EP0318909B1 - Antistatische Rückschicht für einen photographischen Film und Hilfsschicht - Google Patents

Antistatische Rückschicht für einen photographischen Film und Hilfsschicht Download PDF

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Publication number
EP0318909B1
EP0318909B1 EP88119864A EP88119864A EP0318909B1 EP 0318909 B1 EP0318909 B1 EP 0318909B1 EP 88119864 A EP88119864 A EP 88119864A EP 88119864 A EP88119864 A EP 88119864A EP 0318909 B1 EP0318909 B1 EP 0318909B1
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EP
European Patent Office
Prior art keywords
layer
photographic film
film according
coated
conductive compound
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
EP88119864A
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English (en)
French (fr)
Other versions
EP0318909A2 (de
EP0318909A3 (en
Inventor
Thomas Byung-Mo Cho
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication date
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Priority to AT88119864T priority Critical patent/ATE94658T1/de
Publication of EP0318909A2 publication Critical patent/EP0318909A2/de
Publication of EP0318909A3 publication Critical patent/EP0318909A3/en
Application granted granted Critical
Publication of EP0318909B1 publication Critical patent/EP0318909B1/de
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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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • 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
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89—Macromolecular substances therefor
    • 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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
    • G03C2001/7628—Back layer

Definitions

  • This invention is related to Cho U.S. Patent No. 4.585,730. "Antistatic Backing Layer with Auxiliary Layer for a Silver Halide Element", granted April 29, 1986. This invention is also related to Miller U.S. Patent No. 4,701, 403, "Two-Layer Process for Applying Antistatic Compositions to Polyester Supports," granted October 20, 1987, which is directed to a process for applying a thin, clear antistatic layer to a photographic film. The present invention provides an auxiliary layer designed to be coated over such layer.
  • This invention relates to a photographic film. More particularly this invention relates to a photographic film having an improved auxiliary backing layer for said film which can conduct antistatic properties from an antistatic underlayer to the outside surface thereof.
  • Polymeric film supports for photographic film are known for their propensity to accumulate static charges. This is a particular problem where the film is designed to be handled by machine and to be processed rapidly over unlike surfaces. Static charges which may be generated at this time cannot be readily tolerated because discharging these may expose the photographic layer, or layers, coated thereon.
  • Miller U.S. Patent 4,701,403 describes an improvement over the aforementioned Schadt patent wherein a polymer such as component (1), for example, is applied to the support in a first coating, optionally a composition containing component (2), and, after drying, aziridine component (3) is applied as a second coating contiguous thereto.
  • a polymer such as component (1)
  • component (2) for example
  • aziridine component (3) is applied as a second coating contiguous thereto.
  • This improved process permits the application of improved thinner antistatic layers without premature reaction of the aziridine with the other ingredients. Products from such premature reaction can sometimes plug and foul coating equipment, which is not commercially tolerable.
  • Cho U.S. Patent 4,585,730 describes an auxiliary layer containing a conductive polymer in a concentration range of 0.3 to 10 % by weight of the gelatin binder taken from the group consisting of poly(sodium styrene sulfonate), poly(cellulose sulfate), poly(sodium styrene sulfonate-maleic acid), and others.
  • This layer is satisfactory in transporting antistatic properties from underlayers to the surface thereof.
  • the layer described in this patent suffers from certain disadvantages such as problems as problems with anchorage and poor processability in the fluids in which the photographic layer is processed.
  • auxiliary layer over an antistatic layer of a photographic film which is useful in conducting antistatic properties to the surface thereof.
  • a layer also serves as a backing layer for a photographic film which contains an antistatic layer thereon. It is also desired to provide such an auxiliary layer with good anchorage to previously applied layers and which is stable in photographic processing fluids.
  • a photographic film comprising a support, at least one silver halide emulsion coated on one side of said support, and an antistatic layer coated on the opposite side of said support, whereby the antistatic layer is coated with an auxiliary layer and the antistatic properties of the antistatic layers are conducted through said auxiliary layers, characterized in that the antistatic layer is coated at a pH of 3 to 12 with an auxiliary layer consisting essentially of at least one crosslinkable conductive compound having functionally attached carboxylic acid groups and selected from the group consisting of poly(sodium styrene sulfonate-maleic anhydride), hexadecyl betaine, alkyldimethyl betaines, carboxylated imidazolines, coco amido betaines, and mixtures thereof, and a crosslinking agent for the conductive compound dispersed in a gelatine binder and selected from the group consisting of a polyfunctional aziridine, chrome alum, carbodiimides, and is
  • Consisting essentially of as used in the appended claims means that unspecified constituents or conditions are not excluded provided that they do not affect the advantage of the invention from being realized.
  • the crosslinkable conductive compound may be present alone or in combination with at least one other crosslinkable conductive compound.
  • a particularly preferred crosslinkable conductive compound is poly(sodium styrene sulfonate-maleic anhydride).
  • Other crosslinkable, conductive compounds include: hexadecyl betaine, alkyldimethyl betaines wherein alkyl is 1 to 12 carbon atoms, carboxylated imidazolines, coco amido betaines, etc. These conductive compounds which contain functionally attached carboxylic acid groups may be added to the auxiliary layer of this invention in a range of 0.5 to 30% by weight of the gelatin binder, preferably at 1.5 to 2.5% by weight.
