EP0001484B1 - Film sensible à la lumière comprenant un support en plastique portant une couche intermédiaire adhésive de copolymère et méthode de préparation - Google Patents

Film sensible à la lumière comprenant un support en plastique portant une couche intermédiaire adhésive de copolymère et méthode de préparation Download PDF

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Publication number
EP0001484B1
EP0001484B1 EP19780300394 EP78300394A EP0001484B1 EP 0001484 B1 EP0001484 B1 EP 0001484B1 EP 19780300394 EP19780300394 EP 19780300394 EP 78300394 A EP78300394 A EP 78300394A EP 0001484 B1 EP0001484 B1 EP 0001484B1
Authority
EP
European Patent Office
Prior art keywords
subbing
light
sensitive photographic
film
mole
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
Application number
EP19780300394
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German (de)
English (en)
Other versions
EP0001484A1 (fr
Inventor
Cyril John Ealding
Graham Jarrett
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.)
Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/91—Photosensitive materials characterised by the base or auxiliary layers characterised by subbing layers or subbing means
    • G03C1/93—Macromolecular substances therefor

Definitions

  • the present invention relates to a light-sensitive photographic film and to a process for its production.
  • the adhesion of light-sensitive photographic emulsions applied directly to the surface of a plastics support film is generally inadequate to withstand the conditions of handling and treat- m ent to which photographic films are subject- e d.
  • the subbing layers of typical conventional photographic films generally comprise, outwardly from the support film, a copolymeric subbing layer and a gelatinous subbing layer, a light-sensitive photographic emulsion such as a gelatinous emulsion containing a light-sensitive silver halide being adhered to the gelatinous subbing layer.
  • GB 1 001 716 describes certain emulsion copolymers of alkyl esters of a, f3 ethylenically unsaturated monocarboxylic acids, especially copolymers with a monoalkyl ester of itaconic acid including half esters of itaconic acid.
  • the alkyl esters of a, f3 ethylenically unsaturated monocarboxylic acids may be chosen from soft comonomers such as ethyl acrylate and hard comonomers such as methyl methacrylate, whilst the preferred copolymers contain at least some hard and at least some soft comonomer.
  • copolymers are described such as coating uses including the coating of metal, cellulosic, masonry and plastic substrates. It is also contemplated that the copolymers may be used as subbing layers for the light-sensitive portion of a lithographic printing plate.
  • GB 1 146 215 describes a subbing layer for photographic films which includes a subbing copolymer comprising:
  • DE-OS 2 409 969 describes an adhesive subbing layer for a photographic film comprising a copolymer of at least one acrylic monomer selected from alkyl esters of acrylic acid and alkyl esters of methacrylic acid and an ethylenically unsaturated comonomer having a specified structure such as esters, amides, imides and the like of certain acids which include itaconic acid.
  • Optional comonomers include itaconic acid.
  • the coating composition is applied to the film support surface such that the amount of solid copolymer applied is preferably in the range of 0.05 to 5 g/m 2 (0.5 to 50 mg/dm2) .
  • US 2 698 235 describes photographic subbing copolymers derived from vinylidene chloride, an acrylic ester and itaconic acid. Adhesion of a photographic emulsion directly to the copolymer subbing layer with the elimination of the usual gelatin sublayer is contemplated.
  • a light-sensitive photographic film comprises a self-supporting plastics film, a copolymeric subbing layer applied to at least one surface thereof, and a light-sensitive photographic emulsion layer bonded directly to the copolymeric subbing layer, characterised in that said copolymeric subbing layer comprises a copolymer prepared from a comonomer mixture comprising 35 to 55 mole % acrylic acid or a lower alkyl ester thereof in which the alkyl group comprises up to 8 carbon atoms, 35 to 55 mole % methacrylic acid or a lower alkyl ester thereof in which the alkyl group comprises up to 8 carbon atoms, and 1 to 15 mole % of itaconic acid, a half ester of itaconic acid or itaconic anhydride, said copolymeric subbing layer having a dry coat weight in the range 0.05 to 3.00 mg/dm 2 .
  • a process for the production of a light-sensitive photographic film comprises coating at least one surface of a self-supporting plastics film with a subbing composition comprising an aqueous dispersion or a solution in an organic solvent of a copolymer prepared from a comonomer mixture comprising 35 to 55 mole % acrylic acid or a lower alkyl ester thereof in which the alkyl group comprises up to 8 carbon atoms, 35 to 55 mole % methacrylic acid or a lower alkyl ester thereof in which the alkyl group comprises up to 8 carbon atoms, and 1 to 15 mole % of itaconic acid, a half ester of itaconic acid or itaconic anhydride, causing or allowing the coating to dry to a layer having a coat weight in the range 0.05 to 3.00 mg/dm 2 and coating the dried subbing layer directly with a light-sensitive photographic emulsion.
  • a subbing composition comprising an aqueous dispersion or a solution in
