US3749574A - Development of photographic silver halide elements - Google Patents

Development of photographic silver halide elements Download PDF

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Publication number
US3749574A
US3749574A US00144235A US3749574DA US3749574A US 3749574 A US3749574 A US 3749574A US 00144235 A US00144235 A US 00144235A US 3749574D A US3749574D A US 3749574DA US 3749574 A US3749574 A US 3749574A
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United States
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compounds
silver halide
development
group
silver
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US00144235A
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English (en)
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R Pollet
F Sels
H Philippaerts
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Agfa Gevaert NV
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Agfa Gevaert NV
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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
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols

Definitions

  • This invention relates to a process for producing photographic silver images by development of exposed lightsensitive silver halide in the presence of compounds influencing the sensitornetric characteristics of light-sensitive silver halide emulsions by an increase of the speed and/or the gradation.
  • the present invention further relates to photographic materials and developing baths containing said compounds.
  • polyoxyalkylene compounds were found very suitable for use in the lithdevelopment of silver halide emulsions of the graphic arts type i.e. of the type used for photomechanical reproduction of line or half-tone images, which are generally silver chloride and silver bromochloride emulsions comprising at most 50 mole percent of bromide.
  • Polyoxyalkylene compounds when used in silver halide emulsion layers, impair the keeping qualities of these layers, particularly at high temperatures and elevated degrees of relative humidities in that they induce a substantial increase of fog. It was also found that when these polyoxyalkylene compounds are incorporated into silver halide emulsions to increase the speed, they very often impair the image tone of the developed silver by forming brown and reddish-brown images. Moreover, polyoxyalkylene compounds when used in infectious development greatly increase the formation of peppers.
  • Peppers are black spots of a very high density which are irregularly produced during the development in the areas of the light-sensitive emulsion which are slightly exposed. These peppers when they are present in a high amount markedly degrade the quality of a half-tone image reproduction by deforming the screen dots and/ or soiling the areas which were practically unexposed. The phenomenon of pepper particularly arises when partly air oxidized or somewhat exhausted developing baths are used.
  • Z stands for oxygen or the group OY'O wherein Y is a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms such as ethylene, tetramethylene and l-methyltrimethylene,
  • the invention further provides photographic lightsensitive silver halide materials and photographic developing compositions comprising a water-soluble nonpolymeric compound as defined above.
  • reaction products are generally made to react in a stoichiometric ratio, though the use of one of them in an amount exceeding the stoichiometric amount is not harmful since the reaction proceeds very smoothly and generally not in an exothermic Way.
  • reaction products obtained substantially consists of com-pounds corresponding to the following general formula:
  • the possible epoxide groups in the final product obtained which may be due to unreacted bisepoxide or which are terminal epoxide groups in part of the reaction products formed, are determined by titration with perchloric acid in acetic acid medium comprising hexadecyl trimethyl ammonium bromide.
  • the residual epoxide groups are given on a percentage basis of the milliequivalents of epoxide groups found relative to the milliequivalents of epoxide groups used on starting the reaction.
  • Rcac- Residual tion epoxide Comtime groups pound Monoalkyl or monoaryl ether used- Bisepoxide used- (hours) percent I HaCO-CH2CH2OH 32 4 H2C-CHCHg0-(CH2)2OCHzOH-CH2 II NuC4OCH2-CH2OH Same as above--- 60 5.5
  • H2C-CHCH20(CH2)2O-CH2CH-CH2 VI H5020 (CH2CH2O)zH Same as above 36 2. 5 VII Hycto (CHzCHzOhH 62 5 VIII HsCO-(CH2CH20)2H 32 3 H2CCH'CHz-0(CHg)4-0CH2CHGH:
  • IX Moncmethyl ether of polyoxyethylene glycol having 0 56 1 an average molecular weight of 350 which can be represented by: HaCO(OHzCEzO)1H. HsC-OHCHzO0HzCHGHg X do 56 7 H2CCH-CHz-O-(CH3)2O-CHzCH--CH2 XI .11 i O O 32 None HzG-CH-CHz-O-(CHz)40OIE[zOH-(3Hs XII.- Monomethyl ether of polyoxyethylene glycol having 0 56 None an average molecular weight of 550 which can be represented by: H30 O -(CH2CH20)12H- HzC'CHCH2O-CH2G -CHg YTYI nn 0 0 5 4 a V HzCCH'GHz-0(CH2)20CH:CH CH XIV. A 32 None HzC- CH- CH2 0- (CH2)4-0CH:OHCH:
  • an average molecular weight of 750 which can be represented by: HzU0-(CHgCHzO)mH- HzC-CHCHr0CHr-CHCH2 XVI do /O ⁇ /O ⁇ 32 4 H30-CHCHr-O-(CH2)2-0-CHz-CHCH5 XVII do O 32 None
  • the hydrogen atoms of the free hydroxyl groups in the compounds obtained may be partly or wholly substituted by reaction with compounds which are reactive with respect to an active hydrogen atom of a hydroxyl group for example an acid chloride or acid anhydride such as acetic anhydride, succinic anhydride, maleic anhydride and sulphobenzoic anhydride, a sulphonyl chloride, isocyanates or unsaturated alkylating compounds, e.g.
  • the reaction product of the said hydroxyl containing compound with maleic anhydride may further be allowed to react with a bisulphite thus forming a bisulphite addition product.
  • the bisulphite used is preferably an alkali metal bisulphite.
  • the compounds used according to the present invention can be present in the developer bath or can be added to the coating composition of a silver halide emulsion layer and/or incorporated into a water-permeable layer which when coated under or on top of the emulsion layer forms a water-permeable system with the silver halide emulsion layer and is then in eifective contact with the silver halide.
  • the compounds of use according to the invention can be incorporated into the coated emulsion layer either by treating the emulsion layer with an aqueous solution of these compounds or by coating this layer with a waterpermeable layer containing the said compounds, or also by bringing the said compounds from a water-permeable layer lying under the emulsion layer and comprising said compounds by difiusion into effective contact with the silver halide.
  • the water-soluble compounds of the invention can be added to the light-sensitive silver halide emulsion during different preparation steps of the light-sensitive 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 compounds of the invention are preferably added to the silver halide emulsion composition after the chemical ripening process and just before coating the emulsion.
  • the compounds are preferably added from a solution in water or in an aqueous mixture of water and watermiscible organic solvents such as ethanol that do not impair the photographic properties of the light-sensitive silver halide emulsion.
  • the optimum amount of compound added to the silver halide emulsion depends on the compound itself 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. In general, however, the compounds are added to the highsensitive material in amounts ranging from mg. to 5 g. per mole of silver halide. In the developing bath they are normally used in amounts ranging from 10 mg. to 5 g. per liter. If necessary, these compounds can also be added in amounts exceeding these limits.