  • gelatin binder denotes a binder wherein the major component is gelatin.
  • Gelatin substitutes e.g., polyvinyl alcohol, detran, cellulose derivatives, modified gelatins, a water-soluble acrylic latex, etc.
  • minor amounts e.g., less than 17% by weight.
  • Crosslinking agents useful within the ambit of this invention include polyfunctional aziridines such as those described in Schadt U.S. Patent 4.225,665 and Miller U.S. Patent 4,701,403.
  • Other useful crosslinking (hardening) agents include: chrome alum, carbodiimides, isoxazolinium salts, etc. Particularly preferred is pentaerythritol-tri-beta-(2-methyl aziridine) propionate added to the gelatin binder.
  • the crosslinking agent may be present in an amount of 0.5 to 5.0% by weight of the gelatin binder, preferably in an amount of 2.0 to 3.0% by weight.
  • a mixture of the gelatin binder in water, the crosslinkable conductive compound and the crosslinking agent of this invention is made up prior to coating.
  • Other additives such as, for example, antihalation dyes, surfactants, wetting agents and hardeners, etc., may also be present in the mixture.
  • the pH is adjusted to 3 to 12, preferably 6 to 8.
  • the aqueous coating composition made as described above may be applied with good results to any of the conventional photographic film supports but the preferred support is poly(ethylene terephthalate) subcoated with a layer or layers of conventional resins and bearing on one side a photosensitive layer, preferably a silver halide emulsion layer, and on the other side as a backing layer a layer of an antistatic composition, e.g., antistatic coatings of Schadt U.S. Patent 4,225,665, Miller U.S. Patent 4,701,403, etc.
  • the invention is not limited to any particular antistatic coating: however, the antistatic coatings of Miller, U.S. Patent 4,701,403 are preferred (see particularly column 3, line 56 to column 4, line 56).
  • the backing layer of this invention is then coated over the antistatic layer at a coating weight of about 30 to 90 mg/dm2, preferable about 40 to 60 mg/dm2.
  • this invention is represented by a photographic film element which comprises a support, which is preferably dimensionally stable polyethylene terephthalate suitably subbed on both sides with a thin, anchoring substratum of a conventional resin sub over which may be applied a gelatin sublayer.
  • a standard silver halide emulsion layer may be applied and this layer then overcoated with a protective overcoat layer, e.g., a conventional hardened gelatin, abrasion layer.
  • a protective overcoat layer e.g., a conventional hardened gelatin, abrasion layer.
  • the antistatic layer of Miller U.S. Patent 4,701,403 is preferably applied followed by an auxiliary layer represented by this invention.
  • the layer of this invention may be an antihalation layer or may be coated simply as a gelatin anti-curl layer, as is well-known to those of normal skill in the art.
  • the auxiliary layer can be replaced by two separately coated layers, each layer containing gelatin, one layer of which contains at least one crosslinkable conductive compound and the other layer of which contains a crosslinking agent, both as described and in the amounts set out above.
  • the conductive compound dispersed in some gelatin may be coated first followed by a coating of gelatin and crosslinking agent. When wet, the crosslinking agent will migrate into the conductive compound containing layer effectively serving to crosslink gelatin and conductive compound as described above.
  • this layer will provide the desired transmission of antistatic properties from the antistatic layer to the surface of the film.
  • the layer of this invention is stable and will survive the rigors of photographic processing without disintegration. This is very desirable since prior art layers tended to flake off during the processing steps. Loss of layer integrity is a defect that cannot be tolerated since particles of the layer tend to foul the processing fluids and, more importantly, cause loss of antistatic transmission properties.
  • the adhesion between previously coated or subsequently coated layers is enhanced by the presence of a layer of this invention over those of the prior art. This is a surprising result since layers very similar to those described herein, which have the required hardness from gelatin hardeners, among others, and are satisfactory in transmitting the antistatic properties, do not have the characteristics described above.
  • the crosslinking agents such as those described above, interconnect the gelatin, the conductive compound and the carboxyl groups available on the surface of the antistatic under layer providing excellent adhesion. It is surprising, however, that transmission of the antistatic properties is maintained since it was thought that the conductive polymer should have all of the groups on the polymer chains available to provide transmission of the antistatic properties.
  • a host of conventional photosensitive materials may be Present as the emulsion layer described above. These include photopolymer, diazo, vesicular image-forming materials, etc.
  • the films described may be used in any of the well-known imaging fields such as graphic arts, printing, medical and information systems, among others.
  • the photographic film of this invention is particularly useful in processes where rapid transport and handling by machines are practiced such as phototypesetting applications, for example.
  • Particularly useful elements include the so-called "bright-light" films which can be handled in relatively bright safelights, for example.
  • a backing layer antihalation solution was prepared by mixing 1200 g of gelatin in 13,530 g of distilled water for 15 minutes at 49°C. The mixture was cooled to 38°C and the following ingredients added:
  • Example No. Crosslinking Agent (10% Aq. Soln)
  • Conductive Polymer 2% Aq. Soln
  • g (2) 1 42 175 2 84 74 3 84 175 4 126 70 5 100 125 Control 1 0 0 Control 2 Sample 3 from Ex. 1, U.S.
  • Patent 4,585,730 (1) is a solution of pentaerythritol-tri-beta-(2-methyl aziridine) proprionate in distilled water (2) is a crosslinkable conductive polymer polymer(sodium styrene sulfonate-maleic anhydride) diluted in distilled water (no. average molecular wt. ca. 3,000 determined by known osmometry techniques)

