EP0334367B1 - Photographisches lichtempfindliches Material mit Polyesterträger - Google Patents

Photographisches lichtempfindliches Material mit Polyesterträger Download PDF

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Publication number
EP0334367B1
EP0334367B1 EP19890105268 EP89105268A EP0334367B1 EP 0334367 B1 EP0334367 B1 EP 0334367B1 EP 19890105268 EP19890105268 EP 19890105268 EP 89105268 A EP89105268 A EP 89105268A EP 0334367 B1 EP0334367 B1 EP 0334367B1
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EP
European Patent Office
Prior art keywords
acid
sensitive material
film
polyester film
photographic light
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EP19890105268
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English (en)
French (fr)
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EP0334367A2 (de
EP0334367A3 (en
Inventor
Seimi Satake
Yoshihiko Shibahara
Toshiaki Ueda
Kenji Kida
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Fujifilm Holdings Corp
Toray Industries Inc
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Toray Industries Inc
Fuji Photo Film Co Ltd
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Publication of EP0334367A2 publication Critical patent/EP0334367A2/de
Publication of EP0334367A3 publication Critical patent/EP0334367A3/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
    • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • G03C1/7954—Polyesters

Definitions

  • This invention relates to a photographic light-sensitive material and, more particularly, to a photographic light-sensitive material which comprises a support of a polyester material and which has a light transparency and excellent curl-extinguishing properties after development processing, and these properties are independent of environment with a lapse of time.
  • Photographic light-sensitive materials are generally produced by coating at least one photographic light-sensitive layer on a plastic film support.
  • plastic film fiber type polymers represented by triacetyl cellulose (hereinafter abbreviated as " TAC”) and polyester type polymers represented by polyethylene terephthalate (hereinafter abbreviated as “PET”) are generally used.
  • TAC triacetyl cellulose
  • PET polyester type polymers represented by polyethylene terephthalate
  • PET has conventionally been considered to substitute for TAC due to its excellent productivity, mechanical strength and dimensional stability.
  • PET has a strong tendency to retain the curl from being in the rolled state, and hence its handling properties after development processing are so poor that the scope of its application has been limited in spite of the above-described excellent properties.
  • Photographic light-sensitive materials generally include sheet form types such as X-ray films, plate-making films and cut films and roll films.
  • Typical examples of the roll films are color or black-and-white negative-working films of 35 mm or less in width retained in a cartridge and adapted to be loaded in ordinary cameras for taking photographs.
  • the greatest aspect as a photographic support of TAC films mainly used for roll films is that they are optically non-anisotropic and have a high transparency.
  • they have another excellent aspect. That is, they possess excellent properties as to curl-extinguishing after development processing.
  • TAC films have comparatively high water-absorbing properties for plastic films due to their molecular structure, the molecular chain is fluidized upon absorption of water during development processing and the curling tendency imparted by being kept in a rolled state as roll film for a long time is extinguished as a result of rearrangement of the molecular chain which had been set after being rolled for a long time.
  • TAC provides only a fragile film when formed into film due to its rigid molecular structure and cannot be used in for these advances. Additionally, PET films cannot be used as a roll film where the curling tendency is problematical, in spite of their excellent mechanical properties. Thus, considerable improvement in PET films is greatly desired.
  • US-A-4,217,441 and 4,241,170 disclose that a PET film modified by reacting with a certain specific compound is employed as a support for a photographic material. In this case, however, there arise problems that the film becomes whitening by a processing and a lapse of time, and the transparency of the film is diminished. Therefore, further improvements for the transparency of the film have been desired.
  • US-A-3052 543 discloses a photographic material comprising a specific support film having thereon at least one layer of a copolymer of vinylidene chloride, an acrylic ester and itaconic acid and at least one layer of a water-permeable colloid having protective colloid properties.
  • the support film comprises a polyester film formed by reacting a specific dicarboxylic acid (or a derivative thereof) with a specific dihydroxy compound and a specific metal sulfonate.
  • an object of the present invention is to provide a photographic light-sensitive material which comprises a polyester film support having a high transparency and excellent mechanical properties, and which has excellent curl-extinguishing properties after development processing.
  • the object of the present invention can be attained by a photographic light-sensitive material which comprises a polyester film support having provided thereon at least one light-sensitive silver halide emulsion layer, said polyester film having a haze of up to 3%, a water content of from 0.5 wt.-% to 5.0 wt.-%, a curl-extinguishing ratio to 50% or more, and containing as predominant constituents terephthalic acid component and a glycol component, said polyester film further comprising an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms as a copolymerization component in an amount of from 3 to 25 mol% based on the terephthalic acid component, wherein the haze is measured in accordance with ASTM D1003-52 after heat treatment of the film at a temperature of 150°C for ten minutes, the water content is measured after first moisture-conditioning the film under conditiones of 23°C and 30% RH for three hours, next dipping the film in distilled water at
  • the water content of polyester film is measured by moisture-conditioning the film under the conditions of 23°C, 30% RH and 3 hours, dipping the film in 23°C distilled water for 15 minutes, and then using a micromoisture meter (for example, model CA-02, made by Mitsubishi Chemical Industries, Ltd.) at a drying temperature of 150°C.
  • a micromoisture meter for example, model CA-02, made by Mitsubishi Chemical Industries, Ltd.
  • the term "polyester” means a polyester containing as predominant constituents a terephthalic acid component and a glycol.
  • the terephthalic acid component include terephthalic acid and isophthalic acid
  • the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanediol and diethylene glycol.
  • PET polyethylene terephthalate
  • Copolymerized PET films preferably used in the present invention comprise copolymerized PET films containing a metal sulfonate-containing aromatic dicarboxylic acid component as a copolymerizable component.