  • the step of influencing the sensitometric characteristics of silver halide emulsions by means of the compounds of the invention can be combined with a method known as chemical sensitization, in which together with the abovementioned compounds chemical sensitizers are used, e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea or sodium thiosulphate, reducing compounds such as the tin compounds described in the Belgian patent specifications 493,464 filed J an. 24, 1970 and 568,687 filed June 18, 1958 both by Gevaert Photo-Production N.V., the iminoarninomethane sulphinic acid compounds described in the United Kingdom 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 in the Belgian patent specifications 4
  • the compounds employed in the present invention can also be used in combination with stabilzers and fog-inhibiting compounds for the silver halide emulsion, for instance with mercury compounds such as those described in Belgian patent specifications 524,121 filed Nov. 7, 1953 by Kodak Co. and 677,337 filed Mar. 4, 1966 by Gevaert- Agfa N.V. and in published Dutch application 6715932 filed Nov.
  • organic onium compounds and polyonium compounds preferably of the ammonium or sulphonium type, e.g. quaternary tetra-alkylammonium alkylpyrid inium salts, bis-alkylene-pyridinium salts, alkylquinolinine salts, trialkyl-sulphonium salts, onium derivatives of amino-N- oxides as described in United Kingdom patent specification 1,121.696 filed Oct. 7, 1965 by Gevaert-Agfa N.V.
  • organic onium compounds and polyonium compounds preferably of the ammonium or sulphonium type, e.g. quaternary tetra-alkylammonium alkylpyrid inium salts, bis-alkylene-pyridinium salts, alkylquinolinine salts, trialkyl-sulphonium salts, onium derivatives of amino-N- oxides as described in United Kingdom patent specification 1,121.696 filed Oct. 7, 1965 by Gevaert-
  • iodonium compounds for instance diphenyl iodonium chloride as described in United Kingdom patent specification 1,119,075 filed Oct. 7, 1965 by Gevaert-Afga N.V. can be used together with the compounds 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, plasticizers, and wetting agents, can also be added to the emulsion in the ordinary way.
  • the compounds of the invention are also particularly suitable for the development of silver chloride and silver chlorobromide emulsions comprising at most 50 mole percent of silver bromide for reproducing line and half-tone images with hydroquinone/formaldehyde bisulphite developers.
  • EXAMPLE 1 A conventional ammoniacal high-sensitive gelatino silver bromoiodide (4.2 mole percent of iodide) emulsion ready for coating, which comprised per kg. an amount of silver halide corresponding to 50 g. of silver nitrate, 625 mg. of 5-methyl-7-hydroxy-s-triazolo[1,5-a]pyrimidine as a stabilizer as well as other emulsion addenda such as hardener and coating aid, was divided into several aliquot portions. To each of these portions one of the compounds listed in the table below was added as development accelerator in the amount given. The emulsion portions were then coated on a paper support and dried.
  • EXAMPLE 2 An emulsion as described in Example 1 was divided into several aliquot portions. To each of these portions one of the compounds listed in the table below was added as development accelerator in the amount given. The emulsions were then coated on a subbed film support and dried.
  • the emulsion samples were all coated in a similar way on a cellulose triacetate support and dried.
  • EXAMPLE 5 A photographic material as described in Example 4, with the difference that to the emulsion none of the compounds listed in the table of Example 4 was added, was divided into two strips.
  • the strips were exposed for 4 seconds through a graphic magenta contact screen and a yellow filter in order to examine the formation of peppers" due to infectious development in a partly air-oxidized developer.
  • the first strip was developed for 2.5 min. at 20 C. in a developing bath of the composition given in Example 4 to which per litre 0.05 g. polyethylene glycol having an average molecular weight of 4000 had been added.
  • the second strip was developed for 2.5 min, at 20 C. in a developing bath of the composition given in Example 4 to which per litre 0.05 g. of Compound XIII has been added.
  • Z stands for oxygen or the group OYO-- wherein Y is a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms;
  • a monoalkyl ether or a monoaryl ether of ethylene glycol or a polyoxyethylene glycol, is present in an amount sufficient to enhance development without a substantial increase in fog.
  • Z stands for oxygen or the group -OY-O wherein Y is a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms;
  • R stands for alkyl or aryl
  • n stands for an integer from 1 to 20
  • R stands for hydrogen, an alkyl group, a COR group, a CONHR group or a SO R group wherein R stands for a monovalent saturated or unsaturated aliphatic group for example alkyl and alkenyl, a
  • -COCH CHCOOH group or its bisulphite addition product, an aryl group or a heterocyclic group.
  • a photographic light-sensitive material which comprises a silver halide emulsion layer or a water-permeable layer adjacent to a silver halide emulsion layer containing a Water-soluble non-polymeric compound obtained by reaction of a bis-epoxide corresponding to the formula: wherein:
  • Z stands for oxygen or the group -O-Y-O wherein Y is a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms;
  • a photographic material according to claim 5 wherein the said water-soluble non-polymeric compound corresponds to the formula:
  • Z stands for oxygen or the group -OY-O wherein Y is a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms,
  • R stands for alkyl or aryl
  • n stands for an integer from 1 to 20
  • R stands for hydrogen, an alkyl group, a COR group, a -CONHR group or a -S R group wherein R stands for a monovalent saturated or unsaturated aliphatic group for example alkyl and alkenyl, a
  • COCH CH-COOH group or its bisulphite addition product, an aryl group or a heterocyclic group.
  • a photographic material according to claim 5, wherein the said silver halide emulsion is a silver chloride emulsion or a silver chlorobromide emulsion, which comprises at most 50 mole percent of bromide, suitable for the production of line and half-tone, prints.
  • a photographic developing composition comprising a silver halide developing agent and a water-soluble nonpolymeric compound obtained by reaction of a bisepoxide corresponding to the formula:
  • .2 stands for oxygen or the group O-Y-O- wherein Y is a straight-chain or branched-chain alkylene group which has from 2 to 8 C-atoms; with a monoalkyl ether, or a monoaryl ether of ethylene glycol or a polyoxyethylene glycol in an amount suflicient to enhance development without substantial increase in 11.
  • - Z stands for oxygen or the group OY-O- wherein Y is a straight-chain or branched-chain alkylcne group which has from 2 to 8 C-atoms,
  • R stands for alkyl or aryl
  • n stands for an integer from 1 to 20
  • R stands for hydrogen, an alkyl group, a --COR group, a C()NHR group or a SO R group wherein R stands for a monovalent saturated or unsaturated aliphatic group for example alkyl and alkenyl, a
  • a photographic developing composition according to claim 10 wherein Z stands for --0(CH O or 13.
  • a photographic developing composition according to claim 10, comprising hydroquinone and formaldehyde bisulphite.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00144235A 1970-06-11 1971-05-17 Development of photographic silver halide elements Expired - Lifetime US3749574A (en)

