US3434840A - Photographic element comprising subbed polyester film support - Google Patents

Photographic element comprising subbed polyester film support Download PDF

Info

Publication number
US3434840A
US3434840A US572245A US3434840DA US3434840A US 3434840 A US3434840 A US 3434840A US 572245 A US572245 A US 572245A US 3434840D A US3434840D A US 3434840DA US 3434840 A US3434840 A US 3434840A
Authority
US
United States
Prior art keywords
layer
styrene
polyester
acid
ethylene
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
US572245A
Other languages
English (en)
Inventor
Lodewijk Felix De Keyser
Andre Jan Conix
Lodewijk August Van Dessel
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.)
Gevaert Photo Producten NV
Original Assignee
Gevaert Photo Producten NV
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 Gevaert Photo Producten NV filed Critical Gevaert Photo Producten NV
Application granted granted Critical
Publication of US3434840A publication Critical patent/US3434840A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • 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
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes

Definitions

  • a multilayer photographic film including a biaxially stretched polyester film support, a light-sensitive silver halide emulsion layer undersub-bed by a gelatin layer, said gelatin undersubbing being attached to the film support by way of a first subbing layer comprising a copolymer of styrene and at least one carboxy-substituted unsaturated compound copolymerizable therewith, and a second subbing layer contacting the film support and comprising a polyester soluble in chlorinated aliphatic hydrocarbons and obtained by'the condensation of at least one aliphatic diol with a diacid component essentially consisting of at least about 55 mol percent isophthalic acid, up to about 25 mol percent phthalic acid and up to about 20 mole percent of an aliphatic saturated dicarboxylic acid.
  • the carboxy substituent may be replaced by a substituent adapted for ready conversion into a carboxy
  • This invention relates to photographic film elements, more particularly to photographic film elements comprising a silver halide emulsion layer and a biaxially stretched poly(ethylene terephthalate) support, this application being a continuation-in-part of application Ser. No. 242,620, filed Dec. 6, 1962, now abandoned.
  • the subbing layers which are particularly suited for fixing a silver halide emulsion layer to a cellulose ester or a polystyrene support do not satisfy if poly(ethylene terephthalate) is used as a support for the silver halide emulsion layer. Because in many cases and especially when a great dimensional stability of the photographic material is required, poly(ethylene terephthalate) is preferable to cellulose ester or to polystyrene as a support for a light-sensitive silver halide emulsion layer, the search is for a good subbing layer in this case.
  • Polyesters are very often used for the first subbing layer on a poly(ethylene terephthalate) support of a photographic film element.
  • a first object of the present invention is to provide a subbing for adhering the silver halide emulsion layer to a biaxially stretched poly(ethylene terephthalate) support. Said subbing assuring an excellent adherence before, during as well as after processing of the photographic film element.
  • Another object of the present invention is to provide a subbing causing little or almost no coloration after development, which coloration is due to an interaction with sensitizing dyes often applied in light-sensitive silver halide emulsion layers. Such coloration usually manifests itself when cellulose nitrate is present in a subbing layer.
  • a first layer comprising a polyester, which is soluble in chlorinated aliphatic hydrocarbons and which is prepared by condensation of at least one aliphatic diol with a diacid component consisting essentially of about 55 to mole percent of isophthalic acid, about 0 to 25 mole percent of terephthalic acid and obout 0 to 20 mole percent of aliphatic saturated dicarboxylic acid,
  • a layer comprising a copolymer of styrene and one or more unsaturated compounds copolymerizable with styr ene, which bear at least one carboxylic acid substituent or a substituent derived therefrom, which can easily be converted into a carboxylic acid group, and
  • the said first layer comprising a polyester and the layer comprising a copolymer of styrene are joined into but one subbing layer, which replaces the two separate layers mentioned above.
  • the total thickness of the whole subbing usually varies between about 2 and about 7
  • the soluble polyesters for the first subbing layer are coated on a biaxially stretched poly(ethylene terephthalate) support in the form of solutions in suitable solvents e.g. ethylene dichloride, methylene chloride, and symtetrachloroethane, dioxan or in a suitable mixture of solvents.
  • suitable solvents e.g. ethylene dichloride, methylene chloride, and symtetrachloroethane, dioxan or in a suitable mixture of solvents.
  • the polyesters are usually applied from a solution containing preferably from about 3% to about 10% by weight of solid material.
