EP0588331B1 - Matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0588331B1
EP0588331B1 EP19930114872 EP93114872A EP0588331B1 EP 0588331 B1 EP0588331 B1 EP 0588331B1 EP 19930114872 EP19930114872 EP 19930114872 EP 93114872 A EP93114872 A EP 93114872A EP 0588331 B1 EP0588331 B1 EP 0588331B1
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Prior art keywords
light
layer
film
group
silver halide
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EP19930114872
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German (de)
English (en)
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EP0588331A1 (fr
Inventor
Shinpei C/O Fuji Photo Film Co. Ltd. Ikenoue
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • 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
    • G03C1/765—Photosensitive materials characterised by the base or auxiliary layers characterised by the shape of the base, e.g. arrangement of perforations, jags
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/81—Photosensitive materials characterised by the base or auxiliary layers characterised by anticoiling means
    • 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
    • G03C2200/00—Details
    • G03C2200/10—Advanced photographic system

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material to be used as a color photographic film of a format different from conventional formats, in which image qualities, particularly sharpness and color reproducibility are improved and the area of an imaging area and the number of perforations are specified.
  • a camera having a zoom lens or a bifocal lens is increased in size with the increase in focal length on the telephoto side, resulting in a poor portability.
  • miniaturization of the camera is given priority, on the other hand, no sufficient telephoto effect can be imparted to the camera.
  • U.S. Patents 3,490,844, 4,583,831, and 4,650,304 have proposed techniques of so-called pseudo zooming by focusing attention on the advance in performance of recent color negative films.
  • this pseudo zooming technique information about the focal length of a lens, which is input to a film during photographing by some means, is detected in the stage of printing to enlarge portions of an imaging area of a negative film, thereby obtaining the telephoto effect.
  • Miniaturization of a lens can be expected by the use of the pseudo zooming technique because the focal length of the lens can be shortened by this technique.
  • the technique requires a lens with an image circle corresponding to the 135 format and also makes it difficult to realize a camera much more compact than current 135-format cameras because of the use of a cartridge corresponding to the 135 format.
  • the pseudo zooming technique is also unpreferable in terms of resource saving because the ratio of an effective area of an imaging area used in formation of prints to an overall film area is reduced. Furthermore, a variation in image quality between prints obtained from the same film is one of complaints of users.
  • DIR couplers development inhibitor releasing couplers
  • DIR couplers development inhibitor releasing couplers
  • DIR couplers have an effect of improving the sharpness of a color negative film.
  • These couplers are described in, e.g., the patents described in Research Disclosure (RD) No. 17643, items VII to F, JP-A-57-151944 ("JP-A” means Published Unexamined Japanese Patent Application), JP-A-57-154234, JP-A-60-184248, JP-A-60-37346, and U.S. Patent 4,248,962.
  • JP-A means Published Unexamined Japanese Patent Application
  • JP-A-57-154234 JP-A-60-184248
  • JP-A-60-37346 JP-A-60-37346
  • U.S. Patent 4,248,962 U.S. Patent 4,248,962.
  • the effect of these couplers is still unsatisfactory for small-format color negative products which requires larger print magnifications
  • each of JP-A-2-273743 and JP-A-2-273744 discloses a color negative film set in a cartridge, which contains a compound represented by Formula (A) below and releasing a precursor of a development inhibitor, and in which the effective area and the aspect ratio (the ratio of the lateral length to the longitudinal length) of an imaging area of each frame to be exposed are defined:
  • Formula (A) A-(Time) n -W wherein A represents a group capable of releasing (Time) n -W upon reacting with the oxidized form of a color developing agent, Time represents a timing group, W represents a group which exhibits a development inhibiting effect after released from (Time) n -W, and n represents 1, 2, or 3.
  • JP-A-3-078742 discloses a photographic film package in which a color negative film containing a compound which is represented by Formula (A) above and releases a precursor of a development inhibitor is packed in a flatness holding cartridge.
  • TAC cellulose triacetate
  • This TAC base has no optical anisotropy and hence has a high transparency.
  • the TAC base also has an excellent property of eliminating curling once formed after development because it has a high water absorption.
  • This high water absorption leads to a high humidity dependency, with the result that the state of curling at photographing changes in accordance with the humidity at which the film is stored in the form of a roll. This gives rise to a serious problem of inability to obtain a constant image quality.
  • the TAC base also has a drawback of a low dynamic strength.
  • the object of the present invention to provide a silver halide color photographic light-sensitive material which is totally improved in image qualities, particularly sharpness and color reproducibility by taking into account not only light-sensitive layers but also a support constituting the light-sensitive material and the processed form of the material.
  • a silver halide color photographic light-sensitive material having at least one hydrophilic colloid layer containing a compound represented by Formula (A) below, a support comprising a belt-like polyester base, not more than four perforations per frame in one or both of side edge portions of said polyester base, an imaging area of from 3.0 cm 2 to 7.0 cm 2 , and an aspect ratio of the imaging area of from 1.40 to 2.50:
  • Formula (A) A-(Time) n -W wherein A represents a group capable of releasing (Time) n -W upon reacting with an oxidized form of a color developing agent, Time represents a timing group, W represents a group which exhibits a development inhibiting effect after released from (Time) n -W, and n represents 1, 2, or 3.
  • the image qualities, particularly the sharpness and the color reproducibility of the resultant color images are improved, and the support can be made thin. This makes it possible to reduce the area of an imaging area without impairing the image qualities and to decrease the size of a cartridge. Therefore, the silver halide color photographic light-sensitive material of the present invention is useful in miniaturizing cameras.
  • a polyester base used as the support of a silver halide color photographic light-sensitive material according to the present invention will be described first.
  • the method described in JP-A-51-16358, i.e., the method of performing heating at a temperature lower by 30°C to 5°C than the glass transition temperature (Tg) is known.
  • the glass transition temperature is defined as, when a 10-mg portion of a sample film is heated at a rate of 20°C/min in a helium-nitrogen stream by using a differential scanning calorimeter (DSC), an arithmetic mean temperature of a temperature at which an output signal begins to deviate from a base line and a temperature at which it arrives at a new base line. If an endothermic peak appears, however, a temperature indicating the maximum value of this endothermic peak is defined as Tg.
  • DSC differential scanning calorimeter
  • the curl reduction ratio is a value calculated by (true core set curl/absolute core set curl) ⁇ 100.
  • the "core set” is to cause curling by winding a film around a spool, and the “core set curl” means curling caused in the longitudinal direction by the core set.
  • the degree of curling is measured in accordance with Test Method A in ANSI/ASC PH1.
  • the true core set curl is a value calculated by (absolute core set curl) - (controlled core set curl).
  • the absolute core set curl means the core set curl of a photographic film before curling is improved.
  • the controlled core set curl means the core set curl of a photographic film after curling is improved.
  • the heat treatment is preferably performed at temperatures between 50°C and Tg.
  • the effect appears from a treatment time of 0.1 hour or more. Although the effect is enhanced as the treatment time is prolonged, the effect is saturated for a treatment time of 1,500 hours or more.
  • the heat treatment is preferably performed before coating of emulsion layers.
  • polyester preferably has Tg of 90°C or more when these actual use conditions of users are taken into account.
  • Tg 90°C to 200°C.
  • Polyester with a glass transition temperature of 90°C or more which is used as the support in the present invention, can be formed from, e.g., diol and dicarboxylic acid.
  • dicarboxylic acid are terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydro phthalic anhydride, diphenylene-p,p'-dicarboxylic acid, tetrachloro phthalic anhydride, 3,6-endomethylenetetrahydro phthalic anhydride, 1,4-cyclohexanedicarboxylic acid, HOOC-R-SO 2 -R-COOH (R : alkylene with C 3 to C 5 ) and
  • diol examples are ethyleneglycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, and
  • hydroxyl group-containing compound or an acid-containing compound which is either monofunctional or polyfunctional (trifunctional or a higher functionality), may be copolymerized as needed.
  • polyester used in the present invention a compound having both a hydroxyl group and a carboxyl group (or its ester) in its molecule may be copolymerized.
  • polyesters produced by reacting diol with dicarboxylic acid are homopolymers, such as polyethylene, 2,6-dinaphthalate (PEN), polyacrylate (PAr), and polycyclohexanedimethanolterephthalate (PCT), and copolymers produced by using 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), and paraphenylenedicarboxylic acid (PPDC), as dicarboxylic acid, ethyleneglycol (EG), cyclohexanedimethanol (CHDM), neopentylglycol (NPG), bisphenol A (BPA), and biphenol (BP), as diol, and parahydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA), as hydroxycarboxylic acid
  • NDCA 2,6
  • polyesters more preferable polyesters are copolymers, such as a copolymer of naphthalenedicarboxylic acid, terephthalic acid, and ethyleneglycol (the mixing molar ratio of naphthalenedicarboxylic acid to terephthalic acid is preferably 0.3 : 0.7 to 1.0 : 0, and more preferably 0.5 : 0.5 to 0.8 : 0.2), a copolymer of terephthalic acid, ethyleneglycol, and bisphenol A (the mixing molar ratio of ethyleneglycol to bisphenol A is preferably 0.6 : 0.4 to 0 : 1.0, and more preferably 0.5 : 0.5 to 0.1 : 0.9), a copolymer of isophthalic acid, paraphenylenedicarboxylic acid, terephthalic acid, and ethyleneglycol (the molar ratios of isophthalic acid and paraphenylenedicarboxylic acid assuming that the ratio of tere
  • the polyester may also be a polymer blend, such as a polymer blend of PEN and PET (the composition ratio is preferably 0.3 : 0.7 to 1.0 : 0, and more preferably 0.5 : 0.5 to 0.8 : 0.2) and a polymer blend of PET and PAr (the composition ratio is preferably 0.6 : 0.4 to 0 : 1.0, and more preferably 0.5 : 0.5 to 0.1 : 0.9).
  • a polymer blend of PEN and PET the composition ratio is preferably 0.3 : 0.7 to 1.0 : 0, and more preferably 0.5 : 0.5 to 0.8 : 0.2
  • a polymer blend of PET and PAr the composition ratio is preferably 0.6 : 0.4 to 0 : 1.0, and more preferably 0.5 : 0.5 to 0.1 : 0.9.
  • PEN is best balanced and has a high dynamic strength, particularly a high elasticity, and a sufficiently high glass transition point of around 120°C.
  • PEN has a drawback of emitting fluorescence.
