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
  • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
• • 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
  • G03C1/38—Dispersants; Agents facilitating spreading
• • 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
  • G03C1/38—Dispersants; Agents facilitating spreading
  • G03C1/385—Dispersants; Agents facilitating spreading containing fluorine

Definitions

• the present invention relates to a silver halide photosensitive material excellent in coated surface state and antistatic property, as well as a packaged body containing the same.
• surfactants Compounds having a fluoroalkyl chain have been known as surfactants.
• Such surfactants can provide various surface modifications due to the inherent nature of the fluoroalkyl chain (for example, water repellency, oil repellency, lubricity, antistatic property, or the like) and have been used for general surface finishing for base materials such as fibers, cloths, carpets, resins, and the like.
• fluorocarbon surfactants for example, but not only is it possible to form uniform coated films with no repellency but also to form an adsorption layer of the surfactant on the surface of the substrate upon forming a coated film, thereby bringing inherent properties of the fluoroalkyl chains to the surfaces of coated films.
• a photosensitive material is usually prepared by coating a plurality of coating solutions including an aqueous solution of a hydrophilic colloidal binder (for example, gelatin) individually on a support to thereby form a plurality of layers.
• a hydrophilic colloidal binder for example, gelatin
• simultaneous multilayer coating of a plurality of hydrophilic colloidal layers has also been frequently conducted.
• the layers include an antistatic layer, an undercoat layer, an antihalation layer, a silver halide emulsion layer, an intermediate layer, a filter layer, a protective layer, and the like, to each of which various materials are added for providing various functions.
• polymer latex is sometimes incorporated in the hydrophilic colloidal layers for improving physical properties of the film.
• a photosensitive material comprises various hydrophilic colloidal layers, and it is required for their manufacture that a coating solution containing various materials is coated uniformly and at a high speed with no defects such as repellency or coating unevenness. In order to satisfy such a demand, addition of a surfactant as a coating aid to coating solutions has often been conducted.
• photosensitive materials are in contact with various substances during manufacture thereof, photographing, and development treatment.
• a back layer formed on the backside of the support is sometimes in contact with a surface layer.
• photosensitive materials for direct use are sometimes in contact with a screen or human hands.
• the photosensitive material is sometimes brought into contact with a stainless steel material, a rubber roller comprising various compositions, or the like.
• a nonionic hydrocarbon surfactant, a nonionic fluorocarbon surfactant, and an anionic fluorocarbon surfactant are often used in combination in a delicate balance to provide resistance to static charge in silver halide photosensitive materials, particularly in silver halide photosensitive materials sensitive to X-ray irradiation (X-ray photosensitive materials), as disclosed in JP-A Nos. 62-109044 and 7-159929 .
• JP-A No. 2005-03888 discloses a silver halide photosensitive material excellent in resistance to static charge and antistatic property due to the use of a nonionic fluorocarbon compound and an anionic fluorocarbon compound in combination, this cannot cope with the demands upon high-speed coating in view of surface state performance.
• the silver halide photosensitive materials described above are cut into sheets, and a laminate is formed by stacking a plurality of sheets and a non-photosensitive plate material usually referred to as protection cardboard, and then the laminate is packaged with a moisture-proof packaging material and distributed as a sealed packaged body on the market. Further, upon use, it is loaded in this packaged body as it is in an image recording apparatus, the package is opened in the apparatus, and the silver halide photosensitive materials are taken out one by one and subjected to imagewise exposure and development treatment. Therefore, in a case where the silver halide photosensitive material loaded in the lowermost portion is in contact with the protection cardboard for a long time in a press contact state, the silver halide emulsion surface is directly influenced by the packaging material.
• the protection cardboard generates dust
• the silver halide photosensitive material rubs against the protection cardboard and receives scratches on the surface due to vibration generated during transportation or upon loading to the image recording apparatus.
• the protection cardboard is sometimes torn or peeled, resulting in trouble.
• the present invention has been made in view of the above circumstances and provides a silver halide photosensitive material and a packaged body with the following aspects.
• a first aspect of the invention is to provide a silver halide photosensitive material comprising, on at least one side of a transparent support, at least one photosensitive silver halide emulsion layer, and containing an anionic fluorocarbon compound represented by the following formula (1), an anionic hydrocarbon compound represented by the following formula (2), and at least one of an anionic hydrocarbon compound represented by the following formula (3) or an anionic hydrocarbon compound represented by the following formula (4): wherein R B3 , R B4 , and R B5 each independently represent a hydrogen atom or a substituent; A 3 and A 4 each independently represent a fluorine atom or a hydrogen atom; nB3 and nB4 each independently represent an integer of from 4 to 8; L B1 and L B2 each independently represent an alkylene group, an alkyleneoxy group, or a divalent linking group formed by combining groups selected from among these groups; mB represents 0 or 1 ; and M represents a cation; wherein R 31 represents an alkyl group or al
• a second aspect of the invention is to provide a packaged body in which a laminate formed by stacking a sheet of the silver halide photosensitive material according to the first aspect and a non-photosensitive plate material having a layer coated with an organic material on the surface thereof is packed and sealed with a light shielding sack-shaped material.
• An object of the present invention is to provide a silver halide photosensitive material excellent in coated surface state and antistatic property, and a packaged body including the same.
• each group includes any of embodiments including a case where the group is unsubstituted and a case where the group has a substituent, unless otherwise specified.
