US2099374A - Photographic developer and a process of photographic developing - Google Patents
Photographic developer and a process of photographic developing Download PDFInfo
- Publication number
- US2099374A US2099374A US14920A US1492035A US2099374A US 2099374 A US2099374 A US 2099374A US 14920 A US14920 A US 14920A US 1492035 A US1492035 A US 1492035A US 2099374 A US2099374 A US 2099374A
- Authority
- US
- United States
- Prior art keywords
- photographic
- developer
- aldehyde
- developing
- benzaldehyde
- 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
- 238000000034 method Methods 0.000 title description 5
- 230000008569 process Effects 0.000 title description 5
- -1 silver halide Chemical class 0.000 description 17
- 239000000839 emulsion Substances 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 2
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- MCIDYUGTJBLEST-UHFFFAOYSA-N 2,3-dinitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1[N+]([O-])=O MCIDYUGTJBLEST-UHFFFAOYSA-N 0.000 description 1
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 1
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229960003371 protocatechualdehyde Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
Definitions
- My invention relates to the art of developing photographic silver halide emulsions and more especially to the curing of a defect arising 'in particularwhen developing emulsions, on films or paper, which were kept in store beyond the normal period of time or which are exposed to the action of the developer either unduly long or at With these and other objects in view I will now proceed to describe the nature of my invention and the best way in which it may be performed.
- the 2-4-thloketothiazolidine is constituted according'to the formula I I co-NH s 5 0H.- s
- -CH--X is the residue of a non-basic cyclic aldehyde, while X may contain non-basic substituents.
- non-basic cyclic aldehydes e. g.: benzaldehyde, nitrobenzaldehyde, salicylic aldehyde, protocatechuic aldehyde, brombenzaldehyde, anisaldehyde, heliotropine, benzaldehyde-sulphonic acid, cinnamic aldehyde, phenyl acetic aldehyde, furfurol, etc., etc.
- metaleptic benzaldehyde is used for condensation, it makes no difierence on which car bon atom the substitution is found.
- the ortho-nitro-benzaldehyde is just as suitable as the meta-nitro-benzaldehyde or even a benzaldehyde which has two groups; for in- 4 stance, a di-nitro-benzaldehyde. It is only important that the aldehyde shows no basic property, asfor example the p-dimethylamino benzaldehyde which would lead to-unsuitable products.
- the percentage of the colored or decolored antifoggant in the developer may vary within wide limits, for instance between 125000 and 1:100,000. I have found a proportion of 1:20,000 to be particularly useful.
Description
Patented Nov. 16, 1937 UNITED STATES PATENT OFFICE.
PHOTOGRAPHIC DEVELOPER AND A PROC- ESS OF PHOTOGRAPHIC DEVELOPING Georg Schwarz, Anvers, Belgium, assignor to Gevaert Photo-Production N. V., Oude God,
near Anvers, Belgium No Drawing.
Application April 5, 1935, Serial No. 14,920. In Austria April 7, 1934 6 Claims.
My invention relates to the art of developing photographic silver halide emulsions and more especially to the curing of a defect arising 'in particularwhen developing emulsions, on films or paper, which were kept in store beyond the normal period of time or which are exposed to the action of the developer either unduly long or at With these and other objects in view I will now proceed to describe the nature of my invention and the best way in which it may be performed.
I have found that the products resulting in the condensation of 2-4-thioketothiazolidine with a non-basic cyclic aldehyde are powerful antifoggants, while hardly affecting the tint of the image developed, and this quite particularly in thecase of silver chloride emulsions. I have further found that by admixing to a suitable silver halide developer a minute quantity, for instance of the 'order of 0.005 per cent, of a condensation product of the kind here in view, I am enabledto develop old silver halide and more especially silver chloride emulsions, or to develop any such emulsions during an abnormally long period 01' time or at an abnormally elevated temperature without incurring any risk of fog formation'and decoloration.
I have found that this beneficial action of the condensation products mentioned aboveby far.
surpasses that of the imidazols and triazois.