  • PCT on the other hand, also has a high dynamic strength and the high glass transition temperature of around 110°C.
  • the crystallization rate of PCT is very high to make formation of transparent films difficult.
  • PAr has the highest glass transition temperature (190°C), of the polymers, but has a drawback of a lower dynamic strength than that of PET. To compensate for these drawbacks, therefore, it is preferable to blend these polymers or use a copolymer of monomers forming these polymers.
  • polyester synthesized in accordance with known polyester manufacturing methods.
  • the synthesis can be performed by esterifying an acid component directly with a glycol component, or, when dialkylester is to be used as an acid component, by transesterifying the acid component with a glycol component and heating the resultant substance under a reduced pressure to remove an excess glycol component.
  • an acid halide may be used as an acid component and be reacted with glycol.
  • transesterification, a catalyst, or a polymerization reaction catalyst may be used, or a heat-resistant stabilizer may be added, if necessary.
  • These polyester synthesizing methods can be performed by making reference to, e.g., Polymer Experiments, Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pages 103 to 136, and “Synthetic Polymer V" (Asakura Shoten, 1971), pages 187 to 286.
  • a preferable average molecular weight of these polyesters ranges between about 10,000 and about 500,000.
  • Polymer blends of the polymers thus obtained can be easily formed in accordance with the methods described in JP-A-49-5482, JP-A-64-4325, JP-A-3-192718, and Research Disclosure Nos. 283,739-41, 284,779-82, and 294,807-14.
  • polyesters has a higher flexural modulus than that of triacetylcellulose, making formation of thin films possible.
  • PEN has the highest flexural modulus, and hence the use of PEN makes a film thickness of 80 ⁇ m possible, whereas the film thickness obtained by TAC is 122 ⁇ m.
  • the thickness of these polymer films is preferably 40 ⁇ m to 300 ⁇ m.
  • No transparent polymer film with a thickness of 40 ⁇ m or less can have a flexural modulus high enough to resist the shrinkage stress of a light-sensitive layer.
  • a film thickness of 300 ⁇ m or more makes the use of a thin spool insignificant.
  • the film thickness is more preferably 40 to 150 ⁇ m, and most preferably 50 to 120 ⁇ m.
  • An ultraviolet absorbent may be incorporated into these polymer films for the purposes of preventing emission of fluorescence and imparting stability with time.
  • This ultraviolet absorbent preferably has no absorption in a visible region, and the addition amount of the ultraviolet absorbent is normally about 0.5 wt% to 20 wt%, preferably 1 wt% to 10 wt% with respect to the weight of a polymer film. If the addition amount is less than 0.5 wt%, the effect of suppressing degradation in ultraviolet rays cannot be expected.
  • the ultraviolet absorbent examples include benzophenone-based ultraviolet absorbents, such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, benzotriazole-based ultraviolet absorbents, such as 2(2'-hydroxy-5'-methylphenyl)benzotriazole, 2(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, and 2(2'-hydroxy-3'-t-butyl-5'-methylphenyl)benzotriazole, and salicylic acid-based ultraviolet absorbents, such as phenyl salicylate and methyl salicylate.
  • benzophenone-based ultraviolet absorbents such as 2,4-dihydroxybenz
  • the refractive index of polyester, especially aromatic polyester is as high as 1.6 to 1.7, whereas that of gelatin which is a main component of light-sensitive layers coated on the support is low, 1.50 to 1.55. Therefore, light incident from a film edge is easily reflected by the interface between the base and an emulsion layer. As a result, a polyester film brings about a so-called light-piping phenomenon.
  • a light-piping preventing method preferred in the present invention is the method using the addition of dyes, in which a film haze is not increased significantly.
  • dyes for use in film dyeing are not particularly limited, gray dyeing is preferred as a tone when general properties of a light-sensitive material are taken into consideration, and a dye having a high heat resistance within the temperature range of manufacture of polyester films and a high miscibility with polyester is preferred.
  • the above object can be achieved by mixing dyes commercially available as dyes for polyester, such as Diaresin (registered trademark) available from Mitshubishi Kasei Corp. or Kayaset (registered trademark) available from NIPPON KAYAKU CO. LTD.
  • dyes commercially available as dyes for polyester such as Diaresin (registered trademark) available from Mitshubishi Kasei Corp. or Kayaset (registered trademark) available from NIPPON KAYAKU CO. LTD.
  • a color density in a visible light region must be at least 0.01 or more, more preferably 0.03 or more when measured by a Macbeth color densitometer.
  • polyester film used in the present invention can be imparted with a lubricating property in accordance with the intended use.
  • lubricating property imparting means is not particularly limited, incorporating an inert inorganic compound or coating a surfactant, for example, is used as a general method.
  • inert inorganic grains examples include SiO 2 , TiO 2 , BaSO 4 , CaCO 3 , talc, and kaoline.
  • inert grains are added to the polyester synthesis reaction system
  • These lubricating property imparting means are not particularly limited as described above. Since, however, the transparency is an important factor of the support for a photographic light-sensitive material, it is preferable to select, as the external grain system, SiO 2 with a refractive index relatively close to that of a polyester film, or to select the internal grain system capable of decreasing the size of grains to be precipitated.
  • a method of stacking a layer imparted with this property is also preferred in order to obtain a higher transparency of a film.
  • a practical example of this means is a co-extrusion process using a plurality of extruders and a feed block or a multi-manifold die.
  • One is a method of performing a surface activating treatment, such as a chemical treatment, a mechanical treatment, a corona discharge treatment, a flame treatment, an ultraviolet treatment, a highfrequency treatment, a glow discharge treatment, an active plasma treatment, a laser treatment, a mixed acid treatment, or an ozone oxidation treatment, and then coating photographic emulsions directly to obtain an adhesive power.
  • a surface activating treatment such as a chemical treatment, a mechanical treatment, a corona discharge treatment, a flame treatment, an ultraviolet treatment, a highfrequency treatment, a glow discharge treatment, an active plasma treatment, a laser treatment, a mixed acid treatment, or an ozone oxidation treatment
  • the other is a method of forming a subbing layer, after performing any of the above surface treatments or without performing any surface treatment, and then coating photographic emulsion layers on this subbing layer (e.g., U.S. Patents 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, 3,143,421, 3,501,301, 3,460,944, and 3,674,531, British Patents 788,365, 804,005, and 891,469, JP-B-48-43122 ("JP-B” means Published Examined Japanese Patent Application), and JP-B-51-446).
  • U.S. Patents 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, 3,143,421, 3,501,301, 3,460,944, and 3,674,531 e.g., U.S. Patents 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, 3,143,421, 3,501,301,
  • any of these surface treatments more or less forms a polar group on the surface of a support that is originally hydrophobic or increases the crosslinking density of the surface. It is considered that the affinity of the surface for a polar group of a component contained in the subbing solution is increased or the fastness of the bonding surface is increased as a consequence. In addition, various improvements are made for the arrangement of the subbing layers.
  • Examples are a so-called multilayer method, in which a layer (to be abbreviated as a first subbing layer hereinafter) which adheres well to a support is formed as a first layer and a hydrophilic resin layer (to be abbreviated as a second subbing layer hereinafter) which adheres well to a photographic layer is formed as a second layer on the first layer, and a single-layer method, in which only one resin layer containing both a hydrophobic group and a hydrophilic group is coated.
  • a layer to be abbreviated as a first subbing layer hereinafter
  • a hydrophilic resin layer to be abbreviated as a second subbing layer hereinafter
  • the corona discharge treatment is well known to those skilled in the art and can be achieved by any conventional method, such as those disclosed in JP-B-48-5043, JP-B-47-51905, JP-A-47-28067, JP-A-49-83767, JP-A-51-41770, and JP-A-51-131576.
  • a discharge frequency is 50 Hz to 5,000 kHz, preferably 5 kHz to several hundred kHz. If the discharge frequency is too low, not only no stable discharge can be obtained but pin holes are formed in an object to be treated, leading to an undesirable result.
  • the treatment intensity for an object to be treated is appropriately 0.001 to 5 KV ⁇ A ⁇ min/m 2 , preferably 0.01 to 1 KV ⁇ A ⁇ min/m 2 .
  • a proper gap clearance between an electrode and a dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0 mm.
  • the glow discharge treatment which is the most effective surface treatment in many cases can be performed by any conventional method, such as those disclosed in JP-B-35-7578, JP-B-36-10336, JP-B-45-22004, JP-B-45-22005, JP-B-45-24040, JP-B-46-43480, U.S. Patents 3,057,792, 3,057,795, 3,179,482, 3,288,638, 3,309,299, 3,424,735, 3,462,335, 3,475,307, and 3,761,299, British Patent 997,093, and JP-A-53-129262.
  • an appropriate pressure of the glow discharge treatment is 0.005 to 20 Torr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treating effect is weakened. If the pressure is too high, an overcurrent flows to allow easy occurrence of sparks. These sparks are dangerous and may destroy an object to be treated. Discharge occurs upon application of a high voltage across one or more pairs of metal plates or metal bars spaced apart from each other in a vacuum tank. This voltage can take various values depending on the composition and the pressure of an atmospheric gas. Within the above-mentioned pressure range, however, a stable steady glow discharge occurs at a voltage of 500 to 5,000 V. A voltage particularly suitable for improvement in adhesive power ranges between 2,000 and 4,000 V.
  • a discharge frequency is appropriately from 0, i.e., DC, to several thousand Hz, preferably 50 Hz to 20 MHz, as can be seen in conventional techniques.
  • a discharge treatment intensity is properly 0.01 to 5 kV ⁇ A ⁇ min/m 2 , preferably 0.15 to 1 kV ⁇ A ⁇ min/m 2 because a desired adhesive power can be obtained.
  • the subbing methods of item (2) will be described below. These methods have been studied well in this field of art.
  • a monomer selected from, e.g., vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride, as well as the characteristics of many polymers, such as polyethyleneimine, an epoxy resin, graft gelatin, and nitrocellulose.
  • the second subbing layer in the multilayer method the characteristics primarily of gelatin have been investigated.
  • a high adhesive power is in many cases achieved by swelling a support to cause interfacial mixing with a subbing hydrophilic polymer.
  • subbing hydrophilic polymer usable in the present invention are a water-soluble polymer, cellulose ester, a latex polymer, and water-soluble polyester.
  • water-soluble polymer examples include gelatin, a gelatin derivative, casein, agar-agar, soda alginate, starch, polyvinyl alcohol, a polyacrylic acid copolymer, and a maleic anhydride copolymer.