  • the metal sulfonate-containing aromatic dicarboxylic acid examples include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and compounds wherein sodium of the above-described compounds is replaced by another metal (for example, potassium or lithium).
  • the copolymerization proportion of the metal sulfonate-containing aromatic dicarboxylic acid component is preferably about 2 to 15 mol%, particularly preferably about 4 to 10 mol%, based on the aromatic dibasic acid component, e.g., the terephthalic acid component.
  • an aliphatic dicarboxylic acid component containing 4 to 20 carbon atoms in the copolymerized PET film is used in view of transparency, particularly depression of whitening and enhancement of bending resistance of the copolymerized PET film.
  • the aliphatic dicarboxylic acid component containing 4 to 20 carbon atoms there are illustrated succinic acid, adipic acid, sebacic acid, with adipic acid being particularly preferable.
  • the copolymerization proportion of the aliphatic dicarboxylic acid component containing 4 to 20 carbon atoms is 3 to 25 mol%, preferably 5 to 20 mol%, based on the terephthalic acid component.
  • polyester film of the present invention other acid components or glycol components may further be copolymerized in a small proportion so as not to inhibit transparency and mechanical properties.
  • polyalkylene glycol particularly polyethylene glycol
  • polyethylene glycol may be copolymerized in a proportion of 0 to 10 wt% based on the amount of the polyester produced.
  • the polyalkylene glycols to be used for the above-described objects preferably have a molecular weight of about 600 to 10,000.
  • the polyester film of the present invention preferably comprises a polymer having an intrinsic viscosity of about 0.5 to 0.9 measured in o-chlorophenol at 25°C.
  • polyester film of the present invention various additives may be incorporated in the polyester film of the present invention.
  • TAC triacetyl cellulose
  • PET polyester type polymers represented by PET.
  • TAC triacetyl cellulose
  • PET polyester type polymers represented by PET.
  • TAC triacetyl cellulose
  • gelatin mainly used in the subbing layer and photographic emulsion layer has a refractive index of 1.50 to 1.55.
  • the ratio of the refractive index of gelatin to that of PET is 1.5/1.6, which is smaller than 1. Therefore, when light streams through a film edge, the light is liable to be reflected at the interface between the base and emulsion layer, thus polyester type films are liable to cause so-called light piping.
  • a technique of preventing light piping preferably employed in the present invention is the technique of adding a dye which does not seriously raise film haze.
  • Dyes to be used for dyeing film are not particularly limited, but the tone is preferably gray in view of the general properties of light-sensitive materials. Dyes to be employed are preferably those which have an excellent heat resistance in a temperature region where the polyester film is formed and have an excellent compatibility with polyester.
  • dyes commercially available as dyes for polyesters such as Diaresin (made by Mitsubishi Chemical Industries, Ltd) and Kayaset (made by Nippon Kayaku K.K.) may be used for attaining the above-described object.
  • dyeing density at least a color density in the visible region of 0.01 measured by a color densitometer (made by Macbeth Co.) is necessary, with 0.03 or more being more preferable.
  • polyester film in accordance with the present invention may be imparted lubricating properties as the application demands.
  • lubricating properties There are no limits as to techniques for imparting lubricating properties, but a technique of kneading an inert inorganic compound into the film or a technique of coating a surfactant is employed in general.
  • the inert inorganic particles are illustrated by SiO2, TiO2, BaSO4, CaCO3, talc, kaolin.
  • a technique of adding the inert particles to the polyester-synthesizing reaction system to impart lubricating properties by the external particle system and a technique of precipitating catalyst or the like having been added upon the polymerization reaction of polyester to impart lubricating properties by the internal particle system are also employable.
  • SiO2 having a comparatively approximate refractive index to that of polyester film is preferably selected as the external particle system, or an internal particle system capable of precipitating particles of a comparatively small particle size is preferably selected as the internal particle system, which, however, do not limit the technique of imparting lubricating properties.
  • the technique for lamination there is illustrated a coextruding process using a plurality of extruders and a feed block or multi-manifold die.
  • copolymerized PET can be obtained by directly subjecting the dibasic acid component and the glycol component to an esterification reaction at a temperature of 200°C to 270°C and removing a theoretical amount of water or, by using a lower alkyl ester as the dibasic acid component, and conducting an ester interchange reaction between the dibasic acid component and the glycol component at a temperature of 100°C to 250°C and removing a theoretical amount of lower alcohol to obtain a glycol ester of the dibasic acid or a low molecular weight polymer.
  • the product obtained is heated at a temperature of 200°C to 300°C under a pressure gradually reduced to about 133 Pa (1 Torr) to remove excess glycol component.
  • an ester interchange reaction catalyst or a polymerization reaction catalyst described in US-A-2,647,885 and 2,739,957, GB-B-742,196 and 770,531 may be used, or a heat resistant stabilizing agent described in the above patents may be added thereto.
  • the thus-obtained copolymerized PET is generally granulated, dried, melt-extruded to form an unstretched film sheet, then biaxially stretched and heat-treated to obtain the end film.
  • the biaxial stretching may be conducted successively in the order of longitudinal direction and transverse direction or in the reverse order, or simultaneously in two directions.
  • the stretching ratio is not particularly limited, but is usually 2.0 to 5.0 times. Restretching in the transverse or longitudinal direction may be conducted after stretching in the transverse or longitudinal direction.
  • a drying technique in the present invention employed before melt-extrusion a vacuum drying technique or a dehumidification-drying technique is preferable.
  • Stretching temperatures in the present invention are desirably from 70 to 100°C upon longitudinal stretching and from 80 to 160°C upon transverse stretching.
  • Heat-setting temperatures are from 150 to 210°C, particularly preferably from 60 to 200°C.
