EP0557785B1 - Photographischer Film - Google Patents

Photographischer Film Download PDF

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Publication number
EP0557785B1
EP0557785B1 EP19930101989 EP93101989A EP0557785B1 EP 0557785 B1 EP0557785 B1 EP 0557785B1 EP 19930101989 EP19930101989 EP 19930101989 EP 93101989 A EP93101989 A EP 93101989A EP 0557785 B1 EP0557785 B1 EP 0557785B1
Authority
EP
European Patent Office
Prior art keywords
styrene
butyl acrylate
acrylate
latex
silver halide
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
EP19930101989
Other languages
English (en)
French (fr)
Other versions
EP0557785A1 (de
Inventor
John Leslie Cawse
Roy Patrick Barber
Michael Veto Cwykla
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ilford Imaging UK Ltd
Original Assignee
Ilford Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ilford Ltd filed Critical Ilford Ltd
Publication of EP0557785A1 publication Critical patent/EP0557785A1/de
Application granted granted Critical
Publication of EP0557785B1 publication Critical patent/EP0557785B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • This invention relates to photographic silver halide emulsion assemblies.
  • Most camera films consist of a photographic assembly which comprises at least one silver halide emulsion layer coated on a cellulose triacetate or cellulose acetate-butyrate base.
  • Gelatin layers can be coated on to such base materials without the need to treat the base to the same extent as that which is required to render polyethylene terephthalate (polyester) bases capable of being coated with a gelatin layer.
  • all cellulose triacetate or cellulose acetate-butyrate base is supplied to the manufacturers of photographic materials treated in some way to help a gelatin coat to adhere thereto better than untreated base.
  • Each base manufacturer has his own method of treating cellulose-derived bases and often the photographic manufacturer is not privy to the method employed by the base manufacturer.
  • cellulose triacetate or cellulose acetate-butyrate base which has been treated by the base manufacturer to render it more susceptible to be coated with a gelatin layer is hereinafter referred to as sub-coated cellulose triacetate or cellulose acetate-butyrate base.
  • a photographic film assembly which comprises coated on a sub-coated cellulose triacetate or cellulose acetate-butyrate base at least one gelatino silver halide emulsion layer wherein the silver halide emulsion layer which is closest to the base comprises from 1 to 30% by weight of the gelatin in the emulsion layer, a latex polymer whose glass transition temperature does not exceed 30°C and which is a copolymer of an ethylenically unsaturated monomer containing an aromatic moeity, with an acrylate or methacrylate ester monomer.
  • the latex polymer may also contain additional ethylenically unsaturated monomers, as described below.
  • the amount of latex present in the silver halide emulsion layer is from 2 to 10% by weight of the gelatin in the layer.
  • Examples of the monomers which are useful to prepare the latex used in the present invention are:-
  • monomers containing an aromatic moeity styrene, vinyl toluene, 2,4-dimethylstyrene, -methyl styrene, divinyl benzene, vinylnaphthalene, 4-methoxystyrene, 3-nitrostyrene, vinyl phenol, vinyl benzoate, diallyl phthalate, benzyl methacrylate, phenyl methacrylate, N-phenylacrylamide, 2-phenylethylmethacrylate.
  • acrylate or methacrylate monomers cyclohexyl methacrylate, 2-hydroxy-propylmethacrylate, 2-hydroxyethylmethacrylate, ethylene glycol dimethacrylate, butyl acrylate, methyl acrylate, ethyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, n-heptyl acrylate.
  • comonomers which may be present: vinyl cyclohexane, acrylonitrile, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl stearate, acrylic acid and its salts, 2-acrylamido-2-methyl propane sulphonic acid and its salts, acrylamide, methacrylamide, N-vinyl pyrrolidone, ethylene sulphonic acid and its salts.
  • Preferred combinations of monomers are styrene/butyl acrylate; vinyl toluene/butyl acrylate; styrene/ethylhexyl acrylate; styrene/ethyl acrylate; styrene/n-heptyl acrylate; -methyl styrene/butyl acrylate; styrene/divinyl benzene/butyl acrylate; styrene/methyl methacrylate/ butyl acrylate; styrene/2-hydoxypropylmethacrylate/butyl acrylate; styrene/butyl acrylate/2-acrylamido-2-methylpropane sulphonic acid sodium salt.
  • These combinations may include monomers in varying proportions but they preferably contain at least 10% by weight of the aromatic ethylenically unsaturated monomer. Preferably they contain at least 20% by weight of the acrylate or methacrylate ester monomers.
  • Particularly preferred combinations are styrene 50 parts, butyl acrylate 50 parts; vinyl toluene 50 parts, butyl acrylate 50 parts; and styrene 50 parts, ethyl hexyl acrylate 50 parts. The parts being by weight.
  • latices of the above type requires the use of one or more surface active agents, and these may be any of the types well known in the art.
  • anionic surfactants are very useful and these may be used optionally in the presence of a nonionic surfactant.
  • the anionic surfactants may be the sodium, potassium or ammonium salts (but preferably the sodium salt) of a sulphate, sulphonate, phosphonate or phosphate derivative.
  • the hydrophobic part of the surfactant may be an alkyl group, an aryl group, or a combination of an alkyl and an aryl group.
  • the hydrophilic part of the surfactant may contain, in addition to an anionic group, an alkylene oxide chain with up to 50 alkylene oxide units in the chain. In addition, there may be present ethylenically unsaturated units in the surfactant thus enabling it to copolymerise with the other units and thus render the surfactant substantive.
  • the non-ionic surfactants may contain alkyl, aryl or alkyl-aryl groups together with alkylene oxide chains; there are many other suitable nonionic surfactants well known in the art, and these include: alkylolamides; carbohydrate derivatives such as glucosides; alkylesters; and amine oxides.
  • alkylolamides include: alkylolamides; carbohydrate derivatives such as glucosides; alkylesters; and amine oxides.
  • a large number of surfactants are commercially available and details of many suitable types may be found for example in "Surfactants UK", ed. G.L. Hollis, published by Tergo-Data, England.
  • the surfactants may comprise from 0.1 to 15% by weight of the total latex.
