US3492122A - Photographic silver halide film element - Google Patents

Photographic silver halide film element Download PDF

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Publication number
US3492122A
US3492122A US542242A US3492122DA US3492122A US 3492122 A US3492122 A US 3492122A US 542242 A US542242 A US 542242A US 3492122D A US3492122D A US 3492122DA US 3492122 A US3492122 A US 3492122A
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United States
Prior art keywords
layer
parts
halation
film
polyethylene terephthalate
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Expired - Lifetime
Application number
US542242A
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English (en)
Inventor
Haruo Takenaka
Teppei Ikeda
Toshiaki Okiyama
Sueo Miyazaki
Choji Hibino
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3492122A publication Critical patent/US3492122A/en
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    • 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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/835—Macromolecular substances therefor, e.g. mordants

Definitions

  • the disclosure relates to a silver halide film element having a polyethylene terephthalate film base and coated thereon a co-polyester layer under the silver halide emulsion.
  • an organic solvent solution of a mixture of a cellulose ester and a copolyester.
  • An antihalation layer is applied which consists of a member selected from the group consisting of styrenemaleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, and a maleic anhydride copolymer denatured by a monohydric alcohol having 4 to 12 carbon atoms.
  • the present invention relates to a photographic silver halide material, more particularly, it relates to a photographic film comprising a biaxially oriented, crystallized polyethylene terephthalate film support having an improved anti-halation layer.
  • anti-halation layers are generally divided into two kinds according to the position thereof. One is where the anti-halation layer is positioned at the surface of a photographic film opposite to the side of a photographic emulsion layer. The other is where the antihalation layer is positioned between the support and a photographic emulsion layer.
  • This invention relates to the former type, and the following specification is concerned with this kind of anti-halation layer, except where there is a specific designation to the contrary.
  • the anti-halation layer for photographic film must satisfy the following conditions:
  • a suitable treating bath such as a pre-treating bath, a developing bath, or a water-rinsing bath
  • the anti-halation layer should not be transferred to the emulsion layer.
  • An object of this invention is to provide a polyethylene terephthalate film for photography having an anti-halation layer satisfying the above-mentioned factors.
  • Another object of this invention is to improve the adhesion between the polyethylene terephthalate film and the anti-halation layer.
  • Another object of this invention is to provide, after the removal of the anti-halation layer, a substratum of the 'back surface of the photographic film, said substratum having improved mechanical properties such as wear resistance, and scratch strength, as well as improved physical properties such as transparency and flatness, and to provide further desirable properties to the film after development.
  • a biaxially oriented, crystallized polyethylene terephthalate film support has poor adhesive characteristics to other materials. Therefore, when applying an anti-halation layer directly to the surface of the film, the adhesive strength of the anti-halation layer to the polyethylene terephthalate film is insuflicient; therefore, when the film is rolled up with the anti-halation layer being in contact with the emulsion layer, the anti-halation layer is frequently transferred to the emulsion layer. This makes practical use of the photographic film very difficult.
  • the inventors have found that when a layer composed of a mixture of a cellulose ester and a copoly ester of terephthalic acid and glycols is formed on the surface of a biaxially oriented, crystallized, polyethylene terephthalate film support as a substratum, and then an anti-halation layer containing a maleic anhydride copolymer binder is applied to said substratum, the anti-halation layer is adhered firmly to the film support.
  • the polyester used in this invention is preferably a copolyester consisting of terephthalic acid and glycols, that is, a ternary co-condensation polyester consisting of terephthalic acid, ethylene glycol and triethylene glycol, which is soluble in the solvents and mixed solvent described hereinafter.
  • a typical example is a co-condensation product of 1 mol of terephthalic acid residual group, 0.8-0.5 mol of ethylene glycol residual group, and 0.5-0.2 mol of triethylene glycol residual group.