• surfactants particularly fluorocarbon surfactants
• a coating aid for providing homogeneity to a coated film
• an agent for providing antistatic property to photosensitive materials for providing fluorocarbon surfactants
• the inventors found that high-speed coating adaptability can be satisfied by incorporating a specified anionic surfactant into a surfactant containing a fluoroalkyl group, and thereby arrived at the present invention. Further, it has been found that, by constituting a packaged body using a protection cardboard material whose surface is coated, the aforementioned performances and storage stability can be made compatible, whereby the present invention according to the second aspect was achieved.
• the present invention provides a silver halide photosensitive material excellent in coated surface state and antistatic property, and a packaged body containing the same.
• R B3 , R B4 , and R B5 each independently represent a hydrogen atom or a substituent.
• a 3 and A 4 each independently represent a fluorine atom or a hydrogen atom.
• nB3 and nB4 each independently represent an integer of from 4 to 8.
• L B1 and L B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining groups selected from among these groups.
• mB represents 0 or 1.
• M represents a cation.
• R B3 , R B4 , and R B4 each independently represent a hydrogen atom or a substituent.
• substituent T described below can be applied.
• R B3 , R B4 , and R B5 are preferably an alkyl group or a hydrogen atom, more preferably an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, even more preferably a methyl group or a hydrogen atom, and particularly preferably a hydrogen atom.
• a 3 and A 4 each independently represent a fluorine atom or a hydrogen atom.
• a 3 and A 4 may be the same or different from each other.
• it is preferred that both of A 3 and A 4 are simultaneously a fluorine atom or a hydrogen atom, and it is more preferred that both of A 3 and A 4 are a fluorine atom.
• nB3 and nB4 each independently represent an integer of from 4 to 8.
• nB3 and nB4 may be the same or different from each other as far as nB3 and nB4 are an integer of from 4 to 8.
• nB3 and nB4 are preferably an integer of from 4 to 6 and nB3 is equal to nB4. More preferably, nB3 and nB4 are 4 or 6 and nB3 is equal to nB4. Even more preferably, both of nB3 and nB4 are 4.
• mB represents 0 or 1, and both are similarly preferable.
• L B1 and L B2 each independently represent a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining groups selected from among these groups.
• substituent T substituent T described below can be applied.
• L B1 and L B2 each have preferably 6 or less carbon atoms, and preferably, L B1 and L B2 are an unsubstituted alkylene group.
• M represents a cation, and as the cation represented by M, for example, an alkaline metal ion (a lithium ion, a sodium ion, a potassium ion, or the like), an alkaline earth metal ion (a barium ion, a calcium ion, or the like), an ammonium ion, or the like are preferably applied.
• an alkaline metal ion a lithium ion, a sodium ion, a potassium ion, or the like
• an alkaline earth metal ion a barium ion, a calcium ion, or the like
• an ammonium ion, or the like are preferably applied.
• M is preferably a lithium ion, a sodium ion, a potassium ion, or an ammonium ion; more preferably a lithium ion, a sodium ion, or a potassium ion; and even more preferably a sodium ion.
• nB1 and nB2 each independently represent an integer of from 1 to 6.
• nB1 and nB2 may be the same or different from each other as far as these are an integer of from 1 to 6.
• nB1 and nB2 are preferably an integer of 1 to 6 and nB1 is equal to nB2. More preferably, nB1 and nB2 are an integer of from 1 to 3 and nB1 is equal to nB2. Even more preferably, nB1 and nB2 are 2 or 3 and nB1 is equal to nB2. Particularly preferably, both of nB1 and nB2 are 2.
• nB1, nB2, nB3, nB4, mB, and M each have the same meaning as in formula (1-A) described above, and preferable ranges are similar to those in formula (1-A).
• nB5 represents 2 or 3.
• nB6 represents an integer of from 4 to 6.
• mB represents 0 or 1, and both are similarly preferable.
• M has the same meaning as in formula (1) described above, and preferable range is also similar to that in formula (1).
• the coating amount of the compound represented by formula (1) is preferably in a range of from 0.01 mg/m 2 to 100 mg/m 2 , more preferably from 0.1 mg/m 2 to 50 mg/m 2 , and even more preferably from 0.3 mg/m 2 to 10 mg/m 2 .
• R 31 represents an alkyl group or alkenyl group having 6 to 25 carbon atoms.
• R 32 s may be identical or different from one another and each represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 1 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
• L 1 represents an integer of from 0 to 10.
• m 1 represents an integer of from 0 to 30. However, L 1 and m 1 do not simultaneously represent 0.
• n1 represents an integer of from 0 to 4.
• e represents 0 or 1.
• Z 31 represents an OSO 3 M group or an SO 3 M group, and M represents a cation.
• R 31 represents an alkyl group or alkenyl group having 6 to 25 carbon atoms.
• R 31 has preferably 6 to 22 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 8 to 18 carbon atoms.
• the alkyl group and the alkenyl group may have a cyclic structure, a linear alkyl group and a linear alkenyl group are more preferable.
• the alkyl group and the alkenyl group may have a substituent; however, an unsubstituted alkyl group and alkenyl group are preferable.
• the linear alkyl group and the linear alkenyl group may be branched.
• the position of the double bond of the alkenyl group is not particularly limited. An alkyl group is more preferable than an alkenyl group.
• R 32 s each represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, an alkenyl group having 1 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
• the alkyl group and the alkenyl group preferably have 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
• the aralkyl group preferably has 7 to 13 carbon atoms, and particularly preferably 7 to 10 carbon atoms.
