US3615612A - Photographic element containing a phosphoric acid ester of a butynediol-alkylene oxide condensate - Google Patents
Photographic element containing a phosphoric acid ester of a butynediol-alkylene oxide condensate Download PDFInfo
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- US3615612A US3615612A US697323A US3615612DA US3615612A US 3615612 A US3615612 A US 3615612A US 697323 A US697323 A US 697323A US 3615612D A US3615612D A US 3615612DA US 3615612 A US3615612 A US 3615612A
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- photographic element
- phosphoric ester
- phosphoric acid
- butynediol
- silver halide
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- 150000003014 phosphoric acid esters Chemical class 0.000 title abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- -1 silver halide Chemical class 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- 150000002148 esters Chemical class 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 7
- 150000005690 diesters Chemical class 0.000 claims description 5
- 150000005691 triesters Chemical class 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000002345 surface coating layer Substances 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 abstract description 7
- 125000002947 alkylene group Chemical group 0.000 abstract description 5
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 108010010803 Gelatin Proteins 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JEOQACOXAOEPLX-WCCKRBBISA-N (2s)-2-amino-5-(diaminomethylideneamino)pentanoic acid;1,3-thiazolidine-4-carboxylic acid Chemical compound OC(=O)C1CSCN1.OC(=O)[C@@H](N)CCCN=C(N)N JEOQACOXAOEPLX-WCCKRBBISA-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000003381 stabilizer 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
- G03C1/04—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
- PHOTOGRAPHIC ELEMENT CONTAINING A PHOSPHORIC ACID ESTER OF A BUTYNEDIOL- ALKYLENE This invention relates to photographic emulsions and, more particularly, to the sensitization of these emulsions by incorporating therein certain phosphoric acid esters of polyoxyalkylene derivatives of butynediols.
- Sensitization of silver halide emulsions by the use of polyoxyalkylene or polyalkylene oxides is well known and is described in US. Pat. Nos. 2,423,549 and 2,441,389 while the use of various derivatives of polyalkylene oxides as, for example, condensation products of an alkylene oxide with glycols is described in US. Pat. Nos. 2,240,472.
- a deleterious effect with the use of these materials is their tendency to increase fog which is defined as the loss of sensitivity of the emulsion, during storage, resulting from the spontaneous occurrence of a developable species without exposure to light. Since the intensity of the resulting fog is dependent on both the inherent qualities of the emulsion and on the conditions of subsequent processing, the fog quantity becomes dependent, under constant conditions of development, on changes in such storage variables as time, temperature and relative humidity. Fog can also be the result of conditions present in high-temperature processing.
- sensitizer compounds causes an increase in fog during storage, their use had been somewhat limited especially under the aforesaid conditions of high temperature and humidity storage or under conditions of hightemperature processing. This had led to the need for special and somewhat exotic antifoggant compounds for use with these materials (see US. Pat. Nos. 2,704,716, 2,716,062 and 2,728,666). In a later development, described in US. Pat. No.
- this invention is based at least in part in the discovery that compounds of the phosphoric ester are satisfactory sensitizers for silver halide emulsions which do not cause excessive fog on development.
- This invention is also based at least in part on the discovery .that the incorporation of these compounds into silver halide emulsions results in creases in film speed (i.e., a marked increase in density for a given exposure) and improvement in the covering power of the developed silver.
- the covering power is defined as the ratio of the optical density at maximum density to the weight of silver per square decimeter in the developed image layer.
- This invention is also based at least in part on the discovery that the incorporation of these compounds into silver halide emulsions results in a marked reduction in the development of surface static charge.
- the phosphoric esters employed in photographic emulsions in accordance with this invention are compounds of the general formula:
- R is an alkylene group of from two to aboutfour carbon atoms
- the compound can be either a mono-, dior triester of phosphoric acid, or a mixture of the three, and m and n are positive integers such that the molecular weight of the ensuing compound is in excess of 300 and up to 150,000 or more.
- the system was then cooled and the reaction product was decanted from the black residue.
- the product composition a mixture of mono and diester and nonionic material, was determined from Acid Number values.
- a typical product from a 4:1 mole ratio of surfactant to phosphorus pentoxide 'assays 34.8 percent monoester and 17.6 percent diester.
- the phosphoric acid esters may also be advantageously employed in various types of photographic silver halide emulsions, e.g., nonsensitized emulsions, orthochromatic, panchromatic and X-ray emulsions. If used with sensitizing dyes, the ester material may be added to the emulsion before or after the dyes are added.