  • light-sensitive. photographic emulsions are adhered directly to the copolymeric subbing layer, i.e. adequate emulsion adhesion under conventional conditions for handling and treating photographic films is achieved by coating the photographic emulsion layer in face-to-face contact with the copolymeric subbing layer and without the need for an interposed gelatinous subbing layer or any treatment or surface modification of the copolymeric subbing layer, such as corona discharge treatment as described in British patent specification 1 259 506.
  • the self-supporting plastics film may consist of a cellulose ester such as cellulose triacetate or any suitable thermoplastics film which is preferably biaxially oriented, such as films of polysulphones, polystyrene and linear polyesters which may be obtained by condensing one or more dicarboxylic acids or their lower alkyl diesters, e.g.
  • terephthalic acid isophthalic, phthalic, 2,5-, 2,6- and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic acid, adipic acid, azelaic acid, diphenyl dicarboxylic acid, and hexahydroterephthalic acid or bis-p-carboxyl phenoxy ethane, optionally with a monocarboxylic acid, such as pivalic acid, with one or more glycols, e.g. ethylene glycol, 1,3-propanedioi, 1,4-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol.
  • glycols e.g. ethylene glycol, 1,3-propanedioi, 1,4-butanediol, neopentyl glycol and 1,4-cyclohexanedimethanol.
  • Biaxially oriented and heat-set films of polyethylene terephthalate are particularly useful for the production of the photographic films according to this invention.
  • Such self-supporting thermoplastics films may be transparent and light-transmitting, optionally including photographically inert dyestuffs, e.g. blue dyestuffs for X-ray films, or may be rendered opaque by the addition of additives, such as pigments and fillers, and may in particular have a white and paper-like texture which may be achieved by the addition of suitable fillers and/or by voiding.
  • the white and paper-like films may be used as bases for photographic prints.
  • Films suitable for use in "instant" photography may be pigmented black with carbon black particles.
  • the lower alkyl (up to 8 carbon atoms in the alkyl group) esters of acrylic and methacrylic acid as comonomers of the subbing copolymer may comprise the methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, n-octyl and 2-ethylhexyl esters, the preferred esters being ethyl acrylate and methyl methacrylate.
  • Itaconic acid is particularly effective as the third comonomer.
  • Half esters of itaconic acid wherein one carboxylic acid group is esterified are also effective comonomers. It has been found that the use of itaconic acid, a half ester of itaconic acid or itaconic anhydride as comonomers in the subbing copolymer is effective not only in providing the desired adhesive properties of the photographic emulsion applied thereto but also in enhancing the wetting of the plastics film during the application of the subbing composition.
  • the subbing copolymer is prepared from a comonomer mixture containing a molar excess of itaconic acid, a half ester of itaconic acid or itaconic anhydride such that free unpolymerised acid, half ester or anhydride is present in the subbing layer.
  • Stronger dry adhesions are obtained with at least 1.0% by weight of free itaconic acid, half ester or itaconic acid, or itaconic anhydride based on the weight of the copolymer.
  • the subbing copolymer may if desired, be derived from four or more comonomers, the additional comonomers being employed to modify such properties as dry adhesion and being present in the copolymer in an amount comprising up to.8 mole %.
  • additional comonomers include acrylamide, methacrylamide, N-methylol acrylamide, N-ethanol acrylamide, N-propanolacrylamide, N-methylol methacrylamide, N-ethanol methacrylamide, N-methyl acrylamide, N-tertiary-butylacrylamide, acrylonitrile, halo-substituted acrylonitrile and methacrylonitrile, dimethylaminoethyl-methacrylate.
  • Proportions in the range 35 to 55 mole % of acrylic acid or a lower alkyl ester (up to 8 carbon atoms in the alkyl group) thereof and 35 to 55 mole % of methacrylic acid or a lower alkyl ester (up to 8 carbon atoms in the alkyl group) thereof are effective in providing satisfactory adhesions to light-sensitive photographic emul- .sions; smaller or greater proportions result in weaker adhesion.
  • Optimum adhesions to conventional photographic emulsions are achieved with preferred proportions of acrylic acid or the lower alkyl ester (up to 8 carbon atoms in the alkyl group) thereof in the range 42 to 50 mole % and of methacrylic acid or the lower alkyl ester (up to 8 carbon atoms in the alkyl group) thereof in the range 44 to 55 mole %.
  • Ethyl acrylate and methyl methacrylate are particularly effective comonomers and provide satisfactory subbing properties when both are copolymerised together with itaconic acid.
  • Particularly beneficial subbing properties and especially adhesion to photographic emulsions are achieved with subbing copolymers consisting of 43 to 50 mole % ethyl acrylate, 45 to 53 mole % methyl methacrylate and 4 to 10 mole % of itaconic acid.
  • the subbing copolymer may be prepared by conventional emulsion polymerisation techniques in water in the presence of a suitable emulsifying agent or a mixture of emulsifying agents.
  • the total amount of emulsifying agent can influence the adhesion of photographic emulsions to the copolymeric subbing layer and it is therefore preferred to employ up to 5% by weight of emulsifying agent based on .the total weight of the comonomers and preferably about 4% by weight.
  • Anionic emulsifying agents such as unbranched sodium dodecyl benzene sulphonate, which is available commercially as 'Nansa' 1106 provide particularly good adhesions to photographic emulsions which may if desired be used in admixture with other emulsifying agents.
