Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
• • 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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
• • 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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/061—Hydrazine compounds
• • 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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/067—Additives for high contrast images, other than hydrazine compounds

Definitions

• the present invention relates to a silver halide photo­graphic light-sensitive material for graphic arts use, and more particularly to a silver halide photographic light-sensi­tive material for graphic arts use which is excellent in the ultra-high-speed processability as well as in the coatability.
• One method for achieving such a ultra-high-speed process­ ing as in the 60-second dry-to-dry time is to perform develop­ing and fixing at raised temperatures, but the method is unac­ceptable because of affecting the preservability of processing solutions and increasing the vapor therefrom into the process­ing room. It is therefore desirable to manage to perform such the ultra-high-speed processing at a low temperature (not higher than 38°C). Also, reducing the amount of silver is ef­fective in a high-speed processing.
• Another notable problem caused by reducing the amount of gelatin is the appearance of a lot of pinholes attributable to the matting agent contained usually in the outermost layer.
• the drying time is preferably within 15 seconds.
• dry-to-dry 80 to 150 seconds various measures such as increasing the drying air quantity, reducing the drying air humidity, raising the drying temperature, and using a far-infrared heater, ultra­sonic oscillator or microwave dryer.
• the difference between such drying systems largely affects the change in the dimen­sions of a light-sensitive material before and after the pro­cessing thereof. Therefore, it is necessary to provide a light-sensitive material capable of showing the same dimen­sional change even when treated in different drying condi­tions.
• a silver halide photographic light-sensitive material of the invention comprises a support having thereon at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer provided on the outside of said silver halide emulsion layer to the support, in which the total gelatin content of said layers containing said light-sensitive silver halide emulsion layer is 2.0 to 2.8g/m2 and at least one of said non-light-sensitive hydrophil­ic colloid layers contains a polymer latex.
• the polymer latex to be contained in the photographic light-sensitive material of the invention includes those hydr­ates of vinyl polymers with the acrylates, methacrylates, and styrenes described in U.S. Patent Nos. 2,772,166, 3,325,286, 3,411,911, 3,311,912 and 3,525,620; and Research Disclosure No. 19551 (195) (July, 1980).
• polymer latex for the invention include homopolymers of metha-alkyl acrylates such as methyl methacrylate or ethyl methacrylate; copolymers of a metha-­alkyl acrylate or styrene with acrylic acid, N-methylol-acryl­amide or glycidol methacrylate; homopolymers of alkyl acryl­ates such as methyl acrylate, ethyl acrylate or butyl acryl­ate, or copolymers of an alkyl acrylate with acrylic acid or N-methylol-acrylamide (acrylic acid component of the copolymer is preferably up to 30% by weight); homopolymers of butadiene or copolymers of butadiene with one or more of styrene, butoxy­methylacrylamide and acrylic acid; and vinylidene chloride­methyl acrylate-acrylic acid tri-copolymers.
• metha-alkyl acrylates such as methyl
• the polymer latex used in the invention has an average particle size of preferably 0.005 to 1 ⁇ m, more preferably 0.02 to 0.5 ⁇ m, and most preferably not more than 0.1 ⁇ m.
• the polymer latex used in the invention may be contained on either one side or both sides of the support. When contain­ed on both sides, the kind and/or amount of the polymer latex contained on each side may be either the same or different.
• the polymer latex may be added also to any layers other than the non-light-sensitive hydrophilic colloid layer.
• the polymer latex may be contained in the emulsion layer and also in the topmost non-light-sensitive colloid layer as a protective layer, not to mention other layers such as a subbing layer and an intermediate layer, if any, between the silver halide emulsion layer and the topmost layer.
• the polymer latex if present on the multilayer side of the support, may be contained in any single layer.
• the amount of the polymer latex with a particle size of not more than 1 ⁇ m dispersedly contained in at least one of the non-light-sensitive hydrophilic colloid layers provided outside the emulsion layer on the emulsion side of the support is preferably not less than 0.18g/m2, and the total amount of the polymer latex contained in the whole non-light-sensitive hydrophilic colloid layers outside the emul­sion layer is preferably not less than 0.2g/m2.
• the polymer latex content of at least one of the non-­light-sensitive hydrophilic colloid layers on the outside of the silver halide emulsion layer to the support is preferably 0.01g/m2 to 1.0g/m2, and more preferably 0.02g/m2 to 0.6g/m2.
• the gelatin content of the hydrophilic colloid layer to which the polymer latex is added is preferably 0.1g/m2 to 1.5g/m2, and more preferably 0.3g/m2 to 1.2g/m2.
• the polymer latex is contained preferably in an amount of not less than 0.05g/m2 in at least one emulsion layer and not less than 0.1g/m2 in the whole emulsion layers.
• the gela­tin content of the emulsion layers is preferably 0.3 to 2.2g/m2, and more preferably 0.5 to 2.2g/m2.