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

Claims (10)

  1. Photographischer Film, umfassend einen Träger, wenigstens eine auf einer Seite des Trägers aufbeschichtete Silberhalogenid-Emulsion, und eine auf die gegenüberliegende Seite des Trägers aufbeschichtete antistatische Schicht, wobei die antistatische Schicht mit einer Hilfsschicht beschichtet ist und die antistatischen Eigenschaften der antistatischen Schicht durch die Hilfsschicht übertragen werden, dadurch gekennzeichnet, daß die antistatische Schicht bei einem pH von 3 bis 12 mit der Hilfsschicht beschichtet wird, die im wesentlichen besteht aus einer vernetzbaren übertragenden Verbindung, die funktionell gebundene carbonsäure-Gruppen aufweist und ausgewählt ist aus der Gruppe bestehend aus Poly(styrolsulfonat-natrium/maleinsäureanhydrid), Hexadecylbetain, Alkyldimethylbetainen, carboxylierten Imidazolinen, Cocoamidobetainen und deren Mischungen, sowie einem Vernetzungsmittel für die übertragende Verbindung, das in einem Gelatine-Bindemittel dispergiert ist und ausgewählt ist aus der Gruppe bestehend aus einem polyfunktionellen Aziridin, Chromalaun, Carbodiimiden und Isoxazolinium-Salzen, wobei die vernetzbare übertragende Verbindung in einer Menge von 0,5 bis 30 Gew.-% vorhanden ist, und das Vernetzungsmittel in einer Menge von 0,5 bis 5 Gew.-% vorhanden ist, wobei beide Gewichte auf das Gewicht des Gelatine-Bindemittels bezogen sind.
  2. Photographischer Film nach Anspruch 1, wobei die Hilfsschicht ersetzt ist durch zwei getrennt aufbeschichtete gelatinehaltige Schichten, wobei die erste Schicht wenigstens eine vernetzbare übertragende Verbindung enthält, und die zweite Schicht ein Vernetzungsmittel enthält.
  3. Photographischer Film nach Anspruch 1 oder 2, wobei die vernetzbare übertragende Verbindung Poly(styrolsulfonatnatrium/maleinsäureanhydrid) ist.
  4. Photographischer Film nach Anspruch 1 oder 2, wobei das Vernetzungsmittel ein polyfunktionelles Aziridin ist.
  5. Photographischer Film nach Anspruch 4, wobei das polyfunktionelle Aziridin Pentaerythrit-tris-β-(2-methylaziridin) ist.
  6. Photographischer Film nach Anspruch 1, wobei der Träger eine Polyethylenterephthalat-Folie ist.
  7. Photographischer Film nach Anspruch 1, wobei die Silberhalogenid-Emulsion mit einer schützenden Überzugsschicht bedeckt ist.
  8. Photographischer Film nach Anspruch 1, wobei die vernetzbare übertragende Verbindung in einer Menge von 1,5 bis 2,5 Gew.-% vorhanden ist, bezogen auf das Gewicht des Gelatine-Bindemittels.
  9. Photographischer Film nach den Ansprüchen 1 und 8, wobei das Vernetzungsmittel in einer Menge von 2 bis 3 Gew.-% vorhanden ist, bezogen auf das Gewicht des Gelatine-Bindemittels.
  10. Photographischer Film nach Anspruch 1 oder 2, wobei die vernetzbare übertragende Verbindung Poly(styrolsulfonatnatrium/maleinsäureanhydrid) ist, und das Vernetzungsmittel Pentaerythrit-tris-β-(2-methylaziridin) ist.
EP88119864A 1987-11-30 1988-11-29 Antistatische Rückschicht für einen photographischen Film und Hilfsschicht Expired - Lifetime EP0318909B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88119864T ATE94658T1 (de) 1987-11-30 1988-11-29 Antistatische rueckschicht fuer einen photographischen film und hilfsschicht.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US12652487A 1987-11-30 1987-11-30
US19859688A 1988-05-23 1988-05-23
US126524 1988-05-23
US198596 1988-05-23