• the aryl group preferably has 6 to 12 carbon atoms, and particularly preferably 6 to 10 carbon atoms.
• R 32 s in formula (2) described above, may bond to each other to have a cyclic structure. Further, R 32 s may have a substituent and examples of the preferable substituent are shown below.
• a halogen atom for example, a fluorine atom, a chlorine atom, or a bromine atom
• an alkyl group for example, methyl, ethyl, isopropyl, n-propyl, or t-butyl
• an alkenyl group for example, allyl or 2-butenyl
• an alkynyl group for example, propalgyl
• an aralkyl group for example, benzyl
• an aryl group for example, phenyl or naphthyl
• a hydroxy group for example, an alkoxy group (for example, methoxy, ethoxy, butoxy, or ethoxyethoxy), an aryloxy group (for example, phenoxy or 2-naphthyloxy), and the like are described.
• R 32 s each preferably represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or a hydroxymethyl group.
• L 1 represents an integer of from 0 to 10.
• L 1 is preferably an integer of from 0 to 8, more preferably an integer of from 0 to 6, even more preferably an integer of from 0 to 4, and particularly preferably 0.
• m 1 represents an integer of from 0 to 30.
• m 1 is preferably an integer of from 0 to 25, more preferably an integer of from 0 to 20, and particularly preferably an integer of from 0 to 15.
• n1 represents an integer of from 0 to 4. Particularly preferably, n1 is an integer of from 2 to 4.
• Z 31 represents an OSO 3 M group or an SO 3 M group
• M represents a cation.
• the cation represented by M for example, an alkaline metal ion (a lithium ion, a sodium ion, a potassium ion, or the like), an alkaline earth metal ion (a barium ion, a calcium ion, or the like), an ammonium ion, or the like is applied preferably.
• a lithium ion, a sodium ion, a potassium ion, and an ammonium ion are particularly preferable.
• e represents 0 or 1, and e is preferably 0.
• the compound represented by formula (2) described above can be synthesized by the known methods described in JP-A No. 2001-3263 , J. Amer. Chem. Soc., vol. 65, page 2196, (1943 ), J Phys. Chem., vol. 90, page 2413, (1986 ), J. Dispersion Sci. and Tech., vol. 4, page 361, (1983 ), U.S. Patent (USP) No. 5,602,087 , and the like.
• an alkyl group preferably an alkyl group having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 8 carbon atoms; and as examples, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a n-octyl group, a n-decyl group, a n-hexadecyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like are described), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 8 carbon atoms; and as examples, a vinyl group, an allyl group, a 2-butenyl group, a 3-pentenyl group, and the like are described), an alkyl group (preferably an alky
• the coating amount of the compound represented by formula (2) is preferably in a range of from 0.1 mg/m 2 to 300 mg/m 2 , more preferably from 1 mg/m 2 to 150 mg/m 2 , and even more preferably from 5 mg/m 2 to 80 mg/m 2 .
• R 3 may be branched or not, and represents an alkyl group, alkylene group, or aralkyl group having 6 to 24 carbon atoms.
• R 3 has preferably 8 to 10 carbon atoms, and more preferably 10 to 18 carbon atoms.
• L 3 represents an alkylene group having a hydroxy group and 3 to 5 carbon atoms, a vinylene group, a vinylenealkylene group, or a divalent linking group formed by combining groups selected from among these groups.
• the number of the hydroxy group is not limited, however preferably 0 or 1.
• b represents 0 or 1.
• L 3 is preferably an alkylene group having a hydroxy group and 3 to 5 carbon atoms, a vinylenealkylene group, or a divalent linking group formed by combining the alkylene group and the vinylene group.
• Z 3 represents an OSO 3 M group or an SO 3 M group
• M represents a cation.
• the cation represented by M for example, an alkaline metal ion (a lithium ion, a sodium ion, a potassium ion, or the like), an alkaline earth metal ion (a barium ion, a calcium ion, or the like), an ammonium ion, or the like is preferably applied.
• a lithium ion, a sodium ion, a potassium ion, and an ammonium ion are particularly preferable.
• the coating amount of the compound represented by formula (3) is preferably in a range of from 0.01 mg/m 2 to 300 mg/m 2 , more preferably from 1 mg/m 2 to 100 mg/m 2 , and even more preferably from 3 mg/m 2 to 50 mg/m 2 .
• R 41 , R 42 , and R 43 each independently represent a hydrogen atom or a substituent.
• n2 and n3 each independently represent an integer of from 1 to 5.
• L 41 and L 42 each independently represent an alkylene group substituted by a substituent other than a fluorine atom, an unsubstituted alkylene group, a substituted or unsubstituted alkyleneoxy group, or a divalent linking group formed by combining groups selected from among these groups.
• m2 represents 0 or 1.
• M represents a cation.
• the coating amount of the compound represented by formula (4) is preferably in a range of from 0.1 mg/m 2 to 300 mg/m 2 , more preferably from 1 mg/m 2 to 150 mg/m 2 , and even more preferably from 5 mg/m 2 to 80 mg/m 2 .
• n3 represents 15 to 60 and may be single or distributed. When there is a distribution, m3 represents an average value of them. m3 is preferably 20 to 40. n4 represents 8 to 24 and may be single or distributed. When there is a distribution, n4 represents an average value of them. n4 is preferably 10 to 20, more preferably 12 to 20, even more preferably 12 to 18, and particularly preferably 12 to 16.