  • Preferred surfactants to use to prepare the latexes used in the present invention are alkyl phenol ethoxylate sulphates, alkyl sulphonates, sulphosuccinate esters and aryl-and alkyl ethoxylate phosphates, in combination with or in the absence of alkyl phenol ethoxylates, alkylphenol polyglycidolethers or alkanol ethoxylates.
  • Initiators suitable for the preparation of the latexes used in the present invention may be selected from those well known in the prior art. These are usually water soluble azo compounds or water soluble per-oxo compounds.
  • the sodium salt of azobis (cyanopentanoic acid) is a commonly available water soluble azo initiator.
  • Sodium and potassium persulphate are very commonly used in emulsion polymerisation.
  • Hydrogen peroxide and some other peroxides such as tertiary butyl hydroperoxide are also useful initiators.
  • the initiation process may be effected either at higher temperatures (e.g. above 70°C) by using an initiator which decomposes thermally or at lower temperatures (e.g.
  • initiator couples which act by a redox system. Details of these initiation processes may be found for example in "Emulsion Polymerisation” by D.C. Blackley, Applied Science Publishers, London, 1975.
  • the initiators may comprise from 0.1 to 1.0% by weight of the reaction mixture.
  • the procedure for preparing the latexes used in the present invention follows that commonly used in emulsion polymerisation. Typically, the mixture of monomers is added, over a period of from thirty minutes to three hours, to a heated, oxygen-free solution of the chosen surfactant in water and the selected initiators and further surfactant are added either continuously or portionwise over the same period. Following the polymerisation it is necessary to cool the reaction mixture to ambient temperature followed by filtration to remove small quantities of coagulated polymer.
  • additives including biocides and colloid stabilisers.
  • biocides and colloid stabilisers During the polymerisation it may be desirable to limit the molecular weight of the polymer by adding small amounts of chain transfer agents. Additives such as this are covered in Blackley's book (see above).
  • a mixture of 934g of butyl acrylate and 944g of styrene was added at a constant rate over a period of 3 hours to a stirred, aqueous solution consisting of water (1739g), potassium persulphate (4.65g), sodium metabisulphite (2.05g), and the sodium salt of a nonylphenol ethoxylate sulphate surfactant (167g of a 25% active solution), maintained at 70°C.
  • a further solution of the same surfactant 500g of a 25% solution
  • potassium persulphate (2.32g) and sodium metabisulphite (1.02g) in 650g water was added.
  • the mixture was maintained at 70°C for 4 hours before cooling to below 30°C and filtering through a 100 ⁇ m sieve.
  • latex 1 having a solids content of 40%, particle size 114nm.
  • the Tg of the polymer is +3°C. This is latex 1.
  • the silver halide present in the emulsions used in the assembly of the present invention may be of any silver halide composition, eg. pure silver bromide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide.
  • the silver halide grains in the emulsion may be of any habit e.g., tabular or cubic. They may have been chemically sensitised for example by gold and/or sulphur. They may have been optically sensitised by use of any of the well known merocyanine or methin cyanine dyes used for this purpose.
  • the emulsion may contain any of the well known stabilisers, hardening agent and any of the other well known additives often present in camera film silver halide emulsions.
  • silver halide emulsion layers There may be at least two silver halide emulsion layers and the top-most silver halide emulsion layer may be coated with a gelatin supercoat or non-stress layer which may comprise antiblocking agents. There may be gelatin based inter-layers between any of the silver halide emulsion layers.
  • cellulose triacetate or cellulose acetate butyrate base there may be on the reverse side of the cellulose triacetate or cellulose acetate butyrate base to that side which carries the emulsion layer or layers at least one backing layer which may be an anti-halation backing layer.
  • Strips of a photographic material were prepared from a typical assembly made from a sub-coated base of cellulose triacetate film to prepare a high sensitivity black and white negative photographic material.
  • the total silver content of the film was 8.0 - 7.0 g/m 2 .
  • the amount of coating is expressed for each of the layers in terms of g/m 2 ; the amount of silver halide expressed in terms of the weight of silver.
  • 0.2g/m 2 of latex corresponds to 5% of the weight of the gelatin present in the first emulsion layer.
  • Latex (0.4g/m 2 ) Adhesion Grade after/days 7 14 21 29 1 1 1 1 1 2 4 4 5 4 3 2 2 5 2 4 5 4 3 4 5 1 2 1 1 6 1 1 1 1 1 # Control 5 5 5 5 # Control no Latex TABLE 3 Effect of Latex Quantity on Wet Adhesion after processing Latex 1 g/m 2 Adhesion Grade after/days 8 14 21 30 0 5 2 4 5 1% 0.05 5 1 2 3 2% 0.1 1 1 1 1 1 5% 0.2 1 1 1 1 10% 0.4 1 1 1 1 1
  • the percentages are the percent of latex of the gelatin in the emulsion.
  • the film is scratched at various stages of the processing cycle and then rubbed with the finger.
  • Adhesion grade is assigned according to the amount of emulsion removed when the film is rubbed. The grades are described as follows:
  • the wet adhesion test is carried out 7 days after coating.
  • Strips of the photographic material prepared in Examples 1, 5 and 6 together with a control strip which comprised no latex were exposed to a step wedge and the sensitometric properties were compared with the control.
  • the photographic foot speed S0.1 of all the strips was substantially the same as was the contrast G. This showed that the presence of the latex in the emulsion had no deleterious effect on the sensitometric properties of the assembly.
  • the photographic assemblies were processed in a developer at 25°C. They were then fixed in an ammonium thiosulphate fixing bath and the water washed.
  • the developer used had the following formula:- Metol 2.0g Hydroquinone 5.0g Sodium sulphite 100.0g Borax 2.0g Water to 1 litre
  • latexes which comprise an aromatic moiety provide good adhesion, that is to say latexes 1, 5 and 6.
  • latexes which comprise no aromatic moiety had inferior or bad adhesion that is to say latexes 2, 3 and 4.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (3)