  • the thickness of the copolymerized PET film to be used in the present invention may properly be determined depending upon the end-use of photographic film, and is desirably from 25 to 250 »m, more desirably from 40 to 150 »m.
  • the copolymerization formulation in the present invention does not spoil the excellent transparency and mechanical strength which PET essentially possesses, and provides a film haze of up to 3%, a breaking strength of from 8 to 25 kg/mm2, an initial modulus of from 200 to 500 kg/mm2, and a tear strength at a thickness of 120 »m of not less than 30 g. If the strength is less than the above-described range, the excellent mechanical strength which PET essentially possesses is spoiled and, thus, the superiority over TAC is lost.
  • Haze of a film is measured according to ASTM D1003-52 after a heat treatment of the film at a temperature of 150°C for 10 minutes. This heat treatment is usually subjected to a film support at a coating step of a photographic layer.
  • a sample of 10 mm in width and 100 mm in length is subjected to measurement according to JIS Z1702-1976 employing a pulling rate of 300 mm/min for measuring breaking strength and 20 mm/min for measuring initial modulus.
  • the polyester film support to be used in the present invention has excellent curling tendency-extinguishing properties after development processing (hereinafter referred to as curl-extinguishing ratio).
  • the curl-extinguishing ratio measured according to the following method is 50% or more, preferably 80% or more.
  • a sample of 12 cm ⁇ 35 cm in size is wound around a core of 10 mm in diameter and is kept under the conditions of 60°C ⁇ 30% RH ⁇ 72 hrs. Then, it is unwound from the core, dipped in 40°C distilled water for 15 minutes, and dried for 3 minutes in a 55°C air thermostatic chamber while applying a load of 50 g. The length of the thus-treated sample is measured in a perpendicularly suspended state to evaluate the degree of restoration to the original length of 12 cm.
  • the copolymerized PET film to be used in the present invention has a better adhesiveness to various coating layers such as emulsion layers than conventional PET films.
  • the polyester film to be used in the present invention may, if necessary, be previously subjected to corona discharge treatment, treatment with a chemical solution or flame treatment.
  • corona discharge treatment is most preferably used in the present invention, since it causes less precipitation of low-polymerized product on the film surface.
  • the polyester support to be used in the present invention preferably has a subbing layer for enhancing adhesion to a photographic layer such as a light-sensitive layer to be coated thereon.
  • subbing layer there are illustrated a subbing layer using a polymer latex composed of a styrene-butadiene type copolymer or a vinylidene chloride copolymer and a subbing layer using a hydrophilic binder such as gelatin.
  • the subbing layer using a hydrophilic binder is preferably used as the subbing layer in the present invention.
  • hydrophilic binder to be used in the present invention, there are illustrated, for example, water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters.
  • the water-soluble polymers include gelatin, gelatin derivatives, casein, agar-agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers and maleic anhydride copolymers, and the cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose.
  • the latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is most preferable.
  • resorcin chlororesorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate.
  • resorcin and p-chlorophenol are preferable.
  • Various gelatin hardeners may be used in the subbing layer of the present invention.
  • chromium salts e.g., chromium alum
  • aldehydes e.g., formaldehyde and glutaraldehyde
  • isocyanates e.g., 2,4-dichloro-6-hydroxy-s-triazine
  • epichlorohydrin resin e.g., 2,4-dichloro-6-hydroxy-s-triazine
  • the subbing layer to be used in the present invention may contain fine particles of an inorganic substance such as SiO2 or TiO2 or fine particles (1 to 10 »m) of polymethyl methacrylate copolymer as matting agents.
  • the subbing layer to be used in the present invention may be coated according to a generally well known coating process such as a dip coating process, an air knife coating process, a curtain coating process, a wire bar coating process, a gravure coating process, or an extrusion coating process.
  • a generally well known coating process such as a dip coating process, an air knife coating process, a curtain coating process, a wire bar coating process, a gravure coating process, or an extrusion coating process.
  • the light-sensitive material of the present invention may have light-insensitive layers such as an antihalation layer, an interlayer, a backing layer and a surface protecting layer in addition to light-sensitive layers.
  • the binder for the backing layer may be a hydrophobic polymer, or may be a hydrophilic polymer as used for the subbing layer.
  • the backing layer of the light-sensitive material in accordance with the present invention may contain an antistatic agent, a slipping agent, a matting agent, a surfactant a dye.
  • the antistatic agents to be used in the present invention are not particularly limited and are, for example, anionic high molecular weight electrolytes such as high molecular weight polymers containing carboxylic acid groups, carboxylic acid salt groups or sulfonic acid groups (e.g., high polymers as described in JP-A-48-22017 (the term “JP-A” as used herein refers to a "published unexamined Japanese patent application"), JP-B-46-24159 (the term “JP-B” as used herein refers to an "examined Japanese patent publication”), JP-A-51-30725, JP-A-51-129216, JP-A-55-95942) and cationic high polymers as described in JP-A-49-121523, JP-A-48-91165, JP-B
  • Ionic surfactants also include anionic and cationic surfactants and are exemplified by those which are described in JP-A-49-85826, JP-A-49-33630, US-A-2,992,108 and 3,206,312, JP-A-48-87826, JP-B-49-11567, JP-B-49-11568 and JP-A-55-70837.
  • the most preferable antistatic agents for the backing layer of the present invention are fine particles of at least one crystalline metal oxide selected from among ZnO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO and MoO3, or a composite oxide thereof.
  • Fine particles of the conductive crystalline oxides or their composite oxides to be used in the present invention have a volume resistivity of up to 107 ⁇ cm, more preferably up to 105 ⁇ cm, and have a particle size of 0.01 to 0.7 »m, particularly preferably 0.02 to 0.5 »m.