  • 'Nansa' is a registered Trade Mark.
  • copolymeric subbing composition may be included in amounts not exceeding 10% by weight based upon the weight of the subbing copolymer, since larger amounts may adversely affect the adhesion of photographic emulsions.
  • the subbing composition may be applied to the film before, during or after the stretching process employed to achieve orientation.
  • a convenient procedure is to coat the film between the two stretching operations which are applied in mutually perpendicular directions to orient the film, particularly as this enhances the adhesion between the film and the subbing layer.
  • the procedure for applying the subbing composition may be any of the known coating techniques, such as dip coating, bead coating, reverse roller coating, air knife, direct gravure or slot coating and the composition may be applied as an aqueous latex or solution or as a solution in an organic solvent.
  • the pH of the subbing composition should preferably be in the range 2.0 to 5.0 and most preferably 2.5 to 3.0. Whilst coating quality is better with pHs up to 7, it has been found that a satisfactory combination of adhesion and coating quality is obtained in the range 2.5 to 3.0.
  • the subbing copolymer should comprise from 2 to 10% by weight and particularly 5% by weight of the subbing composition since compositions of such concentration dry slowly and provide subbing layers of uniform coating quality having particularly satisfactory adhesions to photographic emulsions.
  • the dried copolymeric subbing layer has a coat weight in the range 0.05 to 3.00 mg/dm 2 and most preferably 0.5 to 1.00 mg/dm z for optimum adhesion to photographic emulsions. Such coat weights may be accomplished by appropriate modifications to the concentration of the subbing composition and/or the conditions of coating.
  • copolymeric subbing layers applied according to this invention to linear polyester films such as polyethylene terephthalate films are such that the film base, i.e. the polyester film carrying the copolymeric subbing layer but not the light-sensitive photographic emulsion, is suitable for recycling through the film-forming extruder and stretching equipment.
  • Any suitable light-sensitive photographic emulsion such as a conventional gelatinous silver halide emulsion, may be applied by conventional techniques directly to the subbing layer.
  • Alternative light-sensitive emulsions based upon binding resins other than gelatin, e.g. those binding resins described in United States patent 4 033 772, may also be applied with good adhesion to the subbing copolymer layers of this invention.
  • Such emulsions may contain any of the conventional additives. It has been found that light-sensitive photographic emulsions bond with good adhesion after direct application to the surface modified layer.
  • Light-sensitive photographic emulsions such as conventional gelatinous silver halide X-ray and graphic arts emulsions, adhere to the copolymeric subbing layers with good adhesions before and after accelerated ageing by incubation when evaluated by the tests described below.
  • Wet adhesion refers to the adhesion of a gelatinous silver halide emulsion via the copolymeric subbing layer to the self-supporting thermoplastics film in the final photographic film, assessed, after processing in the standard photographic chemicals and washing in water for 15 minutes by rubbing with a sponge over a series of lines scored in the still wet emulsion.
  • the adhesion of the emulsion was graded in five progressive grades 1 to 5, Grade 1 being when no emulsion was removed by rubbing 10 times over the scored lines and Grade 5 being when all of the emulsion was removed by rubbing 10 times.
  • subbing compositions for each Example were prepared in batches by conventional emulsion polymerisation in water, the comonomers and other polymerisation ingredients and the quantities employed being shown in Tables 1 to 3 together with the amount of unpolymerised acid in % by weight based on the weight of the copolymer and the pH of the latices.
  • a polyethylene terephthalate film was melt extruded and quenched to the amorphous state on a cooled rotating drum. The resulting film was stretched in the direction of extrusion to 3.0 times its original length. It was then coated on one side with the aqueous subbing composition described in each of the Examples and passed into a stenter oven where the coating was dried.
  • the coating composition which was applied by a roller coating technique, contained 5% by weight of the subbing copolymer based on the total weight of the composition.
  • the dried coated film was then stretched sideways 3.0 times its original width and finally heat set at the temperature of 220°C.
  • the resulting films had an overall thick ness of 100 microns and the dry coat weights of the applied subbing are shown in Tables 1 to 3.
  • a conventional aqueous gelatinous silver halide emulsion was applied directly to the subbing layers and tested for dry and wet adhesions by the procedures described above, the adhesions also being shown in Tables 1 to 3.
  • the measured adhesions between the emulsion layers and the subbing layers are sufficient to resist the conditions of handling and treatment, including wet processing, to which photographic films are normally subjected.
  • subbing layers described in the above Examples provided satisfactory adhesions to other photographic emulsions including modified X-ray emulsions.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Claims (9)