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US (1) US3749574A (OSRAM)
BE (1) BE768365A (OSRAM)
CA (1) CA989869A (OSRAM)
DE (1) DE2128951A1 (OSRAM)
FR (1) FR2096095A5 (OSRAM)
GB (1) GB1346996A (OSRAM)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984243A (en) * 1972-12-21 1976-10-05 Fuji Photo Film Co., Ltd. Photographic developer compositions for obtaining high contrast images
US4017314A (en) * 1976-01-07 1977-04-12 E. I. Du Pont De Nemours And Company Use of crown compounds (cyclic polyethers) in litho developers to improve halftone dot quality and gradation
US4135931A (en) * 1976-08-27 1979-01-23 Fuji Photo Film Co., Ltd. Method of image formation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3984243A (en) * 1972-12-21 1976-10-05 Fuji Photo Film Co., Ltd. Photographic developer compositions for obtaining high contrast images
US4017314A (en) * 1976-01-07 1977-04-12 E. I. Du Pont De Nemours And Company Use of crown compounds (cyclic polyethers) in litho developers to improve halftone dot quality and gradation
US4135931A (en) * 1976-08-27 1979-01-23 Fuji Photo Film Co., Ltd. Method of image formation

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DE2128951A1 (de) 1971-12-16
FR2096095A5 (OSRAM) 1972-02-11
CA989869A (en) 1976-05-25
BE768365A (nl) 1971-12-13
GB1346996A (en) 1974-02-13

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