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

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.
• U.S. Patents 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.
• 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, and the polyester film has a haze of up to 3% and a water content of not less than 0.5 wt%.
• 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 micro-moisture meter (for example, model CA-02, made by Mitsubishi Chemical Industries, Ltd.) at a drying temperature of 150°C.
• a micro-moisture meter for example, model CA-02, made by Mitsubishi Chemical Industries, Ltd.
• the polyester film in accordance with the present invention is characterized in that the water content measured in the above-described manner is not less than 0.5 wt% and preferably is from 0.6 to 5.0 wt%.
• the water content is less than 0.5 wt%, curling tendency-extinguishing properties after development processing are not improved, whereas if the water content is too large, dimensional stability is deteriorated due to absorption of moisture.
• the polyester film of the present invention has a curl-extinguishing ratio of 50% or more and preferably 80% or more.
• polyester means a polyester containing as predominant constituents an aromatic dibasic acid and a glycol.
• dibasic acid include terephthalic acid and isophthalic acid
• glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanediol, diethylene glycol, etc.
• 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.
• Copolymerization of an aliphatic dicarboxylic acid component containing 4 to 20 carbon atoms in the copolymerized PET film is preferable 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, etc., with adipic acid being particularly preferable.
• the copolymerization proportion of the aliphatic dicarboxylic acid component containing 4 to 20 carbon atoms is preferably about 3 to 25 mol%, particu­larly preferably about 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 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, etc.
• 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.
• copolymerized PET can be obtained by directly subjecting the dibasic acid component and the glycol component to an esterification reaction at a temperature of about 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 about 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 about 200°C to 300°C under a pressure gradually reduced to about 1 Torr to remove excess glycol component.
• an ester interchange reaction catalyst or a polymerization reaction catalyst described in U.S. Patents 2,647,885 and 2,739,957, British Patents 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 of 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 of the present invention is characterized in its 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 preferably 50% or more, particularly 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 thermo­ static 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 of 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 of 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 of 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 of 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, etc.
• 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, J
• 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, U.S. Patents 2,992,108 and 3,206,312, JP-A-48-87826, JP-B-49-11567, JP-B-49-11568, JP-A-55-70837, etc.
• 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 U.S. Patent 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 U.S. Patent 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, etc., for ZnO; Nb, Ta, etc., for TiO2; and Sb, Nb, halogen atoms, etc., 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), etc. 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, etc., 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, etc.; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc.; sugar derivatives such as sodium alginate, starch derivative, etc.; 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, etc.) 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, vinyl­sulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds or the like can be used. Specific examples thereof are described in U.S. Patents 2,614,928, 3,123,945, 3,186,846, 3,312,553, British Patents 861,414, 1,033,189, and 1,005,784, JP-B-42-26845, etc.
• 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 or the like 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 or the like are preferable. Examples of these are described in U.S. Patents 2,763,625, 2,831,767, 2,956,884, etc.
• Typical synthetic high molecular weight substances are those described in, for example, West German OLS 2,312,708, U.S. Patents 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), etc.); mercaptopyrimidines; mercapto­triazines; thioketo compounds (e.g., oxazolinethione, etc.); azaindenes
• azoles e.g., benzothi
• 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.
• a polyalkylene oxide or its ether, ester or amide derivative a thioether compound, a thiomorpholine, a quaternary ammonium salt compound, a
• the photographic emulsion used in the present invention may be spectrally sensitized with methine dyes, or the like.
• Suitable dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, etc.
• 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, etc.; nuclei wherein an alicyclic hydrocarbon ring or rings are fused to these nuclei; and 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,
• 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, a thiobarbituric acid nucleus, or the like.
• 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, a thiobarbituric acid nucleus
• Useful sensitizing dyes are described in, for example, German Patent 929,080, U.S. Patents 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, British Patent 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 U.S. Patents 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, British Patents 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 U.S. Patents 2,933,390 and 3,635,721
• aromatic organic acid-formaldehyde condensates for example, those described in U.S. Patent 3,743,510
• cadmium salts for example, those described in U.S. Patent 3,743,510
• cadmium salts for example, those described in U.S. Patent 3,743,510
• cadmium salts for example, those described in U.S. Patent 3,743,510
• cadmium salts for example, those described in U.S. Patent 3,743,510
• cadmium salts for example, those described in U.S. Patent 3,743,510
• cadmium salts for example, those described in
• 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.
• oxonol dyes, hemioxonol dyes, and merocyanine dyes are useful.
• Specific examples of usable dyes are described in British Patents 584,609 and 1,177,429, JP-A-48-85130, JP-A-49-99620, JP-A-49-114420, JP-A-52-108115, U.S.
• 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 U.S. Patents 2,632,701, 3,269,840, 3,359,102, British Patents 852,075 and 1,319,763.
• the following known dye stabilizers can be used in combina­tion.
• 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 U.S. Patents 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, British Patent 1,363,921, etc., gallic acid derivatives described in U.S. Patents 3,457,079, 3,069,262, etc., p-alkoxyphenols described in U.S.
• the light-sensitive material prepared by the present invention may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc., as color fog preventing agents. Specific examples thereof are described in U.S. Patents 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 U.S.
• magenta color-forming couplers pyrazolone type compounds, indazolone type compounds, cyanoacetyl compounds, etc., may be used, with pyrazolone type compounds being particularly advantageous. Specific examples of usable magenta color-forming couplers are described in U.S.