- Various silver halides may be used as the light-sensitive component, such as silver bromide, silver iodide, silver chloride or mixed silver halides.
- the phosphate esters may be used in emulsions intended for black-and-white photography or color photography, e.g., emulsions containing color-forming components.
- a developer compound of the primary aromatic amine type as, for example, dimethyl aininoaniline should be incorporated with a suitable color-forming compound having a group such as hydroxyl or methylene to couple with the oxidizer group of the developer in the emulsion.
- the dispersing agent in the photographic emulsion may be gelatin or some other hydrophilic compound, such as collodion, albumen, methyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone or the like.
- the quantity of the phosphate ester added to the emulsion will depend to a large extent on the layer into which it is incorporated. In any event, the concentration range, dependent on additive location, is from 0.5 to 15 grams per mole of silver halide.
- a gelatin-silver halide emulsion in which the silver halide consists of 4 percent silver iodide and 96 percent silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating on film base, that is, melted at 40 C. and necessary coating finals were added as, for example, sensitizing dyes, antifoggants, surfactants such as saponin and hardeners such as formaldehyde.
- a 10 percent aqueous solution of a phosphoric ester of a condensation product of ethylene oxide and 1,4-butynediol having a molecular weight of about 500 was prepared and 10 cc.
- Phosphoric acid ester Relative Fog Example grams speed Density 2 density 3 1 Control. 2 After 6' dev.
- a gelatin-silver halide emulsion in which the silver halide consists of 4 percent silver iodide and 96 percent silver bromide was prepared in a conventional manner. It was then readied for coating on film base, that is, melted at 40 c. and necessary coating finals were added such as sensitizing dyes, stabilizers and hardeners. The so-prepared emulsion samples 'were coated on a suitable cellulose ester base and dried. A 2 percent aqueous gelatin solution containing 6 percent (on weight of dry gelatin) of the phosphoric acid ester described above in examples l-3 was coated on the emulsion side of the film base as an anti-abrasion layer.
- R is an alkylene group of from two to about four carbon atoms
- R R,, R and R are members selected from the group consisting of hydrogen and an alkyl group of from one to about five carbon atoms
- X is a member selected from the group consisting of hydrogen and the polyoxyalkylene derivative group as set forth in the general fonnula and m and n are positive integers such that the molecular weight of the ensuing compound is in excess of 300 and up to 150,000 or more.
- m and n represent integers providing a molecular weight of at least 750
- X is a member selected from the group consisting of hydrogen and the polyoxyalkylene derivative group as set forth in the formula 3.
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A photographic element having incorporated in the lightsensitive silver halide emulsion layer or in a colloid layer contiguous therewith a phosphoric acid ester of a condensation product of an alkylene oxide with a butynediol.
Description
United States Patent lnventors E. Scudder Mackey Binghamton, N.Y.; Fritz Dersch, Binghamton, N.Y.; Fred S. Eiseman, Maplewood, NJ. Appl. No. 697,323 Filed Jan. 12, 1968 Patented Oct. 26, 1971 Assignee GAF Corporation New York, N.Y.
PHOTOGRAPHIC ELEMENT CONTAINING A PHOSPIIORIC ACID ESTER OF A BUTYNEDIOL- ALKYLENE [50] Field Search 96/107,
[ References Cited UNITED STATES PATENTS 3,255,013 6/1966 Dersch et al 96/107 FOREIGN PATENTS 1,015,023 l2/l965 Great Britain 96/107 Primary Examiner- Norman G. Torchin Assistant Examiner-Richard E. Fichter Attorneys-George L. Tone and Walter G. Hensel ABSTRACT: A photographic element having incorporated in the light-sensitive silver halide emulsion layer or in a colloid layer contiguous therewith a phosphoric acid ester of a condensation product of an alkylene oxide with a butynediol.
PHOTOGRAPHIC ELEMENT CONTAINING A PHOSPHORIC ACID ESTER OF A BUTYNEDIOL- ALKYLENE This invention relates to photographic emulsions and, more particularly, to the sensitization of these emulsions by incorporating therein certain phosphoric acid esters of polyoxyalkylene derivatives of butynediols.
Sensitization of silver halide emulsions by the use of polyoxyalkylene or polyalkylene oxides is well known and is described in US. Pat. Nos. 2,423,549 and 2,441,389 while the use of various derivatives of polyalkylene oxides as, for example, condensation products of an alkylene oxide with glycols is described in US. Pat. Nos. 2,240,472.