• the tetrazolium compound used in the invention is a com­pound represented by the following Formula I:
• R1, R2 and R3 each represents an alkyl group such as methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl or cyclohexyl; an amono group; an acylamino group such as acetylamino; a hydroxyl group; an alkoxy group such as methoxy, ethoxy, propoxy, but­oxy or pentoxy; an acyloxy group such as acetyloxy; a halogen atom such as fluorine, chlorine or bromine; a carbamoyl group; an acylthio group such as acetylthio; an alkoxycarbonyl group such as ethoxycarbonyl; a carboxyl group; an acyl group such as acetyl; a cyano group, a nitro group, a mercapto group, a s
• X ⁇ is an anion, including halogen ions such as a chloride ion, a bromide ion and an iodide ion; acid radicals of inorgan­ic acids such as nitric acid, sulfuric acid and perchloric acid; acid radicals of organic acids such as sulfonic acid and carboxylic acid; anionic activators including lower alkylben­zenesulfonic acid anions such as p-toluenesulfonic acid anion; higher alkylbenzenesulfonic acid anions such as p-dodecylben­zenesulfonic acid anion; higher alkyl sulfonate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl­boron; dialkylsulfo succinate anions such as di-2-ethylhexyl­sulfo succinate anion; polyether-alcohol sulf
• tetrazolium compounds of the invention can be easi­ly synthesized in accordance with those methods described in the Chemical Reviews, vol.55, pp.335 to 483.
• the tetrazolium compound having Formula I of the inven­tion may be used in the amount range of about 1 mg to about 10g, and preferably about 10 mg to about 2g per mole of silver halide.
• the tetrazolium compound having Formula I of the inven­tion may be used alone or in combination of two or more kinds thereof in an arbitrary ratio. Further, the tetrazolium com­pound of the invention may be used in combination in an arbi­trary ratio with other tetrazolium compound outside the inven­tion.
• anion capable of combining with the tetrazolium compound of the invention to lower the hydro­philicity thereof is used in combination therewith, particu­larly good results can be obtained.
• anion include acid radicals of inorganic acids such as perchloric acid; acid radicals of organic acids such as sulfonic acid and carboxylic acid; anionic activators including lower alkylben­zenesulfonic acid anions such as p-toluenesulfonic acid anions, p-dodecylbenzenesulfonic acid anions, alkylnaphthalene­sulfonic acid anions, lauryl sulfate anions, tetraphenyl­borons, dialkylsulfo succinate anions such as di-2-ethylhexyl­sulfo succinate anions, polyether-alcohol sulfate anions such as polyethenoxy cetyl alcohol sulf
• Such the anion may, after being mixed with a tetrazolium compound of the invention, be added to a hydrophilic colloid layer or may be added alone to a silver halide emulsion layer containing or not containing a tetrazolium compound of the invention or to a hydrophilic colloid layer.
• the hydrazine compound used in the invention is preferively a compound represented by the following Formula II: wherein R1 is a monovalent organic residue; R2 is a hydrogen atom or a monovalent organic residue; Q1 and Q2 each repre­sents a hydrogen atom, an alkylsulfonyl group including one having a substituent, or an arylsulfonyl group including one having a substituent; and X1 is an oxygen atom or a sulfur atom.
• R1 is a monovalent organic residue
• R2 is a hydrogen atom or a monovalent organic residue
• Q1 and Q2 each repre­sents a hydrogen atom, an alkylsulfonyl group including one having a substituent, or an arylsulfonyl group including one having a substituent
• X1 is an oxygen atom or a sulfur atom.
• Preferred among those compounds represented by Formula II is one in which X1 is an oxygen atom and R2 is
• the monovalent organic residue represented by the above R1 or R2 includes an aromatic residue, a heterocyclic residue and an aliphatic residue.
• the aromatic residue includes a phenyl group, a naphthyl group and the same groups having a substituent such as an alkyl group, an alkoxy group, an acylhydrazino group, a dialkyl­amino group, an alkoxycarbonyl group, a cyano group, a carboxy group, nitro group, an alkylthio group, a hydroxy group, a sul­fonyl group, a carbamoyl group, a halogen atom, an acylamino group, a sulfonamido group, or a thiourea group.
• a substituent such as an alkyl group, an alkoxy group, an acylhydrazino group, a dialkyl­amino group, an alkoxycarbonyl group, a cyano group, a carboxy group, nitro group, an alkylthio group, a hydroxy group, a sul­fonyl
• phenyl group having such substituents examples include a 4-methyl­phenyl group, a 4-ethylphenyl group, a 4-oxyethylphenyl group, a 4-dodecylphenyl group, a 4-carboxyphenyl group, a 4-diethyl­aminophenyl group, 4-octylaminophenyl group, a 4-benzylamino­phenyl group, 4-acetamido-2-methylphenyl group, a 4-(3-ethyl­thioureido)phenyl group, a 4-[2-(2,4-di-tert-butylphenoxy)but­ylamido]phenyl group, and a 4-[2-(2,4-di-tert-butylphenoxy)­butylamido]phenyl group.
• the heterocyclic residue is a 5- or 6-member single ring or condensed ring which has at least one atom selected from the group consisting of oxygen, nitrogen, sulfur and selenium atoms and which may have a substituent.
• the residue ring include a pyrroline ring, a pyridine ring, a quino­line ring, an indole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, an imidazole ring, a benzimidazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselen­azole ring, and a naphthoselenazole ring.
• heterocyclic rings may be substituted by an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, a halogen atom such as chlorine or bromine, an alkoxycarbonyl group, a cyano group or an amino group.
• an alkyl group having 1 to 4 carbon atoms such as a methyl group or an ethyl group
• an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group
• an aryl group having 6 to 18 carbon atoms such as a phenyl group
• a halogen atom such as chlorine or bromine
• an alkoxycarbonyl group such as a cyano group or an amino group.