According to Richter-Anschiit'z Chemie der Kchlenstoflverbindungen" (12th edition), vol. 3,
p. 143, the 2-4-thloketothiazolidine is constituted according'to the formula I I co-NH s 5 0H.- s
By condensation of this compound with anonbasic cyclic aldehyde there is-formed a compound corresponding to the formula S-C=OHX i which is I 8:0 0:0 tautomeric with HS-C. C=0
wherein -CH--X is the residue of a non-basic cyclic aldehyde, while X may contain non-basic substituents. Such a substituted compound corresponds to the formula which is tautomerlcwith H S =0 wherein Y is a non-basic substituent of the nucleus X, while 11. is 1 or 2. Y
'The following can be used as non-basic cyclic aldehydes e. g.: benzaldehyde, nitrobenzaldehyde, salicylic aldehyde, protocatechuic aldehyde, brombenzaldehyde, anisaldehyde, heliotropine, benzaldehyde-sulphonic acid, cinnamic aldehyde, phenyl acetic aldehyde, furfurol, etc., etc. In case metaleptic benzaldehyde is used for condensation, it makes no difierence on which car bon atom the substitution is found. Thus, for instance, the ortho-nitro-benzaldehyde is just as suitable as the meta-nitro-benzaldehyde or even a benzaldehyde which has two groups; for in- 4 stance, a di-nitro-benzaldehyde. It is only important that the aldehyde shows no basic property, asfor example the p-dimethylamino benzaldehyde which would lead to-unsuitable products.
By adding for instance 1 part by weight of 2-thio-4-keto-5-ortho-hydroxybenzylidene thiazolidine to 20,000 parts of an ordinary metol hydroquinone developer I obtain a yellow colored liquid which can be used to develop old silver halide emulsions and quite particularly silver chloro-bromide paper without any risk of the images becoming foggy.
If the developer with the antifoggant admixed to it is allowed to stand, the yellow color will disappear almost entirely, depending on the content of alkaline substances in the mixture, however the antifoggant eifect will not be diminished.
The percentage of the colored or decolored antifoggant in the developer may vary within wide limits, for instance between 125000 and 1:100,000. I have found a proportion of 1:20,000 to be particularly useful.
In practising my invention I may for instance proceed as follows:
1 mol. 2,4-thioketo-thiazolidine is boiled with 1 mol. benzaldehyde inabout 10 mols glacial acetic acid for about 5 hours with reflux cooling. After cooling, brown crystals precipitate, which presumably have the following constitution:
S: 2 3/4 =0 \NH If of this 2-thio-4-keto-5-benzylidene-thiazolidine 0.05 gram is added to 1000 grams of an ordinary developer, old photographic paper which,
ifdeveloped in the usual manner, would become foggy, can be developed free of fog in this developer. The effect on the colour of the picture is very slight. Even in developing at higher temperatures, as for instance 25 C. (77 F.), no fog will appear, not even if the process of developing is extended far beyond the usual period of time.
Various changes maybe made in the details disclosed in the foregoing specification without departing from the invention or sacrificing the advantages thereof.
I claim: 1. The mixture of a phbtographic silver halide developer with a compound corresponding to the formula which is taul {tomeric with HSC NH N wherein =CH-X is the residue of a non-basic cyclic aldehyde, resulting from the condensation of such aldehyde with 2-thio-4-keto-thiazolidine.
2. The process of developing photographic silver halide emulsions which comprises exposing such emulsions to the action of a mixture of a silver halide developer with a compound corresponding to the formula which is tautomeric with HS- which is tautomeric with' mi L.
NH. I wherein =CHX(Y)1: is the residue of a nonbasic cyclic aldehyde, Y is a non-basic substituent in the nucleus X of said aldehyde, while n is an integer smaller than 3, said compound resulting from the condensation of such aldehyde with 2-tl iio-4-keto-thiazolidine.