  1. Photographischer Filmverbund, enthaltend mindestens eine auf eine Grundlage aufgetragene Gelatine-Silberhalogenidemulsionsschicht, wobei die der Grundlage am nächsten liegende Schicht ein Latexpolymer enthält, dessen Glasübergangstemperatur nicht über 30°C liegt und bei dem es sich um ein Copolymer aus einem eine aromatische Gruppierung enthaltenden ethylenisch ungesättigten Monomer und einem Acrylat- oder Methacrylatester-Monomer handelt, wobei der Latex 1 bis 30 Gew.-% der Gelatine in der Emulsionsschicht enthält, dadurch gekennzeichnet, daß es sich bei der Grundlage um ein substriertes Cellulosetriacetat oder Celluloseacetatbutyrat handelt.
  2. Photographischer Filmverbund nach Anspruch 1, dadurch gekennzeichnet, daß in der Silberhalogenidemulsionsschicht eine Latexmenge von 2 bis 10 Gew.-%, bezogen auf die Gelatine in der Schicht, vorliegt.
  3. Photographischer Filmverbund nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, daß der Latex sich von einer der folgenden Monomerkombinationen ableitet: Styrol/Butylacrylat, Vinyltoluol/Butylacrylat, Styrol/Ethylhexylacrylat, Styrol/Ethylacrylat, Styrol/n-Heptylacrylat, Methylstyrol/Butylacrylat, Styrol/Divinylbenzol/Butylacrylat, Styrol/Methylmethacrylat/Butylacrylat, Styrol/2-Hydroxypropylmethacrylat/Butylacrylat, Styrol/Butylacrylat/2-Acrylamido-2-methylpropansulfonsäure-Natriumsalz.
EP19930101989 1992-02-25 1993-02-09 Photographischer Film Expired - Lifetime EP0557785B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9203951 1992-02-25
GB929203951A GB9203951D0 (en) 1992-02-25 1992-02-25 Photographic assembly

Publications (2)

Publication Number Publication Date
EP0557785A1 EP0557785A1 (de) 1993-09-01
EP0557785B1 true EP0557785B1 (de) 1997-08-06

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ID=10710968

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Application Number Title Priority Date Filing Date
EP19930101989 Expired - Lifetime EP0557785B1 (de) 1992-02-25 1993-02-09 Photographischer Film

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EP (1) EP0557785B1 (de)
DE (1) DE69312761T2 (de)
GB (1) GB9203951D0 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06258749A (ja) * 1993-03-04 1994-09-16 Konica Corp ハロゲン化銀写真感光材料

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1389548A (en) * 1972-11-22 1975-04-03 Ilford Ltd Photographic colloid layers in silver halide materials
US4197127A (en) * 1976-10-08 1980-04-08 Eastman Kodak Company Photographic silver halide composition and element containing sulfonate copolymers
EP0358187A3 (de) * 1988-09-08 1991-09-11 Eastman Kodak Company Photographische Elemente mit tafelförmigen Körnern, die eine Verminderte Druckempfindlichkeit aufweisen (II)

Also Published As

Publication number Publication date
EP0557785A1 (de) 1993-09-01
DE69312761T2 (de) 1998-02-12
GB9203951D0 (en) 1992-04-08
DE69312761D1 (de) 1997-09-11

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