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
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
  • G03C1/7954—Polyesters
• • 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
  • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means

Definitions

• miniature cameras have been generally used for various purposes. In the points of portability and easy handling of the miniature cameras, further miniaturization of the miniature cameras has been demanded. In order to miniaturize the miniature cameras as little as possible, it is indispensable to make a housing space of a photographic film to be loaded more compact.
• polyester has been also conventionally known as a support and has been frequently used for an X-ray film and a process film.
• a polyester film is used as a support for a photographic material, its mechanical strength is excellent, but there is a drawback that roll set curl once formed can hardly be straightened even after development processing of a photographic film.
• a direct polymerization method in which an acid and a glycol are subjected to direct esterification and then polycondensation
• an transesterification (hereinafter referred to as "EI”: ester interchange) method in which an ester of an acid and a glycol are subjected to transesterification reaction and then polycondensation.
• EI ester interchange
• esterification can proceed sufficiently without a catalyst, but in the EI reaction, it is difficult to proceed the reaction within an economical time when an EI catalyst is not used.
• the seventh invention is a support for a photographic material which comprises a copolymerized polyester containing terephthalic acid and ethylene glycol as monomer units and further containing an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolysis and a polyalkylene glycol as a starting material, and has a haze of 1.5 % or less, a center line average roughness of 0.0025 ⁇ m or more and a thickness of 50 to 100 ⁇ m.
• the eighth invention is the support described above wherein the above copolymerized polyester contains an aromatic dicarboxylic acid having a metal sulfonate in an amount of 2 to 7 mole % based on all ester bond units and a polyalkylene glycol or a polyalkylene oxy dicarboxylic acid in an amount of 3 to 10 % by weight based on the total weight of the copolymerized polyester as monomer units.
• the ninth invention is the support described above wherein the above copolymerized polyester is obtained by polymerization using a manganese compound in an amount of 0.5 x 10 ⁇ 2 to 11.0 x 10 ⁇ 2 mole %/all ester bond units and a calcium compound in an amount of 0.5 x 10 ⁇ 2 to 5.0 x 10 ⁇ 2 mole %/all ester bond units in combination as transesterification catalysts.
• the copolymerized polyester in the present invention preferably contains a polyalkylene glycol and/or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms as a copolymer component(s).
• polyethylene glycol there may be mentioned polyethylene glycol and polytetramethylene glycol, and among them, polyethylene glycol is preferred. Its molecular weight is not particularly limited, but it may be 300 to 20,000, preferably 600 to 10,000, more preferably 1,000 to 5,000 in terms of a number average molecular weight. Also, when the polyalkylene oxy dicarboxylic acid or a derivative thereof is used in place of the polyalkylene glycol, a polyethylene oxy dicarboxylic acid or a polytetraethylene oxy dicarboxylic acid is preferably used, and polyethylene oxy dicarboxylic acid is more preferably used.
• the copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit in the present invention preferably contains an aromatic dicarboxylic acid having a metal sulfonate group detected by hydrolyzing said polyester in an amount of 2 to 7 mole %, more preferably 3 to 6 mole % based on all ester bond units and preferably contains the above polyalkylene glycol in an amount of 3 to 10 % by weight, more preferably 4 to 8 % by weight based on the weight of all reaction products.
• the copolymerized polyester to be used in the present invention may contain other kinds of monomer units unless the effect of the present invention is impaired.
• a method for preparing the copolymerized polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a monomer unit is not particularly limited, but the copolymerized polyester may be preferably prepared by, for example, subjecting a dicarboxylic acid component and a glycol component to transesterification preferably at a temperature of 200 to 250 °C, more preferably 220 to 240 °C under ambient pressure, followed by polycondensation at high temperature under reduced pressure, preferably at 250 to 300 °C, more preferably 270 to 285 °C under about 134 Pa or less, particularly 20 to 80 Pa.
• the copolymerized polyester to be used in the present invention may contain phosphoric acid, phosphorous acid and esters thereof, and an inert inorganic particle which are optionally mixed during polymerization, and the above inert inorganic particle may be added optionally after polymerization.
• the content of the inert inorganic particle is within the above range. If the average particle size of the inert inorganic particle exceeds 0.5 ⁇ m, transparency of the support for a photographic material may be lowered, while if it is less than 0.05 ⁇ m, an effect of easy sliding property may not be exhibited sufficiently. Further, if the content of the inert inorganic particle exceeds 2 % by weight, transparency of the support may be lowered, while if the content of the inert inorganic particle is less than 0.01 % by weight, sliding property is insufficient, whereby operatability may be lowered.
