US3573913A - Light-sensitive silver halide materials - Google Patents

Light-sensitive silver halide materials Download PDF

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Publication number
US3573913A
US3573913A US573832A US3573913DA US3573913A US 3573913 A US3573913 A US 3573913A US 573832 A US573832 A US 573832A US 3573913D A US3573913D A US 3573913DA US 3573913 A US3573913 A US 3573913A
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US
United States
Prior art keywords
polyethylene glycol
light
silver halide
urethan
development
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US573832A
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English (en)
Inventor
Jozef Frans Willems
Joseph Louis De Munck
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Agfa Gevaert NV
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Agfa Gevaert NV
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Classifications

    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/711—Monoisocyanates or monoisothiocyanates containing oxygen in addition to isocyanate oxygen
    • 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
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G03C5/3056—Macromolecular additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/15—Lithographic emulsion

Definitions

  • Photographic light-sensitive materials which include a urethan which is the reaction product of (1) an alkoxy polyethylene glycol ester of isocyanatoacetic acid having the formula R represents an alkyl radical having from 1 to 5 carbon atoms, and n represents an integer of from 1 to 35, and
  • This invention relates to novel polyoxyalkylene derivatives, photographic materials comprising such polyoxyalkylene derivatives and to the development of exposed silver halide emulsions in the presence of these derivatives.
  • a monoalkoxy polyoxyethylene glycol is very contrasty, yields very sharply defined screen dots and occurs with the formation of a smaller number of peppers as is the case with known polyoxyalkylene development accelerators, and furthermore can take place within a broad interval of time without harm to the image quality. Comparative tests described furtheron prove the technical progress of developer combinations according to the present invention as compared with developer combinations with known polyoxyalkylene glycols and derivatives thereof.
  • Products which can 'be used according to the present invention are more particularly:
  • R represents an alkyl radical preferably having 1 to 5 carbon atoms
  • n represents a positive integer from 1 to 35, preferably from 8 to 20,
  • alcohols such as methanol, ethanol, propanol, hexadecylol, or with polyols such as ethylene glycol, glycerol etc.
  • diisocyanates such as 2,5-diisocyanato-toluene or 1,6-diisocyanato-n-hexane
  • polyoxyethylene glycol ethers having a molecular weight preferably comprised between and 1000, in which one of the terminal hydroxyl groups is rendered non-reactive in respect of isocyanato groups e.g. by etherification with an alcohol having preferably 1 to 5 carbon atoms.
  • PREPARATION 1 Urethan formed from ethanol and a methoxy polyethylene glycol isocyanato-acetate.
  • PREPARATION 6 Diurethan formed from methoxy polyethylene glycol and 2,S-diisocyanato-toluene.
  • 150 g. (0.2 mole) of methoxy polyethylene glycol with an average molecular Weight of 750 are dissolved in 150 ccs. of anhydrous benzene.
  • 17.4 g. (0.1 mole) of 2,5-diisocyanato-toluene dissolved in 50 ccs. of benzene are added.
  • the temperature of the reaction mixture is maintained between 27 and 30 C. by cooling with ice- Water till the exothermic reaction is terminated.
  • the reaction mixture is refluxed for another 105 minutes.
  • the benzene is distilled off in vacuo on a Water bath at 50 C.
  • PREPARATION 3 Diurethan formed from ethylene glycol and methoxy polyethylene glycol isocyanato-acetate.
  • PREPARATION 4 Diurethan formed from polyethylene glycol with an average molecular weight of 300 and methoxy polyethylene glycol isocyanato-acetate 25 g. (0.03 mole) of methoxy polyethylene glycol isocyanato-acetate are dissolved in 100 ccs. of anhydrous benzene. Then 9 g. of polyethylene glycol with an average molecular weight of 300 are added and the resulting mixture is refluxed for 2 hours on a water bath. The benzene is distilled oif in vacuo. Yield: 31 g.
  • PREPARATION 7 Diurethan of methoxy polyethylene glycol and 1,6-di isocyanato-hexane.
  • the urethans used according to the present invention can be added to the silver halide emulsions or can be incorporated into a water-permeable layer under or on top of the emulsion layer, which Water-permeable layer stand in water-permeable relationship with the emulsion layer.
  • the said products are added to the lightsensitive silver halide emulsions in dissolved form in water or a mixture of water and water-miscible organic solvents, which do not impair the photographic characteristics of the emulsion.
  • these products can also be incorporated into the emulsion by imbibition by treating it with a solution containing these products or by diffusion from an adjacent Water-permeable layer comprising these products.
  • the water-soluble urethans used according to the present invention can be added to the light-sensitive silver halide emulsion during different preparation steps of the light-sensitive material. For example they can be incorporated therein by a separate addition or they can be added as a mixture with one or more ingredients used in the formation of the silver halide grains, during the physical or chemical ripening or during another step preceding the coating of the emulsion.
  • the said products are preferably added to the emulsion after the chemical ripening and just before the coating of the emulsion.
  • the optimun amount of the urethans to be added to the emulsion depends on the very compound, on the nature of the colloid binder of the silver halide grains and on the amount and type of silver halide in the emulsion. In general, however, the above urethan products are added to the light-sensitive material in an amount of 1 mg. to 10 g. per mole of silver halide. When incorporated into the developer they are used in amounts ranging from 50 mg. to 20 g. per litre of developer. If necessary, amounts exceeding these limits can be used as well.