  • JP-A-56-143430 corresponding to US-A-4,495,276
  • JP-A-60-258541 Processes for producing the fine particles of the conductive crystalline metal oxides or their composite oxides to be used in the present invention are described in detail in JP-A-56-143430 (corresponding to US-A-4,495,276) and JP-A-60-258541. They can be easily produced firstly by producing fine particles of metal oxide through baking and heat-treating the particles in the presence of a different atom capable of improving conductivity; secondly by allowing a different metal capable of improving conductivity to coexist upon production of metal oxide fine particles through baking; or thirdly by reducing the oxygen concentration of the atmosphere upon production of metal oxide fine particles through baking to thereby introduce an oxygen deficiency.
  • Examples of different atoms are: Al, In, for ZnO; Nb, Ta, for TiO2; and Sb, Nb, halogen atoms, for SnO2.
  • the different atom is added in an amount of preferably 0.01 to 30 mol%, particularly preferably 0.1 to 10 mol%.
  • Photographic layers of the photographic light-sensitive material for the present invention are now described below.
  • the most preferable examples of the photographic light-sensitive material in accordance with the present invention are silver halide photographic light-sensitive materials which are exemplified by silver halide color negative-working films, color positive-working films, color reversal films and black-and-white negative-working films.
  • the photographic emulsion to be used in the present invention can be prepared by the processes described in P. Glafkides, Chimie et Physique Photographique (Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (The Focal Press, 1966), V.L. Zelikman et al., Making and Coating Photographic Emulsion (The Focal Press, 1964). That is, any of an acidic process, a neutral process and an ammoniacal process may be used. As a manner of reacting a soluble silver salt with a soluble halide salt, any of one side mixing, simultaneous mixing, and combinations thereof may be employed.
  • a process of forming silver halide grains in the presence of excess silver ion can be employed as well.
  • a process called a controlled double jet process wherein the pAg in a liquid phase in which silver halide is formed is kept constant can be employed. This process provides a silver halide emulsion containing silver halide grains of regular crystal form having an approximately uniform grain size.
  • Two or more silver halide emulsions having been separately prepared may be mixed for use.
  • cadmium salts zinc salts, lead salts, thallium salts, iridium salts or the complex salts thereof, rhodium salts or the complex salts thereof, iron salts or the complex salts thereof, may be allowed to coexist.
  • gelatin As a binder or protective colloid for photographic emulsions, gelatin is advantageously used.
  • hydrophilic colloids can be used as well.
  • proteins such as gelatin derivatives, graft polymers between gelatin and other high molecular weight polymers, albumin, casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate; sugar derivatives such as sodium alginate, starch derivative; and various synthetic macromolecular substances such as homopolymers or copolymers (e.g., polyvinyl alcohol, partially acetalized polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole) can be used.
  • gelatin acid-processed gelatin or enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan , No. 16, p. 30 (1966) may be used as well as lime-processed gelatin, and a gelatin hydrolyzate or an enzyme-decomposed product can also be used.
  • gelatin derivatives those obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinyl-sulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds or the like can be used. Specific examples thereof are described in US-A-2,614,928, 3,123,945, 3,186,846, 3,312,553, GB-B-861,414, 1,033,189, and 1,005,784, JP-B-42-26845.
  • gelatin graft polymers products prepared by grafting to gelatin a homo- or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, esters or amides thereof, acrylonitrile, styrene can be used.
  • graft polymers between gelatin and a polymer having some compatibility with gelatin such as a polymer of acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferable. Examples of these are described in US-A-2,763,625, 2,831,767, 2,956,884.
  • Typical synthetic high molecular weight substances are those described in, for example, DE-A-2,312,708, US-A-3,620,751 and 3,879,205 and JP-B-43-7561.
  • various compounds for preventing fog or stabilizing the photographic properties during production steps, storage, or photographic processing of the light-sensitive material may be incorporated. That is, many compounds known as antifogging or stabilizing agents such as azoles (e.g., benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly, 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds (e.g., oxazolinethione); azaindenes (e.g., triazaindene
  • the photographic emulsion layer of the photographic light-sensitive material in accordance with the present invention may contain a polyalkylene oxide or its ether, ester or amide derivative, a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, a 3-pyrazolidone, etc., for the purpose of enhancing sensitivity or contrast or for accelerating development.
  • a polyalkylene oxide or its ether, ester or amide derivative a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, a 3-pyrazolidone, etc.
  • the photographic emulsion used in the present invention may be spectrally sensitized with methine dyes.
  • Suitable dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These dyes may contain as a basic heterocyclic nucleus any of the nuclei usually used for cyanine dyes.
  • a pyrroline nucleus there can be contained a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus.
  • nuclei wherein an alicyclic hydrocarbon ring or rings are fused to these nuclei
  • nuclei wherein an aromatic hydrocarbon ring or rings are fused to these nuclei, i.e., an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a
  • Merocyanine dyes or complex merocyanine dyes contain, as a ketomethylene structure-containing nucleus, a 5- or 6-membered heterocyclic nucleus such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus.
  • a ketomethylene structure-containing nucleus such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus.
  • sensitizing dyes are described in, for example, DE-C-929,080, US-A-2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 3,694,217, 4,025,349, 4,046,572, GB-B-1,242,588, JP-B-44-14030 and JP-B-52-24844.
  • sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used for attaining, in particular, supersensitization. Typical examples thereof are described in US-A-2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707 GB-B-1,344,281 and 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618, and JP-A-52-109925.
  • Dyes which themselves do not show a spectrally sensitizing action or materials which do not substantially absorb visible light, showing supersensitivity may be incorporated in the emulsion together with the sensitizing dyes.