A deleterious effect with the use of these materials is their tendency to increase fog which is defined as the loss of sensitivity of the emulsion, during storage, resulting from the spontaneous occurrence of a developable species without exposure to light. Since the intensity of the resulting fog is dependent on both the inherent qualities of the emulsion and on the conditions of subsequent processing, the fog quantity becomes dependent, under constant conditions of development, on changes in such storage variables as time, temperature and relative humidity. Fog can also be the result of conditions present in high-temperature processing.
Since the addition of sensitizer compounds causes an increase in fog during storage, their use had been somewhat limited especially under the aforesaid conditions of high temperature and humidity storage or under conditions of hightemperature processing. This had led to the need for special and somewhat exotic antifoggant compounds for use with these materials (see US. Pat. Nos. 2,704,716, 2,716,062 and 2,728,666). In a later development, described in US. Pat. No.
' 3,255,013, the use of certain polyoxyalkylene derivatives of butynediols was described in which conventional antifoggants were suitable since these compounds did not cause an excessive increase in fog on storage.
It is an object of this invention, therefore, to provide novel sensitizers for silver halide emulsions.
It is a further object of this invention to provide such sensitizers which prevent formation or, at least, minimize fog development on storage and/or subsequent processing under conditions of high temperature.
It is also an object of this invention to provide such sensitizer compounds which reduce the development of surface static charges.
In accordance with this invention it has been found that certain phosphoric acid esters of the aforesaid polyoxyalkylene derivatives of a butynediol as hereinafter describedeither prevent formation of or substantially curtail fog development without any sacrifice of sensitivity. This is especially true where film is subject to storage and/or subsequent processing at high temperature.
Therefore this invention is based at least in part in the discovery that compounds of the phosphoric ester are satisfactory sensitizers for silver halide emulsions which do not cause excessive fog on development.
This invention is also based at least in part on the discovery .that the incorporation of these compounds into silver halide emulsions results in creases in film speed (i.e., a marked increase in density for a given exposure) and improvement in the covering power of the developed silver. The covering power is defined as the ratio of the optical density at maximum density to the weight of silver per square decimeter in the developed image layer.
This invention is also based at least in part on the discovery that the incorporation of these compounds into silver halide emulsions results in a marked reduction in the development of surface static charge.
The phosphoric esters employed in photographic emulsions in accordance with this invention are compounds of the general formula:
wherein:
R is an alkylene group of from two to aboutfour carbon atoms,
such that the compound can be either a mono-, dior triester of phosphoric acid, or a mixture of the three, and m and n are positive integers such that the molecular weight of the ensuing compound is in excess of 300 and up to 150,000 or more.
The procedure below describes the preparation of a preferred phosphoric acid ester of a polyoxyalkylene derivative of butynediol.
Procedure A Preparation of the phosphoric acid ester of the condensation product of ethylene oxide with l,4-diisobutyl-l,4- dimethyl-butynediol. v
Two hundred grams of a condensation product of ethylene oxide with 1,4-diisobutyl-l ,4-dimethyl butynediol having a molecular weight of about 600 (and sold under the trademark Surfynol 465) were admixed at room temperature with 1 gram of hypophosphorous acid. Eleven grams of phosphorus pentoxide were added slowly over a 1-hour period within a temperature range of 2550." C. The system was then flushed with, and maintained under a blanket of, nitrogen, while the temperature was raised to -95 C. After 4 hours, the system was cooled to 75 C., 2 grams of hydrogen peroxide (35 percent solution) were added and the temperature was again raised to 90-95 C. for 15 minutes. The system was then cooled and the reaction product was decanted from the black residue. The product composition, a mixture of mono and diester and nonionic material, was determined from Acid Number values. A typical product from a 4:1 mole ratio of surfactant to phosphorus pentoxide 'assays 34.8 percent monoester and 17.6 percent diester.
The aforesaid improvements can berealized by incorporating such phosphoric acid esters in the light-sensitive silver halide emulsion itself or in the undercoating, substratum, intermediate coating, overcoating or surface coating.
The phosphoric acid esters may also be advantageously employed in various types of photographic silver halide emulsions, e.g., nonsensitized emulsions, orthochromatic, panchromatic and X-ray emulsions. If used with sensitizing dyes, the ester material may be added to the emulsion before or after the dyes are added. Various silver halides may be used as the light-sensitive component, such as silver bromide, silver iodide, silver chloride or mixed silver halides. The phosphate esters may be used in emulsions intended for black-and-white photography or color photography, e.g., emulsions containing color-forming components. For the emulsion for color photography, a developer compound of the primary aromatic amine type as, for example, dimethyl aininoaniline should be incorporated with a suitable color-forming compound having a group such as hydroxyl or methylene to couple with the oxidizer group of the developer in the emulsion.