• cyan color-forming couplers phenolic compounds, naphtholic compounds, etc.
• phenolic compounds, naphtholic compounds, etc. may be used. Specific examples thereof are those described in U.S. Patents 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, West German patents (OLS) 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, etc.
• DIR couplers those which are described in, for example, U.S. Patents 3,227,554, 3,617,291, 3,701,783, 3,790,384, 3,632,345, West German patents (OLS) 2,414,006, 2,454,301, 2,454,329, British Patent 953,454, JP-A-52-69624, JP-A-49-122335, JP-B-51-16141, etc., 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, U.S. Patents 3,297,445, 3,379,529, West German Patent (OLS) 241,794, JP-A-52-15271, JP-A-53-9116, etc., 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 x 10 ⁇ 3 mol to 5 x 10 ⁇ 1 mol, preferably 1 x 10 ⁇ 2 mol to 5 x 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, U.S. Patent 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°
• 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 U.S. Patent 3,533,794), 4-­thiazolidone compounds (e.g., those described in U.S. Patents 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 U.S. Patents 3,705,805 and 3,707,375), butadiene compounds (e.g., those described in U.S.
• Patent 4,045,229) or benzoxazole compounds e.g., those described in U.S. Patent 3,700,455 may be used. Further, those which are described in U.S. Patent 3,499,762 and JP-A-54-48535 may be used.
• 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.
• any of known processes may be used.
• 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.
• 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, etc.) 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 U.S. Patent 4,083,723, antioxidants described in West German Patent (OLS) 2,622,950, and the like.
• pH buffers such as alkali metal sulfites, carbonates, borates and phosphates
• 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, etc., 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, etc.); persulfates and permanganates; nitrosophenol; etc., 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, etc.
• persulfates and permanganates nitrosophenol; etc.
• 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 U.S. Patents 3,042,520, 3,241,966, JP-B-45-­8506, JP-B-45-8836, etc., 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.
• Gelatin 3 g Distilled Water 250 cc Sodium-sulfo-di-2-ethylhexyl-succinate 0.05 g Formaldehyde 0.02 g
• 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 of the present invention and the commercially available PET film.
• a silver bromoiodide emulsion containing 6 mol% iodide (average grain size: 0.6 ⁇ m; containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) was prepared in an ordinary manner.
• To 1 kg of this emulsion was added 180 cc of a 0.1 wt% methanol solution of anhydro-5,5′-dichloro-9-ethyl-3,3,-di(3-sulfopropyl)­thiacarbocyanine hydroxide pyridinium salt as a red-­sensitive sensitizer.
• Second Layer Red-Sensitive Silver Halide Middle Sensitive Layer
• a silver bromoiodide emulsion containing 6 mol% iodide (average grain size: 0.6 ⁇ m; containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) was prepared in a conventional manner. To 1 kg of this emulsion was added 200 cc of a 0.1 wt% methanol solution of 3,3′-di(3-sulfoethyl)-9-ethylbenzoxacarbocyanine pyridinium salt as a green-sensitive sensitizing agent.
• Emulsification was conducted in the same manner as with Emulsion (3).
• a silver bromoiodide emulsion containing 5 mol% of iodide (average grain size: 0.9 ⁇ m; containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) was prepared in a conventional manner. To 1 kg of this emulsion was added 150 cc of a methanol solution of the green-sensitive sensitizer shown in (2-a). Then, 20 cc of a 5 wt% aqueous solution of 5-methyl-7-hydroxy-2,3,4-­triazaindolizine was added thereto. Further, 285 g of the above-described Emulsion (3) and 15 g of the above-­described Emulsion (4) were added thereto.
• a silver bromoiodide emulsion containing 6 mol% iodide (average grain size: 1.1 ⁇ m; 50 wt% of the grains based on the whole grains having a grain size of 1.0 ⁇ m or more; containing 100 g of silver halide and 70 g of gelatin per kg of emulsion) was prepared in a conven­tional manner.
• To 1 kg of this emulsion was added 80 cc of a methanol solution of the green-sensitive sensitizing agent shown in (2-a). Then, 20 cc of a 5 wt% aqueous solution of 5-methyl-7-hydroxy-2,3,4-triazaindolizine was added thereto and, further, 200 g of Emulsion (3) was added thereto.
• Eighth Layer Yellow Filter Layer (dry thickness: 1.2 ⁇ m) Comprising Yellow Colloidal Silver
• a silver bromoiodide emulsion containing 5 mol% iodide (average grain size: 0.6 ⁇ m; containing 100 g of silver halide and 70 g of gelatin per kg of the emulsion) was prepared in a conventional manner. To 1 kg of this emulsion were added 20 cc of a 5 wt% aqueous solution of 5-methyl-7-hydroxy-2,3,4-triazaindolizine and 600 g of Yellow Coupler Emulsion (5) of the following formulation.
• first layer 1.0 g/m2
• second layer 0.8 g/m2
• third layer 1.2 g/m2
• fifth layer 1.2 g/m2
• sixth layer 1.0 g/m2
• seventh layer 1.2 g/m2
• ninth layer 0.6 g/m2
• tenth layer 0.6 g/m2
• eleventh layer 0.6 g/m2
• 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 was 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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• 1988
  • 1988-03-25 JP JP63071308A patent/JP2565370B2/ja not_active Expired - Lifetime
• 1989
  • 1989-03-22 CA CA 594515 patent/CA1338693C/en not_active Expired - Fee Related
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