  • the cellulose ester used in this invention may be one which is soluble in said solvents and mixed solvents, the compatible range of the weight ratio of the cellulose ester to the polyester being 50:50 to :15 in a preferable concentration, capable of providing a stable coating solution.
  • Cellulose acetate, cellulose acetate propionate, cellulose butyrate and the like may be used.
  • the concentration of the coating solution in this invention may generally be in the range of 0.1 to 2%, but the range of 0.1 to 1.0% is preferable. There are no particular limitations about the degree of polymerization of the polyester and the cellulose ester used and it is preferable to vary the concentration of the coating solution in accordance with the degree of polymerization thereof.
  • the solvents used for the coating solution of this invention may be common industrial solvents.
  • alcohols such as, methanol, ethanol, methyl Cellosolve, and Cellosolve
  • ketones such as, acetone, methyl ethyl ketone, and cyclohexanone
  • esters such as methyl acetate, ethyl acetate, and cellosolve acetate
  • hydrocarbons such as, hexane, cyclohexanone, benzene, and toluene
  • clorinated hydrocarbons such as, methyl chloride, ethylene chloride, tetrachloroethane, and trichloroethylene
  • cyclic ethers such as, tetrahydrofuran and dioxane.
  • an organic solvent capable of swelling, softening and/or dissolving polyethylene terephthalate since by the addition thereof the substratum can be adhered more firm- 1y to the polyethylene terephthalate base.
  • organic solvents capable of swelling, softening and/or dissolving polyethylene terephthalate are phenol, o-chlorophenol, p-chlorophenol, cresol, and other phenol derivatives, benzoic acid, salichlic acid, salicylic acid esters, monochloroacetic acid, trichloroacetic acid, trifiuoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, acetonylacetone, acetophenone, benzamide, benzonitrile, and methyl nicontinate.
  • a suitable additive for example, an anionic surface active agent, such as, sodium dodecylbenzene sulfonate, sodium laurylsulfonate, or sodium N-methyloctyl tauride may be incorporated into the coating solution comprising the polymer and the solvent.
  • an anionic surface active agent such as, sodium dodecylbenzene sulfonate, sodium laurylsulfonate, or sodium N-methyloctyl tauride
  • the anti-halation layer directly coated and formed on the above-mentioned substratum according to the process of this invention is one of a type where the layer is coated using an organic solvent.
  • the binder for the anti-halation layer may comprise an alkali-soluble resin, that is, a copolymer of maleic anhydride and a vinyl compound co-polymerizable with maleic anhydride.
  • an alkali-soluble resin that is, a copolymer of maleic anhydride and a vinyl compound co-polymerizable with maleic anhydride.
  • styrene-maleic anhydride copolymer and a maleic anhydride-vinyl acetate copolymer there is a styrene-maleic anhydride copolymer and a maleic anhydride-vinyl acetate copolymer.
  • the alkali-soluble resin is dissolved in the above-mentioned alcohol or ketone in a resin concentration of above and the solution is kneaded with carbon black or mixed with an anti-halation dye to provide an anti-halation mother liquid.
  • Various additives for improving the coating property, preventing adhesion to the emulsion layer, and controlling the friction coefiicient are added.
  • a suitable solvent selected from the above-mentioned alcohols, ketones, hydrocarbons, and chlorinated hydrocarbons is added to provide the anti-halation coating solution.
  • the transfer of the antihalation layer to the emulsion layer can be effectively prevented.
  • the denature in this specification means the formation of a half ester by opening the ring of the acid anhydride group of the maleic anhydride copolymer.
  • the copolymer is dissolved by heating into the monohydric alcohol having 4 to 12 carbon atoms in an amount of 1.5 to 5 times the weight of the copolymer.
  • a low-boiling point alcohol such as methanol or ethanol, or a ketone is added into the solution in a copolymer concentration of to above 5%.
  • the solution is then kneaded with carbon black or mixed with an anti-halation dye to provide an anti-halation coating mother liquid.
  • the above-prepared coating liquid is applied on the substratum composed of a mixture of polyester and cellulose ester on a polyethylene terephthalate film, and dried to provide the anti-halation layer.
  • FIG. 1 An example of the photographic film having the antihalation layer prepared according to the process of this invention as described above is shown in the accompanying drawing in its cross-sectional view.
  • a substratum 2 composed of a polyester-cellulose ester mixture is formed.
  • the anti-halation layer 4 is then applied.
  • a first layer 2 composed of polyester is formed.
  • a substratum 3 or emulsion layer is formed by coating a gelatin dispersion onto first layer 2.
