US3502472A - Development accelerators for silver halide emulsion layers - Google Patents

Development accelerators for silver halide emulsion layers Download PDF

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Publication number
US3502472A
US3502472A US584650A US3502472DA US3502472A US 3502472 A US3502472 A US 3502472A US 584650 A US584650 A US 584650A US 3502472D A US3502472D A US 3502472DA US 3502472 A US3502472 A US 3502472A
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United States
Prior art keywords
silver halide
compounds
water
emulsion
compound
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Expired - Lifetime
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US584650A
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English (en)
Inventor
Jozef Frans Willems
Francis Jeanne Sels
Robrecht Julius Thiers
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271—Hydroxyamines
    • C08G18/3275—Hydroxyamines containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy compounds

Definitions

  • Reaction time hr. Remarks Add the dioxane solution dropwlse to ether. Filter the solid product by suction. Soluble in water in the tolusulphonate form.
  • Soluble in water in the acetate form Soluble in water in the acetate form.
  • polymeric compounds containing N-alkyl-bis-alkylene-amino groups and obtained by polycondensation of a N-alkyl-bis-w-hydroxyalkyleneamine with a dicarboxylic acid or derivative thereof e.g. an ester, acid chloride, or anhydride or with an organic diisocyanate, are very suitable for substantially increasing the developability and also the sensitivity of photographic silver halide emulsions on development in slow as well as in fast acting developers.
  • a dicarboxylic acid or derivative thereof e.g. an ester, acid chloride, or anhydride or with an organic diisocyanate
  • Polycondensation products which have proved to be ery suitable in that respect, contain recurring units, which can be represented by:
  • R represents an alkyl group of 1 to 5 carbon atoms e.g. methyl, eythl, propyl, isopropyl, .or a substituted alkyl group e.g. Z-hydroxyethyl, or an aralkyl group,
  • both alkylene or alkylene are alkylene groups containing from 2 to carbon atoms, including alkylene groups substituted e.g. with a hydroxyl group and/ or the carbon chain of which is interrupted by (a) heteroatom(s) such as oxygen, sulphur, or a substituted nitrogen atom,
  • n is a positive integer of at least 3
  • A represents a chemical bond or a NHgroup.
  • the compounds according to the invention in which A represents a chemical bond can be prepared by condensing a N-alkyl-bis-w-hydroxy-alkyleneamine with a dicarboxylic acid or derivative of a dicarboxylic acid such as an ester, an acid chloride, or the anhydride.
  • the condensations with the dicarboxylic acids are carried out with elimination of water either as such or by azeotropic distillation e.g. in toluene, anisol, or tetraline.
  • the condensation with an ester of a dicarboxylic acid is performed in such condition that the alcohol from which the ester is prepared, is distilled oiT continuously during the polycondensation reaction.
  • both reagents are made to react in equimolar ratio, though an excess of one of them is not harmful in most cases.
  • Very suitable dicarboxylic acids and derivatives thereof are succinic acid and succinates, diglycollic acid and diglycollates, adipic acid and adipates, maleates and maleic anhydride etc.
  • N-alkyl-bis-w-hydroxyalkyleneamines are N-alkyl-diethanolamines such as methyl-, ethyl-, propyl-, isopropyl-, and butyl-diethanolamine, N- alkyldipropanoliamines such as N-methyl-dipropanolamine, triethanolamine, triisopropanolarnine, N-a-methylbenzyl-diethanolamine etc.
  • Compounds according to the invention in which A represents a -NH-group can be prepared by condensing a N- alkyl-bis-whydroxyalkleneamine with adiisoyanate.
  • the above mentioned N alkyl-bis-w-hydroxyalkyleneamines are also particularly suited therefor.
  • Very suitable diisocyanates are aliphatic diisocyanates e.g. hexamethylene diisocyanates.
  • Aliphatic diisocyanates in which the alkylene chain is interrupted by a hetero atom e.g. bis(2-isocyanatoethyl) succinate can also be used for preparation of polyurethans suited for use according to the present invention.
  • the polycondensations are performed in an inert solvent such as benzene, dioxane etc. Uusually the reaction is continued for some hours at the boiling temperature of the solvent.
  • the polycondensation product is separated either by precipitation with a solvent in which the polycondensation product is insoluble e.g. diethyl ether, or by evaporation of the solvent.
  • the development accelerators used according to the present invention can be added as a base or in the salt form to the coating composition of a silver halide emulsion and/or can be incorporated into a water-permeable layer, which applied under or on top of the emulsion layer forms a water-permeable system with the silver halide emulsion layer and thus can come into effective contact with the silver halide.
  • the development accelerators can be incorporated into the coated emulsion layer either by treating the emulsion layer with an aqueous solution of these development accelerators or by coating this layer with a water-permeable layer containing the development accelerators, or also by bringing the development accelerators from a waterpermeable layer lying under the emulsion layer and comprising said development accelerators into effective contact with the silver halide.
  • the water-soluble development accelerators can be added to the light-sensitive silver halide emulsion during different preparation steps of the lightsensitive material. For instance they can be incorporated therein as a separate addition either mixed with one or more ingredients, which are used in the preparation of the silver halide grains during the physical or chemical ripening process or another moment preceding the application of the emulsion.
  • the development accelerators are preferably added to the silver halide emulsion composition after the chemical ripening process and just before coating the emulsion.