  • aminostilbenes substituted by a nitrogen-containing heterocyclic group for example, those described in US-A-2,933,390 and 3,635,721
  • aromatic organic acid-formaldehyde condensates for example, those described in US-A-3,743,510
  • cadmium salts for example, those described in US-A-3,743,510
  • the light-sensitive material of the present invention may contain water-soluble dyes as filter dyes or for various purposes like antiirradiation.
  • dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes. Of these, oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.
  • photographic emulsion layers and other hydrophilic colloidal layers may contain fluorescent brightening agents of stilbenes, triazines, oxazoles, coumarins, etc. These agents may be of a water-soluble type or water-insoluble type, with the latter being used in the form of a dispersion. Specific examples of the fluorescent brightening agents are described in US-A-2,632,701, 3,269,840, 3,359,102, GB-B-852,075 and 1,319,763.
  • the color image stabilizing agents to be used in the present invention may be used alone or in combinations of two or more.
  • the known dye stabilizers include, for example, hydroquinone derivatives described in US-A-2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801, 2,816,028, GB-B-1,363,921, gallic acid derivatives described in US-A-3,457,079, 3,069,262 p-alkoxyphenols described in US-A-2,735,765 and 3,698,909, JP-B-49-20977, JP-B-52-6623, p-hydroxyphenols described in US-A-3,432,300, 3,573,050, 3,574,627, 3,764,337, JP-A-52-35633, JP-A-52-147434
  • the light-sensitive material prepared by the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, as color fog preventing agents. Specific examples thereof are described in US-A-2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, JP-A-50-92988, JP-A-50-92989, JP-A-50-93928, JP-A-50-110337, JP-A-52-146235, JP-B-50-23813, etc.
  • the present invention may be applied to a multilayered multicolor photographic material having at least two light-sensitive layers different in spectral sensitivity.
  • Multilayered color photographic materials usually comprise a support having provided thereon at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers may be optionally selected as the case demands.
  • the red-sensitive emulsion layer is associated with a cyan-forming coupler
  • the green-sensitive emulsion layer is associated with a magenta-forming coupler
  • the blue-sensitive emulsion layer is associated with a yellow-forming coupler, though different combinations are possible in some cases.
  • the most preferable light-sensitive materials of the present invention are rolled color negative films for photographing use.
  • Known color couplers may preferably be used in the color negative-working films of the present invention.
  • Couplers compounds capable of forming dyes by the reaction with an oxidation product of an aromatic amine (usually primary amine) developing agent (hereinafter abbreviated as "couplers").
  • an aromatic amine (usually primary amine) developing agent hereinafter abbreviated as "couplers"
  • the couplers nondiffusible couplers having a hydrophobic group called a ballast group in the molecule are desirable.
  • the couplers may be of either 4-equivalent type or 2-equivalent type based on silver ion. Colored couplers having color-correcting effects or couplers capable of releasing a development inhibitor upon development (called DIR couplers) may also be incorporated. Couplers may be those which form a colorless coupling reaction product.
  • yellow color-forming couplers known open chain ketomethylene couplers may be used. Of these, benzoylacetanilide type and pivaloylacetanilide type compounds are advantageous. Specific examples of usable yellow color-forming couplers are those described in US-A-2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, 3,891,445, DE-C-1,547,868, DE-A-2,219,917, 2,261,361, 2,414,006, GB-B-1,425,020, JP-B-51-10783, JP-A-47-26133, JP-A-48-73147, JP-A-51-102636, JP-A-50-6341, JP-A-50-123342, JP-A-50-130442, JP-A-51-21827, JP-A-50-87650, JP-A-52-82424, JP-A-52-115219.
  • magenta color-forming couplers pyrazolone type compounds, indazolone type compounds, cyanoacetyl compounds may be used, with pyrazolone type compounds being particularly advantageous.
  • Specific examples of usable magenta color-forming couplers are described in US-A-2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908, 3,891,445, DE-C-1,810,464, DE-A-2,408,665, 2,417,945, 2,418,959, 2,424,467, JP-B-40-6031, JP-A-51-20826, JP-A-52-58922, JP-A-49-129538, JP-A-49-74027, JP-A-50-159336, JP-A-52-42121, JP-A-49-74028, JP-A-50-60233
  • cyan color-forming couplers phenolic compounds, naphtholic compounds, may be used. Specific examples thereof are those described in US-A-2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411, 4,004,929, DE-A-2,414,830 and 2,454,329, JP-A-48-59838, JP-A-51-26034, JP-A-48-5055, JP-A-51-146828, JP-A-52-69624, JP-A-52-90932.
  • DIR couplers those which are described in, for example, US-A-3,227,554, 3,617,291, 3,701,783, 3,790,384, 3,632,345, DE-A-2,414,006, 2,454,301, 2,454,329, GB-B-953,454, JP-A-52-69624, JP-A-49-122335, JP-B-51-16141, may be used.
  • Compounds capable of releasing a development inhibitor upon development may be incorporated in the light-sensitive material in addition to the DIR couplers, and those described in, for example, US-A-3,297,445, 3,379,529, DE-A-241,794, JP-A-52-15271, JP-A-53-9116 may be used.
  • couplers may be used in combinations of two or more in one and the same layer, or the same compound may be used in two or more different layers.
  • couplers are added to a photographic emulsion layer in an amount of 2 ⁇ 10 ⁇ 3 mol to 5 ⁇ 10 ⁇ 1 mol, preferably 1 ⁇ 10 ⁇ 2 mol to 5 ⁇ 10 ⁇ 1 mol, per mol of silver contained in the emulsion layer.
  • the couplers can be introduced into silver halide emulsion layers in a known manner described in, for example, US-A-2,322,027.