  • the soluble polyester is applied on a biaxially stretched poly(ethylene terephthalate) support preferably having a thickness of 50 to 150 mostly in such an amount that after drying 0.5 to 3 g. is present per sq. m.
  • Said soluble polyesters may contain the most divergent ratios of different diols.
  • Copolyesters containing in addition to ethylene glycol units at least 5 mole percent of neopentylene glycol units or 1,6-hexane diol units for increasing the solubility of the polyester, are preferably used.
  • the used polyesters preferably have a molecular weight of at least 4500.
  • PREPARATION 2 table to show the influence of neopentylene glycol units or 1,6-hexane diol units introduced in the poly(ethylene Polyester i g i F i glycol and isophthalate) on the solubility of the polyester used wane according to the invention.
  • the intrinsic viscosity [1 is always measured in sym-tetrachloroethane at 25 C.
  • the polyester is composed of recurring units according to the following structural formulae:
  • the methanol, which is set free, is distilled over for 2 h. through a fractionating column. Then the mixture is condensated for 4 h. at 282 C. under reduced pressure of 0.5 to 20 mm. of Hg. [7;]:020 dl./g.
  • the polyester is composed of recurring units according to the following structural formula:
  • the polyester is composed of recurring units according to the following structural formula:
  • Polyester of isophthalic acid, sebacic acid, and ethylene glycol A mixture of 3 9.8 g. of isophthalic acid, 13.8 g. of dimethyl sebacate, 41 g. of ethylene glycol, 10 mg. of zinc acetate, and 20 mg. of antimony trioxide is heated at 255 C. After 1 h. a completely clear solution is obtained. The Water and the methanol, which are set free during the reaction, are distilled otf for l h. through a fractionating column. Then the excess ethylene glycol is distilled olf for /2 h. without column. The condensation reaction in the melt is continued for 2 h. under reduced pressure of 1 to 10 mm. of Hg at 255 C- 1];0.38 dL/g.
  • the polyester is composed of recurring units according to the following structural formulae:
  • PREPARATION 7 Polyester of isophthalic acid, terephthalic acid, and ethylene glycol
  • the polyester is composed of recurring units corresponding to the following structural formulae:
  • PREPARATION 8 Polyester of isophthalic acid, terephthalic acid, adipic acid, and ethylene glycol to the layer comprising a soluble polyester.
  • This second subbing layer is usually applied from a solution of the copolymer of styrene in organic solvents e.g. acetone or ethanol, or in mixtures of organic solvents.
  • the thickness of this layer preferably varies between 0.3 and 0.7,u. If use is made of an appropriate solvent or mixture of solvents wherein the soluble polyester and the copolymer of styrene can be dissolved, both compounds can also be provided in but one common subbing layer that replaces the two separate subbing layers.
  • sensitizing dyes which with a subbing layer according to the present invention cause no or almost no coloration, but which in the presence of cellulose nitrate cause considerable coloration
  • cyanine dyes with hydrophilic nitrogen substitutes can be mentioned.
  • reaction is continued for 6 h. at 75 C. Then once again 4.5 of azo-bis-isobutyronitrile are added and the reaction is allowed to proceed for another 20 h.
  • the polymer After dilution of the reaction mass with 5 l. of acetone, the polymer is precipitated by pouring the solution into water. The polymer is separated and dried at 50 C.
  • the reaction mass is cooled and the obtained precipitate is separated and dried at 40-5 0 C.
  • EXAMPLE 1 A first layer of poly(ethylene isophthalate) is coated from a 8% solution in ethylene dichloride on a biaxially stretched poly(ethylene terephthalate) film of 100 t in thickness in such a Way, that after drying a layer is obtained having a thickness of 1.6,u.
  • a second layer is coated from a solution of the following composition:
  • This layer is coated in such a way that a thickness of 0.5 1. is obtained after drying.
  • the third layer is coated from a solution of the following composition:
  • This coating is applied in such a way that a thickness of 0.3,u is obtained. Then a common gelatino silver halide emulsion layer is coated thereon.
  • EXAMPLE 2 A first layer is coated on a biaxially streached poly (ethylene terephthalate) film of 120 1. in thickness from a solution of the following composition:
  • the second layer is coated in the same way as described for the third layer in Example 1.
  • Cop oly styrene acrylic acid/ ethyl acrylate (60/20/20) g 60 Acetone cmfi-.. 500 Ethylene chlorohydrin cm. 100 Butanol cm. 100 Isopropanol cm. 300
  • the thickness of the layer amounts to 0.4 1.
  • the thickness of the layer amounts to 0.2 4.
  • the support provided with this subbing layer is treated as in Example 1 and possesses the same properties as described therein.
  • This layer is coated in such a way that the thickness amounts to 0.4,u.
  • a third layer is coated in the same way as the third layer of Example 1.
  • a silver halide emulsion layer is coated thereon.
  • the thus obtained light-sensitive material has the same properties as the material of Example 1.