• formula (5) preferred is the following formula (5-A).
• Formula (5-A) C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCH 2 CH 2 ) ma ⁇ OC na H 2na+1
• ma 20 to 40
• ma is preferably 25 to 40, and may be single or distributed.
• ma represents an average value of them.
• na represents 12 to 18.
• na is preferably 12 to 16, and may be single or distributed.
• na represents an average value of them.
• FS-101 C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCHCH 2 ) 20 ⁇ OC 18 H
• FS-102 C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCHCH 2 ) 21 ⁇ OC 12 H 25
• FS-103 C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCHCH 2 ) 23 ⁇ OC 16 H
• FS-104 C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCHCH 2 ) 25 ⁇ OC 12 H 25
• FS-105 C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCHCH 2 ) 40 ⁇ OC 16 H
• FS-106 C 4 F 9 ⁇ CH 2 CH(OH)CH 2 ⁇ (OCHCH 2 ) 32 ⁇ OC 14 H 29
• the compound represented by formula (5) described above can be synthesized by the method described in Journal of Fluorine Chemistry, vol. 84, pages 53 to 61, 1997 , and the like. That is, various derivatives can be synthesized by heating an epoxide compound having a fluoroalkyl group as a substituent and a compound having a hydroxy group in the presence of Lewis acid.
• the compounds represented by formulae (1) to (5) are preferably used as surfactants in the aqueous coating composition for forming layers constituting the silver halide photosensitive material.
• the use of the compounds is particularly preferred from the standpoints of attaining effective antistatic performance and high-speed coating ability.
• the coating composition containing the compounds represented by formulae (1) to (5) according to the present invention, as surfactants, is described below.
• the aqueous coating composition of the present invention contains the compounds represented by formulae (1) to (5) according to the present invention and a medium for dissolving and/or dispersing the compounds.
• the coating composition may appropriately contain other components depending on the purpose.
• an aqueous medium is preferred as a medium for the aqueous coating composition of the present invention.
• the aqueous medium include water and a mixed solvent of water and an organic solvent other than water (for example, methanol, ethanol, isopropyl alcohol, n-butanol, methyl cellosolve, dimethylformamide, acetone, and the like).
• the medium of the coating composition described above preferably contains 50% by weight or more of water.
• the compounds represented by formulae (1) to (5) each may be used individually or by mixing two or more thereof.
• Other surfactant may also be used in combination with the compounds of the present invention.
• an anionic surfactant, a cationic surfactant, or a nonionic surfactant are described.
• the surfactant that can be used in combination may be a polymer surfactant or may be a fluorocarbon surfactant other than the surfactants of the present invention.
• the surfactant used in combination is preferably an anionic surfactant or a nonionic surfactant.
• a polymer compound is a representative example of the other component that can be used in the aqueous coating composition of the present invention.
• the polymer compound may be a polymer which is soluble in the aqueous medium (hereinafter referred to as "soluble polymer”) or may be an aqueous dispersion of polymer (so-called polymer latex).
• the soluble polymer is not particularly limited but examples thereof include gelatin, poly(vinyl alcohol), casein, agar, gum arabic, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, and the like.
• polymer latex examples include homopolymer or copolymer of vinyl monomer (for example, an acrylate derivative, a methacrylate derivative, an acrylamido derivative, a methacrylamido derivative, a styrene derivative, a conjugated diene derivative, an N-vinyl compound, an O-vinyl compound, vinyl nitrile, and other vinyl compounds (for example, ethylene or vinylidene chloride)), and a dispersion of condensed polymer (for example, polyester, polyurethane, polycarbonate, or polyamide).
• specific examples of the polymer compound include polymer compounds described in, for example, JP-A No.
• the aqueous coating composition according to the present invention may contain other various compounds, which may be either dissolved or dispersed in the medium. Examples thereof include a coupler, an ultraviolet absorber, an anti-color mixing agent, an antistatic agent, a scavenger, an antifoggant, a hardener, a dye, a rust-preventing agent, and the like.
• the aqueous coating composition according to the present invention is preferably used for forming a hydrophilic colloidal outermost layer of the silver halide photosensitive material, and in this case, in addition to the hydrophilic colloid (for example, gelatin) and the fluorocarbon compound of the present invention, the coating composition can contain a surfactant other than the above, a matting agent, a lubricant, a colloidal silica, a gelatin plasticizer, and the like.
• the photosensitive silver halide emulsion for use in the silver halide emulsion layer according to the present invention is described below.
• an average iodide content of the photosensitive silver halide grain is preferably in a range of from 0 mol% to 0.45 mol%.
• the average iodide content is preferably in a range of from 0.05 mol% to 0.40 mol%, and more preferably from 0.10 mol% to 0.30 mol%.
• the "average" iodide content of the photosensitive silver halide grain herein means an average value of the iodide contents obtained from halogen compositions of the respective photosensitive silver halide grains.
• the distribution of the halogen composition in a photosensitive silver halide grain may be uniform or the halogen composition may be changed stepwise, or it may be changed continuously. Further, a photosensitive silver halide grain having a core/shell structure can also be used.
• Halogen conversion type (conversion type) grains as described in GB Patent No. 635,841 and USP No. 3,622,318 can be effectively used in the present invention.
• Halogen conversion is generally conducted by addition of an aqueous solution of halogen, which has a solubility product of halogen and silver being lower than that of a halogen composition on the surface of the grains before halogen conversion.