• the aliphatic residue includes a straight-chain or branched-chain alkyl group, a cycloalkyl group, the same groups having a substituent, an alkenyl group and an alkinyl group.
• the straight-chain or branched-chain alkyl group is an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an iso­butyl group and a 1-octyl group.
• the cycloalkyl group is one having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclohexyl group and an adamant­yl group.
• a substituent to the above alkyl group or cycloalkyl group includes an alkoxy group such as methoxy, ethoxy, prop­oxy or butoxy; an alkoxycarbonyl group; a carbamoyl group; a hydroxy group; an alkylthio group; an amido group; an acyloxy group; a cyano group; a sulfonyl group; a halogen atom such as chlorine, bromine, fluorine or iodine; and an aryl group such as phenyl, halogen-substituted phenyl, alkyl-substituted phenyl.
• Examples of the group substituted include a 3-methoxy­ propyl group, an ethoxycarbonylmethyl group, a 4-chlorocyclo­hexyl group, a benzyl group, a p-methylbenzyl group, and a p-­chlorobenzyl group.
• the above alkenyl group includes an allyl group
• the alkinyl group includes a propargyl group.
• the place into which is incorporated a hydrazine compound represented by Formula II is a silver halide emulsion layer and/or a non-light-sensitive layer located on the silver halide emulsion layer side of the support, and preferably the silver halide emulsion layer and/or a layer thereunderneath.
• the adding amount of the hydrazine compound is preferably 10 ⁇ 5 to 10 ⁇ 1 mole, and more preferably 10 ⁇ 4 to 10 ⁇ 2 mole per mole of silver.
• the silver halide of the silver halide emulsion used in the light-sensitive material of the invention may be any arbi­trary one for conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide or silver chloroiodobromide, and preferably a silver chlorobromide containing more than 50 mole% silver chlo­ride for a negative-type silver halide emulsion.
• the silver halide grain may be one that is obtained by any of an acid method, a neutral method and an ammoniacal method.
• the silver halide emulsion used in the invention may be either of a single composition or of a plurality of grains different in the composition, which may be contained together in a single layer or separately in a plurality of layers.
• Configuration of the silver halide grain of the invention is not restricted, but one preferred example is a cubic grain having a ⁇ 100 ⁇ face as a crystal surface.
• the grain may also be of an octahedral, tetradecahedral or dodecahedral configura­ tion, which may be prepared in accordance with those methods described in U.S. Patent Nos. 4,183,756 and 4,225,666; Japan­ese Patent O.P.I. Publication No. 26589/1980, and Japanese Patent Examined Publication No. 42737/1980; and the Journal of Photographic Science, 21. 39 (1973). Further, the grain may also be a crystal having a twin plane.
• the silver halide grains of the invention may be either grains of unified form or mixed grains of varied forms.
• the silver halide grains may be of any grain size distri­bution; the emulsion used may be an emulsion of a wide grain size distribution (referred to as a polydisperse emulsion), a single emulsion or a mixture of different emulsions having a narrow grain size distribution (referred to as monodisperse emulsions), or a mixture of a polydisperse emulsion and a mono­disperse emulsion.
• a polydisperse emulsion a wide grain size distribution
• monodisperse emulsions referred to as monodisperse emulsions
• the silver halide emulsion may be a mixture of separately prepared two or more different emulsions.
• the monodisperse emulsion is preferred.
• the monodisperse silver halide grains in the monodisperse emul­sion are such that the weight of the silver halide grains included within the grain size range of 20% ⁇ average grain size r account for not less than 60%, more preferably not less than 70%, and most preferably not less than 80% of the weight of the whole silver halide grains.
• the average grain size r herein is defined as the grain diameter ri obtained when the product ni x ri3 of the frequency ni of a grain having a grain diameter ri and ri3 becomes maxi­mum (calculated and rounded to three places of decimals).
• the grain diameter in the case of a spherical silver halide grain, is its diameter and, in the case of a non-spheri­cal grain, is the diameter of a circular image equivalent in the area to its projection image.
• the grain diameter can be obtained by measuring the dia­meter of a grain image on a photographed print or the area of a projected image obtained by magnifying the grain 10,000 to 50,000 times by an electron microscope, provided that the number of grains to be measured is 1000 or more selected at random.
• the particularly preferred high monodisperse emulsion of the invention is one in which the grain size distribution width defined by is 20% or less, and more preferably 15% or less.
• the monodisperse emulsion can be prepared by making refer­ence to Japanese Patent O.P.I. Publication Nos. 48521/1979, 49938/1983 and 122935/1985.
• the light-sensitive silver halide emulsion although allowed to be used remaining unchemically-sensitized, i.e., in a primitive emulsion, is usually subjected to chemical sensiti­zation.
• the chemical sensitization may be carried out in ac­cordance with appropriate ones of those methods described in the publications by Glafkides and Zelikman, and the 'Die Grund­lagen der Photographischen mit Silberhalogeniden', Aka­demische Verlagsgesellschaft, 1968, compiled by H. Frieser.
• a sulfur sensitization method which uses an ac­tive gelatin or a compound containing sulfur capable of react­ing with silver ions; a reduction sensitization method which uses a reducing substance; and a noble-metal sensitization method which uses a gold compound or other noble metal com­pounds may be used alone or in combination.
• a sulfur sen­sitizer a thiosulfate, a thiourea, a thiazole, a rhodanine and other compound may be used, examples of which are describ­ed in U.S. Patent Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668 and 3,656,955.