  • cellulose ester are a carboxymethylcellulose and hydroxyethylcellulose.
  • the latex polymer examples include a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylic ester-containing copolymer, a vinyl acetate-containing copolymer, and a butadiene-containing copolymer.
  • Gelatin is most preferred of the polymers.
  • Examples of a compound for swelling a support which can be used in the present invention, are 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 can be used in the subbing layer.
  • gelatin hardener examples include chromium salt (e.g., chromium alum), aldehydes (e.g., formaldehyde and glutaraldehyde), isocyanates, an active halogen compound (e.g., 2,4-dichloro-6-hydroxy-S--triazine), and an epichlorohydrin resin.
  • chromium salt e.g., chromium alum
  • aldehydes e.g., formaldehyde and glutaraldehyde
  • isocyanates e.g., an active halogen compound
  • an active halogen compound e.g., 2,4-dichloro-6-hydroxy-S--triazine
  • the subbing layer can contain fine grains of an inorganic substance, such as SiO 2 , TiO 2 , or a matting agent, or fine grains (1 to 10 ⁇ m) of a polymethylmethacrylate copolymer.
  • an inorganic substance such as SiO 2 , TiO 2 , or a matting agent, or fine grains (1 to 10 ⁇ m) of a polymethylmethacrylate copolymer.
  • the subbing solution may contain various additives as needed.
  • the additives are a surfactant, an antistatic agent, an antihalation agent, a coloring dye, a pigment, a coating aid, and an antifoggant.
  • this subbing solution need not contain any etching agent, such as resorcin, chloral hydrate, or chlorophenol. It is, however, also possible to add such etching agents as needed.
  • the subbing solution for use in the present invention can be coated by well-known coating processes, such as a dip coating process, an air knife coating process, a curtain coating process, a roller coating process, a wire bar coating process, a gravure coating process, and the extrusion coating process using a hopper, described in the specification of U.S. Patent 2,681,294. If necessary, it is also possible to coat two or more layers simultaneously in accordance with any of the processes described in the specifications of U.S. Patents 2,761,791, 3,508,947, 2,941,898, and 3,526,528 and the process described in Yuji Harazaki, "Coating Engineering," page 253 (published by Asakura Shoten, 1973).
  • a binder used in the back layer may be either a hydrophobic polymer or a hydrophilic polymer such as used in the subbing layer.
  • the back layer of the light-sensitive material of the present invention may contain, e.g., an antistatic agent, a lubricating agent, a matting agent, a surfactant, and a dye.
  • the antistatic agent usable in the back layer is not particularly limited.
  • an anionic polymer electrolyte as the antistatic agent are polymers containing carboxylic acid, carboxylate, and sulfonate, such as those described in JP-A-48-22017, JP-B-46-24159, JP-A-51-30725, JP-A-51-129216, and JP-A-55-95942.
  • a cationic polymer examples include JP-A-49-121523, JP-A-48-91165, and JP-B-49-24582.
  • the ionic surfactant also involves both anionic and cationic compounds, such as those 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, and JP-A-55-70837.
  • the most preferable substance as the antistatic agent used in the back layer of the present invention is a fine grain of at least one crystalline metal oxide selected from ZnO, TiO 3 , SnO 2 , Al 2 O 3 , In 2 O 3 , SiO 2 , MgO, BaO, and MoO 3 , or a fine grain of a composite oxide of these oxides.
  • the fine grains of the conductive crystalline oxides or their composite oxide used in the present invention have a volume resistivity of 10 7 ⁇ cm or less, more preferably 10 5 ⁇ cm or less and a grain size of 0.01 to 0.7 ⁇ m, most preferably 0.02 to 0.5 ⁇ m.
  • Methods of manufacturing the fine grains of the conductive crystalline metal oxides or their composite oxide used in the present invention are described in detail in JP-A-56-143430 and JP-A-60-258541.
  • Examples of a method that can be performed easily are: 1) a method of forming fine metal oxide grains by calcination and heat-treating the resultant fine grains in the presence of a hetero-atom for improving the conductivity, 2) a method of allowing a hetero-atom for improving the conductivity to be present in the manufacture of fine metal oxide grains performed by calcination and 3) a method of reducing an oxygen concentration in an atmosphere to introduce oxygen defects in the manufacture of fine metal oxide grains performed by calcination.
  • hetero-atom examples include Al and In, for ZnO, Nb and Ta, for TiO 2 , and Sb, Nb, and a halogen element, for SnO 2 .
  • the addition amount of the hetero-atom is preferably 0.01 to 30 mol%, and most preferably 0.1 to 10 mol%.
  • perforations are formed in one or both of side edge portions along the longitudinal direction of a roll-like support. It is also possible to form perforations in only one side edge portion and magnetically or optically record information obtained during the manufacture of a light-sensitive material and information concerning the exposure conditions in photographing in the other side edge portion. When perforations are formed in both side edge portions, the above information can be recorded between these perforations.
  • Figs. 1 to 8 are plan views each showing a part of a film according to the present invention
  • Fig. 9 is a view showing the section in the direction of thickness of the film shown in each of Figs. 1 to 8.
  • a film is a long belt-like product constituted by imaging areas 1 formed through photographing (exposure) and frame portions 2 and 3 formed on both sides of the imaging areas 1 in the widthwise direction of the film.
  • the frame portions 2 and 3 preferably function as information recording portions.
  • optical information recording portions or magnetic recording portions consisting of magnetic layers are formed as the frame portions 2 and 3.
  • a magnetic recording track 4 can be formed in the frame portion 2 along the longitudinal direction of the film F. As shown in Fig. 9, this magnetic recording track 4 is formed by coating a magnetic material 7 on the surface of the film F opposite to the surface on which a hydrophilic colloid layer 8 is formed.
  • the magnetic recording track 4 can also be formed on the same surface as the hydrophilic colloid layer 8.
  • the magnetic recording track 4 is formed in the frame portion 3 or in the both side edge portions (frame portions 2 and 3).
  • specific information of the film, photographing information, and laboratory processing information are magnetically recorded for one film or for each imaging area in the manufacture of the film, in photographing, and in the processing of the film.
  • the specific information of the film includes the name of the manufacturer, the type of the film, the date of manufacture, and the frame number
  • the photographing information includes the data of photographing, the use/nonuse of a flash bulb, a shutter speed, and an f-number
  • the laboratory processing information includes the name of a color laboratory company, the type of color development, the type of a developing machine, the date of processing, the name of a person in charge of processing, and the conditions of exposure for color paper.
  • reading means such as a magnetic head, is brought into contact with the magnetic recording track 4 to extract the information as an electrical signal.
  • Perforations (holes) 5 for feeding or positioning the film inside, e.g., a camera are formed in the frame portion 3.
  • the number of the perforations is preferably as small as possible. Although films are fed by using perforations in currently available cameras, perforations can be decreased in number by using a film feeding mechanism which does not use perforations so that perforations in a number required to position a film in a camera or a printer need only be formed.
  • the number of perforations is one to four, and most preferably one or two per frame (S 1 ). In this case, the frame corresponds to an area A ⁇ B in the film shown in Fig. 2.
  • the perforations 5 are formed in the frame portion 2 or 3 formed in the side edge portion in the widthwise direction of the film F, as shown in Figs. 1, 2, 4, and 6, or in both of the frame portions 2 and 3, as shown in Figs. 3, 5, 7, and 8.
  • the shape of the perforations is not particularly limited.
  • the perforations may take rectangular shapes as shown in Figs. 1, 2, and 4, polygonal shapes such as a hexagon (note that the corners of such a polygonal perforation may be formed by curved lines with a certain predetermined radius of curvature), or circular shapes (which may be an ellipse or other deformed circles) as shown in Figs. 3 and 8.
  • the shapes of these perforations may be either the same, as shown in Figs. 3, 4, and 8, or different, as shown in Figs. 5, 6, and 7.
  • the size of the perforations is also not particularly limited, smaller perforations are preferred in order for the frame portions 2 and 3 described above to function as the information recording portions.
  • an area of an imaging area (an exposure portion in the frame) is set to 3 to 7 cm 2 , most preferably 4.0 to 6.0 cm 2 .
  • the length of the long belt-like film F is 200 cm or less, preferably 180 cm or less, and most preferably 165 cm or less.
  • the lower limit of the length of the film F is 40 cm.
  • the width of the film F is 35 mm or less, preferably 10 to 32 mm, and most preferably 15 to 30 mm.
  • the three aspect ratios are as follows. (1) Low aspect ratio 1.40 to 1.60 (2) Middle aspect ratio 1.70 to 1.90 (3) High aspect ratio 2.00 to 3.00
  • the aspect ratio of the imaging area of the color negative film is set between 1.40 and 2.50, preferably 1.60 and 2.20, and furthermore preferably 1.70 and 1.90.
  • the aspect ratio it is preferable to set the aspect ratio at a value close to the aspect ratio (1.78) of an HDTV because hybridization of a silver salt photographic system and an electronic imaging system can be advanced smoothly. That is, the most preferable aspect ratio is 1.75 to 1.85.
  • the area of one imaging area is 3.0 cm 2 or more in order to maintain the image quality of the print. If, however, the area exceeds that of an imaging area of a current 135-size film, the dimensions of a magazine or a camera are undesirably increased. Therefore, the area of one imaging area is 3.0 to 7.0 cm 2 .
  • the upper limit of the area of an imaging area is preferably as low as possible in order to keep the area of the optical or magnetic information recording portion, and this is also preferable in miniaturizing a magazine for containing the film. It is, however, difficult to bring about the effects of the present invention to thereby achieve the object of the invention if the area of an imaging area is reduced to one-half or less of the current size. For this reason, the area of an imaging area is set between 3.0 and 7.0 cm 2 , preferably 4.0 and 6.0 cm 2 .
  • the ratio (S 2 /S 1 ) of the area (S 2 ) of the imaging area (a ⁇ b) to the area (S 1 ) of one frame (A ⁇ B) is preferably 0.25 to 0.90.
  • the S 2 /S 1 ratio is preferably 0.50 to 0.90, more preferably 0.60 to 0.80, and most preferably 0.65 to 0.75.
  • the above light-sensitive material using the polyester support according to the present invention is preferably used as a color photographic light-sensitive material for photographing, and most preferably color negative photographic light-sensitive material for photographing.