• conversion is effected by adding an aqueous solution of potassium bromide and/or an aqueous solution of potassium iodide to tabular silver chloride grains or tabular silver chlorobromide grains, or by adding an aqueous solution of potassium iodide to tabular silver bromide grains or tabular silver iodobromide grains.
• the concentration of the aqueous solution to be added is low. A concentration of 30% or lower is preferred, and a concentration of 10% or lower is more preferred.
• the halogen solution for conversion is preferably added at a rate of 1 mol%/minute or lower per 1 mol of silver halide before halogen conversion. Further, a part or the whole of sensitizing dye and/or silver halide-adsorbing material may be present during the halogen conversion. Alternatively, fine grains of silver bromide, silver iodobromide or silver iodide may be added in place of the aqueous halogen solution for conversion.
• the grain size of the fine grain is generally 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, and particularly preferably 0.05 ⁇ m or less.
• the halogen conversing method that can be used in the present invention is not limited to the above, and various methods may be properly employed in combination depending on the purpose.
• the method of forming photosensitive silver halide grain is well-known in the relevant art and, for example, methods described in JP-A No. 2-68539 , USP No. 3,700,458 , and Research Disclosure, Item 17029 (Jun., 1978 ) can be used.
• JP-A Nos. 2-68539 As a chemical sensitizing method for use in the present invention, the methods described in JP-A Nos. 2-68539 , page 10, upper right column, line 13 to lower left column, line 16, JP-A Nos. 5-313282 and 6-110144 can be applied.
• chemical sensitizing method for silver halide emulsion specifically, in the presence of a silver halide-adsorbing compound, well-known method such as sulfur sensitizing method, selenium sensitizing method, reduction sensitizing method, or gold sensitizing method may be used individually or in combination.
• Gold sensitizing method is a representative example of the noble metal sensitizing method, and a gold compound, mainly a gold complex salt, is used.
• Complex salt of noble metal other than gold such as platinum, palladium, iridium, or the like may also be employed. Specific examples thereof are described in USP No. 2,448,060 and GB Patent No. 618,061 .
• sulfur sensitizer in addition to a sulfur compound included in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, and the like can be used. Specific examples thereof are described in USP Nos. 1,574,944 , 2,278,947 , 2,410,689 , 2,728,668 , 5,501,313 , and 8,656,955 . Examples of the selenium sensitizer are described in JP-A No. 6-110144 .
• the combined use of the sulfur sensitization by thiosulfate and the selenium sensitization or the gold sensitization is very useful.
• the reduction sensitizer include a tin (I) salt, amines, formamidinesulfinic acid, a silane compound, and the like.
• azoles for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroimidazoles, benztriazoles, aminotriazoles, and the like
• mercapto compounds for example, mercaptothiazoles, mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, and the like
• thioketo compounds such as oxazoline thione; azaindenes (for example, triazaindenes, tetraazaindenes (especially, 4-hydroxy-substituted (1,3,3a,7) tetraazaindenes), pentaazaindenes, and the like);
• a nitron and a derivative thereof described is JP-A Nos. 607673 and 60-87322 , a mercapto compound described in JP-A No. 60-80839 , a heterocyclic compound described in JP-A No. 57-164735 , a complex salt of a heterocyclic compound and an acid (for example, 1-phenyl-5-mercaptotetrazoles) and the like are preferably used.
• purines, nucleic acids and polymer compounds described in Japanese Patent Application Publication ( JP-B) No. 61-36213 , JP-A No. 59-90844 , and the like are also used.
• azaindenes, purines, and nucleic acids are particularly preferably used.
• the addition amount of the compound is from 0.5 mmol to 5.0 mmol, and preferably from 0.5 mmol to 3.0 mmol, per 1 mol of silver halide.
• Color-tone-improving agents usable in the present invention are described in JP-A Nos. 62-276539 , page 2, lower left column, line 7 to page 10, lower left column, line 20, and JP-A No. 3-94249 , page 6, lower left column, line 15 to page 11, upper right column, line 19.
• a dye having a maximum absorption wavelength in the wavelength range of from 520 nm to 560 nm and a dye having a maximum absorption wavelength in the wavelength range of from 570 nm to 700 nm can be added in at least one of the silver halide emulsion layer and the other layers in such an amount that the increase in transmission density due to the presence of the dye at the unexposed portion after development is 0.03 or less.
• Typical examples of the silver halide emulsion layer having a covering power of 60 or more include a tabular grain emulsion, a fine grain emulsion, and the like.
• the silver halide emulsion comprising tabular silver halide grains having a mean grain thickness of 0.4 ⁇ m or less is used, or when a mixed emulsion of a surface-photosensitive emulsion with high iodide content and an emulsion comprising fine internally fogged silver halide grains is used, the effect for improving color tone becomes large.
• Examples of the dyes used for improving color tone in the present invention include the combined use of a dye having a maximum absorption wavelength in the wavelength range of from 520 nm to 560 nm, preferably from 530 nm to 555 nm, and a dye having a maximum absorption wavelength in the wavelength range of from 570 nm to 700 nm, preferably from 580 nm to 650 nm.
• the maximum absorption wavelength herein means a maximum absorption wavelength obtained in the state where the dye is incorporated in the photosensitive material.
• Examples of the dye for use in the present invention include those having the aforesaid maximum absorption wavelength selected from an anthraquinone dye, an azo dye, an azomethine dye, an indoaniline dye, an oxonol dye, a carbocyanine dye, a styryl dye, a triphenylmethane dye, and the like.