1. Film photographique photosensible comportant une pellicule de matière plastique autoporteuse, une couche d'ancrage de type copolymère appliquée sur au moins une surface de cette pellicule et une couche d'émulsion photographique photosensible liée directement à la couche d'ancrage de type copolymère, caractérisé en ce que cette couche d'ancrage de type copolymère est constituée par un copolymère préparé à partir d'un mélange de comonomères renfermant de 35 à 55 moles % d'acide acrylique ou d'un ester d'alkyle inférieur de celui-ci dans lequel le groupe alkyle renferme jusqu'à 8 atomes de carbone, de 35 à 55 moles % d'acide méthacrylique ou d'un ester d'alkyle inférieur de celui-ci dans lequel le groupe alkyle renferme jusqu'à 8 atomes de carbone, et de 1 à 15 moles % d'acide itaconique, d'un hémi-ester d'acide itaconique ou d'anhydride itaconique, cette couche d'ancrage de type copolymère ayant un poids de revêtement à sec compris entre 0,05 et 3,00 mg/dm2.
2. Film photographique photosensible suivant la revendication 1, caractérisé en ce que la pellicule de matière plastique autoporteuse est constituée par une pellicule à orientation biaxiale stabilisée thermiquement en téréph- talate de polyéthylène.
3. Film photographique photosensible suivant la revendication 1 ou 2, caractérisé en ce que le copolymère d'ancrage est préparé à partir d'un mélange de comonomères qui renferme de l'acrylate d'éthyle et du méthacrylate de méthyle.
4. Film photographique photosensible suivant la revendication 1, 2 ou 3, caractérisé en ce que la couche d'ancrage comprend au moins 1,0 % en poids, sur la base du poids du copolymère d'ancrage, d'acide itaconique libre non polymérisé, d'hémi-ester d'acide itaconique ou d'anhydride itaconique.
5. Film photographique photosensible suivant l'une quelconque des revendications précédentes, caractérisé en ce que le copolymère d'ancrage renferme de 43 à 50 moles % d'acrylate d'éthyle, de 45 à 53 moles 96 de méthacrylate de méthyle et de 4 à 10 moles % d'acide itaconique.
6. Film photographique photosensible, suivant l'une quelconque des revendications précédentes, caractérisé en ce que le poids de revêtement séché de la couche d'ancrage va de 0,5 à 1,00 mg/dm2.
7. Procédé pour la production d'un film photographique photosensible suivant l'une quelconque des revendications 1 à 6, caractérisé en ce qu'on enduit au moins une surface de la pellicule en matière plastique autoporteuse avec une composition d'ancrage constituée par une dispersion aqueuse ou une solution dans un solvant organique du copolymère d'ancrage, on provoque ou on permet le séchage du revêtement pour donner une couche ayant un poids de revêtement compris entre 0,05 et 3,00 mg/dm2 et on enduit directement la couche d'ancrage séchée avec une émulsion photographique photosensible.
8. Procédé suivant la revendication 7, caractérisé en ce que la pellicule de matière plastique autoporteuse est orientée biaxialement et en ce que la composition d'ancrage est appliquée sur la surface de la pellicule entre les deux opérations d'étirage utilisées pour orienter cette pellicule.
9. Procédé suivant la revendication 7 ou 8, caractérisé en ce que la composition d'ancrage à un pH compris entre 2,5 et 3,0.
EP19780300394 1977-10-03 1978-09-18 Film sensible à la lumière comprenant un support en plastique portant une couche intermédiaire adhésive de copolymère et méthode de préparation Expired EP0001484B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB4097077 1977-10-03
GB4097077 1977-10-03