• a stan­nous salt, an amine, a hydrazine derivative, formamizinesulfin­ic acid, and a silane compound may be used, examples of which are described in U.S. Patent Nos. 2,478,850, 2,419,974, 2,518,698, 2,983,609, 2,983,610 and 2,694,637.
• a complex salt of a metal such as plati­num, iridium or palladium, belonging to Group VII of the period­ic table, can be used, examples of which are described in U.S. Patent Nos. 2,399,083 and 2,448,060, and British Patent No. 618,061.
• pH is pre­ferably 4 to 9, particularly 5 to 8
• pAg is preferably 5 to 11, particularly 8 to 10
• temperature is preferably 40 to 90°C, particularly 45 to 75°C.
• the photographic emulsion used in the invention may be chemically sensitized by combined use of the above-mentioned sulfur sensitization, gold-sulfur sensitization, reduction sen­sitization and noble-metal sensitization.
• the foregoing emul­sion may be used alone or in a mixture of two or more kinds thereof.
• emulsion after com­pletion of the above chemical sensitization, may be used 4-hydr­oxy-6-methyl-1,3,3a,7-tetrazaindene, 5-mercapto-1-phenyltetr­azole, 2-mercaptobenzothiazole, and various other stabilizers.
• a silver halide solvent such as thio­ether, a mercapto group-containing compound, and a crystal habit control agent such as a sensitizing dye may be used.
• the silver halide grain for the emulsion of the invention may contain in the inside thereof and/or on the surface thereof metallic ions by adding thereto in the grain forming and/or growing process a cadmium salt, a zinc salt, a lead salt, a thalium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt thereof.
• the emulsion of the invention may have its useless solu­ble salt either removed therefrom after completion of the growth of the silver halide grain or remain contained therein.
• the removal of the salt can be carried out in accordance with the method described in Research Disclosure 17643.
• the emulsion may be spectrally sensitiz­ed to relatively longer wavelength-having blue, green and red lights or infrared light by using sensitizing dyes.
• the dyes to be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
• the particularly useful ones are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
• the basic heterocyclic nucleus of these dyes may be any one of those nuclei usually applied to cyanine dyes, which includes a pyrroline nucleus, an oxazol­ine nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxa­zole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus; a nucleus formed by the fusion of an alicyclic hydrocarbon ring with one of these nuclei; and a nucleus formed by the fusion of an aromatic hydrocarbon ring with one of these nuclei, such as an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a be
• the ketomethylene structure-having nucleus of the mero­cyanine dye or complex merocyanine dye may be a 5- or 6-member heterocyclic nucleus such as a pyrazolin-5-one nucleus, a thio­hydantoin nucleus, a 2-thiooxazlidin-2,4-dione nucleus, a thia­zolidin-2,4-dione nucleus, rhodanine nucleus, a thiobarbituric acid nucleus.
• the sensitizing dye for use in the invention is used in the same concentration as used in conventional negative-type silver halide emulsions. Particularly, it is advantageous to use the sensitizing dye in a concentration range substantially not to deteriorate the inherent sensitivity of the silver halide emulsion; preferably about 1.0x10 ⁇ 5 to 5x10 ⁇ 4 mole of the sensitizing dye per mole of silver halide, and particu­larly preferably about 4x10 ⁇ 5 to 2x10 ⁇ 4 mole per mole of silver halide.
• the sensitizing dye of the invention may be used alone or in combination of two or more kinds thereof.
• Useful examples of the sensitizing dye of the invention are as follows:
• the sensitizing dyes for the blue-sensitive silver halide emulsion include those described in West German Patent No. 929,080; U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,956, 3,672,897, 3,694,217, 4,025,349 and 4,046,572; British Patent No. 1,242,588; Japan­ese Patent Examined Publication Nos. 14030/1969 and 24844/­1977; and Japanese Patent O.P.I. Publication Nos. 73137/1973 and 172140/1986.
• the sensitizing dyes for the green-sensitive silver halide emulsion include those cyanine dyes, merocyanine dyes, and complex cyanine dyes described in U.S. Patent Nos. 1,939,201, 2,072,908, 2,739,149 and 2,945,763; British Patent No. 505,979; and Japanese Patent Examined Publication No. 42172/1973.
• the sensitizing dyes for the red-sensitive emulsion and infrared-sensitive emulsion include those cyanine dyes, merocyanine dyes and complex cyanine dyes described in U.S. Patent Nos.
• sensitizing dyes may be used alone or in combina­tion. Combination of such sensitizing dyes is often used for the purpose of supersensitization. Typical examples of the combination are described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4,026,707; British Patent Nos. 1,344,281 and 1,507,803; Japanese Patent Examined Publica­ tion Nos. 4936/1968 and 12375/1978; and Japanese Patent O.P.I. Publication Nos. 110618/1977 and 109925/1977.
• the silver halide photographic light-sensitive material of the invention may contain in the hydrophilic colloid layers thereof a water-soluble dye as a filter dye or for the anti­irradiation, antihalation and some other purposes.
• a water-soluble dye as a filter dye or for the anti­irradiation, antihalation and some other purposes.
• the dye include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, the oxonole dyes, hemioxonol dyes and merocyanine dyes are particularly useful.
• the hydrophilic colloid layers thereof contain a dye or a ultraviolet absorbing agent
• the dye or the agent may be mordanted by a cationic polymer.