  • a compound represented by Formula (A) used in the present invention will be described below: Formula (A) A-(Time) n -W wherein A represents a group capable of releasing (Time) n -W upon reacting with the oxidized form of a color developing agent, Time represents a-timing group, W represents a group which exhibits a development inhibiting effect after released from (Time) n -W, and n represents an integer of 1, 2, or 3.
  • W examples include a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a tetrazolylseleno group, a benzoxazolylthio group, a tetrazolyl group, a benzotriazolyl group, a triazolyl group, a benzoindazolyl group, and derivatives of these groups. These groups are described in, e.g., U.S.
  • Time examples are a group which uses cleavage of hemiacetal, described in U.S. Patent 4,146,396, 4,652,516, or 4,698,297; a timing group which causes cleavage by using an intramolecular nucleophilic reaction, described in U.S. Patent 4,248,962; a timing group which causes cleavage by using electron transfer, described in U.S. Patent 4,409,323 or 4,421,845; a group which causes hydrolysis of iminoketal, described in U.S. Patent 4,546,073; and a group which causes cleavage by using hydrolysis of ester, described in DE-OS 2,626,317.
  • Time binds to A at a hetero atom, preferably an oxygen atom, a sulfur atom, or a nitrogen atom contained in it.
  • Time is a methyleneoxy group, a 4-methylene-3-pyrazolyloxy group, a 2(or 4)-methylenephenoxy group, a 2-carbonylaminomethylphenoxy group, a carboxyl group, and a carbomethoxy group.
  • n 2 or 3
  • a plurality of Time's may be the same or different.
  • A specifically represents a coupler moiety.
  • Examples of the coupler moiety represented by A are a yellow coupler moiety (e.g., an open-chain ketomethylene type coupler moiety, such as acylacetanilide or malondianilide), a magenta coupler moiety (e.g., a 5-pyrazolone type, pyrazolotriazole type, or pyrazoloimidazole type coupler moiety), a cyan coupler moiety (e.g., a phenol type or naphthol type coupler moiety or an imidazole type coupler moiety described in Published Unexamined European Patent 249,453), and a colorless compound forming coupler moiety (e.g., an indanone type or acetophenone type coupler moiety).
  • the coupler moiety represented by A can also be a heterocyclic coupler moiety described in U.S. Patent 4,315,070, 4,183,752, 4,174,969, 3,961,959, or 4,171,223.
  • a compound represented by Formula (A) is preferably a compound represented by Formula (A1) below:
  • a and W represent the same meanings as those of A and W in a compound represented by Formula (A).
  • X represents an oxygen atom, a sulfur atom, or a substituted imino group. It is preferred that the substituent of X combine with L 1 to form a 5- to 7-membered nitrogen-containing heterocyclic ring (which may have a substituent or may be a condensed ring) together with a nitrogen atom of the imino group.
  • Each of R 1 and R 2 represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, benzyl, dodecyl, and cyclohexyl) with 1 to 36 carbon atoms or an aryl group (e.g., phenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-nitrophenyl, and naphthyl) with 6 to 36 carbon atoms.
  • an alkyl group e.g., methyl, ethyl, benzyl, dodecyl, and cyclohexyl
  • an aryl group e.g., phenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-nitrophenyl, and naphthyl
  • L 1 represents a linking group in which W cleaves from a moiety [-C(R 1 )(R 2 )-W] on the right of L 1 through electron transfer after a bond on the left of L 1 cleaves in a compound represented by Formula (A1).
  • a represents 0, 1, or 2. If a represents 2, two L 1 's may be the same or different.
  • each of V 1 and V 2 represents a nonmetallic atomic group required to form a 5- to 7-membered nitrogen-containing heterocyclic ring (which may have a substituent or may be a condensed ring) together with an atomic group to which it binds
  • V 3 represents a nonmetallic atomic group required to form a 5- to 7-membered heterocyclic ring (which may have a substituent or may be a condensed ring) or a benzene ring (which may have a substituent or may be a condensed ring) together with an atomic group to which it binds
  • R 3 represents a hydrogen atom or a monovalent group.
  • R 3 may combine with V 2 to form a ring.
  • a basic portion of the development inhibitor represented by W is the heterocyclic group or the heterocyclic thio group enumerated above in the description of Formula (A). Examples are as follows.
  • a substituent (contained in the portion of W in Formula (A)) represented by Z represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkaneamide group, an alkeneamide group, an alkoxy group, a sulfonamide group, or an aryl group
  • Y represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group
  • L 2 includes a chemical bond which cleaves in a developing solution. This chemical bond involves examples listed in Table 1 below. These chemical bonds are cleaved by a nucleophilic reagent such as hydroxylamine or hydroxy ion as a component of a color developing solution.
  • Each of m and n represents an integer of 0 to 4.
  • the development inhibiting component represented by W is most preferably the following compound.
  • R 9 represents an alkyl group (e.g., methyl, benzyl, and dodecyl) with 1 to 24 carbon atoms or an aryl group (e.g., phenyl, 4-tetradecyloxyphenyl, 4-methoxyphenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 4-methylphenyl, and 4-nitrophenyl) with 6 to 36 carbon atoms
  • R10 represents a hydrogen atom, an alkyl group (e.g., methyl, ethyl, undecyl) with 1 to 24 carbon atoms, an aryl group (e.g., phenyl and 4-methoxyphenyl) with 8 to 36 carbon atoms, an alkoxy group (e.g., methoxy, e
  • a in Formula (A-V) is preferably a cyan dye forming coupler moiety (e.g., a phenol-based cyan coupler moiety or an ⁇ -naphthol-based cyan coupler moiety).
  • A is most preferably a coupler moiety which flows out into a processing solution during color development as described in The Journal of The Japan Photographic Society Vol. 52 (1989), No. 2, pages 150 to 155 (Kida et al.), or a coupler moiety the dye formed from which loses its color when bleached.
  • Each of R 1 and R 2 is preferably a hydrogen atom
  • R 9 is preferably an aryl group
  • R 10 is preferably an alkyl group.
  • Patent 4,248,962 JP-A-56-114946, JP-A-57-154234, JP-A-58-98728, JP-A-58-209736, JP-A-58-209737, JP-A-58-209738, JP-A-58-209740, JP-A-61-156043, JP-A-61-255342, and JP-A-62-24252.
  • timing DIR compound represented by Formula (A) is contained in at least one of hydrophilic colloid layers.
  • the hydrophilic colloid layers involve layers except the support, the back layer, and the subbing layer described above, i.e., involve both light-sensitive layers and non-light-sensitive layers (e.g., an antihalation layer, interlayers, a yellow filter layer, and protective layers) formed on the surface to be exposed of the support.
  • the timing DIR compound represented by Formula (A) is contained in at least one of these light-sensitive layers and non-light-sensitive layers.
  • the addition amount is 0.01 to 20 mol%, preferably 0.05 to 10 mol%, and more preferably 0.1 to 5 mol% with respect to the amount of a silver halide in that layer.
  • the addition amount is 0.01 to 20 mol%, preferably 0.05 to 10 mol%, and more preferably 0.1 to 5 mol% with respect to the amount of a silver halide in a silver halide emulsion layer closest to that non-light-sensitive layer.
  • the timing DIR compound represented by Formula (A) can be used singly in two or more layers, or two or more types of these compounds can be used together. It is also possible to use this timing DIR compound in combination with other DIR compounds.
  • a given mixing ratio can be taken in accordance with the performance that the light-sensitive material is required to have.
  • the timing DIR compound represented by Formula (A) is used in hydrophilic colloid layers, and is preferably used in a light-sensitive silver halide emulsion layer and/or a layer adjacent to that emulsion layer.
  • the timing DIR compound represented by Formula A has a startling effect of improving the image qualities.
  • the silver halide color photographic light-sensitive material (to be abbreviated simply as a light-sensitive material hereinafter) of the present invention will be described in more detail below.
  • the light-sensitive material of the present invention needs only to have at least one of silver halide emulsion layers, i.e., a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, formed on a support.
  • the number or order of the silver halide emulsion layers and the non-light-sensitive layers are particularly not limited.
  • a typical example is a silver halide photographic light-sensitive material having, on a support, at least one unit light-sensitive layer constituted by a plurality of silver halide emulsion layers which are sensitive to essentially the same color but have different sensitivities or speeds.
  • the unit light-sensitive layer is sensitive to blue, green or red light.
  • the unit light-sensitive layers are generally arranged such that red-, green-, and blue-sensitive layers are formed from a support side in the order named. However, this order may be reversed or a layer having a different color sensitivity may be sandwiched between layers having the same color sensitivity in accordance with the application.
  • Non-light-sensitive layers such as various types of interlayers may be formed between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.
  • the interlayer may contain, e.g., couplers and DIR compounds as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037, and JP-A-61-20038 or a color mixing inhibitor which is normally used.
  • a two-layered structure of high- and low-speed emulsion layers can be preferably used as described in West German Patent 1,121,470 or British Patent 923,045.
  • layers are preferably arranged such that the sensitivity or speed is sequentially decreased toward a support, and a non-light-sensitive layer may be formed between the silver halide emulsion layers.
  • layers may be arranged such that a low-speed emulsion layer is formed remotely from a support and a high-speed layer is formed close to the support.
  • layers may be arranged from the farthest side from a support in an order of low-speed blue-sensitive layer (BL)/high-speed blue-sensitive layer (BH)/high-speed green-sensitive layer (GH)/low-speed green-sensitive layer (GL)/high-speed red-sensitive layer (RH)/low-speed red-sensitive layer (RL), an order of BH/BL/GL/GH/ RH/RL, or an order of BH/BL/GH/GL/RL/RH.
  • BL low-speed blue-sensitive layer
  • BH high-speed blue-sensitive layer
  • GH high-speed green-sensitive layer
  • GL high-speed red-sensitive layer
  • RH red-sensitive layer
  • RL low-speed red-sensitive layer
  • layers may be arranged from the farthest side from a support in an order of blue-sensitive layer/GH/RH/GL/RL.
  • layers may be arranged from the farthest side from a support in an order of blue-sensitive layer/GL/RL/GH/RH.
  • three layers may be arranged such that a silver halide emulsion layer having the highest sensitivity is arranged as an upper layer, a silver halide emulsion layer having sensitivity lower than that of the upper layer is arranged as an intermediate layer, and a silver halide emulsion layer having sensitivity lower than that of the intermediate layer is arranged as a lower layer.
  • three layers having different sensitivities may be arranged such that the sensitivity is sequentially decreased toward the support.