Publications (2)

Publication Number Publication Date
EP0001484A1 EP0001484A1 (fr) 1979-04-18
EP0001484B1 true EP0001484B1 (fr) 1981-12-23

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ID=10417507

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19780300394 Expired EP0001484B1 (fr) 1977-10-03 1978-09-18 Film sensible à la lumière comprenant un support en plastique portant une couche intermédiaire adhésive de copolymère et méthode de préparation

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EP (1) EP0001484B1 (fr)
DE (1) DE2861457D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4842950A (en) * 1985-01-14 1989-06-27 Hoechst Celanese Corporation Overlay proofing film
US4748101A (en) * 1985-01-14 1988-05-31 Hoechst Celanese Corporation Overlay proofing film

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2698235A (en) * 1950-03-16 1954-12-28 Du Pont Photographic elements
BE579177A (fr) * 1958-05-29 1900-01-01
NL293009A (fr) * 1962-05-21
US3307950A (en) * 1963-09-19 1967-03-07 Du Pont Stripping films
US3297477A (en) * 1965-03-30 1967-01-10 Avisun Corp Heat-sealable composite sheet
DE1694777A1 (de) * 1966-05-03 1970-08-27 Du Pont Fotografischer Film
BE697801A (fr) * 1966-05-03 1967-10-30
DE1904743C3 (de) * 1969-01-31 1975-08-14 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Haftklebeartikeln
GB1264338A (fr) * 1969-07-15 1972-02-23
GB1427026A (en) * 1972-11-20 1976-03-03 Ici Ltd Synthetic film materials
JPS49113868A (fr) * 1973-03-05 1974-10-30

Also Published As

Publication number Publication date
EP0001484A1 (fr) 1979-04-18
DE2861457D1 (en) 1982-02-11

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