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
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment

Definitions

• This invention relates to a Process for Producing a form linked through hydroxy-substituted oxyalkylene P aphic silver image by de e opment of exposed groups and such polymeric compounds wherein the hylight-sensitive silver halide in the presence of compounds drogen atoms of the said hydroxy groups are partly or influenc ng the Sensito e ric Characteristics Q a g wholly substituted, are very suitable for substantially insensitive silver halide emulsion by an increase of the creasing the developability and also the sensitivity of Speed and/01 the g
• stablllty' R represents a C -C alkyl group including a substituted It 1s also known that an increase of sensitivity can be C1435 alkyl group, e'g methyl ethyl, propyl, isopropyl obtained by incorporating mto the photograph1c material or z hydroxyethyl or an aralkyl group 60g benzyl polyethylene glycols alkylepe oxide polymers obtallled each of Alk and Alk represents an alkylene group conby polymerising alkylene oxide in the presence of hexrtol taming from 2 to 10 carbon atoms, including Such ring dehydration products, aliphatic alcohols, aliphatic group Substituted by 6% a hydroxyl group and/Or acids, amines, amides, and phenols (British specifications such group the carboll chain of which is interrupted by Nos.
• n is apositiveinteger of atleast 3 and It is further known that these polyglycols and alkylene R1 represents a hydrogen atom, an alkyl group including oxide polymers should possess a molecular Weight of at Sub ted 1k 1 m an th la n cu least 400. In order to obtain a noticeable effect, it is in a S1 u a y g e y y 1 n e gr practice necessary to use compounds having a molecular aO-Rz, C-N-R2 or -SO2R2 weight of 1500 to 2000 and more. N H
• the polyaddition is carried out in such a way that the polyaddition products either in the form of the base or in the salt form are soluble in water.
• reaction temperature is adapted to each polyaddition and usually varies between 50 and 180 C.
• the reaction mixture After the addition of the bis-epoxide, the reaction mixture is allowed to react further (see Table 1) in order to obtain products with a higher molecular weight. Care should be taken, however, that the reaction is stopped when formation of water-insoluble gummy products begins. With very reactive starting products it is sometimes necessary to add water to the reaction mixture after the addition of the bis-epoxide to avoid gum formation.
• the starting products are made to react in an equimolar ratio, though an excess of one of them is not harmful in most cases, except in a polyaddition reaction between very reactive compounds, in which an excess of bis-epoxide should be avoided always in order to prevent the formation of polyaddition products, which either in the form of a base or a salt are insoluble in water.
• Bisepoxides suitable for use are, e.g., 1,2:5,6-diepoxy-hexane, bis(2,3-ep0xypropyl)ether, 1,2 bis(2,3 epoxypropoxy)- ethane, 1,3-bis(2,3-epoxypropoxy)-propane, 1,4-bis(2,3- epoxypropoxy) butane, 1,3 bis(2,3 epoxypropoxy)-2- propanol, 1,3-bis(2,3-epoxypropoxy)-butane, 2,3:2,3-diepoxy-N-alkyl-dipropylamine, 5,6-epoxy-hexane carboxylic acid-2,3-epoxypropyl ester, bis(2,3-epoxypropyl)-sulphone.
• Tri-epoxides such as tri(2,3-epoxypropoxy)-phosphate and 2,4,6-tri(2,3-epoxypropoxy)-s-triazine can also be used.
• Particularly suitable secondary amine alkanols are N- alkyl-ethanolamines such as methyl-, ethyl-, propyl-, isopropyl-, and butyl-ethanolamines, N-alkyl-propanolamines, e.g., N-methylisopropanolamine, N-a-methylbenzylethanolamine, etc.
• condensation products according to the present invention wherein the hydrogen atoms of the free hydroxyl groups are partly or wholly substituted reagents of the type of those reacting with an active hydrogen atom are used, e.g., an acid chloride or acid anhydride such as acetic anhydride, succinic anhydride, or maleic anhydride, a sulfonyl chloride, an isocyanate or an unsaturated alkylating compound, e.g., a vinyl compound such as acrylonitrile and methacrylonitrile.
• the reaction product of the hydroxyl-containing polymer with maleic anhydride is preferably allowed to react with a bisulphite thus forming a bisulphite addition product.
• the bisulphite used is preferably an alkali metal bisulphite.
• the bisulphite addition compounds applied in the present invention are very less fog-producing and are therefore preferred for being incorporated into the light-sensitive material.
• the preparations of the compounds 7 to 12 are given to illustrate these reactions.
• 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 incorporated into a water-permeable layer, which applied under or on top of the emulsion layer for-ms 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, by diffusion 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 light-sensitive material:
• 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.
• the polyaddition products are not sufliciently soluble in water in their base form, they are converted into their salt form by neutralization, e.g., with an acid such as sulphuric acid, hydrochloric acid, p-toluenesulphonic acid, or 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 lightsensitive material in amounts ranging from mg. to 10 g. per mole of silver halide. In the developing bath they are normally used in amounts ranging from 0.1 g. 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 sensitisation, in which together with the above-mentioned development accelerators usual amounts of chemical sensitisers 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 in our Belgian patent specifications 493,464, filed J an. 24, 1950, and 568,687, filed June 18, 1958, both by Gevaert Photo-Producten N.V., the iminoaminomethane sulphinic acid compounds described in the British patent specification 789,823, filed Apr.