  • a photographic light-sensitive emulsion layer 5 is applied to layer 3.
  • the anti-halation layer is sufiiciently adhered to the support according to the process of this invention, the anti-halation layer is not transferred by adhesion to the emulsion layer even if the film is rolled up such that the anti-halation layer is in contact with the emulsion layer. Further, since the anti-halation layer, as taught by this invention, can be removed very easily by processing, it can be completely removed during the usual de-filming procedure by adding a light-squeezing procedure.
  • the substratum as taught by this invention appears on the back surface of the light-sensitive film, and, since the substratum has sufiiciently high wear resistance and scatch strength, the film can be sufliciently used in practice after development.
  • Example 1 A polyester was formed by adding an ester exchange reaction catalyst to a mixture of 1 mol of dimethyl terephthalate, 1.7 mols of ethylene glycol, and 0.8 mol of triethylene glycol. Into a mixed solvent of parts of ethylene dichloride, 10 parts of phenol, and 10 parts of tetrachloroethane 2 parts of the above-prepared polyester was dissolved. The solution was then applied to one surface of an oriented polyethylene terephthalate film at 60 C. and dried for 5 minutes at C.
  • a gelatin dispersion consisting of 1.0% of gelatin, 2.0% of water, 4.0% of acetic acid, 40.0% of methanol and 55.0% of acetone was then coated into this just formed layer, and coating was dried for twenty minutes at 60 C. (second layer).
  • the anti-halation layer had good adhesive property to the polyethylene terephthalate film, and also good flatness.
  • the anti-halation layer was completely removed when the photographic film was immersed for 60 to 90- seconds in an usual defilming treating bath mainly consisting of sodium sulfate, and then rinsed with water. Also, no stain was left. Further, the transference of the anti-halation layer to the emulsion layer was not observed at a humidity of 80% RH and at a temperature lower than 20 C.
  • EXAMPLE 2 The procedure as in Example 1 was repeated except that a copolymer of styrene and maleic anhydride was dissolved in 3 parts of butanol by heating and the solution was used instead of the copolymer solution in Example 1. In this example, almost the same results as in Example 1 were obtained. Also, no transference of the anti-halation layer to the emulsion layer was observed at a humidity of 80% RH and at a temperature of 30 C.
  • EXAMPLE 5 A polyester was prepared by adding an ester-exchange reaction catalyst into a mixture of 1 mol of dimethyl terephthalate, 1.3 mols of ethylene glycol and 1.2 mols of triethylene glycol. After dissolving 15 parts of the thus prepared polyester into 1000 parts of trichloroethylene,
  • the solution was applied to one surface of an oriented polyethylene terephthalate film at 60 C. and dried for 5 minutes at 80 C. On thus formed layer was applied the gelatin dispersion as described in Example 1 followed by drying.
  • the layer was dried for 20 minutes at 90 C.
  • gelatino silver halide photographic emulsion was coated as usual, on the gelatin layer of the polyethylene terephthalate film, and dried.
  • the anti-halation layer had thus formed high adhesive strength to the polyethylene terephthalate film base, and also good flatness.
  • EXAMPLE 6 A polyester was prepared by adding an ester-exchange reaction catalyst to a mixture of 1 mol of dimethyl terephthalate, 1.5 mole of ethylene glycol, and 1 mol of triethylene glycol. After dissolving 0.7 parts of this polyester and 1 part of cellulose nitrate into a mixture of 150 parts of ethylene dichloride, 50 parts of acetone, 13 parts of phenol and 15 parts of tetrachloroethane, the solution was applied to one side of an oriented polyethylene terephthalate film at 50 C. It was then dried for 10 minutes at 210 C.
  • gelatin dispersion consisting of 1.0 part of gelatin, parts of water, 4 parts of acetic acid, 55 parts of ethylene dichloride, 10 parts of acetone, and parts of methanol was applied to the above layer, and dried for 20 minutes at 100 C.
  • gelatin layer on the polyethylene terephthalate film was coated a gelatino silver halide emulsion followed by drying.
  • the thus obtained anti-halation layer had high adhesive strength to the polyethylene terephthalate base, and exhibited good flatness characteristics.
  • a photographic silver halide light-sensitive element which consists essentially of:
  • an anti-halation layer having incorporated therein, as a binder, a member selected from the group consisting of styrene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer, and a maleic anhydride copolymer denatured by a monohydric alcohol having 4 to 12 carbon atoms.
  • maleic anhydride copolymer is selected from the group consisting of styrene-maleic anhydride copolymer and vinyl acetate-maleic anhydride copolymer.

