US3173790A - Silver halide emusions containing polyoxyalkylene sensitizers - Google Patents

Silver halide emusions containing polyoxyalkylene sensitizers Download PDF

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Publication number
US3173790A
US3173790A US224835A US22483562A US3173790A US 3173790 A US3173790 A US 3173790A US 224835 A US224835 A US 224835A US 22483562 A US22483562 A US 22483562A US 3173790 A US3173790 A US 3173790A
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silver halide
condensation product
sensitizers
emusions
pentaerythritol
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US224835A
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Dersch Fritz
Jr William A Wurth
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GAF Chemicals Corp
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General Aniline and Film Corp
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Priority to BE637243D priority Critical patent/BE637243A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US224835A priority patent/US3173790A/en
Priority to GB33287/63A priority patent/GB1048016A/en
Priority to FR947107A priority patent/FR1403637A/en
Priority to DEG38652A priority patent/DE1177003B/en
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    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • the present invention relates to photographic silver halide emulsions and in particular to the sensitization thereof by the use of certain water-soluble polyoxyalkylene derivatives.
  • polyoxyethylene or the alkylene oxide derivatives have a molecular weight of at least 300, but preferably from 1500 to 10,000 or more.
  • 2,704,716 there is used as an anti-foggant hydromelonic acid or cyarneluric acid; in U.S.P. 2,716,062, 4-hydroxy-6-alkyl-1,3,3a-7-tetrazaindenes and in USP. 2,728,666, specific compounds of mercury with amines or amine salts.
  • alkylene oxide derivatives obtained by the condensation of pentaerythritol with 1,2-propylene oxide having molecular weight of at least 300 and which are still water-soluble are completely efiective sensitizers for silver halide emulsions without showing the excessive fogging tendency of the previously mentioned alkylene oxide compounds and that whatever fogging takes place can be controlled by the employment of conventional anti-foggants.
  • condensation products not only have the function stated but in addition portray the properties of reducing brittleness and static in film in which they are located.
  • Silver halide emulsions in intimate association or contact with condensation products of pentaerythritol with 1,2-pyropylene oxide having a molecular weight of at least 300 or more constitute the purposes and objects of the present invention.
  • condensation product contemplated for use herein may be typified by the following structural formula:
  • U.S.P. 1,970,578 describes the formation of condensation products of alkylene oxides on compounds containing a reactive hydrogen, such as alcohols, phenols, amines, acids and the like. The procedure envisioned by this patent may be used to produce the condensation products hereof.
  • the increase in sensitivity reduction of brittleness and static by the use of the pentaerythritol condensation products may be brought about through intimate contact or association with the silver halide emulsion.
  • the desired sensitivity may be achieved by adding the condensation product to the silver halide emulsion, to an undercoating, an intermedicate coating, an overcoating, or a surface coating prior to the coating operation. If desired, the condensation product may even be added during the actual preparation of the emulsion either before or after washing the emulsion.
  • the condensation product described herein may be used in various types of photographic emulsions, e.g., in non sensitized emulsions, orthochromatic, panchromatic and X-ray emulsions. If used with sensitizing dyes, it will be added before or after the dyes are added.
  • the emulsions may be prepared with any of the usual silver halides such as silver bromide, silver iodide, silver chloride or mixed silver halide.
  • the condensation products may be employed in emulsions intended for color photography, that is those containing color-forming compounds.
  • the dispersing agents or colloid carrier for the light-sensitive halides may be any of the colloids used in photography such as gelatin, collodion, albumen, cellulose derivatives, PVA, or the like.
  • Example I A silver halide emulsion in gelatin containing 4% silver iodide and 96% silver bromide was prepared in a conven tional manner and brought up to its maximum lightsensitivity. It was then readied for coating on film base, that is, melted at 40 C., and coating finals such as sensitizing dyes, stabilizers and hardeners were added. A 10% aqueous solution of a polyether produced by condensing 8 moles of 1,2-propylene oxide with pentaerythritol was prepared and 10 cc. of this solution was added to a sample of the above described emulsion, containing about 0.4 mol of silver halide.
  • a sample of the same emulsion, but not containing the speed increasing additive served as a control.