• various compounds e.g., those compounds known as stabilizers, which include azoles such as a benzothiazolium salt, a nitroindazole, a triazole, a benzotriazole, a benzimid­azole (particularly nitro- or halogen-substituted one), a heterocyclic mercapto compound such as a mercaptothiazole, a mercaptorbenzothiazole, a mercaptobenzimidazole, a mercapto­thiadiazole, a mercaptotetrazole (particularly 1-phenyl-5-mer­captotetrazole): mercaptopyridines; heterocyclic mercapto com­ pounds, similar to the above, having a water-soluble group such as a carboxyl group or
• the silver halide photographic light-sensitive material of the invention may contain the following various additives: Those materials as viscosity increasing agents or plasticizers such as a styrene-sodium maleate copolymer and dextran sulfate as described in U.S. Patent Nos. 2,960,404 and 3,767,410; Japanese Patent Examined Publication Nos. 4939/1968 and 15462/­1970; West German DAS Patent No. 1,904,604; Japanese Patent O.P.I. Publication No. 63715/1973; and Belgian Patent Nos.
• plasticizers such as a styrene-sodium maleate copolymer and dextran sulfate as described in U.S. Patent Nos. 2,960,404 and 3,767,410
• Japanese Patent Examined Publication Nos. 4939/1968 and 15462/­1970 West German DAS Patent No. 1,904,604
• hardeners such as aldehyde-type, epoxy-­type, ethyleneimine-type, active halogen-type, vinylsulfone-­type, isocyanate-type, sulfonate-type, carbodiimide-type, muco­chloric acid-type and acyloyl-type compounds; ultraviolet absorbing agents including those compounds as described in U.S. Patent No. 3,253,921 and British Patent No. 1,309,349, such as 2-(2′-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2′-­hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole.
• surfactants are sulfone group-having anionic surfactants such as sulfonated succin­ates, sulfonated alkylnaphthalenes, and sulfonated alkylben­zenes.
• the pH range of the coating liquid is preferably 5.3 to 7.5.
• a mixture of the respective layers' coating liquids mixed in proportion of their coating amounts is preferred to have a pH of 5.3 to 7.5. If the pH is 5.3 or lower, the hardening makes slow progress, while if the pH exceeds 7.5, it badly affects the photographic character­istics.
• the component layers of the light-sensitive material of the invention may also contain a lubricant, examples of which include those higher alcohol esters of higher fatty acids described in U.S. Patent Nos. 2,588,756 and 3,121,060; the casein described in U.S. Patent No. 3,295,979; those higher fatty acid's calcium salts described in British Patent No. 1,263,722; and those silicon compounds described in British Patent No. 1,313,384, U.S. Patent Nos. 3,042,522 and 3,489,567. Liquid paraffin-dispersed products may also be used for this purpose.
• the light-sensitive material may also contain a brighten­ing agent, examples of which include stilbene-type, triazine-­type, pyrazoline-type, cumarine-type and acetylene-type com­pounds.
• These compounds may be either water-soluble ones or insol­uble ones to be used in the form of dispersion.
• anionic surfactant is preferably one con­taining an acid group such as a carboxy group, a sulfo group, a phospho group, a sulfate group or a phosphate group, exam­ples of which surfactant include alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkylsulfuric acid esters, alkylphosphoric acid esters, N-acyl-alkyltaurines, sul­ fosuccinic acid esters, sulfoalkylpolyoxyethylenealkylphenyl ethers, and polyoxyethylenealkylphosphoric acid esters.
• Preferred compounds as the amphoteric surfactant include amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric or phosphoric esters, alkylbetaines, and amine oxides.
• Preferred compounds as the cationic surfactant include alkylamines aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and aliphatic or heterocyclic ring-containing phosphonium or sulfonium salts.
• nonionic surfactant examples include sapo­nin (steroid type); alkylene oxide derivatives such as poly­ethylene glycol, polyethylene glycol/polypropylene glycol con­densate, polyethylene glycol-alkyl ethers or polyethylene glycol-alkylaryl ethers, polyethylene glycol esters, polyethyl­ene glycol sorbitan esters, polyalkylene glycol alkylamines or -amides and silicone-polyethylene oxide adducts; glycidol deri­vatives such as alkenylsuccinic acid polyglycerides, alkyl­phenol polyglycerides; polyhydric alcohol's fatty acid esters; and sugar's alkylesters.
• alkylene oxide derivatives such as poly­ethylene glycol, polyethylene glycol/polypropylene glycol con­densate, polyethylene glycol-alkyl ethers or polyethylene glycol-alkylaryl ethers, polyethylene glycol est
• the matting agent there may be suitably used any of those organic matting agents described in British Patent No. 1,055,713; U.S. Patent Nos. 1,939,213, 2,221,873, 2,268,662, 2,332,037, 2,376,005, 2,391,181, 2,701,245, 2,992,101, 3,079,257, 3,262,782, 3,516,832, 3,539,344, 3,591,379, 3,754,924 and 3,767,448, and those inorganic matting agents described in West German Patent No. 2,592,321; British Patent Nos. 760,775 and 1,260,772; and U.S. Patent Nos.
• the particularly preferred embodiment of the invention is to use a tetrazolium compound, a polyethylene oxide deriva­tive, a quaternary phosphate compound or a hydrazine compound as a tone control agent for increasing contrast as described in Japanese Patent O.P.I. Publication Nos. 210458/1987 and 139546/1987.