• the antioxidant is not particularly limited, and may specifically include a hindered pnenol type compound, an arylamine type compound, a phosphor type compound and a sulfur type antioxidant. Among them, a hindered phenol type compound is preferred. As the hindered phenol type compound, compounds represented by Compounds No. 1 and No. 2 shown below are preferred.
• a dye is preferably contained for the purpose of preventing light piping phenomenon (edge fog) caused when light is incident from an edge upon the support for a photographic material on which a photographic emulsion layer is provided by coating.
• the dye which is contained for such a purpose is not particularly limited, but a dye having excellent heat resistance is preferred for a film-forming step, and, for example, an anthraquinone type chemical dye may be included. From the point of a color tone of the support for a photographic material, a gray dye used in a common light-sensitive material is preferred, and one dye or a mixture of two or more dyes may be used.
• dyes there may be used dyes such as SUMIPLAST (trade name) produced by Sumitomo Kagaku Kogyo Kabushiki Kaisha, Diaresin (trade name) produced by Mitsubishi Kasei Corporation and MACROLEX (trade name) produced by BAYER AG singly or in suitable combination.
• SUMIPLAST trade name
• Diaresin trade name
• MACROLEX trade name
• the copolymerized polyester in the present invention preferably has an intrinsic viscosity measured at 20 °C in a mixed solution of phenol and 1,1,2,2-tetrachloroethane (weight ratio: 60 : 40) of 0.4 to 1.0, more preferably 0.5 to 0.8.
• the silver halide emulsion layer may be provided by coating silver halide emulsion layers with different sensitivities, i.e. high sensitivity and low sensitivity separately.
• an intermediate layer may be provided between the respective silver halide emulsion layers. That is, an intermediate layer comprising hydrophilic colloid may be provided, if necessary.
• a non-light-sensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer and a backing layer may be provided.
• Copolymer latex solution (solid component: 30 %) comprising 30 % by weight of butyl acrylate, 20 % by weight of t-butyl acrylate, 25 % by weight of styrene and 25 % by weight of 2-hydroxyethyl acrylate 270 g
• Compound (UL-1) 0.6 g Hexamethylene-1,6-bis(ethylene urea) 0.8 g made up to 1 liter with water.
• the silver iodobromide emulsion used in the tenth layer was prepared by the following method.
• the resulting emulsion was a monodispersed emulsion containing an octahedral silver iodobromide grain having an average grain size of 0.80 ⁇ m, a distribution width of 12.4 % and a silver iodide content of 8.5 mole %.
• All emulsions were core/shell type monodispersed emulsions having a distribution width of 20 % or less.
• the respective emulsions were subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added.
• Colorimetric values (L and b) were calculated from reflectance of the print measured under C light source by using a reflection system and Hitachi Color Analyzer Model 607 (trade name, manufactured by Hitachi Ltd.) according to JIS standard.
• the light-sensitive photographic material was loaded in a camera and charts of three colors (yellow, magenta and cyan) shown in Macbeth Color Checker (trade name, produced by Kollmorgen Co.) were photographed.
• Colorimetric values (L and b) were calculated from reflectance of the print measured under C light source by using a reflection system and Hitachi Color Analyzer Model 607 (trade name, manufactured by Hitachi Ltd.) according to JIS standard.
• Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxylethyl)aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g made up to 1 liter with addition of water, and adjusted to pH 10.06 by using potassium hydroxide or 20 % sulfuric acid.
• the supports containing SIP in an amount of 2 to 7 mole % (based on all ester bond units) and containing a polyalkylene glycol, particularly polyethylene glycol in an amount of about 3 to 10 % by weight (based on polymer) are particularly effective as a support for a photographic material.
• Example 4 In the same manner as in Example 3 except for changing polymerisation temperature and the amount of dimethyl adipate (DMA) used in Example 4 (see Table 4), copolymerised polyesters having copolymer composition ratios shown in Table 4 were obtained (No. 16 and No. 17 in Table 4). After supports for a photographic material were prepared in the same manner as in Example 3, emulsion layers and backing layers were provided by coating to prepare light-sensitive materials. The light-sensitive materials were evaluated in the same manner as in Example 1. The results are shown in Table 4.
• DMA dimethyl adipate
• the supports containing SIP in an amount of about 2 to 7 mole % (based on all ester bond units) and containing dimethyl adipate in an amount of about 3 to 25 mole % (based on polymer) are particularly effective as a support for a photographic material.
• the support using the copolymerized polyester having the L value and b value outside the range specified in the present invention also has poor color reproducibility even when a dye is added, and the support has a problem in practical use as a support for a photographic material.
• the copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film.
• the unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 220 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 ⁇ m.
• its diethylene glycol content was measured according to the following recipe and its flatness and recovering property from roll set curl were evaluated according to the following evaluation methods. The results are shown in Table 1.
• the film was slightly colored, but such a coloring degree was not a problem in practical use.
• the diethylene glycol content was 4 mole %, and both of the flatness and the recovering property from roll set curl were good.