• chemical sensitisers e.g., sulphur-containing compounds such as allyl isothiocyanate, allylthiourea or sodium thiosulphate
• reducing compounds such as the tin compounds described in our Belgian patent
• the sensitising action of the development accelerators used in the present invention comes in additiorr to the sensitising action of the sensitising compounds originally present in gelatin.
• the development accelerators applied in the present invention can also be used in combination with stabilisers 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 thioxo compounds such as benzothiazolin- Z-thione and l-phenyl-tetrazolin-S-thione, the compounds described in our Belgian patent specifications 571,916 and 571,917, both filed Oct.
• Other compounds, which sensitise the photo-graphic emulsion by development acceleration such as organic onium compounds and polyonium compounds, preferably of the ammonium or sulphonium type, e.g., quaternary tetra-alkylammonium salts, alkylpyridinium salts, bisalkylene-pyridinium salts, alkylquinolinine salts and trialkyl-sulphonium 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 emulsion in the ordinary way.
• EXAMPLE 1 A washed negative gelatin silver bromo-iodide emul sion (average grain size of the silver halide. 0.8 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 sensitiser according to the following structural formula:
• This emulsion is divided into several aliquot portions and to the separate portions is added one of the development accelerators according to the present invention.
• the emulsion portions are separately applied to a cellulose triacetate support and dried.
• test strips obtained are then exposed in the same conditions through a grey wedge and developed for 7 minutes at 20 C. in a fine-grain developer of the following composition:
• the speed is given in exposure values which have to be compared with the exposure value of an emulsion to which no sensitiser was added.
• Borax granular2 g.
• Sensltometrle results Amount of added per kg.
• COIIfiDOUFd pelr Scnsitometric results Added compound emulsion Fog Gamma Speed 'g. o emu Added compound sion (mg)
• Fog Gamma Speed 0.10 0.48 187 Polyethylene glymg 0. 28 0. 58 0. 08 0. 52 124 col with average Polyethylene glycol 100 0. 50 0. 53 11-; molecular weight with average mo- 6, 000 lecular weight 6,000.
• R represents a hydrogen atom, an alkyl group, a sub- A washed negative coarse-grained gelatin silver bromosmutfid alkyl group or a iodide emulsion, in which the silver halide consists of F 2 r 1 a r up 98.2 mole percent of silver bromide and 1.8 mole percent 0 0 H of silver iodide, is ripened at 42 C. After addition of 5 630 mg.
• R represents an alkyl group, a monovalent unsaturated aliphatic group or a heterocyclic group including said groups in substitution form
• the emulsion is coated on a support nisapositive integer of at1east3 p 2.
• Process for developing photographic materials con- Othef samples are Prepared by add11 1g separately to taining light-sensitive silver halide according to claim 1,
• a photographic light-sensitive material comprising tron: a silver halide and a polymeric compoundcontaining the Water 800 ccs. following structural units or these umts in salt form:
• each of Alk and Alk represent an alkylene group containing from 2 to 10 carbon atoms wherein said chain may contain elements such as oxygen, sulphur, phos- Amount Meow Sensitomemc results phorus, and nitrogen directly linked to two carbon po d pe atoms of said alkylene chain,
• Added compound emulswn Gamma speed R represents an alkyl group of 1 to 5 carbon atoms, a
• R represents a hydrogen atom, an alkyl group, a substituted alkyl group or a What we claim is: -R?,%, IT-Rz or --SO2R2 1.
• Process for developing photographic materials con- 40 o 0 H taining light-sensitive silver halide which comprises the wherein R re resents an all: 1 rou a monovalent step of developing said materials m the presence of a 2 p y g p unsaturated aliphatic group or a heterocyclic group inpolymeric compound, containing the following structura cluding said groups in substituted form, and umts these umts 111 Salt form: n is a positive integer of at least 3.

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• Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Metallurgy (AREA)
• Mechanical Engineering (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Epoxy Resins (AREA)
• Chemical Treatment Of Metals (AREA)

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• 1966
  • 1966-08-30 GB GB38552/66A patent/GB1184434A/en not_active Expired
  • 1966-09-09 DE DE19661521885 patent/DE1521885A1/de active Pending
• 1967
  • 1967-07-06 CH CH963767A patent/CH484292A/de not_active IP Right Cessation
  • 1967-08-09 US US659334A patent/US3523796A/en not_active Expired - Lifetime
  • 1967-08-14 NL NL6711152A patent/NL6711152A/xx unknown
  • 1967-08-21 SE SE11678/67A patent/SE327323B/xx unknown
  • 1967-08-24 BE BE703047D patent/BE703047A/xx unknown
  • 1967-08-26 DE DE1597475A patent/DE1597475C2/de not_active Expired
  • 1967-08-28 BE BE703147D patent/BE703147A/xx unknown
  • 1967-09-05 NL NL6712174A patent/NL6712174A/xx unknown
  • 1967-09-08 ES ES344841A patent/ES344841A1/es not_active Expired

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