  • the so prepared emulsion samples were coated on a cellulose ester base and dried. Samples of these film coatings were then exposed in a Type I B Sensitometer and developed in a developer of the following composition:
  • Example 11 A silver halide emulsion in gelatin containing 4% silver iodide and 96% silver bromide was coated on film base in a manner known'to the art. After the coating was performed, an aqueous gelatin solution containing 20 grams of gelatin per liter and 1.2 grams of the condensation product of 1,2-propylene oxide and pentaerythritol was coated thereon'asan antiabrasion layer, said condensation product having a molecular weight of 450. After drying, film samples were exposed and processed as described in Example I.
  • the samples described exhibited a relative speed of 175 with a fog of .20 as compared With a type coating of the same emulsion having an antiabr-asion layer similar to that described above, but lacking the speed increasing additive andhaving a speed of 100 and a fog of .13;
  • a light-sensitive silver halide emulsion layer having in intimate contact therewith a condensation product of pentaerythritol with 1,2- ropylene oxide, such condensation product having a molecular Weight of at least 300.
  • a light-sensitive silver halide emulsion layer which contains the condensation product of pentaerythritol and 1,2-propylene oxide, such condensation product having molecular Weight of at least 300.
  • a photographic element comprising a support, a light-sensitive silver halide emulsion layer containing a condensation product of pentaerythritol With 1,2-propylene oxide, such condensation product having molecular Weight of from 300 to at least 10,000.
  • a photographic element comprising a support bear- 7 ing a light-sensitive silver brom-iodide emulsion containing about 1 gram per .4 mol of silver halide of the condensation product of 1 mol of pentaerythritol With 8 moles of 1,2-propylene oxide.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Laminated Bodies (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent Johnson City, N.Y., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed Sept. 19, 1962, Ser. No. 224,835
4 Claims. (Cl. 96-107) The present invention relates to photographic silver halide emulsions and in particular to the sensitization thereof by the use of certain water-soluble polyoxyalkylene derivatives.
The use of polyoxyethylenes or derivatives of alkylene oxides with amines, phenols, alcohols and hexetolring dehydration products as sensitizer for silver halide emulsions have been described in the prior art and in this connection reference is made to United States Patents 2,423,549, 2,441,389, 2,240,472 and 2,400,532 and the like.
Generally the polyoxyethylene or the alkylene oxide derivatives have a molecular weight of at least 300, but preferably from 1500 to 10,000 or more.
It has been recognized that these compounds are powerful sensitizers. Their use, however, has been limited because of their marked tendency to increase the fog of photographic silver halide emulsions during storage, especially at elevated temperatures and humidities. To counteract this tendency and at the same time to take advantage of the sensitizing characteristics of the compounds, it has been necessary to use with the sensitizers special anti-foggants. This is attributable to the fact that conventional anti-foggants such as referred to on pages 459 et seq. of Mees The Theory of the Photographic Process, published 'by the MacMillan Company, New York, in 1946, are powerless to control the fog induced by the sensitizer. Thus in U.S.P. 2,704,716 there is used as an anti-foggant hydromelonic acid or cyarneluric acid; in U.S.P. 2,716,062, 4-hydroxy-6-alkyl-1,3,3a-7-tetrazaindenes and in USP. 2,728,666, specific compounds of mercury with amines or amine salts.
We have now discovered and rather surprisingly so that the alkylene oxide derivatives obtained by the condensation of pentaerythritol with 1,2-propylene oxide having molecular weight of at least 300 and which are still water-soluble are completely efiective sensitizers for silver halide emulsions without showing the excessive fogging tendency of the previously mentioned alkylene oxide compounds and that whatever fogging takes place can be controlled by the employment of conventional anti-foggants. Furthermore and rather unusually such condensation products not only have the function stated but in addition portray the properties of reducing brittleness and static in film in which they are located.
Silver halide emulsions in intimate association or contact with condensation products of pentaerythritol with 1,2-pyropylene oxide having a molecular weight of at least 300 or more constitute the purposes and objects of the present invention.
The condensation product contemplated for use herein may be typified by the following structural formula:
3,173,790 Patented Mar. 16, 1965 'ice in which the values of a, b, c, and d are such that the molecular weight of the compound is 300 and preferably 10,000 or more.