  • they are dissolved in an alkyl phthalate (e.g., dibutyl phthalate or dioctyl phthalate), a phosphoric ester (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctylbutyl phosphate), a citric acid ester (e.g., tributyl acetylcitrate), a benzoic acid ester (e,g., octyl benzoate), an alkylamide (e.g., diethyllaurylamide), a fatty acid ester (e.g., dibutoxyethyl succinate or dioctyl azelate) or in an organic solvent having a boiling point of about 30°C to about 150°C such as
  • a dispersing process using a polymer as described in JP-B-51-39853 and JP-A-51-59943 may also be employed.
  • couplers having an acid group such as a carboxylic acid or a sulfonic acid group
  • they are introduced into a hydrophilic colloid as an alkaline aqueous solution.
  • the light-sensitive material prepared according to the present invention may contain in its hydrophilic colloidal layer an ultraviolet ray absorbent.
  • an ultraviolet ray absorbent for example, aryl group-substituted benzotriazole compounds (e.g., those described in US-A-3,533,794), 4-thiazolidone compounds (e.g., those described in US-A-3,314,794 and 3,352,681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid esters (e.g., those described in US-A-3,705,805 and 3,707,375), butadiene compounds (e.g., those described in US-A-4,045,229) or benzoxazole compounds (e.g., those described in US-A-3,700,455) may be used.
  • benzotriazole compounds e.g., those described in US-A-3,533,794
  • 4-thiazolidone compounds e.g.
  • Ultraviolet ray-absorbing couplers e.g., ⁇ -naphtholic cyan dye-forming couplers
  • ultraviolet ray-absorbing polymers may also be used. These ultraviolet ray-absorbing agents may be mordanted to a specific layer or layers.
  • the processing temperature is usually selected between 18°C and 50°C. However, temperatures lower than 18°C or higher than 50°C may be employed.
  • Either of development processing forming only silver images (black-and-white photographic processing) or color photographic processing comprising dye image-forming development processing may be used depending upon the end use.
  • Color developer generally comprises an alkaline aqueous solution containing a color developing agent.
  • a color developing agent known primary aromatic amines such as phenylenediamines (for example, 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N- ⁇ -methoxyethylaniline) may be used.
  • the color developer may further contain pH buffers such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or anti-foggants such as bromides, iodides and organic anti-foggants and, if necessary, may contain water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agent, polycarboxylic acid type chelating agents described in US-A-4,083,723, antioxidants described in DE-A-2,622,950.
  • pH buffers such as alkali metal sulfites, carbonates, borates and phosphates
  • development inhibitors or anti-foggants such as
  • Color developed photographic emulsion layers are usually bleached. Bleaching may be conducted separately or simultaneously with fixing.
  • bleaching agents compounds of polyvalent metals such as iron(III), cobalt(III), chromium(VI), copper(II), etc., peracids, quinones, nitroso compounds are used.
  • ferricyanides, dichromates, organic complex salts of iron(III) or cobalt(III) such as complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid) or organic acids (e.g., citric acid, tartaric acid, malic acid); persulfates and permanganates; nitrosophenol may be used.
  • aminopolycarboxylic acids e.g., ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid
  • organic acids e.g., citric acid, tartaric acid, malic acid
  • persulfates and permanganates nitrosophenol
  • Couplers of the present invention show a large color-forming ability even in a bleaching solution or bleach-fixing solution containing iron(III) sodium ethylenediaminetetraacetate or iron(III) ammonium ethylenediaminetetraacetate, thus being advantageous in this point as well.
  • Iron(III) ethylenediaminetetraacetate complex salts are useful in both an independent bleaching solution and a monobath bleach-fixing solution.
  • bleaching or bleach-fixing solution may be added various additives such as bleaching accelerators described in US-A-3,042,520, 3,241,966, JP-B-45-8506, JP-B-45-8836 and thiol compounds described in JP-A-53-65732.
  • copolymerized PET was obtained after the lapse of 3 hours from the start of the reduction of pressure.
  • the intrinsic viscosity of the copolymerized PET was 0.65 measured in o-chlorophenol at 25°C.
  • the resulting copolymerized PET was dried at 130°C for 5 hours, then melt-extruded at 280°C to obtain an unstretched film.
  • the film was then successively stretched in a longitudinal direction at 90°C with a stretching ratio of 3.5 times and then in a transverse direction at 95°C with a stretching ratio of 3.7 times, and heat-set at 200°C for 5 seconds to obtain a 50 »m thick biaxially stretched film.
  • This film had a haze of 1.2%, a breaking strength of 12 kg/mm, and an initial modulus of 340 kg/mm, and had good transparency and mechanical properties.
  • Haze of a sample film was measured according to ASTM D1003-52 after a heat treatment of the film at a temperature of 150°C for 10 minutes.
  • a sample of 10 mm in width and 100 mm in length was subjected to measurement according to JIS Z1702-1976 employing a pulling rate of 300 mm/min for measuring breaking strength and 20 mm/min for measuring initial modulus.
  • polyester film (50 »m thick) of the present invention prepared as described above, a commercially available PET film (50 »m thick) and a commercially available TAC film (125 »m thick) were subjected to measurement of water content according to the method of the present invention.
  • a sample film of 12 cm ⁇ 35 cm in size was wound around a core of 10 mm in diameter and was subjected to treatment at 60°C ⁇ 30% RH ⁇ 72 hr. Then, the film was unwound from the core, dipped in 40°C distilled water for 15 minutes, and dried for 3 minutes in a 55°C air thermostatic chamber while applying a load of 50 g. The length of the thus-treated sample was measured in a perpendicularly suspended state to evaluate the degree of restoration to the original length of 12 cm.
  • polyester film in accordance with the present invention having a water content of 0.7 wt% shows an extremely large curl-extinguishing ratio.