  • these layers may be arranged in an order of medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer from the farthest side from a support in a layer having the same color sensitivity as described in JP-A-59-202464.
  • an order of high-speed emulsion layer/low-speed emulsion layer/medium-speed emulsion layer, or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer may be adopted. Furthermore, the arrangement can be changed as described above even when four or more layers are formed.
  • a donor layer (CL) of an interlayer effect can be arranged directly adjacent to, or close to, a main light-sensitive layer such as BL, GL or RL.
  • the donor layer has a spectral sensitivity distribution which is different from that of the main light-sensitive layer.
  • Donor layers of this type are disclosed in U.S. Patent 4,663,271, U.S. Patent 4,705,744, U.S. Patent 4,707,436, JP-A-62-160448, and JP-A-63-89850.
  • a preferable silver halide contained in photographic emulsion layers of the photographic light-sensitive material of the present invention is silver bromoiodide, silver chloroiodide, or silver chlorobromoiodide containing about 30 mol% or less of silver iodide.
  • the most preferable silver halide is silver bromoiodide or silver chlorobromoiodide containing about 2 mol% to about 10 mol% of silver iodide.
  • Silver halide grains contained in the photographic emulsion may have regular crystals such as cubic, octahedral, or tetradecahedral crystals, irregular crystals such as spherical, or tabular crystals, crystals having defects such as twin planes, or composite shapes thereof.
  • the silver halide may consist of fine grains having a grain size of about 0.2 ⁇ m or less or large grains having a projected-area diameter of up to 10 ⁇ m, and the emulsion may be either a polydisperse emulsion or a monodisperse emulsion.
  • the silver halide photographic emulsion which can be used in the present invention can be prepared by methods described in, for example, Research Disclosure (RD) No. 17643 (December 1978), pp. 22 to 23, "I. Emulsion preparation and types", RD No. 18716 (November 1979), page 648, and RD No. 307105 (November 1989), pp. 863 to 865; P. Glafkides, "Chemie et Phisique Photographique", Paul Montel, 1967; G.F. Duffin, "Photographic Emulsion Chemistry", Focal Press, 1966; and V.L. Zelikman et al., “Making and Coating Photographic Emulsion", Focal Press, 1964.
  • Monodisperse emulsions described in, for example, U.S. Patents 3,574,628 and 3,655,394, and British Patent 1,413,748 are also preferred.
  • tabular grains having an aspect ratio of about 3 or more can be used in the present invention.
  • the tabular grains can be easily prepared by methods described in, e.g., Gutoff, "Photographic Science and Engineering", Vol. 14, PP. 248 to 257 (1970); U.S. Patents 4,434,226; 4,414,310; 4,433,048 and 4,499,520, and British Patent 2,112,157.
  • the crystal structure may be uniform, may have different halogen compositions in the interior and the surface thereof, or may be a layered structure.
  • silver halides having different compositions may be joined by an epitaxial junction, or a compound other than a silver halide such as silver rhodanide or zinc oxide may be joined.
  • a mixture of grains having various types of crystal shapes may be used.
  • the above emulsion may be of any of a surface latent image type in which a latent image is mainly formed on the surface of each grain, an internal latent image type in which a latent image is formed in the interior of each grain, and a type in which a latent image is formed on the surface and in the interior of each grain.
  • the emulsion must be of a negative type.
  • the emulsion is of an internal latent image type, it may be a core/shell internal latent image type emulsion described in JP-A-63-264740. A method of preparing this core/shell internal latent image type emulsion is described in JP-A-59-133542.
  • the thickness of a shell of this emulsion changes in accordance with development or the like, it is preferably 3 to 40 nm, and most preferably, 5 to 20 nm.
  • a silver halide emulsion layer is normally subjected to physical ripening, chemical ripening, and spectral sensitization steps before it is used. Additives for use in these steps are described in RD Nos. 17,643; 18,716 and 307,105 and they are summarized in the table represented later.
  • two or more types of emulsions different in at least one of features such as a grain size, a grain size distribution, a halogen composition, a grain shape, and sensitivity can be mixed and used in the same layer.
  • colloidal silver can be preferably used in a light-sensitive silver halide emulsion layer and/or a substantially non-light-sensitive hydrophilic colloid layer.
  • the internally fogged or surface-fogged silver halide grains are silver halide grains which can be uniformly (non-imagewise) developed despite the presence of a non-exposed portion and exposed portion of the light-sensitive material.
  • a method of preparing the internally fogged or surface-fogged silver halide grain is described in U.S. Patent 4,626,498 or JP-A-59-214852.
  • the silver halides which form the core of the internally fogged or surface-fogged core/shell silver halide grains may be of the same halogen composition or different halogen compositions.
  • Examples of the internally fogged or surface-fogged silver halide are silver chloride, silver bromochloride, silver bromoiodide, and silver bromochloroiodide.
  • the grain size of these fogged silver halide grains is not particularly limited, an average grain size is preferably 0.01 to 0.75 ⁇ m, and most preferably, 0.05 to 0.6 ⁇ m.
  • the grain shape is also not particularly limited, and may be a regular grain shape.
  • the emulsion may be a polydisperse emulsion, it is preferably a monodisperse emulsion (in which at least 95% in weight or number of silver halide grains have a grain size falling within a range of ⁇ 40% of the average grain size).
  • a non-light-sensitive fine grain silver halide is preferably used.
  • the non-light-sensitive fine grain silver halide means silver halide fine grains not sensitive upon imagewise exposure for obtaining a dye image and essentially not developed in development.
  • the non-light-sensitive fine grain silver halide is preferably not fogged beforehand.
  • the fine grain silver halide contains 0 to 100 mol% of silver bromide and may contain silver chloride and/or silver iodide as needed. Preferably, the fine grain silver halide contains 0.5 to 10 mol% of silver iodide.
  • An average grain size (an average value of equivalent-circle diameters of projected areas) of the fine grain silver halide is preferably 0.01 to 0.5 ⁇ m, and more preferably, 0.02 to 0.2 ⁇ m.
  • the fine grain silver halide can be prepared by a method similar to a method of preparing normal light-sensitive silver halide. In this preparation, the surface of a silver halide grain need not be subjected to either chemical sensitization or spectral sensitization. However, before the silver halide grains are added to a coating solution, a known stabilizer such as a triazole compound, an azaindene compound, a benzothiazolium compound, a mercapto compound, or a zinc compound is preferably added.
  • This fine grain silver halide grain-containing layer preferably contains colloidal silver.
  • a coating silver amount of the light-sensitive material of the present invention is preferably 6.0 g/m 2 or less, and most preferably, 4.5 g/m 2 or less.
  • the light-sensitive material of the present invention preferably contains a mercapto compound described in U.S. Patents 4,740,454 and 4,788,132, JP-A-62-18539, and JP-A-1-283551.
  • the light-sensitive material of the present invention preferably contains compounds which release, regardless of a developed silver amount produced by the development, a fogging agent, a development accelerator, a silver halide solvent, or precursors thereof, described in JP-A-1-106052.
  • the light-sensitive material of the present invention preferably contains dyes dispersed by methods described in International Disclosure WO 88/04794 and JP-A-1-502912 or dyes described in European Patent 317,308A, U.S. Patent 4,420,555, and JP-A-1-259358.
  • yellow couplers are described in, e.g., U.S. Patents 3,933,501; 4,022,620; 4,326,024; 4,401,752 and 4,248,961, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968; 4,314,023 and 4,511,649, and European Patents 249,473A, 447,969A and 482,552A.
  • magenta coupler examples are preferably 5-pyrazolone type and pyrazoloazole type compounds, and more preferably, compounds described in, for example, U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, RD No. 24220 (June 1984), JP-A-60-33552, RD No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Patents 4,500,630; 4,540,654 and 4,556,630, and WO No. 88/04795.
  • Examples of a cyan coupler are phenol type and naphthol type ones. Of these, preferable are those described in, for example, U.S. Patents 4,052,212; 4,146,396; 4,228,233; 4,296,200; 2,369,929; 2,801,171; 2,772,162; 2,895,826; 3,772,002; 3,758,308; 4,343,011 and 4,327,173, West German Patent Laid-open Application 3,329,729, European Patents 121,365A and 249,453A, U.S.
  • the pyrazoloazole type couplers disclosed in JP-A-64-553, JP-A-64-554, JP-A-64-555 and JP-A-64-556, and imidazole type couplers disclosed in U.S. Patent 4,818,672 can be used as cyan coupler in the present invention.
  • Typical examples of a polymerized dye-forming coupler are described in, e.g., U.S. Patents 3,451,820; 4,080,211; 4,367,282; 4,409,320 and 4,576,910, British Patent 2,102,173, and European Patent 341,188A.
  • a coupler capable of forming colored dyes having proper diffusibility are those described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, and West German Laid-open Patent Application No. 3,234,533.
  • a colored coupler for correcting unnecessary absorption of a colored dye are those described in RD No. 17643, VII-G, RD No. 30715, VII-G, U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, British Patent 1,146,368 and JP-A-3-223750.
  • a coupler for correcting unnecessary absorption of a colored dye by a fluorescent dye released upon coupling described in U.S. Patent 4,774,181 or a coupler having a dye precursor group which can react with a developing agent to form a dye as a split-off group described in U.S. Patent 4,777,120 may be preferably used.
  • DIR couplers i.e., couplers releasing a development inhibitor
  • those described in the patents cited in the above-described RD No. 17643, VII-F and RD No. 307105, VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350, and U.S. Patents 4,248,962 and 4,782,012 may be used together with the above described compound represented by formula (A).
  • RD Nos. 11449 and 24241, and JP-A-61-201247 disclose couplers which release bleaching accelerator. These couplers effectively serve to shorten the time of any process that involves bleaching. They are effective, particularly when added to light-sensitive material containing tabular silver halide grains.
  • a coupler which imagewise releases a nucleating agent or a development accelerator are preferably those described in British Patents 2,097,140 and 2,131,188, JP-A-59-157638, and JP-A-59-170840.
  • compounds releasing e.g., a fogging agent, a development accelerator, or a silver halide solvent upon redox reaction with an oxidized form of a developing agent, described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687, can also be preferably used.