• a film of 12 cm x 35 mm was wound around a core with a diameter of 10 mm, and the wound film was left to stand at 55 °C and 20 % RH (relative humidity) for 3 days to form roll set curl of the film. Thereafter, the film was released from the core and dipped in pure water of 38 °C for 15 minutes. Thereafter, the film was loaded with 50 g and dried for 3 minutes by means of a hot air dryer at 55 °C. After 3 minutes, the load was removed from the film and the film was hung perpendicularly. The distance between both ends of the hung film was measured and a recovering rate from roll set curl based on the original length of 12 cm was evaluated.
• the recovering rate is preferably 50 % or more, particularly 80 % or more in practical use. If the value is within the above range, there is no problem as a photographic film.
• Example 8 In the same manner as in Example 8 except for adding 0.07 % by weight of tetraethylhydroxy ammonium in place of sodium hydroxide used in Example 8, a biaxially stretched film having a thickness of 80 ⁇ m was obtained.
• the film was evaluated in the same manner as in Example 8, and the results are shown in Table 8.
• the film was slightly colored similarly as in Example 8, but such a coloring degree was not a problem in practical use.
• the diethylene glycol content was 5 mole %, and there was no practical problem in both of the flatness and the recovering property from roll set curl.
• Example 8 In the same manner as in Example 8 except for adding 0.04 % by weight of sodium acetate in place of sodium hydroxide used in Example 8 at transesterification reaction, a biaxially stretched film having a thickness of 80 ⁇ m was obtained.
• the film was evaluated in the same manner as in Example 8, and the results are shown in Table 8.
• the film was slightly colored similarly as in Example 8, but such a coloring degree was not a problem in practical use.
• the diethylene glycol content was 3 mole %, and there was no practical problem in both of the flatness and the recovering property from roll set curl.
• a photographic film prepared by providing light-sensitive photographic layers on the film according to a known method did not have any particular problem in practical use and had good characteristics.
• the copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film.
• the unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 200 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 ⁇ m.
• its diethylene glycol content was measured in the same manner as in Example 8 and its flatness and recovering property from roll set curl were evaluated according to the same evaluation methods as in Example 8. The results are shown in Table 8.
• the film was colorless and transparent. As can be clearly seen from Table 8, the diethylene glycol content was 3 mole %, and both of the flatness and the recovering property from roll set curl were good.
• the copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film.
• the unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 180 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 100 ⁇ m.
• the biaxially stretched film was evaluated in the same manner as in Example 8, and the results are shown in Table 8.
• the film was colored in yellow and its quality as a support for a photographic material was inferior to those of the films obtained in Examples 8 to 11, but it could be used practically.
• the diethylene glycol content was 5 mole %, and both of the flatness and the recovering property from roll set curl were good.
• the copolymerized polyester was dried under vacuum at 150 °C, melt extruded at 280 °C and set by quenching on a cooling drum to prepare an unstretched film.
• the unstretched film was stretched by 3.3-fold in the longitudinal direction at 80 °C, stretched by 3.3-fold in the lateral direction at 90 °C and then thermally fixed at 180 °C for 30 seconds to obtain a biaxially stretched film having a thickness of 80 ⁇ m.
• its diethylene glycol content was measured in the same manner as in Example 8 and its flatness and recovering property from roll set curl were evaluated according to the same evaluation methods as in Example 8. The results are shown in Table 8.
• the film was colorless and transparent, but as can be clearly seen from Table 8, the diethylene glycol content was 9 mole % and the flatness was poor.
• the unstretched films were stretched by 3.5-fold in the lateral direction at 80 °C, stretched by 3.5-fold in the longitudinal direction at 90 °C and then thermally fixed at 200 °C to obtain biaxially stretched films having a thickness of 80 ⁇ m.
• Haze of the film was measured according to JIS K-6714.
• Property of a support for a photographic material 1.5 % or less is preferred in practical use.
• center line average roughness is a value less than 0.0025 ⁇ m, there may be obstacles in handling.
• a support for a photographic material suitable for a light-sensitive silver halide photographic material having excellent photographic characteristics that roll set curl can be easily resolved, and no bad influence is exerted on emulsion characteristics of photographs and color reproducibility of a positive type light-sensitive material.
• a support for a photographic material having excellent recovering property from roll set curl after development processing while maintaining strength.
• a support for a photographic material having excellent transparency, easy sliding property and recovering property from roll set curl.

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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)
• Polyesters Or Polycarbonates (AREA)

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Citations (7)

• 1993
  • 1993-04-14 EP EP93106077A patent/EP0566094A2/fr not_active Withdrawn

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