US2588538A - Stabilizers in photographic emulsions and developers - Google Patents
Stabilizers in photographic emulsions and developers Download PDFInfo
- Publication number
- US2588538A US2588538A US108418A US10841849A US2588538A US 2588538 A US2588538 A US 2588538A US 108418 A US108418 A US 108418A US 10841849 A US10841849 A US 10841849A US 2588538 A US2588538 A US 2588538A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- emulsions
- photographic
- fog
- silver halide
- 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
- 239000000839 emulsion Substances 0.000 title claims description 42
- 239000003381 stabilizer Substances 0.000 title description 4
- -1 SILVER HALIDE Chemical class 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 238000007792 addition Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000126 substance Substances 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
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
Definitions
- the degree to which an emulsion produces fog on development usually increases with the age of the emulsion so that photographic materials which have been kept a long time, especially in warm and humid conditions, or emulsions which have been kept a long time in the molten condition, may produce images associated with a heavy fog density.
- Many compounds have been suggested in the past for use as additions to emulsions or to developers which tend to reduce the formation of fog, but almost all of them, if reasonably effective as anti-fogging agents, have caused a serious reductionin the speed of the photographic emulsion.
- the tendency to the formation of fog in silver halide photographic emulsions is reduced by incorporating in the emulsion or the developer or both a small quantity of a compound of the general formula:
- the compounds are of particular Value as emulsion or developer additions Claims. (Cl. 957) in cases where the emulsions or developers are to be used in tropical conditions or, in the case of emulsions, where the emulsions are to be kept for a long time in the molten condition.
- the compounds present the further advantage that they do not seriously'reduce the effective speed of emulsions in which they are incorporated.
- the new anti-fogging agents may be prepared by the processes described in our co-pending application Serial No. 108,417, new U. S. Patent No. 2,534,914, filed on even date herewith.
- group R1 in the general formula may be a hydrogen atom or an alkyl group.
- suitable alkyl groups are methyl, ethyl and higher alkyl groups.
- the quantity of the compound employed will depend on the emulsion or the developer to which it is added, but as a general indication it may be stated that for incorporation in an emulsion, 1 to 5 or up to 50 cc. of a 1:1,000 solution of the compound per litre of emulsion is suitable, whilst for incorporation in a developer; the optimum quantity may vary from 1 part of the compound in 3,000 to 30,000 parts of the developer solution according to the particular compound used.
- the addition of the compound to an emulsion is preferably effected after the digestion of the emulsion as a final addition before coating.
- a process for red iifg the tendency to the formation of fog in s i ver halide photographic emulsions which comprises developing latent images in such emulsions by means of 9, developing solution containing a small quantity of a compound of the general formula:
- R1 is selected from the class consisting of the hydrogen atom and alkyl groups, thequantity of the said compound included in the developer being equivalent to 1 part of the compound per 3000 to 30,000 parts of the developing solution.
- a process for reducing the tendency to the formation of fog in silver halide photographic emulsions which comprises developing the emulsions, in the presence of a small quantity of 3.3- bis 1.2.4-tri'a'zolyl) -formamidine.
- a process for reducing the tendency to the formation of fog in silver halide photographic emulsions which comprises developing the emulsions, in the presence of a small quantity of 3.3- bis (-methyl-1.2.4-triazolyl) -formamidine.
- a process for reducing the tendency to the formation of fog in silver halide photographic emulsions which comprises developing the emulsions, in the presence of a small quantity of 3 .3-bis(5-ethy1-1.2.4-triazolyl) -formamidine.
- R1 is selected from the class consisting of the hydrogen atom and alkyl groups.
- a photographic silver halide emulsion containing in the proportion of 1 to 50 cc. of a 1:1000 5 solution per litre of emulsion a compound of the general formula:
- R1 is seltii'd from the class consisting of the hydrogen atom and alkyl groups.
- a photographic silver halide emulsion containing in the proportion of 1 to 50 cc. of a 1:1000 solution per litre of emulsion 3.3-bis(1.2.4-triazolyl) -formamidine.