  • EXAMPLE 5 On a biaxially stretched poly(ethylene terephthalate) support of 100 1. in thickness, coated with a first layer as described in Example 1, a second layer is applied from a solution of the following composition:
  • the thickness of the layer amounts to 0.5 4.
  • a third layer is coated from a solution of the following composition:
  • the thus obtained light-sensitive material has the same properties as the material of Example 1.
  • the thickness of the layer amounts to 0.244.
  • the thus obtained light-sensitive material has the same properties as the material of Example 1.
  • a first photographic film element is prepared by consecutively applying to a biaxially streached poly(ethylene terephthalate) support having a thickness of 100,141 a thin layer of the polyester prepared according to preparation 8 from a 7% solution in ethylene dichloride, a thin gelatin layer as described in Example 1 and a common gelatino silver halide emulsion layer.
  • a second photographic film element is prepared in the same way as the first with the proviso, however, that the thin layer of the polyester prepared according to preparation 8 is replaced by a thin layer of a polyester of ethylene glycol, terephthalic acid, isophthalic acid, and sebacic acid (50/25/25) (see the Example 9 of the United States patent specification 2,698,237 referred to above) coated from a 3% solution in trichloroethylene.
  • a third photographic film element is also prepared in the same way as the first, with the proviso, however, that the thin layer of the polyester prepared according to preparation 8 is replaced by a thin layer of a polyester of ethylene glycol with terephthalic acid and isophthalic acid (60/40) coated from a solution in ethylene dichloride.
  • This polyester is within the broad scope of polyesters of the ethylene tereisophthalate type disclosed in the United States patent specification 3,178,287 referred to above.
  • a fourth, a fifth, and a sixth photographic film element only differs from the first, second, and third respectively, in that the layer of a copolymer of styrene described in Example 1 is applied between the polyester subbing layer and the gelatin layer.
  • a seventh photographic film element is prepared in the same way as the first, with the proviso, however, that the thin layer of the polyester prepared according to preparation 8 is replaced by a thin polyester-copolymer of styrene layer as described in Example 2.
  • the adhesion of the emulsion layer to the support is tested for all 7 film elements before processing, after fixing, after rinsing, and after drying again.
  • the adhesion tests of dry material are carried out by applying an adhesive tape to the emulsion layer and tearing off this tape with a jerk or by tearing the photographic film element.
  • the adhesion tests of wet material are carried out by scratching the emulsion layer by means of a pointed member and then rubbing it with a finger.
  • the fifth and the sixth film element show an insuficient adhesion of the emulsion layer to the support in dry condition, especially after processing.
  • a photographic film element comprising consecutively:
  • a layer comprising a polyester, which is soluble in chlorinated aliphatic hydrocarbons and which is prepared by condensation of at least one aliphatic diol with a diacid component consisting essentially of about 55 to mol percent of isophthalic acid, about 0 to 25 mole percent of terephthalic acid and about 0 to 20 mole percent of aliphatic saturated dicarboxylic acid,
  • a layer comprising a copolymer of styrene and one or more unsaturated compounds copolymerizable with styrene, which bear at least one carboxylic acid substituent or a substituent derived therefrom, which can easily be converted into a carboxylic acid group,
  • a photographic film element comprising consecutively:
  • a layer comprising a polyester, which is soluble in chlorinated aliphatic hydrocarbons and Which is prepared by condensation of at least one aliphatic diol with a diacid component consisting essentially of about 55 to 100 mole percent of isophthalic acid, about 0 to 25 mole percent of terephthalic acid and about 0 to 20 mole percent of aliphatic saturated dicarboxylic acid and further comprising a copolymer of styrene and one or more unsaturated compounds copolymerizable with styrene, which bear at least one carboxylic acid substituent or a substituent derived therefrom, which can easily be converted into a carboxylic acid group,
  • the copolymer of styrene is a member selected from the group consisting of copoly styrene/ acrylic acid),
  • a photographic film element according to claim 2, wherein said aliphatic diol of the polyester, which is soluble in chlorinated aliphatic hydrocarbons, comprises at least about 5 mole percent of a member selected from the group consisting of neopentylene glycol and 1,6- hexane diol.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Polyesters Or Polycarbonates (AREA)
US572245A 1961-12-07 1966-08-15 Photographic element comprising subbed polyester film support Expired - Lifetime US3434840A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE2041190 1961-12-07