  • the development accelerators are preferably added in dissolved form in water or in an aqueous mixture of water and water-miscible organic solvents that do not impair the photographic properties of the light-sensitive silver halide emulsion.
  • condensation products are not sufficiently soluble in water in their base form they are converted into the salt form by neutralisation e.g. with an acid such as sulphuric acid, hydrochloric acid, p-toluenesulphonic acid, and acetic acid.
  • the optimum amount of development accelerator added to the silver halide emulsion depends on the very compound, on the nature of the colloid binding agent for the silver halide grains, and on the amount and the kind of the silver halide in the emulsion.
  • the development accelerators are added to the light-sensitive material in amounts ranging from 100 mg. to g. per mole of silver halide. In the developing bath they are normally used in amounts ranging from 0.1 to 10 g. per liter. If necessary, these compounds can also be added in amounts exceeding these limits.
  • the step of increasing the sensitivity according to the present invention can be combined with a method known as chemical sensitization, in which together with the above-mentioned development accelerators usual amounts of chemical sensitizers are added to the silver halide emulsion, e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea, or sodium thiosulphate, reducing compounds such as the tin compounds described 1950 by Gevaert Photo-Producten, N.V., and 568,687 filed June 18, 1958 by Gevaert Photo-Producten N.V., the iminoaminomethane sulphinic acid compounds described in the British patent specification 789,823 filed Apr.
  • chemical sensitizers e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea, or sodium thiosulphate
  • reducing compounds such as the tin compounds described 1950 by Gevaert Photo
  • the sensitizing action of the development accelerators used in the present invention comes in addition to the sensitzing action of the sensitizing compounds originally present in gelatin.
  • the development accelerators applied in the present invention can also be used in combination with stabilizers and fog-inhibiting compounds for the silver halide emulsion, for instance with mercury compounds or organic sulphur-containing compounds that form an insoluble silver salt with silver ions, preferably heterocyclic nitrogen-containing thione compounds such as benzothiazolin- 2-thione and 1-phenyltetrazolin-S-thione, the compounds described in the Belgain patent specifications 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo- Producten N.V., and compounds of the oxytriazolopyrimidine type, e.g. 5-methyl-7-hydroxy-s-triazolo[l,5-a]pyrimidine.
  • the combination with sensitizing and stabilizing cadmium salts in the light-sensitive material as well as in the developing bath can also be applied.
  • Other compounds, which sensitize the photographic emulsion by development acceleration such as organic onium compounds and polyonium compounds, preferably of the ammonium or snlphonium type, e.g. quaternary tetraalkylammonium salts, alkylpyridinium salts, bisalkylenepyridinium salts, alkylquinoline salts, and trialkylsulphonium salts can be used together with the development-accelerators according to the invention in the developing solution as well as in the light-sensitive material.
  • Other ingredients, such as colour couplers, developing substances, hardening agents, and wetting agents can also be added to the emulsions in the ordinary way.
  • EXAMPLE 1 A washed negative gelatin silver bromoiodide emulsion (average grain size of the silver halide:0.8;t), the silver halide of which consists of 94.5 mole percent of silver bromide and 5.5 mole percent of silver iodide, is ripened at 45 C.
  • the emulsion ready for coating contains per kg. 50 g. of silver halide, 75 g. of gelatin, 30 mg. of optical sensitizer with the following structural formula:
  • This emulsion is divided into several aliquot portions and to the separate portions is added one of the development accelerators as mentioned in the following Table 1. These emulsion portions are separately applied to a cellulose triacetate support and dried. All test stri s are then exposed in the same conditions through a grey wedge and developed for 7 min. at 20 C. in a fine-grain developer of the following composition:
  • the speed is represented by exposure values.
  • a decrease in exposure value of -30 means a doubling in sensitivity.
  • Process for developing photographic materials containing light-sensitive silver halide which comprises the step of developing said materials in the presence of a polymeric compound, containing the following structural units or these units in salt form:
  • R represents an alkyl group of 1 to 5 carbon atoms
  • both alkylene and alkylene are alkylene chains containing from 2 to 10 carbon atoms, including substituted alkylene chains and such chains interrupted by (a) heteroatom(s),
  • n is a positive integer of at least 3, and A represents a chemical bond or a NH-group.
  • Process for developing photographic materials containing light-sensitive silver halide which comprises the step of developing said materials in the presence of a water-soluble polymeric compound in basic or salt form and which is obtained in basic form by allowing to react a N-alkyl-bis-w-hydroxylkyleneamine with a dicarboxylic acid or derivative thereof or with an organic diisocyanate.
  • R represents an alkyl group of: 1 to 5 carbon atoms, an aralkyl group, or a hydroxy-substituted alkyl group, both alkylene and alkylene are alkylene chains containing from 2 to 10 carbon atoms, including substituted alkylene chains and such chains interrupted by (a) heteroatom s) n is a positive integer of at least 3, and
  • A represents a chemical bond or a NH-group.
  • a photographic light-sensitive silver halide material according to claim 3 containing said polymeric compound in an amount ranging from mg. to 10 g. per mole of silver halide.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US584650A 1965-10-11 1966-10-06 Development accelerators for silver halide emulsion layers Expired - Lifetime US3502472A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB42972/65A GB1150558A (en) 1965-10-11 1965-10-11 Improvements relating to the Development of Light-Sensitive Silver Halide Materials