The dispersing agent in the photographic emulsion may be gelatin or some other hydrophilic compound, such as collodion, albumen, methyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone or the like.
The quantity of the phosphate ester added to the emulsion will depend to a large extent on the layer into which it is incorporated. In any event, the concentration range, dependent on additive location, is from 0.5 to 15 grams per mole of silver halide.
Several examples are set forth below to illustrate the nature of the invention and the manner of carrying it out. However, the invention should not be considered as being limited to the details thereof.
EXAMPLES l-3 These examples illustrate the effectiveness of compounds of the type described above in increasing the speed of silver halide emulsions without any resultant increase in fog.
A gelatin-silver halide emulsion in which the silver halide consists of 4 percent silver iodide and 96 percent silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. it was then readied for coating on film base, that is, melted at 40 C. and necessary coating finals were added as, for example, sensitizing dyes, antifoggants, surfactants such as saponin and hardeners such as formaldehyde. A 10 percent aqueous solution of a phosphoric ester of a condensation product of ethylene oxide and 1,4-butynediol having a molecular weight of about 500 was prepared and 10 cc. of this solution were 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 phosphoric acid ester, served as control. The so-prepared emulsion samples were coated on a suitable cellulose ester film 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:
Distilled water 500 ml.
Metol 2.2 grams Sodium sulfile, anhydrous 72.0 grams Hydroquinone 8.8 grams Sodium carbonate, monohydrated 56.0 grams Potassium bromide l4.0 grams Water to make l liter.
The results are tabulated below:
Phosphoric acid ester, Relative Fog Example grams speed Density 2 density 3 1 Control. 2 After 6' dev.
After 6 days oven test and 6 dev.
EXAMPLES 4-7 Polyethylene oxide Phoslauryl phoric ether, ester, Rel. Fog Example grams grams speed Density 2 density a 1 Control. After 6' dev. After 1 day at 140 F. and 50% R.H. and 6 dev.
EXAMPLES 8-9 These examples illustrate the effectiveness of the phosphoric ester compounds when added to other than the emulsion layer.
A gelatin-silver halide emulsion in which the silver halide consists of 4 percent silver iodide and 96 percent silver bromide was prepared in a conventional manner. it was then readied for coating on film base, that is, melted at 40 c. and necessary coating finals were added such as sensitizing dyes, stabilizers and hardeners. The so-prepared emulsion samples 'were coated on a suitable cellulose ester base and dried. A 2 percent aqueous gelatin solution containing 6 percent (on weight of dry gelatin) of the phosphoric acid ester described above in examples l-3 was coated on the emulsion side of the film base as an anti-abrasion layer. A sample of the same emulsion coated film base was also coated with an anti-abrasion layer consisting of a 2 percent aqueous gelatin solution without the phosphoric acid ester. After drying, the film samples were exposed and processed as described in examples l-3 above. The results are tabulated below:
Relative Fog Example Anti-abrasion coating speed Density 1 density 1 8 2% gelatin solution 150 0.13 O. 20
plus 0.12% of phosphoric acid ester. 9 2% gelatin solution.. 100 0. 18 0.30
1 After 6 dev. 2 After 6 days oven test and 4' dev.
The data tabulated below list the results of measurements made on surface resistivity. Since these measurements are indicative of the static susceptibility of the film surface, they noncurl emulsion formulations prepared in the conventional manner. Phosphate esters with the condensation products of ethylene oxide and l,4-diisobutyl-l,4-dimethylbutynediols in which the molecular weights were 500 (Surtynol440) and 600 (Surtynol 465), respectively, were evaluated.
All samples contained 6 percent of the phosphate ester of a Surfynol (based on dry gelatin) and were conditioned for 12 hours at 72 F. and 50 percent relative humidity. Resistivity was determined using a Megohm Meter. The results are tabuiated below.
Phosphate Surface Example Ester Added Resistivity (Meg.)
10 Control l2Xl0 l l Phosphate Ester of Surl'ynol 440 2.6Xl0 l2 Phosphate Ester of Surfynol 465 1.900
While exemplary embodiments of the invention have been described, the true scope of the invention is to be determined from the following claims.