• Preferred examples thereof are selected from an anthraquinone dye, an azo dye, an azomethine dye, and an indoaniline dye, in consideration of stability to development treatment, durability to light, and influence on photographic performance such as desensitization, fogging, stain, and the like.
• Preferred compounds are described in JP-A No.62-276539 , page 3, upper left column, line 5 to page 9, upper left column, line 9.
• dyes can be incorporated in the emulsion layer or other hydrophilic colloidal layers (an intermediate layer, a protective layer, an antihalation layer, and a filter layer) by dispersing them according to various known methods. Specific examples of the method are described in JP-A No. 62-276539 , page 9, upper left column, line 14 to page 10, lower left column, line 20.
• cyanine dye examples include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like.
• the addition amount of the sensitizing dye is preferably in a range of 0.5 mmol or more and less than 4 mmol, and more preferably in a range of 0.5 mmol or more and 1.5 mmol or less, per 1 mol of silver halide.
• sensitizing dye examples include dyes II-1 to II-47 described in JP-A No. 2-68539 , pages 5 to 8.
• surfactants described in JP-A No. 2-68539 , page 11, upper left column, line 14 to page 12, upper left column, line 9 can be used as a coating aid, an antistatic agent, or a static-controlling agent.
• the surfactant used for the aforesaid purpose include nonionic surfactants such as saponin (steroid type), alkylene oxide derivatives (for example, polyethylene glycol, a condensation product of polyethylene glycol/ propylene glycol, polyethylene glycol alkylethers, polyethylene glycol alkylarylethers, or silicone-polyethylene oxide compounds), sugar-alkyl esters, and the like; anionic surfactants such as alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkylsulfate esters, N-acyl-N-alkyltaurines, sulfosuccinate esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, and the like; amphoteric surfactants such as alkyl betaines, alkylsulfo betaines, and the like; and cationic surfactants such as aliphatic surfactants
• anionic surfactants such as saponin, sodium dodecylbenzenesulfonate, sodium di-2-ethylhexyl- ⁇ -sulfosuccinate, sodium p-octylphenoxy ethoxyethanesulfonate, sodium dodecylsulfate, sodium triisopropyl naphthalenesulfonate, N-methyl-oleoyl taurine sodium salt, and the like; cationic surfactants such as dodecyltrimethylammonium chloride, N-oleoyl-N',N',N'-trimethylammonio diaminopropane bromide, dodecylpyridium chloride, and the like; betaine surfactants such as N-dodecyl-N,N-dimethylcarboxy betaine, N-oleoyl-N,N-dimethylsulfobutyl betaine, and the like; nonionic surfactants
• Matting agents, plasticizers, and lubricants usable in the present invention are described in JP-A No. 2-68539 , page 12, upper left column, line 10 to upper right column, line 10; ibid., page 14, lower left column, line 10 to lower right column, line 1.
• the matting agent include fine particles of homopolymer of poly(methyl methacrylate), fine particles of copolymer of methyl methacrylate and methacrylic acid, fine particles of an organic compound such as starch or the like, and fine particles of an inorganic compound such as silica, titan dioxide, strontium barium sulfate, or the like; as described in USP Nos. 2,992,101 , 2,701,245 , 4,142,894 , and 4,396,706 .
• the grain size thereof is preferably from 1.0 ⁇ m to 10 ⁇ m, and particularly preferably from 2 ⁇ m to 5 ⁇ m.
• the surface layer of the photosensitive materials according to the present invention can contain a silicone compound described in USP Nos. 3,489,576 and 4,047,958 , and the like, and colloidal silica described in JP-B No. 56-23139 as a lubricant.
• a silicone compound described in USP Nos. 3,489,576 and 4,047,958 , and the like and colloidal silica described in JP-B No. 56-23139 as a lubricant.
• paraffin wax, an ester of a higher fatty acid, and a starch derivative can be also employed.
• the hydrophilic colloidal layer of the silver halide photosensitive material according to the present invention can contain polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol, glycerine, or the like as a plasticizer.
• the emulsion layer of the silver halide photosensitive material according to the present invention can include a plasticizer such as a polymer or an emulsified product to improve pressure characteristic.
• GB Patent No. 738,618 discloses the use of a heterocyclic compound
• GB Patent No. 738,637 discloses the use of alkyl phthalate
• GB Patent No. 738,639 discloses the use of an alkyl ester
• USP No. 2,960,404 discloses the use of poly-alcohol
• USP No. 3,121,060 discloses the use of carboxyalkyl cellulose
• JP-A No. 49-5017 discloses the use of paraffin and a salt of carboxylic acid
• JP-B No. 53-28086 discloses the use of alkylacrylate and an organic acid.
• the above methods can also be applied for the present invention.
• gelatin is used advantageously, but any other hydrophilic colloid can also be used.
• hydrophilic colloid that can be used in the present invention, there are mentioned those described in JP-A No. 2-68539 , page 12, upper right column, line 11 to lower left column, line 16.
• protein such as a gelatin derivative, a graft polymer of gelatin and other polymer, albumin, casein, or the like; a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, or the like; a sugar derivative such as sodium alginate, dextran, a starch derivative, or the like; and various synthetic hydrophilic polymer including homopolymer such as poly(vinyl alcohol), poly(vinyl alcohol) partial acetal, poly(N-vinylpyrrolidone), poly(acrylic acid), poly(methacrylic acid), polyacrylamide, poly(vinyl imidazole), poly(vinyl pyrazole) or the like, and copolymer thereof can be used.