U.S.P. 1,970,578 describes the formation of condensation products of alkylene oxides on compounds containing a reactive hydrogen, such as alcohols, phenols, amines, acids and the like. The procedure envisioned by this patent may be used to produce the condensation products hereof.
It has been noted that the increase in sensitivity reduction of brittleness and static by the use of the pentaerythritol condensation products may be brought about through intimate contact or association with the silver halide emulsion. Thus it has been found that the desired sensitivity may be achieved by adding the condensation product to the silver halide emulsion, to an undercoating, an intermedicate coating, an overcoating, or a surface coating prior to the coating operation. If desired, the condensation product may even be added during the actual preparation of the emulsion either before or after washing the emulsion.
The condensation product described herein may be used in various types of photographic emulsions, e.g., in non sensitized emulsions, orthochromatic, panchromatic and X-ray emulsions. If used with sensitizing dyes, it will be added before or after the dyes are added. The emulsions may be prepared with any of the usual silver halides such as silver bromide, silver iodide, silver chloride or mixed silver halide. The condensation products may be employed in emulsions intended for color photography, that is those containing color-forming compounds. The dispersing agents or colloid carrier for the light-sensitive halides may be any of the colloids used in photography such as gelatin, collodion, albumen, cellulose derivatives, PVA, or the like.
The following examples are illustrated for effectiveness of our condensation products of pentaerythritol with 1,2-pyropylene oxide as a speed increasing element for photographic silver halide emulsions but it is to be understood that this invention is not restricted thereto.
Example I A silver halide emulsion in gelatin containing 4% silver iodide and 96% silver bromide was prepared in a conven tional manner and brought up to its maximum lightsensitivity. It was then readied for coating on film base, that is, melted at 40 C., and coating finals such as sensitizing dyes, stabilizers and hardeners were added. A 10% aqueous solution of a polyether produced by condensing 8 moles of 1,2-propylene oxide with pentaerythritol was prepared and 10 cc. of this solution was added to a sample of the above described emulsion, containing about 0.4 mol of silver halide. A sample of the same emulsion, but not containing the speed increasing additive served as a control. The so prepared emulsion samples were coated on a cellulose ester base and dried. Samples of these film coatings were then exposed in a Type I B Sensitometer and developed in a developer of the following composition:
Grams Metol 1.5 Sodium sulfite, anhydrous 45.0 Sodium bisulfite 1.0
Hydroquinone 3.0 Sodium carbonate, monohydrate 6.8 Potassium bromide z- .8
Water to make 1.0 liter.
Condensation Product'of 1,2- 6 Days Propylene Oxide and Relative After 12' Oven Test Pentaerythritol Speed Dev. 7 and 4 Dev.
0 100 .13 .08 1 gram. 160 20 09 Quantity of Polyoxyethylene Laurylether' Added:
1 gram 150 28 16 Example 11 A silver halide emulsion in gelatin containing 4% silver iodide and 96% silver bromide was coated on film base in a manner known'to the art. After the coating was performed, an aqueous gelatin solution containing 20 grams of gelatin per liter and 1.2 grams of the condensation product of 1,2-propylene oxide and pentaerythritol was coated thereon'asan antiabrasion layer, said condensation product having a molecular weight of 450. After drying, film samples were exposed and processed as described in Example I. The samples described exhibited a relative speed of 175 with a fog of .20 as compared With a type coating of the same emulsion having an antiabr-asion layer similar to that described above, but lacking the speed increasing additive andhaving a speed of 100 and a fog of .13;
We claim:
1. In a photographic element a light-sensitive silver halide emulsion layer having in intimate contact therewith a condensation product of pentaerythritol with 1,2- ropylene oxide, such condensation product having a molecular Weight of at least 300.
2, In a photographic element a light-sensitive silver halide emulsion layer which contains the condensation product of pentaerythritol and 1,2-propylene oxide, such condensation product having molecular Weight of at least 300.
' 3. A photographic element comprising a support, a light-sensitive silver halide emulsion layer containing a condensation product of pentaerythritol With 1,2-propylene oxide, such condensation product having molecular Weight of from 300 to at least 10,000.
4. A photographic element comprising a support bear- 7 ing a light-sensitive silver brom-iodide emulsion containing about 1 gram per .4 mol of silver halide of the condensation product of 1 mol of pentaerythritol With 8 moles of 1,2-propylene oxide.
References Cited in the file of this patent UNITED STATES PATENTS 2,743,180 Carroll Apr. 24, 1956 2,927,918 Anderson Mar. 8, 1960 2,995,444 Dersch Aug. 8, 1961

