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

• a multilayer photographic film including a biaxially stretched polyester film support, a light-sensitive silver halide emulsion layer undersubbed by a mixed gelatincellulose nitrate layer, and a subbing layer intervening between the polyester film support and the undersubbing layer, consisting essentially of -a polyester soluble in chlorinated aliphatic hydrocarbons and prepared by the condensation of at least one aliphatic diol with a diacid component essentially consisting of about 55 to 100 mol percent of isophthalic acid, about 0 to 25 mol percent of terephthalic acid, and about 0 to 20 mol percent of aliphatic saturated dicarboxylic acid.
• 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 of application Ser. No. 572,217, filed Aug. 15, 1966, now abandoned, which is a continuation-in-part of application Ser. No. 201,281, filed June 11, 1963, 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.
• the most important 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.
• this object is accomplished by providing between the biaxially stretched poly- (ethylene terephthalate) support and the silver halide emulsion layer consecutively:
• a first subbing 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 about 0 to 20 mole percent of aliphatic saturated dicarboxylic acid, and
• the latter layer may be replaced by two separate layers. Indeed a cellulose nitrate layer and a gelatin layer can be applied consecutively to the first subbing layer.
• the polyesters for the preparation of the said first subbing layer can be formed from the most divergent ratios of different diols.
• the preferably used polyesters contain in addition to ethylene glycol units at least 5 mole percent of neopentylene glycol units or 1,6-hexane diol units.
• the used polyesters preferably have a molecular weight of at least 4500 and a solubility of at least 10% in ethylene dichloride. Indeed, in order to obtain a good adhesion the layer comprising a polyester used according to the invention has to be applied from a solution containing preferably from about 3% to about 10% by weight of solid matter. Comparative solubiliti'es are listed in the following tableto show the influence of neopentylene glycol units or 1,6-hexane diol units introduced in the polyester structure on the solubility of the polyester used according to the invention.
• the polyester is composed of recurring units according to the following structural iorrnulap tate, and 20 mg. of antimony trioxide is melted at 255 C. After 1 h. of heating Whilst stirring with a moderate current of nitrogen, a completely clear melt is obtained.
• the resulting polyester is composed of recurring units according to the following structural formulae:
• the polyester is composed of recurring units according to the following structural formulae:
• 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:
• the polyester is composed of recurring units according to the following structural formulae:
• the polyester is composed of recurring units corresponding to the following structural formulae:
• the polyester is composed of recurring units according to the following structural formulae:
• the soluble polyesters are preferably applied to the biaxially stretched poly(ethylene terephthalate) support in the form of solutions in low-boiling organic solvents eg in chlorinated aliphatic hydrocarbons, such as ethylene dichloride, in dioxan, or in a mixture of chlorinated aliphatic hydrocarbons and dioxan, in which solvents the polyesters can be dissolved for at least 10% by weight.
• low-boiling organic solvents eg in chlorinated aliphatic hydrocarbons, such as ethylene dichloride, in dioxan, or in a mixture of chlorinated aliphatic hydrocarbons and dioxan, in which solvents the polyesters can be dissolved for at least 10% by weight.
• a second thin subbing layer of cellulose nitrate and a third thin layer of gelatin are applied consecutively to the first subbing layer. These two layers can also be applied in the form of one single layer.
• the thickness of the whole subbing consisting of the above 2 or 3 layers, generally varies between approximately 2 and 7
• the transparency of the three superposed subbing layers is excellent.
• the flexibility of the photographic film element and the adhesion of the emulsion layer to the support in dry as well as in wet state is extremely satisfactory.
• Example 1 A first subbing layer of the polyester according to Preparation 5 is coated from a 8% solution in ethylene dichloride on a biaxially stretched poly(ethylene tereph- 7 thalate) film of 100 t in thickness, so that 2 g. of polyester are present per sq. In.
• Example 2 On a poly(ethylene terephthalate) support as described in Example 1 a first subbing layer is coated from a solution of the polyester of Preparation 3 in ethylene dichloride, in a ratio of 1.5 g. of polyester per sq. m. The second and third subbing layers are applied as in Example 1.
• Example 3 A poly(ethylene terephthalate) support as described in Example 1 is coated with a first subbing layer from a solution of the polyester of Preparation 2 in ethylene dichloride in a ratio of 1 g. of polyester per sq. m. The second and the third subbing layers are applied as in Example 1.
• Example 4 A biaxially stretched poly(ethylene terephthalate) support of 75 in thickness is coated with a first subbing layer from a 8% solution of the polyester of Preparation 7 in ethylene dichloride in such a way, that 1.5 g. of polyester is present per sq. m. of support.
• the third subbing layer is coated as in Example 1. After having been dried, the subbing is coated with a common gelatino silver halide emulsion layer.