  • a subbing layer of the following formulation was coated on each of the aforesaid polyester film and commercially available PET film after corona discharge treatment of both sides of them.
  • the corona discharge treatment was conducted to a degree of 0.02 KVA ⁇ min/m2.
  • a backing layer of the following formulation was coated on one side of the subbed polyester films.
  • the reddish brown colloidal precipitate was separated by centrifugal separation. In order to remove excess ions, water was added to the precipitate, followed by centrifugal separation to wash with water. This washing procedure was repeated 3 times to remove excess ions.
  • a mixture of 40 parts by weight of the above-described fine powder and 60 parts by weight of water was adjusted to 7.0 in pH and, after being roughly dispersed by a stirrer, the mixture was dispersed by a horizontal sand mill (trade name: Dyno mill made by WILLY A. BACHOFEN AG) until a residential time became 30 minutes.
  • a horizontal sand mill trade name: Dyno mill made by WILLY A. BACHOFEN AG
  • Formulation (A) shown below was coated in a dry thickness of 0.3 »m, and dried at 130°C for 30 seconds.
  • Coating Solution (B) shown below was coated in a dry thickness of 0.1 »m and dried at 130°C for 2 minutes.
  • Photographic layers as described below were provided on the side opposite to the backing layer-coated side of the PET film used in the present invention and the commercially available PET film.
  • the thus-obtained color negative film was cut into a 35 mm size, and was loaded in a cartridge. After leaving it for 10 days at 40°C, photographing was conducted using an ordinary camera, followed by development processing the film as follows.
  • Processing solutions used have the following formulations.
  • the curling state after development processing was as follows. Light-sensitive materials containing a commercially available PET film as a support failed to extinguish curling properties, whereas light-sensitive materials containing polyester film of the present invention scarcely curled.
  • the light-sensitive material of the present invention contains as a support a polyester film with an excellent mechanical strength, and enables removal of curling properties while maintaining the mechanical properties.
  • a 50 »m thick biaxially stretched polyester film having an intrinsic viscosity of 0.67 was prepared in the same manner as described in Example 1 except that 10 parts by weight of polyethylene glycol having a molecular weight of 4,000 were used in place of the same amount of dimethyl adipate.
  • the resulting film had a haze of 4.5%, a breaking strength of 8 kg/mm2, an initial modulus of 320 kg/mm2, and very poor transparency.
  • this film was not subjected to a heat treatment for the measurement of haze, it had a high transparency and had a haze of 2.0%.
  • a light-sensitive material was prepared in the same manner as described in Example 1 using the biaxially stretched polyester film obtained above. After development treatment, the exposed part of the film became opaque and developed images were not sharp. It is clear from the above that the polyester film prepared in Comparative Example 1 above is not useful as a support for a light-sensitive material.
  • the light-sensitive materials of the present invention have excellent mechanical properties and enable easy extinguishing of curling, they permit a marked reduction in the thickness of the support even when used as roll films and therefore render the size of the cartridge compact or, in using the same cartridge, enable loading of longer film.
  • the polyester film of the present invention can be produced at a low casting temperature and is not broken upon stretching and, in spite of its high water content, it maintains the essential merits of polyester film.

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Claims (13)

  1. Photographisches lichtempfindliches Material, umfassend einen Polyesterfilmträger mit wenigstens einer darauf angeordneten lichtempfindlichen Silberhalogenidemulsionsschicht, wobei der Polyesterfilm einen Schleier von bis zu 3%, einen Wassergehalt von 0,5 Gew.-% bis 5,0 Gew.-%, ein Kräusel-Löschverhältnis von 50% oder mehr besitzt und als vorherrschende Bestandteile eine Terephthalsäurekomponente und eine Glykolkomponente besitzt, wobei der Polyesterfilm weiterhin eine aliphatische Dicarbonsäurekomponente mit 4 bis 20 Kohlenstoffatomen als Copolymerisationskomponente in einer Menge von 3 bis 25 Mol%, bezogen auf die Terephthalsäurekomponente, besitzt, worin der Schleier im Einklang mit ASTM D1003-52 nach einer Wärmebehandlung des Films bei einer Temperatur von 150°C für 10 Minuten gemessen wird, und der Wassergehalt gemessen wird, nachdem zuerst der Film unter den Bedingungen von 23°C und 30% RH für 3 Stunden auf Feuchtigkeit eingestellt worden ist, und als nächstes der Film in destilliertes Wasser bei 23°C für 15 Minuten eingetaucht wird und anschließend der Wassergehalt unter Verwendung einer Mikrofeuchtigkeitsmeßvorrichtung bei einer Trocknungstemperatur von 150°C gemessen wird, und das Kräusel-Löschverhältnis gemessen wird, nachdem zuerst der Film in destilliertes Wasser bei 40°C für 15 Minuten eingetaucht worden ist und anschließend für 3 Minuten in Luft in einer bei 55°C gehaltenen thermostatischen Kammer unter Anwendung einer Belastung von 50 g getrocknet worden ist.
  2. Photographisches lichtempfindliches Material nach Anspruch 1, worin der Polyesterfilm ein Polyesterfilm ist, enthaltend eine aromatische Dicarbonsäure mit einer Metallsulfonatgruppe als eine Copolymerisationskomponente und eine Bruchfestigkeit von 8 bis 25 kg/mm² und einem anfänglichen Modul von 200 bis 500 kg/mm² besitzt.
  3. Photographisches lichtempfindliches Material nach Anspruch 1 oder 2, worin der Polyesterfilm ein copolymerisierter Polyethylenterephthalatfilm ist.