  • Examples of other compounds which can be used in the light-sensitive material of the present invention are competing couplers described in, for example, U.S. Patent 4,130,427; poly-equivalent couplers described in, e.g., U.S. Patents 4,283,472, 4,338,393, and 4,310,618; a DIR redox compound releasing coupler, a DIR coupler releasing coupler, a DIR coupler releasing redox compound, or a DIR redox releasing redox compound described in, for example, JP-A-60-185950 and JP-A-62-24252; couplers releasing a dye which restores color after being released described in European Patent 173,302A and 313,308A; a ligand releasing coupler described in, e.g., U.S. Patent 4,553,477; a coupler releasing a leuco dye described in JP-A-63-75747; and a coupler releasing a fluorescent dye described in U
  • the couplers for use in this invention can be introduced into the light-sensitive material by various known dispersion methods.
  • Examples of a high-boiling point organic solvent to be used in the oil-in-water dispersion method are described in, e.g., U.S. Patent 2,322,027.
  • Examples of a high-boiling point organic solvent to be used in the oil-in-water dispersion method and having a boiling point of 175°C or more at atmospheric pressure are phthalic esters (e.g., dibutylphthalate, dicyclohexylphthalate, di-2-ethylhexylphthalate, decylphthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-di-ethylpropyl) phthalate), phosphate or phosphonate esters (e.g., triphenylphosphate, tricresylphosphate, 2-ethylhexyldiphenylphosphate,
  • An organic solvent having a boiling point of about 30°C or more, and preferably, 50°C to about 160°C can be used as an auxiliary solvent.
  • Typical examples of the auxiliary solvent are ethyl acetate, butyl acetate, ethyl propionate, methylethylketone, cyclohexanone, 2-ethoxyethylacetate, and dimethylformamide.
  • antiseptics and fungicides agent are preferably added to the color light-sensitive material of the present invention.
  • Typical examples of the antiseptics and the fungicides are phenethyl alcohol, and 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole, which are described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-80941.
  • the sum total of film thicknesses of all hydrophilic colloidal layers at the side having emulsion layers is preferably 28 ⁇ m or less, more preferably, 23 ⁇ m or less, much more preferably, 18 ⁇ m or less, and most preferably, 16 ⁇ m or less.
  • a film swell speed T 1/2 is preferably 30 seconds or less, and more preferably, 20 seconds or less.
  • the film thickness means a film thickness measured under moisture conditioning at a temperature of 25°C and a relative humidity of 55% (two days).
  • the film swell speed T 1/2 can be measured in accordance with a known method in the art. For example, the film swell speed T 1/2 can be measured by using a swello-meter described by A.
  • T 1/2 is defined as a time required for reaching 1/2 of the saturated film thickness.
  • the film swell speed T 1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating.
  • a swell ratio is preferably 150% to 400%.
  • the swell ratio is calculated from the maximum swell film thickness measured under the above conditions in accordance with a relation: (maximum swell film thickness - film thickness)/film thickness.
  • a hydrophilic colloid layer having a total dried film thickness of 2 to 20 ⁇ m is preferably formed on the side opposite to the side having emulsion layers.
  • the back layer preferably contains, e.g., the light absorbent, the filter dye, the ultraviolet absorbent, the antistatic agent, the film hardener, the binder, the plasticizer, the lubricant, the coating aid, and the surfactant, described above.
  • the swell ratio of the back layer is preferably 150% to 500%.
  • the color photographic light-sensitive material according to the present invention can be developed by conventional methods described in RD. No. 17643, pp. 28 and 29, RD. No. 18716, the left to right columns, page 651, and RD. No. 307105, pp. 880 and 881.
  • a color developer used in development of the light-sensitive material of the present invention is an aqueous alkaline solution containing as a main component, preferably, an aromatic primary amine color developing agent.
  • an aromatic primary amine color developing agent preferably, an aminophenol compound is effective, a p-phenylenediamine compound is preferably used.
  • Typical examples of the p-phenylenediamine compound are: 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-4-hydroxybutylaniline described in European Patent 410,450A, 1-(4-amino-3-ethylphenyl)-2,5-bis-(2-hydroxyethyl)pyrrolidine described in JP-A-4-11255, and the sulfates, hydrochlorides and p-toluenesulfonates thereof.
  • the above compounds can be used in a combination of two or more thereof in accordance
  • the color developer contains a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal, and a development restrainer or an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
  • a pH buffering agent such as a carbonate, a borate or a phosphate of an alkali metal
  • an antifoggant such as a chloride, a bromide, an iodide, a benzimidazole, a benzothiazole, or a mercapto compound.
  • the color developer may also contain a preservative such as hydroxylamine, diethylhydroxylamine, a sulfite, a hydrazine such as N,N-biscarboxymethylhydrazine, a phenylsemicarbazide, triethanolamine, or a catechol sulfonic acid; an organic solvent such as ethyleneglycol or diethyleneglycol; a development accelerator such as benzylalcohol, polyethyleneglycol, a quaternary ammonium salt or an amine; a dye-forming coupler; a competing coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a viscosity-imparting agent; and a chelating agent such as an aminopolycarboxylic acid, an aminopolyphosphonic acid, an alkylphosphonic acid, or a phosphonocarboxylic acid.
  • a preservative such as hydroxylamine, diethylhydroxylamine, a
  • the chelating agent examples include ethylene-diaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, and ethylenediamine-di(o-hydroxyphenylacetic acid), and salts thereof.
  • black-and-white development is performed and then color development is performed.
  • a black-and-white developer a well-known black-and-white developing agent, e.g., a dihydroxybenzene such as hydroquinone, a 3-pyrazolidone such as 1-phenyl-3-pyrazolidone, and an aminophenol such as N-methyl-p-aminophenol can be used singly or in a combination of two or more thereof.
  • the pH of the color and black-and-white developers is generally 9 to 12.
  • the quantity of replenisher of the developers depends on a color photographic light-sensitive material to be processed, it is generally 3 liters or less per m 2 of the light-sensitive material.
  • the quantity of replenisher can be decreased to be 500 ml or less by decreasing a bromide ion concentration in a replenisher.
  • a contact area of a processing tank with air is preferably decreased to prevent evaporation and oxidation of the solution upon contact with air.
  • the above aperture is preferably 0.1 or less, and more preferably, 0.001 to 0.05.
  • a shielding member such as a floating cover may be provided on the surface of the photographic processing solution in the processing tank.
  • a method of using a movable cover described in JP-A-1-82033 or a slit developing method descried in JP-A-63-216050 may be used.
  • the aperture is preferably reduced not only in color and black-and-white development steps but also in all subsequent steps, e.g., bleaching, bleach-fixing, fixing, washing, and stabilizing steps.
  • the quantity of replenisher can be reduced by using a means of suppressing storage of bromide ions in the developing solution.
  • a color development time is normally 2 to 5 minutes.
  • the processing time can be shortened by setting a high temperature and a high pH and using the color developing agent at a high concentration.
  • the photographic emulsion layer is generally subjected to bleaching after color development.
  • the bleaching may be performed either simultaneously with fixing (bleach-fixing) or independently thereof.
  • bleach-fixing may be performed after bleaching.
  • processing may be performed in a bleach-fixing bath having two continuous tanks, fixing may be performed before bleach-fixing, or bleaching may be performed after bleach-fixing, in accordance with the application.
  • the bleaching agent are compounds of a polyvalent metal, e.g., iron (III); peracids; quinones; and nitro compounds.
  • Typical examples of the bleaching agent are an organic complex salt of iron (III), e.g., a complex salt with an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid; or a complex salt with citric acid, tartaric acid, or malic acid.
  • an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, and 1,3-diaminopropanetetraacetic acid, and glycoletherdiaminetetraacetic acid
  • a complex salt with citric acid, tartaric acid, or malic acid e.g
  • an iron (III) complex salt of an aminopolycarboxylic acid such as an iron (III) complex salt of ethylenediaminetetraacetic acid or 1,3-diaminopropanetetraacetic acid is preferred because it can increase a processing speed and prevent an environmental contamination.
  • the iron (III) complex salt of an aminopolycarboxylic acid is useful in both the bleaching and bleach-fixing solutions.
  • the pH of the bleaching or bleach-fixing solution using the iron (III) complex salt of an aminopolycarboxylic acid is normally 4.0 to 8. In order to increase the processing speed, however, processing can be performed at a lower pH.
  • a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary.
  • a useful bleaching accelerator are: compounds having a mercapto group or a disulfide group described in, for example, U.S.
  • Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and RD No.
  • a compound having a mercapto group or a disulfide group is preferable since the compound has a large accelerating effect.
  • Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are preferred.
  • a compound described in U.S. Patent 4,552,834 is also preferable.
  • These bleaching accelerators may be added in the light-sensitive material. These bleaching accelerators are useful especially in bleach-fixing of a photographic color light-sensitive material.
  • the bleaching solution or the bleach-fixing solution preferably contains, in addition to the above compounds, an organic acid in order to prevent a bleaching stain.
  • the most preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, e.g., acetic acid, propionic acid, or hydroxy acetic acid.
  • Examples of the fixing agent used in the fixing solution or the bleach-fixing solution are a thiosulfate salt, a thiocyanate salt, a thioether-based compound, a thiourea and a large amount of an iodide.
  • a thiosulfate especially, ammonium thiosulfate, can be used in the widest range of applications.
  • a combination of a thiosulfate with a thiocyanate, a thioether-based compound or thiourea is preferably used.
  • a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in European Patent 294,769A is preferred.
  • various types of aminopolycarboxylic acids or organic phosphonic acids are preferably added to the solution.
  • 0.1 to 10 moles, per liter, of a compound having a pKa of 6.0 to 9.0 are added to the fixing solution or the bleach-fixing solution in order to adjust the pH.
  • a compound having a pKa of 6.0 to 9.0 are added to the fixing solution or the bleach-fixing solution in order to adjust the pH.
  • the compound are imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
  • the total time of a desilvering step is preferably as short as possible as long as no desilvering defect occurs.
  • a preferable time is one to three minutes, and more preferably, one to two minutes.
  • a processing temperature is 25°C to 50°C, and preferably, 35°C to 45°C. Within the preferable temperature range, a desilvering speed is increased, and generation of a stain after the processing can be effectively prevented.
  • stirring is preferably as strong as possible.
  • a method of intensifying the stirring are a method of colliding a jet stream of the processing solution against the emulsion surface of the light-sensitive material described in JP-A-62-183460, a method of increasing the stirring effect using rotating means described in JP-A-62-183461, a method of moving the light-sensitive material while the emulsion surface is brought into contact with a wiper blade provided in the solution to cause disturbance on the emulsion surface, thereby improving the stirring effect, and a method of increasing the circulating flow amount in the overall processing solution.
  • Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution.
  • the above stirring improving means is more effective when the bleaching accelerator is used, i.e., significantly increases the accelerating speed or eliminates fixing interference caused by the bleaching accelerator.
  • An automatic developing machine for processing the light-sensitive material of the present invention preferably has a light-sensitive material conveyer means described in JP-A-60-191257, JP-A-60-191258, or JP-A-60-191259.
  • this conveyer means can significantly reduce carry-over of a processing solution from a pre-bath to a post-bath, thereby effectively preventing degradation in performance of the processing solution. This effect significantly shortens especially a processing time in each processing step and reduces the quantity of replenisher of a processing solution.
  • the photographic light-sensitive material of the present invention is normally subjected to washing and/or stabilizing steps after desilvering.
  • An amount of water used in the washing step can be arbitrarily determined over a broad range in accordance with the properties (e.g., a property determined by the substances used, such as a coupler) of the light-sensitive material, the application of the material, the temperature of the water, the number of water tanks (the number of stages), a replenishing scheme representing a counter or forward current, and other conditions.
  • the relationship between the amount of water and the number of water tanks in a multi-stage counter-current scheme can be obtained by a method described in "Journal of the Society of Motion Picture and Television Engineering", Vol. 64, PP. 248 - 253 (May, 1955).
  • a germicide such as an isothiazolone compound and a cyabendazole described in JP-A-57-8542, a chlorine-based germicide such as chlorinated sodium isocyanurate, and germicides such as benzotriazole, described in Hiroshi Horiguchi et al., "Chemistry of Antibacterial and Antifungal Agents", (1986), Sankyo Shuppan, Eiseigijutsu-Kai ed., “Sterilization, Antibacterial, and Antifungal Techniques for Microorganisms", (1982), Kogyogijutsu-Kai, and Nippon Bokin Bobai Gakkai ed., “Dictionary of Antibacterial and Antifungal Agents", (1986), can be used.
  • the pH of the water for washing the photographic light-sensitive material of the present invention is 4 to 9, and preferably, 5 to 8.
  • the water temperature and the washing time can vary in accordance with the properties and applications of the light-sensitive material. Normally, the washing time is 20 seconds to 10 minutes at a temperature of 15°C to 45°C, and preferably, 30 seconds to 5 minutes at 25°C to 40°C.
  • the light-sensitive material of the present invention can be processed directly by a stabilizing agent in place of water-washing. All known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used in such stabilizing processing.
  • stabilizing is performed subsequently to washing.
  • An example is a stabilizing bath containing a dye stabilizing agent and a surface-active agent to be used as a final bath of the photographic color light-sensitive material.
  • the dye stabilizing agent are an aldehyde such as formalin or glutaraldehyde, an N-methylol compound, hexamethylenetetramine, and an adduct of aldehyde sulfite.
  • Various chelating agents and fungicides can be added to the stabilizing bath.
  • An overflow solution produced upon washing and/or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
  • the silver halide color light-sensitive material of the present invention may contain a color developing agent in order to simplify processing and increases a processing speed.
  • a color developing agent for this purpose, various types of precursors of a color developing agent can be preferably used.
  • the precursor are an indoaniline-based compound described in U.S. Patent 3,342,597, Schiff base compounds described in U.S. Patent 3,342,599 and RD Nos. 14850 and 15159, an aldol compound described in RD No. 13924, a metal salt complex described in U.S. Patent 3,719,492, and a urethane-based compound described in JP-A-53-135628.
  • the silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
  • Typical examples of the compound are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.
  • Each processing solution in the present invention is used at a temperature of 10°C to 50°C. Although a normal processing temperature is 33°C to 38°C, processing may be accelerated at a higher temperature to shorten a processing time, or image quality or stability of a processing solution may be improved at a lower temperature.
  • Supports A to D below were manufactured in accordance with the following method.
  • the supports A-1 and A-2 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and 2 parts by weight of Tinuvin P.326 (available from Ciba Geigy Co.) as a ultraviolet absorbent were dried by a conventional method and melted at 300°C. Thereafter, the resultant material was extruded from a T-die and longitudinally oriented by 3.3 times at 140°C. Subsequently, the resultant material was laterally oriented by 3.3 times at 130°C and thermally fixed at 250°C for six seconds, yielding films 80 ⁇ m and 122 ⁇ m in thickness.
  • Tinuvin P.326 available from Ciba Geigy Co.
  • the support B-1 A commercially available polyethyleneterephthalate polymer was biaxially oriented and thermally fixed in accordance with a conventional method to obtain a 90 ⁇ m thick film.
  • the supports D-1 to D-3 In accordance with the formation method of the support A, materials were kneaded and extruded at 280°C by using a biaxial kneading extruder. The resultant materials were then pelletized and formed into films 80 ⁇ m in thickness.
  • a corona discharge treatment was performed on both the surfaces of each of the supports A, B, and D, and a subbing layer with the following composition was formed on each resultant support.
  • the corona discharge treatment was performed for a 30-cm wide support at a rate of 20 m/min by using a Solid-State Corona Processor 6KVA Model available from Pillar Co. It was observed from the read values of a current and a voltage that a treatment of 0.375 kV ⁇ A ⁇ min/m 2 was performed for each object to be treated. In this treatment, the discharge frequency was 9.6 kHz, and the gap clearance between an electrode and a dielectric roll was 1.6 mm.
  • Gelatin 3 g Distilled water 250 cc Sodium ⁇ -sulfodi-2-ethyl hexylsuccinate 0.05 g Formaldehyde 0.02 g
  • a back layer was coated on the surface of each of the subbed supports A to D opposite to the surface on which the subbing layer was formed in accordance with the following procedures.
  • the resultant reddish blown colloidal precipitate was separated by centrifugal separation. To remove excess ions, the precipitate was washed three times with water through centrifugal separation.
  • a mixture of 40 parts by weight of the above fine grain powder and 60 parts by weight of water was controlled to have a pH of 7.0 and coarsely dispersed by a stirring machine. Thereafter, the resultant dispersion was further dispersed for a residence time of 30 minutes by using a horizontal sand mill (DYNOMILL (tradename); available from WILLY A. BACHOFENAG).
  • DYNOMILL tradename
  • WILLY A. BACHOFENAG a horizontal sand mill
  • the following formulation A was so coated as to have a dry film thickness of 0.3 ⁇ m and dried at 130°C for 30 seconds.
  • the following coating solution (B) for forming a coating film was further coated on the resultant film so as to have a dry film thickness of 0.1 ⁇ m and dried at 130°C for two minutes.
  • a bending modulus which is the most important factor among other dynamic strengths of a support in decreasing the thickness of the support was measured.
  • the measurement of the bending modulus was performed by a method called a loop stiffness method. That is, a 35-mm wide sample which was slit, i.e., cut in the longitudinal direction was formed into a torus with a circumference of 10 cm and placed horizontally. A load applied when the torus deformed by 12 mm in the direction of the diameter was measured as the bending modulus. The measurement was performed at a temperature of 25°C and a relative humidity of 60% such that the subbing layer of each sample was located inside the torus.
  • PEN with a thickness of 80 ⁇ m and PET with a thickness of 90 ⁇ m exhibited the values of bending modulus nearly equivalent to that of TAC with a thickness of 122 ⁇ m.
  • the thickness of PEN was increased up to 122 ⁇ m, the same thickness as that of TAC, the bending modulus of PEN was three times that of TAC.
  • Layers with the following compositions were multi-coated on each of the supports formed by the above method, manufacturing multilayered color light-sensitive materials. Note that the symbols representing the individual supports are used directly to represent the corresponding multilayered color light-sensitive materials. As an example, a light-sensitive material obtained by coating these light-sensitive layers on the support A-1 is labeled a multilayered color light-sensitive material A-1.
  • the main materials used in the individual layers are classified as follows.
  • the number corresponding to each component indicates the coating amount in units of g/m 2 .
  • the coating amount of a silver halide is represented by the amount of silver.
  • the coating amount of each sensitizing dye is represented in units of mols per mol of a silver halide in the same layer.
  • the individual layers contained W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum salt, iridium salt, palladium salt, and rhodium salt.
  • Each multilayered color light-sensitive material thus manufactured was slit into a film 35 mm wide and 1.15 m long, and perforations with dimensions of 2 mm ⁇ 2.8 mm were formed with an interval of 4.75 mm at positions 2 mm from the both ends in the widthwise direction of the film as same as those in a current 135 format.
  • Each resultant film was wound around a spool 14 mm in diameter and set in a 135-size magazine, forming a photographing film similar to the current 135-format film. These films were labeled Group I.
  • a mannequin (upper half) placed with a resolving power chart and a Macbeth color checker chart was photographed under the following conditions, in which Fuji Zoom Cardia 800 (available from Fuji Photo Film Co. Ltd.), for the Group I films, or Fuji Zoom Cardia 800 remodelled such that the area of an imaging area was 5.01 cm 2 (30.0 mm ⁇ 16.7 mm, aspect ratio 1.80) and a film with two perforations per frame could be fed, for the Group II films, was used. Photographing was similarly performed by using the Group II films by changing only the area of an imaging area to 2.55 cm 2 (21.4 mm ⁇ 11.9 mm, aspect ratio 1.8). The resultant films were labeled Group III.
  • the distance was set such that a complete view of a main portion of the object to be photographed could be photographed in an imaging area (an exposure portion in a frame) when the Group I films were used.
  • the photographing was performed such that the same complete view was photographed in an image portion by performing a zooming operation without changing the set distance.
  • the photographed films were processed in accordance with the following color developing steps by using processing solutions with the following compositions. Note that the processing was performed by using the processing solutions obtained after continuous (running) processing was performed for a sample, which was separately imagewise-exposed, at a rate of 1 m 2 /day for 15 days.
  • the stabilizing solution was used by a counter flow system from (2) to (1), and the overflow solution of the washing solution was introduced entirely to the fixing bath.
  • the replenishment of the bleach-fixing solution was performed by forming notches in the upper portions of the bleaching tank and the fixing tank of the automatic developing machine so that the overflow solution produced when the replenishers were supplied to the bleaching and fixing tanks was flowed entirely to the bleach-fixing bath.
  • the quantities of the developing solution, the bleaching solution, the bleach-fixing solution, and the fixing solution carried over to the bleaching step, the bleach-fixing step, the fixing step, and the washing step were 2.5 ml, 2.0 ml, 2.0 ml, and 2.0 ml, respectively, per 1.1 m of the 35-mm wide light-sensitive material.