  • the increase of the dot defininition and development latitude obtained with urethan products according to the present invention can be combined with a chemical sensitisation by using in combination with the abovementioned urethan products chemical sensitising agents such as sulphur-containing compounds e.g. allyl isothio cyanate, allyl thiourea or sodium thiosulphate, reducing agents such as the tin compounds described in the Belgian patent specifications 493,464, filed Jan. 24, 1950 and 568,687, filed June 18, 1958 by Gevaert Photo-Producten N.V., the imino-amino methane sulphinic acid compounds described in the British patent specification 789,823, filed Apr.
  • chemical sensitising agents such as sulphur-containing compounds e.g. allyl isothio cyanate, allyl thiourea or sodium thiosulphate
  • reducing agents such as the tin compounds described in the Belgian patent specifications 493,464,
  • sensitising action also manifests itself, of course, when combing the above-mentioned urethan products with the sensitising compounds present by nature in gelatin.
  • the urethan products according to the present invention can also be used in combination with stabilising agents for silver halide emulsions, such as mercury compounds and the compounds described in the Belgian patent specifications 571,916 and 571,917, filed Oct. 10, 1958 by Gevaert Photo-Producten N.V., and in combination with sensitising and stabilising cadmium salts in the lightsensitive material as well as in the developer.
  • stabilising agents for silver halide emulsions such as mercury compounds and the compounds described in the Belgian patent specifications 571,916 and 571,917, filed Oct. 10, 1958 by Gevaert Photo-Producten N.V.
  • Water-soluble compounds which also accelerate the development, such as those described e.g. in the British patent specification 954,205, filed June 30, 1960 by Gevaert Photo-Producten N.V. can be applied together with the urethans according to the present invention in a developing bath as well as in the light-sensitive material.
  • each of R and R represents a hydrogen atom, an alkyl
  • R represents a hydrogen atom, an alkyl, a carboxy or an alkoxy carbonyl group.
  • Such compounds can be prepared shtarting from 1 mole of fl-ketoester or a a-ethoxymethylene-B-ketoester with 1 mole of a suitable 3-amino-1,2,4-triazole.
  • fl-ketoester or a a-ethoxymethylene-B-ketoester with 1 mole of a suitable 3-amino-1,2,4-triazole.
  • 5-methyl-7-hydroxy-s-triazolo- (l,5-a)-pyrimidine can be mentioned.
  • agents such as hardening agents, wetting agents, plasticisers, developing agents, and optical sensitising agents can be incorporated into the emulsion in the usual way.
  • the urethans according to the present invention can preferably be used in the development of screen prints on silver chloride and silver bromo-chloride emulsions with a hydroquinone-formaldehyde-bisulphite developer, but they can also be used in combination with silver halide emulsions of any other type.
  • EXAMPLE 1 After ripening of a green-sensitised silver chlorobromide emulsion (35 mole percent of bromide) containing 5-methyl-7-hydroxy-s-triazolo-( l,5-a)-pyrimidine and cadmium chloride, a polyoxyalkylene derivative listed in the following Table 1 is added. After the addition of the usual wetting agent, of 25% by weight of a latex-plasticiser calculated on the weight of gelatin, and of a hardening agent such as formaldehyde and glyoxal, the emulsion samples are coated in the same way on a cellulose triacetate support and dried.
  • the latex-plasticiser consists in a latex of a 20% by weight aqueous dispersion of poly(ethyl acrylate) prepared according to known techniques of emulsion polymerisation carrying out the polymerisation in the presence of 8% by weight calculated on the monomer of an emulsifying agent of one of the following types: the condensation product of oleic acid and methyltaurine, the sodium salt of l-aurylsulphonic acid or the sodium salt of an alkylbenzene sulphonic acid wherein the alkyl radical contains from 8 to 12 carbon atoms.
  • the light-sensitive material is exposed through a continuous wedge and a glass screen by means of a lightsource having a colour temperature of 37CO K.
  • the exposure is regulated such that the wedge print of the screen embraces the beginning of dot formation as well as the disappearance of the high lights.
  • the development is performed at 20 C. in a developing bath having the following composition:
  • the numbers 0 to 4 represent the number of peppers:
  • Example 1 is repeated with a similar type of emulsion but the polyoxyalkylene derivatives stated in Table 2 are used.
  • Example 1 is repeated with the same emulsion type, but the polyoxyalkylene derivatives listed in Table 3 are used.
  • R represents an alkyl radical having fro 1 to 5 carbon atoms
  • n represents an integer of from 1 to 35 and an unsubstituted, saturated, aliphatic mono, di or trihydric alcohol or polyethylene glycol; or (2) a monoor di-isocyanate and a mono-alkyl ether of polyoxyethylene glycol having a molecular weight of from about to 1,000, said alkyl being from 1-5 carbon atoms.
  • urethan is present in an amount of from 50 milligrams to 20 grams per litre.
  • a process for developing photographic materials containing a light-sensitive silver halide in which a photographic silver chloride or silver chlorobromide emulsion sutable for the production of line and screen prints is developed with a hydroquinone-formaldehyde-bisulphite developer characterized in that the development is carried out in the presence of a monoor di-urethan which is the non-polymeric reaction product of (1) an alkoxy polyethylene glycol ester of isocyanate-acetic acid having the formula R represents an alkyl radical having from 1 to 5 carbon atoms, and n represents an integer of from 1 to 35 and an unsubstituted, saturated, aliphatic mono, di, or trihydric alcohol or polyethylene glycol; or (2) a monoor di-isocyanate and a mono-alkyl ether of a polyoxyethylene glycol having a molecular weight of from about 100 to 1,000, said alkyl being from 1-5 carbon atoms.
  • the alcohol is an alcohol having only one