What is claimed is:
wherein R is an alkylene group of from two to about four carbon atoms, R R,, R and R are members selected from the group consisting of hydrogen and an alkyl group of from one to about five carbon atoms, X is a member selected from the group consisting of hydrogen and the polyoxyalkylene derivative group as set forth in the general fonnula and m and n are positive integers such that the molecular weight of the ensuing compound is in excess of 300 and up to 150,000 or more.
2. The photographic element as defined in claim 1 wherein the phosphoric ester is a compound having the following formula:
(!)x H: H: OX
wherein m and n represent integers providing a molecular weight of at least 750, and X is a member selected from the group consisting of hydrogen and the polyoxyalkylene derivative group as set forth in the formula 3. The photographic element as defined in claim 2 wherein the phosphoric ester is the monoester.
'4. The photographic element as defined in claim 2 wherein the phosphoric ester is the diester.
5. The photographic element as defined in claim 2 wherein the phosphoric ester is the triester.
6. The photographic element as defined in claim 2 wherein the phosphoric ester is a mixture of the mono-, diand triesters.
7. The photographic element as defined in claim 1 wherein the phosphoric ester is located in the silver halide emulsion.
8. The photographic element as defined in claim 1 wherein the phosphoric ester is located in the surface coating layer.
9. The photographic element as defined in claim 1 wherein said phosphoric ester product is employed in an amount of from about 0.5 to 15 grams per mole of silver halide.
mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,615,612 Dated 10/ 26/71 Inventol-(s) E. Scudder Mackey, Fritz Dersch, Fred S. Eiseman It is certified thaterror appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
In Title after "Butynediol-Alkylehe" add --Oxide Condensate Signed and sealed this 9th day of May 1972.
(SEAL) Attest:
EDWARD ILFLETCHEILJR. ROBERT GOTTSCHALK Actesting Officer Commissioner of Patents
Claims (8)
- 2. The photographic element as defined in claim 1 wherein the phosphoric ester is a compound having the following formula: wherein m and n represent integers providing a molecular weight of at least 750, and X is a member selected from the group consisting of hydrogen and the polyoxyalkylene derivative group as set forth in the formula
- 3. The photographic element as defined in claim 2 wherein the phosphoric ester is the monoester.
- 4. The photographic element as defined in claim 2 wherein the phosphoric ester is the diester.
- 5. The photogrAphic element as defined in claim 2 wherein the phosphoric ester is the triester.
- 6. The photographic element as defined in claim 2 wherein the phosphoric ester is a mixture of the mono-, di- and triesters.
- 7. The photographic element as defined in claim 1 wherein the phosphoric ester is located in the silver halide emulsion.
- 8. The photographic element as defined in claim 1 wherein the phosphoric ester is located in the surface coating layer.
- 9. The photographic element as defined in claim 1 wherein said phosphoric ester product is employed in an amount of from about 0.5 to 15 grams per mole of silver halide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US69732368A | 1968-01-12 | 1968-01-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3615612A true US3615612A (en) | 1971-10-26 |
Family
ID=24800687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US697323A Expired - Lifetime US3615612A (en) | 1968-01-12 | 1968-01-12 | Photographic element containing a phosphoric acid ester of a butynediol-alkylene oxide condensate |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3615612A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3850644A (en) * | 1971-12-04 | 1974-11-26 | Agfa Gevaert Ag | Silver halide grains precipitated in the presence of a phosphoric acid amide sensitizer |
| US3915714A (en) * | 1971-11-30 | 1975-10-28 | Agfa Gevaert Ag | Silver halide emulsion containing a phosphoric acid amide |
| US4256830A (en) * | 1977-11-22 | 1981-03-17 | Agfa-Gevaert, A.G. | Photographic material containing a stabilizer |
-
1968
- 1968-01-12 US US697323A patent/US3615612A/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915714A (en) * | 1971-11-30 | 1975-10-28 | Agfa Gevaert Ag | Silver halide emulsion containing a phosphoric acid amide |
| US3850644A (en) * | 1971-12-04 | 1974-11-26 | Agfa Gevaert Ag | Silver halide grains precipitated in the presence of a phosphoric acid amide sensitizer |
| US4256830A (en) * | 1977-11-22 | 1981-03-17 | Agfa-Gevaert, A.G. | Photographic material containing a stabilizer |
| USRE31514E (en) * | 1977-11-22 | 1984-01-31 | Agfa-Gevaert Aktiengesellschaft | Photographic material containing a stabilizer |
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