  • the crossover time of each step was six seconds, and this time was included in the processing time of each previous step.
  • compositions of the processing solutions are presented below.
  • Color developing solution Tank solution (g) Replenisher (g) Diethylenetriamine pentaacetic acid 2.0 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg - Hydroxylamine sulfate 2.4 3.3 2-methyl-4-[N-ethyl-N-( ⁇ -hydroxyethyl) amino]aniline sulfate 4.5 6.0 Water to make 1.0 l 1.0 l pH (controlled by potassium hydroxide and sulfuric acid) 10.05 10.15 Bleaching solution Tank solution (g) Replenisher (g) Ammonium 1,3-diaminopropane tetraacetato-ferrate(III) monohydrate 130 195 Ammonium bromide 70 105 Ammonium nitrate 14 21 Hydroxyacetic acid 50 75 Acetic
  • (pH 7.0) Fixing solution Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Aqueous ammonium thiosulfate solution (700 g/l) 280 l 840 l Imidazole 15 45 Ethylenediamine tetraacetic acid 15 45 Water to make 1.0 l 1.0 l pH (controlled by ammonia water and acetic acid) 7.4 7.45
  • Tap water was supplied to a mixed-bed column filled with an H type strongly acidic cation exchange resin (Amberlite IR-120B: available from Rohm & Haas Co.) and an OH type strongly basic anion exchange resin (Amberlite IR-400) to set the concentrations of calcium and magnesium to be 3 mg/l or less. Subsequently, 20 mg/l of sodium dichloroisocyanurate and 150 mg/l of sodium sulfate were added. The pH of the solution ranged from 6.5 to 7.5.
  • Stabilizing solution common to tank solution and replenisher g
  • Polyoxyethylene-p-monononylphenylether (average degree of polymerization 10) 0.2
  • 1,2,4-triazole 1.3
  • 1,4-bis(1,2,4-triazole-1-ylmethyl) piperazine 0.75 Water to make 1.0 l pH 8.5
  • the resultant prints were so cut as to leave only image portions behind, and the sharpness of each print was evaluated on a gray plate (reflection density 0.18) under a fluorescent lamp for color evaluation by ten male monitors and ten female monitors.
  • the evaluation was performed by using the print obtained from the film made from the multilayered color light-sensitive material C-1 of Group I as a reference and sequentially comparing this reference with other prints one at a time. A print found to be better than the reference was given +1, a print found to be equivalent to the reference or difficult to determine was given 0, and a print found to be worse than the reference was given -1. After the determination, an arithmetic means of these values was calculated for each print.
  • the color reproducibility was evaluated by measuring the cyan density of a magenta dye image of the color checker chart photographed in a color negative film and checking the degree of color turbidity by obtaining the difference with respect to the value of the multilayered color light-sensitive material C-1 as a reference.
  • Table 4 reveals that the films of Group II each having the polyester support were found to be better in sharpness than those of Group I which were current 135-format films. The reason for this is considered that the flatness of an imaging area to be exposed could not be maintained during photographing because the number of perforations per frame was large in the films of Group I. In fact, some monitors backed up this by pointing out that blurs were found in peripheral portions or central portions of these prints. On the other hand, the films of Group III each having an imaging area of 3 cm 2 or less was found to be obviously poor in sharpness, demonstrating that it is difficult to reduce the size of an imaging area to 3 cm 2 or less while maintaining the image quality. In addition, as can be readily seen by comparing the multilayered color light-sensitive material A-1 of the present invention and the comparative light-sensitive material C-1, A-1 was superior to C-1 in sharpness.
  • the films of Groups II and III having reduced imaging areas were improved in color reproducibility compared to the films of Group I having large imaging areas although the differences were small. The reason for this is unknown, but it is estimated that this was caused by some dynamic factor applied on a hydrophilic colloid layer when a film was wound around a spool.
  • PBC-2, PBC-3, PBC-6, PBC-9, PBC-10, and PBB-3 exemplified as polyester compounds were used to perform melting, biaxial orientation, and thermal fixing in accordance with the method described in Example 1, forming supports 80 ⁇ m thick. A subbing layer and a back layer were coated on each support, and a heat treatment was performed for each resultant support at a temperature lower by 10°C than the glass transition point (Tg) of each polyester compound. Layers with the compositions shown in Example 1 were multi-coated on each of these supports to manufacture multilayered color light-sensitive materials.
  • the multilayered color light-sensitive materials A-1, D-1, and D-3 manufactured in Example 1 were processed to have a width of 24 mm, and perforations were formed in the both side edges in the longitudinal direction of each resultant film such that one perforation was formed per frame in each side edge.
  • Each resultant film was put into the film cartridge described in JP-A-2-273740.
  • a camera was also remodeled so as to be able to load this cartridge.
  • An object to be photographed was photographed following the same procedures as in Example 1 such that the size of an imaging area was 30.0 mm ⁇ 12.0 mm (area of imaging area to be exposed 3.60 cm 2 , aspect ratio 2.5).
  • each resultant film was put into the cartridge described in JP-A-2-273740. Photographing was similarly performed such that the imaging area size was 30.0 mm ⁇ 21.4 mm (area of imaging area to be exposed 6.42 cm 2 , aspect ratio 1.4) and was 30.0 mm ⁇ 16.7 mm (area of imaging area to be exposed 5.01 cm 2 , aspect ratio 1.80). In this photographing, a feed length of one frame of the film was set to 31.7 mm in correspondence with the imaging area size described above.
  • the distance was determined such that an object to be photographed (the upper half of a mannequin with a resolving power chart and a color checker chart) was just fitted in a longitudinal position of an image portion.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)

Claims (10)

  1. Matériau photographique couleur à l'halogénure d'argent sensible à la lumière ayant au moins une couche de colloïde hydrophile contenant un composé représenté par la formule (A) ci-dessous, un support comprenant une base en polyester analogue à une bande, pas plus de 4 perforations par vue dans une partie de bord latéral ou dans les deux parties de bord latéral de ladite base en polyester, une zone de formation d'image de 3,0 cm2 à 7,0 cm2 et un format de la zone de formation d'image de 1,40 à 2,50 : Formule (A)   A-(temps)n-W où A représente un groupe capable de libérer (temps)n-W par réaction avec une forme oxydée d'un développateur chromogène, temps représente un groupe de réglage du temps, W représente un groupe qui présente un effet d'inhibition du développement après avoir été libéré de (temps)n-W et n représente 1, 2 ou 3.
  2. Matériau selon la revendication 1, caractérisé en ce que ledit support est traité thermiquement à une température inférieure de 30°C à 5°C à la température de transition vitreuse dudit support.
  3. Matériau selon la revendication 1, caractérisé en ce que l'épaisseur dudit support est de 40 µm à 300 µm.
  4. Matériau selon la revendication 1, caractérisé en ce que ledit support contient des colorants.
  5. Matériau selon la revendication 1, caractérisé en ce que ledit matériau a une couche dorsale qui contient un grain fin d'au moins un oxyde métallique cristallin choisi dans le groupe consistant en ZnO, TiO3, SnO2, Al2O3, In2O3, SiO2, MgO, BaO et MoO3 ou un grain fin d'un oxyde composite de ces oxydes.
  6. Matériau selon la revendication 1, caractérisé en ce que le rapport de la surface totale desdites perforations à la surface d'une vue est de 5 % ou moins.
  7. Matériau selon la revendication 1, caractérisé en ce que ledit composé représenté par la formule (A) est contenu dans une couche d'émulsion d'halogénure d'argent sensible à la lumière, et la quantité d'addition dudit composé est de 0,01 à 20 mol % par rapport à la quantité d'un halogénure d'argent dans cette couche.
  8. Matériau selon la revendication 1, caractérisé en ce que ledit composé représenté par la formule (A) est contenu dans une couche non sensible à la lumière et la quantité d'addition dudit composé est de 0,01 à 20 mol % par rapport à la quantité d'un halogénure d'argent dans une couche d'émulsion d'halogénure d'argent la plus proche de ladite couche non sensible à la lumière.
  9. Matériau selon la revendication 1, caractérisé en ce que ledit support est constitué par du poly(2,6-dinaphtalate d'éthylène).
  10. Matériau selon la revendication 9, caractérisé en ce que ledit support est traité thermiquement à une température inférieure de 30°C à 5°C à la température de transition vitreuse du poly(2,6-dinaphtalate d'éthylène).
EP19930114872 1992-09-16 1993-09-15 Matériau photographique couleur à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0588331B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP270783/92 1992-09-16
JP27078392A JPH0695313A (ja) 1992-09-16 1992-09-16 ハロゲン化銀カラー写真感光材料

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EP0588331A1 EP0588331A1 (fr) 1994-03-23
EP0588331B1 true EP0588331B1 (fr) 1999-03-24

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EP (1) EP0588331B1 (fr)
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DE (1) DE69324087T2 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3248016B2 (ja) * 1993-02-23 2002-01-21 コニカ株式会社 ハロゲン化銀写真感光材料及びその処理方法
FR2716985B1 (fr) * 1994-03-04 1996-04-05 Aaton Sa Format d'enregistrement d'images.
EP0697629B1 (fr) 1994-08-16 2001-02-07 Gretag Imaging Ag Procédé et dispositif pour créer des images composés avec une imprimante photographique
DE59509010D1 (de) * 1994-08-16 2001-03-15 Gretag Imaging Ag Verfahren und Vorrichtung zur Erzeugung von Index-Prints auf bzw. mit einem photographischen Printer

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2266191A1 (en) * 1974-03-28 1975-10-24 Teijin Ltd Polyethylene 2,6-naphthalate film - as biaxially oriented photographic film with dimensional stability
US4141735A (en) * 1975-03-31 1979-02-27 Eastman Kodak Company Process for reducing core-set curling tendency and core-set curl of polymeric film elements
JP2565370B2 (ja) * 1988-03-25 1996-12-18 富士写真フイルム株式会社 写真感光材料
EP0476327B1 (fr) * 1990-08-20 1999-11-17 Fuji Photo Film Co., Ltd. Produit de pellicule photographique retenant des informations et procédé de production d'épreuve en couleurs

Also Published As

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EP0588331A1 (fr) 1994-03-23
DE69324087T2 (de) 1999-08-05
JPH0695313A (ja) 1994-04-08
DE69324087D1 (de) 1999-04-29

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