- a photographic silver halide emulsion containing in the proportion of 1 to 50 cc. of a 1:1000 solution per litre or emulsion 3.3-bis(5-methyl- 1 .2.4-triazolyl) -forniamidine.
- a photographic silver halide emulsion containing in the proportion of 1 to cc. of a 121000 solution per litre of emulsion 3.3-bis(5-ethyl- 1.2.4-triazolyl) -formamidihe.
- a photographic developing composition including a silver halide photographic developer and a small quantity of a compound of the general formulai where R1 is selected from the class consisting of the hydrogen atom and alkyl groups.
- a photographic developing solution containing a silver halide photographic developer and, per 3000 to 30,000 parts of the solution, 1 part of 3.3'-bis(1.2.4-triazolyl)-formamidine.
- a photographic developing solution containing a silver halide photographic developer and, per 3000 to 30,000 parts of the solution, 1 part of 3.3-bis(5-methyl-1.2.4-triazolyl)-formamidine.
Description
Patented ar. 11, 1952 STABILIZERS IN PHOTOGRAPHIC EMUL SIGNS AND DEVELOPERS John David Kendall and Harold Gordon Suggate, Ilford, England, assignors to Ilford Limited, Ilford, England, a British company No Drawing. Application August 3, 1949, Serial No. 108,418. In Great Britain August 6, 1948 density of which bears no relation to the variations in luminosity of the subject. This overall deposit is referred to as the chemical fog or development fog. Its effect is to increase the general density of the negative obtained and to depress the contrast of the image in the less exposed parts. In general the fog density produced is greater in the case of high speed than in slow emulsions and is invariably greater the higher the temperature of development and when vigorous developers are used. 'Moreover, the degree to which an emulsion produces fog on development usually increases with the age of the emulsion so that photographic materials which have been kept a long time, especially in warm and humid conditions, or emulsions which have been kept a long time in the molten condition, may produce images associated with a heavy fog density. Many compounds have been suggested in the past for use as additions to emulsions or to developers which tend to reduce the formation of fog, but almost all of them, if reasonably effective as anti-fogging agents, have caused a serious reductionin the speed of the photographic emulsion.
According to the present invention the tendency to the formation of fog in silver halide photographic emulsions is reduced by incorporating in the emulsion or the developer or both a small quantity of a compound of the general formula:
Bl l l t.
N N l l periods of time and they enable development to be effected with vigorous developers or at high temperatures. Thus the compounds are of particular Value as emulsion or developer additions Claims. (Cl. 957) in cases where the emulsions or developers are to be used in tropical conditions or, in the case of emulsions, where the emulsions are to be kept for a long time in the molten condition. The compounds present the further advantage that they do not seriously'reduce the effective speed of emulsions in which they are incorporated.
The new anti-fogging agents may be prepared by the processes described in our co-pending application Serial No. 108,417, new U. S. Patent No. 2,534,914, filed on even date herewith.
As indicated above the group R1 in the general formula may be a hydrogen atom or an alkyl group. Examples of suitable alkyl groups are methyl, ethyl and higher alkyl groups.
The quantity of the compound employed will depend on the emulsion or the developer to which it is added, but as a general indication it may be stated that for incorporation in an emulsion, 1 to 5 or up to 50 cc. of a 1:1,000 solution of the compound per litre of emulsion is suitable, whilst for incorporation in a developer; the optimum quantity may vary from 1 part of the compound in 3,000 to 30,000 parts of the developer solution according to the particular compound used. The addition of the compound to an emulsion is preferably effected after the digestion of the emulsion as a final addition before coating.