6. The process of developing photographic silver halide emulsions which comprises exposing such emulsions to the action of a mixture of a silver halide developer with a compound corresponding to the formula I which is tau- =0 tomeric with E8- wherein =CHX("-Y)n is'the residue of a nonbasic cyclic aldehyde, Y is a non-basic substituent in the nucleus x of said aldehyde, while 12. is an integer smaller than 3, saidcompound resulting from the'condensation of such aldehyde with 2-thio-4-keto-thiazolidine.
GEORG SCHWARZ.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT454870X | 1934-04-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2099374A true US2099374A (en) | 1937-11-16 |
Family
ID=3674469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14920A Expired - Lifetime US2099374A (en) | 1934-04-07 | 1935-04-05 | Photographic developer and a process of photographic developing |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2099374A (en) |
| BE (1) | BE408842A (en) |
| FR (1) | FR788511A (en) |
| GB (1) | GB454870A (en) |
| NL (1) | NL41539C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2563034A (en) * | 1949-07-05 | 1951-08-07 | Goodrich Co B F | Rhodanine beta-substituted propionic acid |
| US2573027A (en) * | 1944-11-13 | 1951-10-30 | Ilford Ltd | Photographic element and process utilizing antibronzing agents |
| US2658890A (en) * | 1951-04-13 | 1953-11-10 | Rohm & Haas | 5-alkoxymethylene rhodanines |
| US2739888A (en) * | 1954-03-29 | 1956-03-27 | Eastman Kodak Co | Photographic elements containing thiazolidine derivatives |
| US2808330A (en) * | 1952-10-31 | 1957-10-01 | Eastman Kodak Co | Photographic elements containing thiazolidine derivatives |
| US2860976A (en) * | 1956-08-03 | 1958-11-18 | Eastman Kodak Co | Antifoggants for photographic developers |
| US3081170A (en) * | 1958-10-06 | 1963-03-12 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
| US3966753A (en) * | 1974-08-09 | 1976-06-29 | Sterling Drug Inc. | Thiazolidinylidene isoindoline pigments |
| US4066653A (en) * | 1975-04-03 | 1978-01-03 | Sterling Drug Inc. | 1-imino-3-(4-imino-5-thiazolidinylidene)isoindolines |
-
0
- BE BE408842D patent/BE408842A/xx unknown
- NL NL41539D patent/NL41539C/xx active
-
1935
- 1935-04-05 US US14920A patent/US2099374A/en not_active Expired - Lifetime
- 1935-04-08 FR FR788511D patent/FR788511A/en not_active Expired
- 1935-04-08 GB GB10876/35A patent/GB454870A/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2573027A (en) * | 1944-11-13 | 1951-10-30 | Ilford Ltd | Photographic element and process utilizing antibronzing agents |
| US2563034A (en) * | 1949-07-05 | 1951-08-07 | Goodrich Co B F | Rhodanine beta-substituted propionic acid |
| US2658890A (en) * | 1951-04-13 | 1953-11-10 | Rohm & Haas | 5-alkoxymethylene rhodanines |
| US2808330A (en) * | 1952-10-31 | 1957-10-01 | Eastman Kodak Co | Photographic elements containing thiazolidine derivatives |
| US2739888A (en) * | 1954-03-29 | 1956-03-27 | Eastman Kodak Co | Photographic elements containing thiazolidine derivatives |
| US2860976A (en) * | 1956-08-03 | 1958-11-18 | Eastman Kodak Co | Antifoggants for photographic developers |
| US3081170A (en) * | 1958-10-06 | 1963-03-12 | Gen Aniline & Film Corp | Fog reduction in photographic silver halide emulsions |
| US3966753A (en) * | 1974-08-09 | 1976-06-29 | Sterling Drug Inc. | Thiazolidinylidene isoindoline pigments |
| US4066653A (en) * | 1975-04-03 | 1978-01-03 | Sterling Drug Inc. | 1-imino-3-(4-imino-5-thiazolidinylidene)isoindolines |
Also Published As
| Publication number | Publication date |
|---|---|
| GB454870A (en) | 1936-10-08 |
| NL41539C (en) | |
| BE408842A (en) | |
| FR788511A (en) | 1935-10-11 |
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