• a technique for improving dimen­sional stability by incorporating a polymer latex into the silver halide emulsion layer or backing layer.
• Examples of such the technique are disclosed in Japanese Patent Examined Publication Nos. 4272/1964, 17702/1964 and 13482/1968; U.S. Patent Nos. 2,376,005, 2,763,625, 2,772,166, 2,852,386, 2,853,457 and 3,397,988.
• gelatin As a binder for the light-sensitive material of the inven­ tion, gelatin is normally used.
• the binder may be composed of gelatin in combination with other hydrophilic colloid mate­rials including gelatin derivatives.
• the gelatin usable includes lime-treated gelatin, acid-­treated gelatin, the oxygen-treated gelatin described in Bull. Soc. Sci. Phot. Japan No.16, p.30 (1966), hydrolyzed gelatin and enzyme-decomposed gelatin.
• the gelatin derivative includes those obtained by the reaction of gelatin with various compounds such as an acid halide, an acid anhydride, an isocyanate, bromoacetic acid, an alkanesultone, a vinylsulfonamide, a maleic imide compound, a polyalkylene oxide, and epoxy compound.
• various compounds such as an acid halide, an acid anhydride, an isocyanate, bromoacetic acid, an alkanesultone, a vinylsulfonamide, a maleic imide compound, a polyalkylene oxide, and epoxy compound.
• examples of the gela­tin derivative are described in U.S. Patent Nos. 2,614,928, 3,132,945, 3,186,846 and 3,312,553; British Patent Nos. 861,414, 1,033,189 and 1,005,784; and Japanese Patent Examined Publication No. 26845/1967.
• the light-sensitive material of the invention may further contain various additives according to purposes. These addi­tives are detailed in Research Disclosure vol.176, Item 17643 (Dec. 1978) and vol.187, Item 18716 (Nov. 1979). The relevant pages and columns in the publications are listed in the follow­ing table.
• Additives RD 17643 RD 18716 1. Chemical sensitizers p.23 p.648, right col. 2. Sensitivity increasing agents p.648, right col. 3. Spectral sensitizers, supersensitizers p.23 to 24 p.648, right col. to p.649, right col. 4. Brightening agents p.24 5.
• the support used for the light-sensitive material of the invention includes an elastic reflection support such as a paper laminated with an ⁇ -olefin polymer such as polyethylene, polypropylene, ethylene/butene copolymer, or a synthetic paper; a film support composed of a semisynthetic or synthetic high molecular material such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene tere­phthalate, polycarbonate or polyamide; an elastic support obtained by providing a reflection layer on the above film; and a metallic support.
• the most preferred among these sup­ports is a polyethylene terephthalate support.
• a subbing layer usable in the invention includes those of the organic solvent type including polyhydroxybenzenes describ­ed in Japanese Patent O.P.I. Publication No. 3972/1974, and those aqueous latex subbing layers described in Japanese Patent O.P.I. Publication Nos. 11118/1974, 104913/1977, 19941/­1984, 19940/1984, 18945/1984, 112326/1976, 117617/1976, 58469/­1976, 114120/1976, 121323/1976, 123139/1976, 114121/1976, 13920/1977, 65422/1977, 109923/1977, 119919/1977, 65949/1980, 128332/1982 and 19941/1984.
• the subbing layer may have its surface usually subjected to chemical or physical treatment for surface activation, such as treatment with chemicals, mechanical treatment, corona dis­charge treatment, flame treatment, ultraviolet ray treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone-oxidation treatment.
• chemical or physical treatment for surface activation such as treatment with chemicals, mechanical treatment, corona dis­charge treatment, flame treatment, ultraviolet ray treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone-oxidation treatment.
• the subbing layer is distinguished from the provided layers for the invention in that no restrictions be put on its coating point of time and conditions.
• dyes may be used as filter dyes and for antihalation and various other purposes.
• the dyes for such purposes include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes and azo dyes.
• the oxanol dyes, hemioxanol dyes and merocyanine dyes are useful.
• Usable examples of such dyes include those described in West German Patent No. 616,007; British Patent Nos. 584,609 and 1,177,429; Japanese Patent Examined Publica­tion Nos. 7777/1951, 22069/1964 and 38129/1979; Japanese Patent O.P.I.
• these dyes may be suitably used for room­light reversing light-sensitive materials; it is particularly preferable to use such dyes so as to make the sensitivity to 400nm light more than 30 times as high as that to 360nm light.
• an organic desensitizer as described in Japanese Patent O.P.I. Publication No. 26041/1986, whose sum of the anode poten­tial and the cathode potential in a polarographic analysis is positive.
• the light-sensitive material of the invention can be ex­posed to an electromagnetic wave light in the spectral region to which the component emulsion layer thereof is sensitive. Exposure of the light-sensitive material can be carried out by using any one of known light sources including natural light (sunlight), tungsten lamp light, fluorescent lamp light, iodine quartz light, mercury vapor lamp light, microwave-emit­ting UV light, xenon arc light, carbon arc light, xenon flash light, cathod ray tube flying spot, various laser lights, light-emitting diode light, and those lights released from a phosphor excited by electron beam, X-rays, ⁇ -rays and ⁇ -rays.