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US573832A 1965-10-07 1966-08-22 Light-sensitive silver halide materials Expired - Lifetime US3573913A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB42590/65A GB1107022A (en) 1965-10-07 1965-10-07 Improvements in the development of light-sensitive silver halide materials

Publications (1)

Publication Number Publication Date
US3573913A true US3573913A (en) 1971-04-06

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ID=10425110

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US573832A Expired - Lifetime US3573913A (en) 1965-10-07 1966-08-22 Light-sensitive silver halide materials

Country Status (6)

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US (1) US3573913A (enrdf_load_stackoverflow)
BE (1) BE686518A (enrdf_load_stackoverflow)
DE (1) DE1522397A1 (enrdf_load_stackoverflow)
FR (1) FR1496295A (enrdf_load_stackoverflow)
GB (1) GB1107022A (enrdf_load_stackoverflow)
NL (1) NL6612597A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108662A (en) * 1976-01-28 1978-08-22 Fuji Photo Film Co., Ltd. Process for developing photographic light-sensitive materials for the graphic arts
EP1203780A1 (de) * 2000-11-06 2002-05-08 Bayer Ag Isocyanate mit Aminogruppen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108662A (en) * 1976-01-28 1978-08-22 Fuji Photo Film Co., Ltd. Process for developing photographic light-sensitive materials for the graphic arts
EP1203780A1 (de) * 2000-11-06 2002-05-08 Bayer Ag Isocyanate mit Aminogruppen
US6521707B2 (en) * 2000-11-06 2003-02-18 Bayer Aktiengesellschaft Isocyanates containing amino groups

Also Published As

Publication number Publication date
FR1496295A (fr) 1967-09-29
DE1522397A1 (de) 1969-07-24
BE686518A (enrdf_load_stackoverflow) 1967-03-07
GB1107022A (en) 1968-03-20
NL6612597A (enrdf_load_stackoverflow) 1966-11-25

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