The following examples illustrate the invention:
, Examples To an iodobromide emulsion containing 1 /2 gram-molecules of silver were added 20 cc. of a 1:1000 ethyl alcohol solution of 3.3-bis(1.2.ltriazolyll-formamidine. The emulsion was then coated on glass, dried and stored, part of the product under normal conditions and part in a sealed container at F. A control emulsion containing no stabiliser was similarly treated. Sensitometric results were as follows:
It will be seen that the emulsion containing the stabiliser gave less fog than the control on keeping, but without serious effect on the speed formation of fog in silver halide photographic l I H H where R1 is selectiefi frofii theclass consisting of the hydrogen atom ans alkyl groups;
3. A process for red iifg the tendency to the formation of fog in s i ver halide photographic emulsions which comprises developing latent images in such emulsions by means of 9, developing solution containing a small quantity of a compound of the general formula:
where R1 is selected from the class consisting of the hydrogen atom and alkyl groups, thequantity of the said compound included in the developer being equivalent to 1 part of the compound per 3000 to 30,000 parts of the developing solution.
4. A process for reducing the tendency to the formation of fog in silver halide photographic emulsions which comprises developing the emulsions, in the presence of a small quantity of 3.3- bis 1.2.4-tri'a'zolyl) -formamidine.
5. A process for reducing the tendency to the formation of fog in silver halide photographic emulsions which comprises developing the emulsions, in the presence of a small quantity of 3.3- bis (-methyl-1.2.4-triazolyl) -formamidine.
6. A process for reducing the tendency to the formation of fog in silver halide photographic emulsions which comprises developing the emulsions, in the presence of a small quantity of 3 .3-bis(5-ethy1-1.2.4-triazolyl) -formamidine.
7. A photographic silverhalide emulsion con-* taining a small quantity of a compound of the general formula:
where R1 is selected from the class consisting of the hydrogen atom and alkyl groups.
8. A photographic silver halide emulsion containing in the proportion of 1 to 50 cc. of a 1:1000 5 solution per litre of emulsion a compound of the general formula:
where R1 is seltii'd from the class consisting of the hydrogen atom and alkyl groups.
9. A photographic silver halide emulsion containing in the proportion of 1 to 50 cc. of a 1:1000 solution per litre of emulsion 3.3-bis(1.2.4-triazolyl) -formamidine.
10. A photographic silver halide emulsion containing in the proportion of 1 to 50 cc. of a 1:1000 solution per litre or emulsion 3.3-bis(5-methyl- 1 .2.4-triazolyl) -forniamidine.
11. A photographic silver halide emulsion containing in the proportion of 1 to cc. of a 121000 solution per litre of emulsion 3.3-bis(5-ethyl- 1.2.4-triazolyl) -formamidihe.
12. .A photographic developing composition including a silver halide photographic developer and a small quantity of a compound of the general formulai where R1 is selected from the class consisting of the hydrogen atom and alkyl groups.
13. A photographic developing solution containing a silver halide photographic developer and, per 3000 to 30,000 parts of the solution, 1 part of 3.3'-bis(1.2.4-triazolyl)-formamidine.
14. A photographic developing solution containing a silver halide photographic developer and, per 3000 to 30,000 parts of the solution, 1 part of 3.3-bis(5-methyl-1.2.4-triazolyl)-formamidine.
F0 15. A photographic developing solution containing a silver halide photographic developer and, per 3000 to 30,000 parts of the solution, 1
part of 3.3'-bis(5-ethyl-1.2.4-triazoly1)-f0rmamidine.