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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)
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US542242A 1965-04-16 1966-04-13 Photographic silver halide film element Expired - Lifetime US3492122A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993629A (en) * 1973-12-21 1976-11-23 Fuji Photo Film Co., Ltd. Polyester based adhesive
US4093458A (en) * 1972-11-20 1978-06-06 Imperial Chemical Industries Limited Polyurethane-polyanhydride subbing layer for photo sensitive elements
US4120724A (en) * 1972-10-02 1978-10-17 Fuji Photo Film Co., Ltd. Subbing material for styrene bases used in photographic elements
US4124395A (en) * 1973-08-10 1978-11-07 Fuji Photo Film Co., Ltd. Subbing layer on polyester film for light-sensitive material
US4988612A (en) * 1986-12-01 1991-01-29 Minnesota Mining And Manufacturing Company Resistively heatable photothermographic element
US6355405B1 (en) * 1999-02-26 2002-03-12 Eastman Kodak Company Multi-layer article with improved adhesion and method of making

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE626241A (sl) * 1961-12-19
US2698239A (en) * 1951-01-20 1954-12-28 Du Pont Photographic films
GB790023A (en) * 1954-11-12 1958-01-29 Agfa Ag Photographic light-sensitive material with an antihalation layer
US2984569A (en) * 1954-05-19 1961-05-16 Gevaert Photo Prod Nv Manufacture of photographic films
US3178287A (en) * 1960-05-23 1965-04-13 Minnesota Mining & Mfg Thin photographically sensitive film element

Patent Citations (5)

* 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
US2984569A (en) * 1954-05-19 1961-05-16 Gevaert Photo Prod Nv Manufacture of photographic films
GB790023A (en) * 1954-11-12 1958-01-29 Agfa Ag Photographic light-sensitive material with an antihalation layer
US3178287A (en) * 1960-05-23 1965-04-13 Minnesota Mining & Mfg Thin photographically sensitive film element
BE626241A (sl) * 1961-12-19

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120724A (en) * 1972-10-02 1978-10-17 Fuji Photo Film Co., Ltd. Subbing material for styrene bases used in photographic elements
US4093458A (en) * 1972-11-20 1978-06-06 Imperial Chemical Industries Limited Polyurethane-polyanhydride subbing layer for photo sensitive elements
US4124395A (en) * 1973-08-10 1978-11-07 Fuji Photo Film Co., Ltd. Subbing layer on polyester film for light-sensitive material
US3993629A (en) * 1973-12-21 1976-11-23 Fuji Photo Film Co., Ltd. Polyester based adhesive
US4988612A (en) * 1986-12-01 1991-01-29 Minnesota Mining And Manufacturing Company Resistively heatable photothermographic element
US6355405B1 (en) * 1999-02-26 2002-03-12 Eastman Kodak Company Multi-layer article with improved adhesion and method of making
US6436622B1 (en) 1999-02-26 2002-08-20 Eastman Kodak Company Thermographic material with adhesion-promoting layer and method of making

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BE679431A (sl) 1966-09-16

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