Publications (1)

Publication Number Publication Date
US3434840A true US3434840A (en) 1969-03-25

Family

ID=3864757

Family Applications (1)

Application Number Title Priority Date Filing Date
US572245A Expired - Lifetime US3434840A (en) 1961-12-07 1966-08-15 Photographic element comprising subbed polyester film support

Country Status (5)

Country Link
US (1) US3434840A (en(2012))
BE (1) BE611224A (en(2012))
CH (1) CH443895A (en(2012))
DE (1) DE1267975B (en(2012))
GB (1) GB1020054A (en(2012))

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629054A (en) * 1967-08-16 1971-12-21 Gavert Agfa Nv Composite film support
US3658541A (en) * 1969-10-09 1972-04-25 Eastman Kodak Co Photographic subbing materials
US3775152A (en) * 1969-10-09 1973-11-27 Eastman Kodak Co Photographic subbing material
US3948625A (en) * 1972-07-24 1976-04-06 Environmental Master Systems, Inc. Irradiation and electrostatic separator
US4042399A (en) * 1974-07-26 1977-08-16 E. I. Du Pont De Nemours And Company Photographic element with improved slip
US4113493A (en) * 1977-03-17 1978-09-12 Eastman Kodak Company Amorphous polyester adhesives for photographic materials
US4181528A (en) * 1977-04-27 1980-01-01 E. I. Du Pont De Nemours And Company Subbing composition comprising treated gelatin-polyester-aziridine material for adhering photographic emulsion to polyester film base
US4645731A (en) * 1985-12-27 1987-02-24 E. I. Du Pont De Nemours And Company Distortion resistant polyester support for use as a phototool
US4699869A (en) * 1985-12-27 1987-10-13 E. I. Du Pont De Nemours And Company Process for the preparation of a distortion resistant polyester support for use as a phototool
US5698329A (en) * 1992-02-17 1997-12-16 Imperial Chemical Industries Plc Polymeric film
US5770312A (en) * 1992-02-17 1998-06-23 Imperial Chemical Industries Plc Polymeric film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1589926A (en) 1977-03-25 1981-05-20 Bexford Ltd Coated films

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2698239A (en) * 1951-01-20 1954-12-28 Du Pont Photographic films
US2892747A (en) * 1955-12-15 1959-06-30 New linear copolyesters
US3072483A (en) * 1958-12-22 1963-01-08 Eastman Kodak Co Photographic element comprising polyethylene terephthalate film base
US3178287A (en) * 1960-05-23 1965-04-13 Minnesota Mining & Mfg Thin photographically sensitive film element