• a gelatin derivative such as a gelatin derivative, a graft polymer of gelatin and other polymer, albumin, casein, or the like
• a cellulose derivative such as hydroxyethyl cellulose, carboxymethyl
• gelatin acid-processed gelatin or enzyme-processed gelatin as well as lime-processed gelatin may be used. Additionally, hydrolyzed gelatin or enzyme-decomposed gelatin can be used.
• dextran or polyacrylamide having an average molecular weight of 100,000 or less in combination with gelatin.
• the methods described in JP-A Nos. 63-68887 and 63-149641 are also useful in the present invention.
• the hydrophilic colloid incorporated in the emulsion layer and non-photosensitive layer used in the present invention may contain an inorganic or organic hardener. Examples of the hardener for use in the present invention are described in JP-A No. 2-68539 , page 12, lower left column, line 17 to page 13, upper right column, line 6.
• a chrome salt chrome alum, chrome acetate, or the like
• aldehydes formaldehyde, glyoxal, glutaraldehyde, or the like
• an N-methylol compound dimethylolurea, methyloldimethylhydantoin, or the like
• a dioxane derivative (2,3-dihydroxy dioxane or the like)
• an active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl) methyl ether, N,N'-methylene bis-( ⁇ -(vinylsulfonyl)propionamide), or the like
• an active halogen compound (2,4-dichloro-6-hydroxy-s-trazine or the like
• a mucohalogen acids mucochloric acid, mucophenoxychloric acid, or the like
• isooxazoles dialdehyde star
• a polymer hardener can also be used effectively in the present invention.
• the polymer hardener used in the present invention include a polymer having an aldehyde group such as dialdehyde starch, polyacrolein, or an acrolein copolymer described in USP No. 3,396, 029 ; a polymer having an epoxy group described in USP No. 3,623,878 ; a polymer having a dichlorotriazine group described in USP No. 3,362,827 , Research Disclosure, Item 17333 (1978 ) and the like; a polymer having an active ester group described in JP-A No.
• the hydrophilic colloidal layers included in the silver halide photosensitive material of the present invention are preferably hardened by the hardener described above so that the layers have a swelling ratio in water of 300% or less, and particularly preferably 230% or less.
• Examples of the support used in the present invention are described in JP-A No. 2-68539 , page 13, upper right column, line 7 to line 20. Specifically, as the support, a poly(ethylene terephthalate) film and a cellulose triacetate film are preferable.
• the surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment, in order to improve adhesion strength between the support and the hydrophilic colloidal layer.
• an undercoat layer comprising styrene-butadiene latex, vinylidene chloride latex, or the like can be disposed on the support, on which a gelatin layer may be further provided.
• An undercoat layer formed by using an organic solvent containing a polyethylene swelling agent and gelatin may be provided.
• the undercoat layer can be further improved in adhesion strength with the hydrophilic colloidal layer by applying surface treatment.
• USP No. 4,800,150 discloses such a technique that a dye having a fine crystal dispersion form is provided between a support and an emulsion layer to decrease crossover light to 10% or less.
• JP-A No. 63-305345 discloses such a technique that an anionic dye is fixed in a specific layer by using a cationic polymer latex
• JP-A No. 1-166031 discloses such a technique that a dye fixing layer is provided as an undercoat layer. While all the methods described above may be applied for the photosensitive material of the present invention, a colored layer with a dye is preferably used as an undercoat layer where the dye is preferably fixed by the method described in JP-A No. 1-166031 , and especially, the dye is preferably fixed in the undercoat layer in the form of a fine crystal dispersion described in USP No. 4,803,150 . In the present invention any proper combination of the above methods are available.
• mordant layer those described in JP-A No. 2-264944 , page 9, lower right column, to page 14, upper right column can be used.
• polyhydroxybenzenes for use in the present invention are described in JP-A No. 3-39948 , page 11, upper left column to page 12, lower left column, and EP No. 452,772A .
• the addition amount of the polyhydroxybenzene compound is less than 5 ⁇ 10 -1 mol per 1 mol of silver halide.
• the addition amount of the polyhydroxybenzene compound is in a range of from 5 ⁇ 10 -3 mol to 1 ⁇ 10 -1 mol per 1 mol of silver halide.
• the silver halide photosensitive material of the present invention has, on a support, a silver halide emulsion layer (photosensitive layer) including photosensitive silver halide grains and at least one non-photosensitive hydrophilic colloidal layer such as an intermediate layer, a surface protective layer, a back layer, a back surface protective layer, an antihalation layer, a filter layer, or the like.
• a silver halide emulsion layer including photosensitive silver halide grains and at least one non-photosensitive hydrophilic colloidal layer such as an intermediate layer, a surface protective layer, a back layer, a back surface protective layer, an antihalation layer, a filter layer, or the like.
• Other matters used herein, such as an emulsion sensitizing method or various additives are not particularly limited, and for example, those described in JP-A No.2-68539 and the like can be preferably used.
• the silver halide photosensitive material of the present invention preferably has a surface protective layer and a back surface protective layer.
• the surface protective layer and the back surface protective layer contain various compounds by using hydrophilic colloid such as gelatin as a binder. In the case where the main component of the layer is gelatin, the use of an antiseptic is necessary.
• the layer preferably contains a matting agent, a lubricant, a plasticizer, an antistatic agent, a surfactant, a hardener, a viscosity increasing agent, a dye, an electrically conductive material, and the like, depending on needs.