• natural light unlight
• tungsten lamp light fluorescent lamp light
• iodine quartz light mercury vapor lamp light
• microwave-emit­ting UV light xenon arc light
• carbon arc light xenon flash light
• cathod ray tube flying spot various laser lights, light-emitting
• the exposure time may be not only a shorter time than 1 millisecond to 1 second which are used in usual camera expo­sure but also a much shorter time than 1 microsecond such as from 100 nanosecond to 1 microsecond by a cathode ray tube or xenon flash tube. And it is also possible to use a longer exposure time than 1 second.
• the exposure may be made either continuously or intermittently.
• the invention can be applied to various light-sensitive materials such as graphic-arts, X-ray, general negative-type, general reversal-type, general positive-type and direct posi­tive-type light-sensitive materials, but can exhibit remark­able effects particularly when applied to a graphic-arts light-­sensitive material which requires a very high dimensional sta­bility.
• the light-sensitive material of the invention may be sub­jected to known black-and-white, color or reversal processing, but is particularly effective when subjected to a high-con­trast processing for graphic arts light-sensitive materials.
• a fixer solution for use in the processing of the light-­sensitive material of the invention may contain a thiosulfate, a sulfite, various acids, salts, a fixing accelerator, a wet­ting agent, a surfactant, a chelating agent and a hardener;
• the thiosulfate and sulfite include potassium, sodium and ammonium sulfates and sulfites;
• the acids include sulfuric acid, hydrochloric acid, nitric acid, boric acid, formic acid, acetic acid, propionic acid, oxalic acid, tar­taric acid, citric acid, malic acid and phthalic acid; and the salts include potassium salts, sodium salts and ammonium salts of these acids.
• the fixing accelerator includes those thio­urea derivatives and intramolecular triple bond-having alco­hols as described in Japanese Patent Examined Publication No. 35754/1970, Japanese Patent O.P.I. Publication Nos. 122535/­ 1983 and 122536/1983; those thioethers described in U.S. Patent No. 4,126,459, anion-liberating cyclodextran ethers, crown ethers, diazabicycloundecene and di-(hydroxyethyl)but­amine.
• the wetting agent includes alkanolamines and alkylene glycols.
• the chelating agent includes nitrilotriacetic acid and amino acids such as EDTA.
• the hardener includes chrome alum potassium alum and other aluminum compounds.
• the fixer solution in the invention in order to increase the hardening of the light-sensitive material, contains preferivelyably an aluminum compound.
• the aluminum compound content of the fixer solution is preferably 0.1 to 3g/liter in aluminum equivalent.
• the sulfite content of the fixer solution is preferably 0.03 to 0.4 mole/liter, and more preferably 0.04 to 0.3 mole/­liter.
• the fixer solution has a pH of preferably 3.9 to 6.5.
• the pH range of the fixer solution not only provides satisfac­tory photographic characteristics but has remarkable effects upon packaging materials of the invention.
• the most preferred pH of the solution is 4.2 to 5.3.
• the light-sensitive material of the invention is devel­oped at a temperature of preferably not higher than 50°C, and more preferably 25°C to 40°C, for a period of normally within two minutes; particularly 5 to 25 seconds high spped process­ing also gives a good photographic image.
• Those processes other than the developing and fixing process, such as washing, stopping, stabilizing and prehardening or neutralizing pro­cesses may be excluded.
• the present invention exhibits its merits largely even when the light-sensitive material of the invention is subject severelyed to a ultra-high-speed processing, whose processing time is as short as 20 to 60 seconds.
• the 'ultra-high-speed processing' herein means a process­ing by an antomatic processor in which the quotient obtained when the overall period of time from the insertion of the lead­ing end of a light-sensitive material traveling through the developer bath, crossover section, fixer bath, crossover sec­tion, washing bath and drying section until the ejection of the leading end therefrom, i.e., the overall length of the processing line, is divided by the line transport speed is 20 seconds to 60 seconds.
• the reason why the crossover sections are included, although well-known to those skilled in the art, is that even in the crossover sections, the solution in the preceding process remains in a transported light-sensitive material to have its processing effect substantially make pro­gress.
• Negative-type silver halide light-sensitive material samples as roomlight reversing light-sensitive materials were prepared in the following manner:
• Silver chlorobromide emulsions containing 2 mole% silver bromide and 50 mole% silver chloride, were prepared in the following manner:
• a silver nitrate aqueous solution and an aqueous solution containing potassium pentabromorhodium in an amount of 23.9mg per 60g of silver nitrate, sodium chloride and potassium bromide were simultaneously mixed into a gelatin aqueous solu­tion with stirring in 25 minutes at 40°C, whereby silver chloro­bromide emulsions each having an average grain size of 0.20 ⁇ m were prepared.
• the emulsions after adding thereto further 20mg of 6-­methyl-4-hydroxy-1,3,3a,7-tetrazaindene, were subjected to sulfur sensitization. After the sulfur sensitization, respec­tively necessary amounts of gelatin and a stabilizer 6-methyl-­4-hydroxy-1,3,3a,7-tetrazaindene were added, and then water was added to each of the emulsions to make its quantity 260ml.
• a mixture liquid of 4.51kg of n-butyl acrylate, 5.49kg of styrene and 0.1kg of acrylic acid was added spending an hour to, with stirring at 81°C under a nitrogen atmosphere, a solu­tion of 0.25kg of KMDS (dextran sodium sulfate) produced by Meito Industry Co. and 0.05kg of ammonium persulfate dissolved into 40 liters of water, and then 0.005kg of ammonium persul­fate was added. After that, the liquid was stirred for 1.5 hours, cooled and then adjusted to pH 6 with ammonia water.