Claims (1)

1. IN A PHOTOGRAPHIC ELEMENT A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER HAVING IN INTIMATE CONTACT THEREWITH A CONDENSATION PRODUCT OF PENTAERYTHRITOL WITH 1,2PROPYLENE OXIDE, SUCH CONDENSATION PRODUCT HAVING A MOLECULAR WEIGHT OF AT LEAST 30.
US224835A 1962-09-19 1962-09-19 Silver halide emusions containing polyoxyalkylene sensitizers Expired - Lifetime US3173790A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE637243D BE637243A (en) 1962-09-19
US224835A US3173790A (en) 1962-09-19 1962-09-19 Silver halide emusions containing polyoxyalkylene sensitizers
GB33287/63A GB1048016A (en) 1962-09-19 1963-08-22 Improvements in or relating to photographic silver halide emulsions
FR947107A FR1403637A (en) 1962-09-19 1963-09-10 Improvements in sensitization of photographic silver halide emulsions
DEG38652A DE1177003B (en) 1962-09-19 1963-09-11 Photographic material chemically sensitized with alkylene oxide condensates

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US224835A US3173790A (en) 1962-09-19 1962-09-19 Silver halide emusions containing polyoxyalkylene sensitizers

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532501A (en) * 1967-02-10 1970-10-06 Gaf Corp Water-soluble acid esters of polyoxyalkylenated pentaerythritol in silver halide emulsions
US3663230A (en) * 1968-06-12 1972-05-16 Konishiroku Photo Ind Light-sensitive silver halide photographic emulsions
EP0699952A1 (en) 1994-08-30 1996-03-06 Agfa-Gevaert N.V. A novel core-shell latex for use in photographic materials
US20100256423A1 (en) * 2009-03-31 2010-10-07 Nof Corporation Method for producing polyoxyalkylene derivative and polyoxyalkylene derivative

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743180A (en) * 1953-07-01 1956-04-24 Eastman Kodak Co Pentazaindene stabilizers for photo-graphic emulsions sensitized with alkylene oxide polymers
US2927918A (en) * 1956-12-24 1960-03-08 Dow Chemical Co Hydroxypropylation of hydroxy compounds
US2995444A (en) * 1957-09-26 1961-08-08 Gen Aniline & Film Corp Stabilization of photographic emulsions sensitized with alkylene oxide polymers

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2743180A (en) * 1953-07-01 1956-04-24 Eastman Kodak Co Pentazaindene stabilizers for photo-graphic emulsions sensitized with alkylene oxide polymers
US2927918A (en) * 1956-12-24 1960-03-08 Dow Chemical Co Hydroxypropylation of hydroxy compounds
US2995444A (en) * 1957-09-26 1961-08-08 Gen Aniline & Film Corp Stabilization of photographic emulsions sensitized with alkylene oxide polymers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532501A (en) * 1967-02-10 1970-10-06 Gaf Corp Water-soluble acid esters of polyoxyalkylenated pentaerythritol in silver halide emulsions
US3663230A (en) * 1968-06-12 1972-05-16 Konishiroku Photo Ind Light-sensitive silver halide photographic emulsions
EP0699952A1 (en) 1994-08-30 1996-03-06 Agfa-Gevaert N.V. A novel core-shell latex for use in photographic materials
US20100256423A1 (en) * 2009-03-31 2010-10-07 Nof Corporation Method for producing polyoxyalkylene derivative and polyoxyalkylene derivative
US8501998B2 (en) * 2009-03-31 2013-08-06 Nof Corporation Method for producing polyoxyalkylene derivative and polyoxyalkylene derivative

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FR1403637A (en) 1965-06-25
GB1048016A (en) 1966-11-09
BE637243A (en)
DE1177003B (en) 1964-08-27

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