Publications (3)

Publication Number Publication Date
EP0318909A2 EP0318909A2 (de) 1989-06-07
EP0318909A3 EP0318909A3 (en) 1989-09-27
EP0318909B1 true EP0318909B1 (de) 1993-09-15

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EP88119864A Expired - Lifetime EP0318909B1 (de) 1987-11-30 1988-11-29 Antistatische Rückschicht für einen photographischen Film und Hilfsschicht

Country Status (7)

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EP (1) EP0318909B1 (de)
JP (1) JPH0687128B2 (de)
AU (1) AU603019B2 (de)
DE (1) DE3884152T2 (de)
DK (1) DK666988A (de)
FI (1) FI885536A (de)
NO (1) NO885324L (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4960687A (en) * 1989-09-29 1990-10-02 E. I. Du Pont De Nemours And Company Process of making photographic silver halide element with backing layers with improved coating properties
CA2034788A1 (en) * 1990-01-26 1991-07-27 Rudolf W. Beisswenger Element having improved adhesion of auxiliary layers to film supports containing antistatic layers
JPH0451041A (ja) * 1990-06-18 1992-02-19 Konica Corp ハロゲン化銀写真感光材料
JP7224207B2 (ja) 2019-03-05 2023-02-17 株式会社日立ハイテク 遺伝子型解析装置及び方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701403A (en) * 1985-01-16 1987-10-20 E. I. Du Pont De Nemours And Company Two-layer process for applying antistatic compositions to polyester supports

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5321646B2 (de) * 1973-04-27 1978-07-04
JPS5313223A (en) * 1976-07-23 1978-02-06 Mitsui Toatsu Chemicals Automatic valve
DE2648286C3 (de) 1976-10-26 1982-01-28 Du Pont de Nemours (Deutschland) GmbH, 4000 Düsseldorf Verfahren zum Härten von photographischen Silberhalogenidemulsionen
JPS5950986B2 (ja) * 1979-01-11 1984-12-11 富士写真フイルム株式会社 カルボン酸ポリマ−層を有する写真感光材料
JPS5941177B2 (ja) * 1979-10-15 1984-10-05 富士写真フイルム株式会社 写真感光材料
JPS57204540A (en) * 1981-06-12 1982-12-15 Fuji Photo Film Co Ltd Photographic sensitive material
JPS5950986A (ja) * 1982-09-16 1984-03-24 Hitachi Ltd 管と管板のレ−ザ溶接装置
US4585730A (en) * 1985-01-16 1986-04-29 E. I. Du Pont De Nemours And Company Antistatic backing layer with auxiliary layer for a silver halide element

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701403A (en) * 1985-01-16 1987-10-20 E. I. Du Pont De Nemours And Company Two-layer process for applying antistatic compositions to polyester supports

Also Published As

Publication number Publication date
AU2634588A (en) 1989-06-01
JPH02851A (ja) 1990-01-05
FI885536A0 (fi) 1988-11-29
NO885324D0 (no) 1988-11-29
DE3884152T2 (de) 1994-04-21
FI885536A (fi) 1989-05-31
AU603019B2 (en) 1990-11-01
DK666988A (da) 1989-05-31
EP0318909A2 (de) 1989-06-07
DK666988D0 (da) 1988-11-29
DE3884152D1 (de) 1993-10-21
NO885324L (no) 1989-05-31
EP0318909A3 (en) 1989-09-27
JPH0687128B2 (ja) 1994-11-02

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