• KMDS extran sodium sulfate
• the obtained latex liquid was filtered through a GF/D filter manufactured by Whotman Co., and the quantity of the filtrate was made 50.5kg by adding water thereto, whereby a monodisperse latex L-6 having an average particle size of 0.25 ⁇ was prepared.
• Each of the emulsions after adding thereto 9mg of phenol as a fungicide, was adjusted to pH 6.5 with a 0.5N sodium hydr­oxide solution, to which were then added in sequence 360mg of the following compound T, 5ml of a 20% saponin solution per mole of silver halide, 180mg of sodium dodecylbenzenesulfon­ate, 80mg of 5-methylbenzenetriazole 43ml of the above latex liquid L-6, 60mg of the following compound M and 280mg of an aqueous styrene-maleic acid copolymer, and added water to make the whole quantity 475ml, whereby emulsion coating liquids were prepared.
• a protective layer coating liquid was prepared in the following manner.
• a backing layer coating liquid was prepared in the following manner.
• a protective layer coating liquid B-2 for protection of the backing layer was prepared in the following manner.
• the backing layer coating liquid B-1 so as to make the dry gelatin weight 2g/m2
• the protective layer coating liquid B-2 so as to make the dry gelatin weight 1g/m2.
• Each of the above coating liquids was coated so as to have a wet layer thickness adjusted to 64 ⁇ m by a slide hopper method at a line speed of 70m/min. Exposure of each of these samples was made with its emulsion side contacted with an original placed in a roomlight printer P-627FM, manufactured by Dai-Nippon Screen Co., provided with an anelectric dis­ charge tube light source, manufactured by FUSION Inc. of U.S.
• Each sample was processed in the following processing sol­utions under the following conditions.
• the amount of silver was analyzed by an X-ray fluorescence analyzer.
• the amount of silver after the processing was expressed in terms of the amount of silver in an area that gives the maximum density.
• evaluation was made by examin­ing each sample's whole area overall exposed and processed so as to give a density of 1.3 by using the above-mentioned printer.
• evaluation was made by examining how rainbow mottles appear on the coated side of each sample exposed and processed so as to give a density of 4.0 or more.
• Developer Composition A Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% W/V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide, an amount necessary to adjust pH to 10.9 Potassium bromide 4.5 g
• Composition B Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg
• Fixer bath Composition A Ammonium thiosulfate (72.5% W/V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate, trihydrated 15.9 g Boric acid 6.7 g Sodium citrate, dihydrated 2 g Acetic acid (90% W/W aqueous solution) 8.1 ml
• Composition B Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% W/W aqueous solution) 5.8 g
• the time of each step includes the transport time in the crossover section prior to the following step. Dry-to-dry time is 50 seconds.
• Table 1 Sample No. Amounts of gelatin Em/Pro Amt of latex in protective layer ⁇ Coating unevenness ranked Effective amt of dev'd Ag Rainbow mottle level Pin hole level Dimensional changes Drying temp. 40°C 55°C A-1 (Comp.) 2.0/1.8g/m2 0 g/m2 8.0 4 4.0g/m2 2 2 23 ⁇ m 45 ⁇ m A-2 (Comp.) 2.0/0.5 0 9.0 3 4.2 2 2 20 40 A-3 (Inv.) 2.0/0.8 0.2 10.1 5 4.1 5 5 18 27 A-4 (Inv.) 2.0/0.5 0.2 9.5 5 4.2 4 4 19 26 A-5 (Comp.) 1.8/1.0 0 10.2 3 4.2 2 21 39 A-6 (Comp.) 1.8/0.5 0 10.5 2 4.2 1 2 22 43 A-7 (Inv.) 1.8/1.0 0.2 9.8 4 4.2 5 5 20 30 A-8 (Inv.) 1.8/0.5 0.2 9.5 5 4.2 4 18 29
• Example 1 Experiments were made in the same manner as in Example 1 except that the following sensitizing dye C was added at the time of chemical sensitization for preparation of samples in Example 1, and exposure was made through the same glass wedge to a tungsten lamp, and consequently, quite the same results as in Example 1 were obtained.
• Example 2 Experiments were made in the same manner as in Example 1 except that the polymer latex L-6 added after the emulsion coating in Example 1 was replaced by polymer latex L-3 and the polymer latex L-6 added to the protective layer coating liquid was replaced by polymer latex L-7 (provided R: -CH3).
• polymer latex L-7 provided R: -CH3
• 2.5g/m2 of polymer latex L-3 was added as a latex component to the emulsion layer, which was coated so as to have a wet thickness of 80 ⁇ m, and to the protective layer was added latex L-7 as specified in Table 2, whereby samples B-1 to B-12 were prepared.
• Table 2 Sample No.
• Table 2 shows that the invention can provide a light-sen­sitive material which is capable of forming a high- ⁇ and high-­density image excellent in the dimensional stability even in either a super-high-speed processing or a conventional process­ing, and which is free of pinholes and coating defects.

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Cited By (5)

• 1990
  • 1990-02-14 EP EP90102837A patent/EP0383283A2/fr not_active Withdrawn
  • 1990-02-16 CA CA002010252A patent/CA2010252A1/fr not_active Abandoned
  • 1990-02-16 KR KR1019900001975A patent/KR900013342A/ko not_active Application Discontinuation

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