Publications (1)

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US3502472A true US3502472A (en) 1970-03-24

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US (1) US3502472A (enExample)
BE (1) BE688063A (enExample)
DE (1) DE1522399A1 (enExample)
FR (1) FR1496598A (enExample)
GB (1) GB1150558A (enExample)
NL (1) NL6614291A (enExample)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3960569A (en) * 1973-11-20 1976-06-01 Fuji Photo Film Co., Ltd. Diffusion transfer color film unit with hydroxy substituted alkylene amino development accelerators
US4147543A (en) * 1972-04-01 1979-04-03 Fuji Photo Film Co., Ltd. Developer compositions for high contrast diffusion transfer photographic materials and process therefor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129100A (en) * 1961-03-16 1964-04-14 Agfa Ag Developing accelerators for silver halide emulsion layers
US3307948A (en) * 1964-06-02 1967-03-07 Gevaert Photo Prod Nv Development accelerators

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129100A (en) * 1961-03-16 1964-04-14 Agfa Ag Developing accelerators for silver halide emulsion layers
US3307948A (en) * 1964-06-02 1967-03-07 Gevaert Photo Prod Nv Development accelerators

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4147543A (en) * 1972-04-01 1979-04-03 Fuji Photo Film Co., Ltd. Developer compositions for high contrast diffusion transfer photographic materials and process therefor
US3960569A (en) * 1973-11-20 1976-06-01 Fuji Photo Film Co., Ltd. Diffusion transfer color film unit with hydroxy substituted alkylene amino development accelerators

Also Published As

Publication number Publication date
FR1496598A (fr) 1967-09-29
GB1150558A (en) 1969-04-30
DE1522399A1 (de) 1969-07-24
BE688063A (enExample) 1967-04-11
NL6614291A (enExample) 1967-03-28

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