• Example 5 A poly(ethylene terephthalate) support as described in Example 4 is coated with the same first subbing layer as in Example 1. On top thereof a second subbing layer is applied from the following solution, so that 1 1. thereof covers 25 sq. m. of support:
• the third subbing layer is applied as in Example 1.
• a common gelatino silver halide emulsion layer is then applied to the dry subbing layer.
• Example 6 A poly (ethylene terephthalate) support as described in Example 1 is coated with a first subbing layer from a 4% solution of the polyester of Preparation 6 in ethylene dichloride, in a ratio of 1.5 g. of polyester per sq. m. of support. After drying, a second and a third layer are applied thereto as in Example 1.
• the dry subbing is coated with a common gelatino silver halide emulsion layer.
• Example 7 A poly (ethylene terephthalate) support as described in Example 1 is coated with a first subbing layer from a 8% solution of the polyester of Preparation 8 in ethylene dichloride in a ratio of 1.3 g. of polyester per sq. m. of support. After drying, a second subbing layer is applied from the following composition in a ratio of l 1. thereof per 40 sq. m.:
• the dry subbing is coated with a common gelatino silver halide emulsion layer.
• Example 8 On a biaxially stretched poly(ethylene terphthalate) support having a thickness of 100 1., a subbing layer of the polyester of ethylene glycol and isophthalic acid prepared as described in Preparation 5 is coated from a 7% solution in ethylene dichloride. After drying, a gelatincellulose nitrate subbing layer is applied thereto as described in Example 7. Subsequently a common gelatino silver halide emulsion layer is applied to the dried material.
• a second photographic film element is prepared in an analogous manner, with the proviso, however, that the polyester of ethylene glycol and isophthalic acid is replaced by the polyester prepared according to Preparation 8.
• a third photographic film element is prepared by coating a biaxially stretched poly(ethylene terephthalate) support having a thickness of 100 with a subbing according to the United States patent specification 2,698,239 and then with a common gelatino silver halide emulsion layer.
• the subbing comprises consecutively:
• a thin layer coated from a composition comprising:
• a fourth photographic film element is prepared by coating a biaxially stretched poly(ethylene terephthalate) support having a thickness of 100 with a first subbing layer comprising a polyester, which is closely related with the polyesters of the first subbing layer of the photographic film element according to the present invention and which is within the broad scope of polyesters of the ethylene tereisophthalate type disclosed in the United States patent specification 3,178,287.
• This polyester subbing layer is applied from the following coating solution disclosed in said United States patent specification:
• Polyester of ethyleneglycol with terephthalic acid and isophthalic acid 50/50
• Polyester of ethylene glycol with terephthalic acid and isophthalic acid 60/40
• a fifth photographic film element is prepared by coating a biaxially stretched poly(ethylene terephthalate) support having a thickness of 100g with a first thin subbing layer of the polyester of ethylene glycol, terephthalic acid, and maleic anhydride, as described in Example 1 of said United States patent specification, 2,874,046, from a 5% solution in ethylene dichloride.
• the adhesion of the emulsion layer to the support is tested for all 5 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 ofif 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 adhesion of the emulsion layer in the third and the fifth film element is bad in dry as well as in Wet condition.
• the adhesion of the. fourth film element is good in wet condition, but bad in dry condition, especially after processing of the film element.
• a photographic film element comprising consecutively:
• a biaxially stretched poly(ethylene terephthalate) support a layer consisting essentially of 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 essentially consisting of about 55 to mole percent of isophthalic acid, about 0 to 25 mole percent of terephthalic acid,
• a layer comprising a mixture of gelatin and cellulose nitrate
• a photographic film element comprising consecutively:
• polyester which is soluble in chlorinated aliphatic hydrocarbons, has a molecular weight of at least about 4500 and a solubility in ethylene dichloride of at least about 10% by weight.
• polyester which is soluble in chlorinated aliphatic hydrocarbons, has a molecular weight of at least about 4500 and a solubility in ethylene dichloride of at least about 10% by weight.
• 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.
• 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.
• polyester is polyethylene isophthalate.

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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)
• Polyesters Or Polycarbonates (AREA)
• Laminated Bodies (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=25655505

Family Applications (1)

Country Status (6)

Cited By (5)

Families Citing this family (1)

Citations (3)

Family Cites Families (1)

• 1961
  • 1961-06-12 BE BE604869D patent/BE604869A/de unknown
• 1962
  • 1962-06-08 DE DEG35169A patent/DE1282453B/de active Pending
  • 1962-06-08 GB GB22296/62A patent/GB1014344A/en not_active Expired
  • 1962-06-12 FR FR900420A patent/FR1455758A/fr not_active Expired
  • 1962-06-12 CH CH703362A patent/CH431266A/de unknown
• 1968
  • 1968-11-25 US US778862A patent/US3495985A/en not_active Expired - Lifetime

Patent Citations (3)

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