved away as in the reversal process of development; or it may be applied to a developed photographic image in metallic silver which has been fixed by the removal of unchanged silver halide, and subsequently converted to a developable silver salt by means of known photographic bleaching agents. In the last two cases the residual silver halide and the silver salt respectively may be made developable by the action of light or in any other way, e. g. by treatment with sodium arsenite.
The production of colored images by means of the color formers of this invention may be applied to colloid layers sensitised by bichromate. Thus the color formers may be incorporated in colloid layers (e. g. gelatin, gum arabic or albumin), the layers exposed, the unexposed colloid removed, e. g. by treatment with hot water, and the color developed in the exposed portions by treatment with p-nitro'so-dialkyl-aniline or its derivatives.
I claim:
1. A photographic color forming developer which comprises an aromatic amino developing compound and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
2. A photographic color forming developer which comprises an aromatic amino developing compound and a color former of the general formula:
wherein R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups, and R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
3. A photographic color forming developer which comprises an asymmetric di-alkyl-p-phenylene diamine and a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
4. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with an aromatic amino developing agent in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
5. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion withan aromatic amino developing agent in the presence of a color former of the general formula:
ncoomcoom wherein R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups, and R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
6. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with .an asymmetrical dialkyl-p-phenylene diamine in the presence of a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
7. A method of producing a colored image in a silver halide emulsion which comprises developing the emulsion with a developing solution which contains an aromatic amino developing agent and a malonic acid mono-ester monoamide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
8. A light sensitive silver halide photographic emulsion containing a color former which is a malonic acid mono-ester mono-amide having a methylene radical attached directly to the two carbonyl radicals of the malonic acid nucleus.
9. A photographic element bearing at least one light sensitive silver halide emulsion layer containing a color former of the general formula:
wherein R1 and R2 are groups selected from the class consisting of hydrogen atoms and substituted and unsubstituted hydrocarbon groups and heterocyclic groups, and R3 is a group selected from the class consisting of substituted and unsubstituted hydrocarbon groups.
10. A light sensitive silver halide emulsion containing as a color former a compound of the general formula:
wherein R is an aromatic hydrocarbon radical containing an alkoxy group, and R" is a lower alkyl group.
11. A light sensitive silver halide emulsion containingas a color former the mono-o-anisidide of malonic acid ethyl ester.
12. A photographic color forming developer comprising an aromatic amino developing compound and the mono-o-anis-idicle of malonic acid ethyl ester.
13. The process which comprises developing a photographic element bearing silver halide image in the presence of the mono-o-anisidide of malonic acid ethyl ester with a color coupling aromatic amino developing agent containing an unsubstituted amino group.
JOHN HUBERT REINDORR- CERTIFICATE OF commoners. Patent No. 2,269,l;81. January 1 191;.2.
JOHN HUBERT REINDORP.
It is hereby, certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page l', second column, line 20, for "malonis" reed malonio--; page 2, second column, line 5, in the for-mule, for "NC" read --NH--; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.
Signed and sealed this 5rd. day of March, A. D.- 19)+2.
Henry Van Arsdale, (Seal) Acting Commis sioner of Patents.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB22987/38A GB518017A (en) | 1938-08-03 | 1938-08-03 | Improvements in or relating to the colour-development of silver halide photographic emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2269481A true US2269481A (en) | 1942-01-13 |
Family
ID=10188261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US286281A Expired - Lifetime US2269481A (en) | 1938-08-03 | 1939-07-24 | Production of colored photographic images |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US2269481A (en) |
| GB (1) | GB518017A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2441491A (en) * | 1944-05-12 | 1948-05-11 | Ilford Ltd | Cyanacetylamino phenol color formers for color photography |
| US2533185A (en) * | 1947-10-22 | 1950-12-05 | Gen Aniline & Film Corp | Alkyl malonamates as azo coupling components in diazotype layers |
| US2645578A (en) * | 1949-01-22 | 1953-07-14 | Harris Seybold Co | Lithograph-plate preparation |
| DE1124356B (en) * | 1960-04-28 | 1962-02-22 | Eastman Kodak Co | Process for photographic color developing |
| US4157916A (en) * | 1976-07-13 | 1979-06-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| US4560646A (en) * | 1983-11-23 | 1985-12-24 | Ciba Geigy Ag | Protected developing agents |
-
1938
- 1938-08-03 GB GB22987/38A patent/GB518017A/en not_active Expired
-
1939
- 1939-07-24 US US286281A patent/US2269481A/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2441491A (en) * | 1944-05-12 | 1948-05-11 | Ilford Ltd | Cyanacetylamino phenol color formers for color photography |
| US2533185A (en) * | 1947-10-22 | 1950-12-05 | Gen Aniline & Film Corp | Alkyl malonamates as azo coupling components in diazotype layers |
| US2645578A (en) * | 1949-01-22 | 1953-07-14 | Harris Seybold Co | Lithograph-plate preparation |
| DE1124356B (en) * | 1960-04-28 | 1962-02-22 | Eastman Kodak Co | Process for photographic color developing |
| US4157916A (en) * | 1976-07-13 | 1979-06-12 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| US4560646A (en) * | 1983-11-23 | 1985-12-24 | Ciba Geigy Ag | Protected developing agents |
Also Published As
| Publication number | Publication date |
|---|---|
| GB518017A (en) | 1940-02-15 |
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