JOHN DAVID KENDALL. HAROLD GORDON SUGGATE.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 1,763,989 Sheppard June 17, 1930 2,153,930 Kendall Apr. 11, 1939 2,353,754 Peterson July 18, 1944 2,475,136 Heimbach July 5, 1949 2,476,525 Anish July 19, 1949 2,534,914 Kendall Dec. 19, 1950
Claims (1)
1. A PROCESS FOR REDUCING THE TENDENCY TO THE FORMATION OF FOG IN SILVER HALIDE PHOTOGRAPHIC EMULSIONS WHICH COMPRISES DEVELOPING THE EMULSIONS, IN THE PRESENCE OF A SMALL QUANTITY OF A COMPOUND OF THE GENERAL FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2588538X | 1948-08-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2588538A true US2588538A (en) | 1952-03-11 |
Family
ID=10910890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US108418A Expired - Lifetime US2588538A (en) | 1948-08-06 | 1949-08-03 | Stabilizers in photographic emulsions and developers |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2588538A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3079255A (en) * | 1958-11-12 | 1963-02-26 | Agfa Ag | Processes of developing exposed silver halide photographic emulsions and compositions for use therein |
| US3106467A (en) * | 1960-10-19 | 1963-10-08 | Eastman Kodak Co | Bis-pyrazoles as antifoggants for photographic silver halide emulsions |
| US3525622A (en) * | 1966-03-15 | 1970-08-25 | Agfa Gevaert Nv | Light-sensitive silver halide emulsions |
| USB235011I5 (en) * | 1971-03-16 | 1975-01-28 | ||
| WO2014127297A1 (en) | 2013-02-15 | 2014-08-21 | Cambrios Technologies Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
| US10720257B2 (en) | 2013-02-15 | 2020-07-21 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
| US10971277B2 (en) | 2013-02-15 | 2021-04-06 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1763989A (en) * | 1930-06-17 | Photoctbaphic light-sensitive matebiax and pbocesb pob itakxng pat | ||
| US2153930A (en) * | 1935-05-08 | 1939-04-11 | Ilford Ltd | Sensitized photographic emulsion |
| US2353754A (en) * | 1942-11-07 | 1944-07-18 | Eastman Kodak Co | Color photography using metallic salt coupler compounds |
| US2475136A (en) * | 1946-06-07 | 1949-07-05 | Gen Aniline & Film Corp | Stabilizers for photographic silver-halide emulsions |
| US2476525A (en) * | 1946-08-15 | 1949-07-19 | Gen Aniline & Film Corp | Trinuclear cyanine dyes |
| US2534914A (en) * | 1950-12-19 | Triazole compounds |
-
1949
- 1949-08-03 US US108418A patent/US2588538A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1763989A (en) * | 1930-06-17 | Photoctbaphic light-sensitive matebiax and pbocesb pob itakxng pat | ||
| US2534914A (en) * | 1950-12-19 | Triazole compounds | ||
| US2153930A (en) * | 1935-05-08 | 1939-04-11 | Ilford Ltd | Sensitized photographic emulsion |
| US2353754A (en) * | 1942-11-07 | 1944-07-18 | Eastman Kodak Co | Color photography using metallic salt coupler compounds |
| US2475136A (en) * | 1946-06-07 | 1949-07-05 | Gen Aniline & Film Corp | Stabilizers for photographic silver-halide emulsions |
| US2476525A (en) * | 1946-08-15 | 1949-07-19 | Gen Aniline & Film Corp | Trinuclear cyanine dyes |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3079255A (en) * | 1958-11-12 | 1963-02-26 | Agfa Ag | Processes of developing exposed silver halide photographic emulsions and compositions for use therein |
| US3106467A (en) * | 1960-10-19 | 1963-10-08 | Eastman Kodak Co | Bis-pyrazoles as antifoggants for photographic silver halide emulsions |
| US3525622A (en) * | 1966-03-15 | 1970-08-25 | Agfa Gevaert Nv | Light-sensitive silver halide emulsions |
| USB235011I5 (en) * | 1971-03-16 | 1975-01-28 | ||
| US3925086A (en) * | 1971-03-16 | 1975-12-09 | Minnesota Mining & Mfg | Azotriazole and azotetrazole antifog, antistain and selective desensitizers for silver halide emulsions |
| WO2014127297A1 (en) | 2013-02-15 | 2014-08-21 | Cambrios Technologies Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
| EP3598185A2 (en) | 2013-02-15 | 2020-01-22 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
| US10720257B2 (en) | 2013-02-15 | 2020-07-21 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
| US10971277B2 (en) | 2013-02-15 | 2021-04-06 | Cambrios Film Solutions Corporation | Methods to incorporate silver nanowire-based transparent conductors in electronic devices |
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