  4. Photographisches lichtempfindliches Material nach Anspruch 2, worin die aromatische Dicarbonsäure mit einer Metallsulfonatgruppe ausgewählt ist aus der Gruppe, bestehend aus 5-Natriumsulfoisophthalsäure, 5-Kaliumsulfoisophthalsäure, 5-Lithiumsulfoisophthalsäure, 2-Natriumsulfoterephthalsäure, 2-Kaliumsulfoterephthalsäure, 2-Lithiumsulfoterephthalsäure, 4-Natriumsulfophthalsäure, 4-Kaliumsulfophthalsäure, 4-Lithiumsulfophthalsäure, 4-natriumsulfo-2,6-naphthalindicarbonsäure, 4-Kaliumsulfo-2,6-naphthalindicarbonsäure und 4-Lithiumsulfo-2,6-naphthalindicarbonsäure.
  5. Photographisches lichtempfindliches Material nach Anspruch 2, worin der Polyesterfilm hauptsächlich Terephthalsäure als Dicarbonsäurekomponente umfaßt, und die Copolymerisationsmenge der aromatischen Dicarbonsäurekomponente mit einer Metallsulfonatgruppe 2 bis 15 Mol%, bezogen auf die Terephthalsäurekomponente, beträgt.
  6. Photographisches lichtempfindliches Material nach Anspruch 1, worin die aliphatische Dicarbonsäurekomponente ausgewählt ist aus der Gruppe, bestehend aus Succinsäure, Adipinsäure und Sebacinsäure.
  7. Photographisches lichtempfindliches Material nach Anspruch 1, worin ein Polyalkylenglykol als eine zusätzliche copolymerisierbare Komponente verwendet wird.
  8. Photographisches lichtempfindliches Material nach Anspruch 3, worin der Polyesterfilm einen Farbstoff enthält.
  9. Photographisches lichtempfindliches Material nach Anspruch 3, worin der Polyesterfilm eine Unterschicht auf seiner Oberfläche trägt.
  10. Photographisches lichtempfindliches Material nach Anspruch 1, worin das lichtempfindliche Material ein Rollenfilm ist.
  11. Photographisches lichtempfindliches Material nach Anspruch 1, worin der Polyesterfilm ein Kräusel-Löschverhältnis von 80% oder mehr besitzt.
  12. Photographisches lichtempfindliches Material nach Anspruch 1 oder 2, worin der Polyesterfilm eine Dicke von 25 bis 250 »m besitzt.
  13. Photographisches lichtempfindliches Material nach Anspruch 12, worin der Polyesterfilm eine Dicke von 40 bis 150 »m besitzt.
EP19890105268 1988-03-25 1989-03-23 Photographisches lichtempfindliches Material mit Polyesterträger Expired - Lifetime EP0334367B1 (de)

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JPH0293641A (ja) * 1988-09-30 1990-04-04 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JP2526282B2 (ja) * 1989-01-06 1996-08-21 チッソ株式会社 大きな屈折率異方性を有する新規な液晶化合物
EP0476535B1 (de) * 1990-09-14 1997-08-06 Fuji Photo Film Co., Ltd. Photographisches Material
US5225319A (en) * 1990-11-07 1993-07-06 Konica Corporation Light-sensitive silver halide photographic material
US5215825A (en) * 1990-12-21 1993-06-01 Toray Industries, Inc. Polyester film and photosensitive material
EP0496346A1 (de) * 1991-01-21 1992-07-29 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial
JPH05323484A (ja) * 1991-01-21 1993-12-07 Fuji Photo Film Co Ltd 磁気記録要素を有するハロゲン化銀写真感光材料
US5138024A (en) * 1991-01-25 1992-08-11 Eastman Kodak Company Modified polyester useful as photographic roll film support
JP2903265B2 (ja) * 1991-06-12 1999-06-07 コニカ株式会社 ハロゲン化銀写真感光材料
JPH05134332A (ja) * 1991-11-14 1993-05-28 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
EP0545439A1 (de) * 1991-12-05 1993-06-09 Konica Corporation Träger für photographisches Material und lichtempfindliches, photographisches Silberhalogenidmaterial unter Verwendung desselben
EP0568285A1 (de) * 1992-05-01 1993-11-03 Konica Corporation Verarbeitungsverfahren für lichtempfindliches Silberhalogenid-Farbmaterial
US5372925A (en) * 1992-05-29 1994-12-13 Konica Corporation Multilayer polyester support of photographic material
JPH0695313A (ja) * 1992-09-16 1994-04-08 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5462824A (en) * 1992-12-03 1995-10-31 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5411843A (en) * 1993-05-24 1995-05-02 Agfa-Gevaert, N.V. Photographic material comprising a copolyester support
DE69412239T2 (de) * 1993-12-07 1999-04-29 Teijin Ltd., Osaka Laminierter schichtträger für photographischen film
TW346555B (en) * 1994-04-19 1998-12-01 Teijin Ltd Base film for photographic film
TW434453B (en) * 1996-11-14 2001-05-16 Teijin Ltd Base film for photographic films
TW458999B (en) * 1997-05-06 2001-10-11 Teijin Ltd Biaxially oriented film made of polyethylene napthalate copolymer
TW460380B (en) * 1997-10-29 2001-10-21 Teijin Ltd Biaxially oriented film formed from polythylene naphthalate copolymer
US6511738B2 (en) 2000-01-31 2003-01-28 Konica Corporation Support for rolled light-sensitive photographic material

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JPS5933894B2 (ja) * 1977-02-10 1984-08-18 東レ株式会社 写真フイルム
US4217441A (en) * 1977-04-19 1980-08-12 E. I. Du Pont De Nemours And Company Modified polyester films
JPS5728336A (en) * 1980-07-26 1982-02-16 Mitsubishi Electric Corp Forming method for electrode of semiconductor device
JPS57185345A (en) * 1981-05-08 1982-11-15 Diafoil Co Ltd Production of polyester film
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

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