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE971996C (de) * 1951-01-20 1959-05-06 Du Pont Mehrschichtfilme
BE520491A (en(2012)) * 1952-06-07
BE548613A (en(2012)) * 1956-06-11 1900-01-01
DE1083121B (de) * 1958-08-21 1960-06-09 Perutz Photowerke G M B H Haftschicht fuer photographische Filme mit Polyesterunterlage

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2698239A (en) * 1951-01-20 1954-12-28 Du Pont Photographic films
US2892747A (en) * 1955-12-15 1959-06-30 New linear copolyesters
US3072483A (en) * 1958-12-22 1963-01-08 Eastman Kodak Co Photographic element comprising polyethylene terephthalate film base
US3178287A (en) * 1960-05-23 1965-04-13 Minnesota Mining & Mfg Thin photographically sensitive film element

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3629054A (en) * 1967-08-16 1971-12-21 Gavert Agfa Nv Composite film support
US3658541A (en) * 1969-10-09 1972-04-25 Eastman Kodak Co Photographic subbing materials
US3775152A (en) * 1969-10-09 1973-11-27 Eastman Kodak Co Photographic subbing material
US3948625A (en) * 1972-07-24 1976-04-06 Environmental Master Systems, Inc. Irradiation and electrostatic separator
US4042399A (en) * 1974-07-26 1977-08-16 E. I. Du Pont De Nemours And Company Photographic element with improved slip
US4113493A (en) * 1977-03-17 1978-09-12 Eastman Kodak Company Amorphous polyester adhesives for photographic materials
US4181528A (en) * 1977-04-27 1980-01-01 E. I. Du Pont De Nemours And Company Subbing composition comprising treated gelatin-polyester-aziridine material for adhering photographic emulsion to polyester film base
US4645731A (en) * 1985-12-27 1987-02-24 E. I. Du Pont De Nemours And Company Distortion resistant polyester support for use as a phototool
US4699869A (en) * 1985-12-27 1987-10-13 E. I. Du Pont De Nemours And Company Process for the preparation of a distortion resistant polyester support for use as a phototool
US5698329A (en) * 1992-02-17 1997-12-16 Imperial Chemical Industries Plc Polymeric film
US5770312A (en) * 1992-02-17 1998-06-23 Imperial Chemical Industries Plc Polymeric film

Also Published As

Publication number Publication date
GB1020054A (en) 1966-02-16
BE611224A (en(2012))
DE1267975B (de) 1968-05-09
CH443895A (fr) 1967-09-15

Similar Documents

Publication Publication Date Title
US3434840A (en) Photographic element comprising subbed polyester film support
US2698241A (en) Photographic elements and process of preparing the same
US4394442A (en) Post-stretch water-dispersible subbing composition for polyester film base
US4978740A (en) Copolyester and polyester film having said copolyester as subbing layer
JPS5884867A (ja) ポリエステルフイルムの下塗りに好適な水性コポリエステル分散液
US4181528A (en) Subbing composition comprising treated gelatin-polyester-aziridine material for adhering photographic emulsion to polyester film base
US2698239A (en) Photographic films
GB820865A (en) Foils consisting of highly polymeric substances pre-treated for the application of hydrophilic colloids
US4241169A (en) Gelatin-polyester-aziridine product subbing layer for polyester photographic base
US4087574A (en) Method of subbing plastic films
US3495985A (en) Subbing layers
US3035916A (en) Process for rendering polyester film receptive to photographic materials and resulting elements
US3220844A (en) Photographic products
US2096616A (en) Manufacture of photographic film
US3589905A (en) Inking properties of matte-surfaced polyester sheeting
US4072639A (en) Undercoating composition for polyesters containing epoxy compounds
JP3243041B2 (ja) 下塗した樹脂フイルム
US5334457A (en) Plastic film having a coating layer comprising a copolyester and a conductive polymer and light-sensitive photographic material using the same
US3495984A (en) Polyester film and subbing layers therefor
JP2649457B2 (ja) 制電性易接着性ポリエステルフィルム及びその製造方法
US2400989A (en) Photographic materials
US3725329A (en) Photographic subbing material
US3658541A (en) Photographic subbing materials
US3492122A (en) Photographic silver halide film element
US3460944A (en) Polymer compositions,strata and elements