• the outermost layer has non-photosensitive hydrophilic colloid as a binder, and contains the compound represented by formula (1) described above. It is more preferred that the outermost layer contains the compound represented by formula (1) and at least one of an anionic fluorocarbon compound and an anionic hydrocarbon compound.
• the anionic fluorocarbon compound is preferably the compound represented by formula (1) described above, and the anionic hydrocarbon compound is preferably the compound represented by formula (2) described above.
• the method of development treatment used for the silver halide photosensitive material of the present invention can be selected from the methods described in JP-A No. 2-103037 , page 16, upper right column, line 7 to page 19, lower left column, line 15; JP-A No. 2-115837 , page 3, lower right column, line 5 to page 6, upper right column, line 10; and JP-A No. 2000-112078 , page 34, left column, line 42 to page 35, left column, line 2.
• the packaged body used in the present invention has a constitution, in which a laminate comprising a sheet of the photographic silver halide material described above and a non-photosensitive plate material referred to as protection cardboard is packed with a light shielding sack-shaped material.
• a non-photosensitive plate material having a layer coated with an organic material on the surface thereof is employed.
• the non-photosensitive plate material used in the present invention is a plate material on which plural sheets of the silver halide photosensitive material are piled to constitute a laminate therewith, and generally referred to as protection cardboard.
• protection cardboard is used in the following explanation.
• any pulp manufactured by any manufacturing method may be employed.
• mechanical pulp, chemical pulp, or semi-chemical pulp can be used, and cellulose pulp such as pulp of wastepaper can be properly mixed therewith.
• natural wood pulp such as conifer pulp, broad-leaved tree pulp, and mixed pulp thereof are used.
• conifer kraft pulp Nadelholz Bleached Kraft Pulp
• LKP Laubholz Bleached Kraft Pulp
• the raw material of protection cardboard used in the present invention may be bleached or unbleached.
• a bleached protection cardboard is preferred.
• the ECF (Elemental Chlorine Free) method is preferred.
• the raw material of the protection cardboard used in the present invention may be prepared by cutting fibers by a beater to make a fiber length distribution to a desired range.
• the fiber length distribution can be adjusted by controlling the processing amount and the pressure of the beater.
• a sizing agent such as alkylketene dimer, a fixing agent such as cationic starch or polymer, or the like may be also used.
• the papermaking method is not particularly limited. Any papermaking methods known in the art can be applied.
• As the paper machine a cylinder machine or Fourdrinier paper machine can be used, but Fourdrinier paper machine is preferably employed.
• the protection cardboard used in the present invention is preferably subjected to surface treatment to maintain storage stability in a packaged embodiment.
• Various types of surface treating method are there, but a surface coating method with an organic substance is preferred.
• the organic substance used in the coating described above is not limited, but especially, when used for storing the silver halide photographic material, a packaging material coated with cationic starch or poly(vinyl alcohol) is preferably used.
• Poly(vinyl alcohol) is preferably coated in a coating amount of from 0.04 g/m 2 to 0.90 g/m 2 per one side, more preferably from 0.08 g/m 2 to 0.60 g/m 2 per one side, and even more preferably from 0.12 g/m 2 to 0.48 g/m 2 per one side.
• Poly(vinyl alcohol) is preferably coated on both sides of the packaging material.
• a coating method using an ultraviolet curing resin is also preferably used.
• the ultraviolet curing resin described in JP-B No.4-13697 can be used.
• the thickness of the ultraviolet curing resin-coated layer is preferably in a range of from 0.05 to 15 ⁇ m, and more preferably from 0.1 ⁇ m to 5 ⁇ m.
• a density of the packaging material used in the present invention is preferably in a range of from 0.70 g/m 3 to 0.90 g/m 3 , more preferably from 0.75 g/m 3 to 0.85 g/m 3 , and even more preferably from 0.77 g/m 3 to 0.81 g/m 3 .
• the packaging material used in the present invention has a sufficient light-shielding ability to prevent the silver halide photosensitive material from exposing to undesired light. Further preferably, the packaging material comprises a packaging material having low oxygen permeability and low vapor permeability.
• oxygen permeability is 50 mL ⁇ atm -1 m -2 day -1 or lower (at 25°C), and vapor permeability is 10 g ⁇ atm -1 m -2 day -1 or lower (at 25°C).
• oxygen permeability is 50 mL ⁇ atm -1 m -2 day -1 or lower (at 25°C), more preferably 10 mL ⁇ atm -1 m -2 day -1 or lower (at 25°C), and even more preferably 1.0 mL ⁇ atm -1 m -2 day -1 or lower (at 25°C).
• vapor permeability is 10 g ⁇ atm -1 m -2 day -1 or lower (at 25°C), more preferably 5 g ⁇ atm -1 m -2 day -1 or lower (at 25°C), and even more preferably, 1 g ⁇ atm -1 m -2 day -1 or lower (at 25°C).
• the oxygen permeability used herein means a value obtained by the measurement at the condition B defined in JIS Z0208.
• the vapor permeability used herein means vapor transmittance obtained by the measuring method defined in JIS K7129-1992 wherein the measurement condition is at 40°C and relative humidity of 90%RH.
• packaging material having low oxygen permeability and/or low vapor permeability reference can be made to, for instance, the packaging material described in JP-A Nos. 8-254793 and 2000-206653 . Details thereof are described below.
• the raw material of the packaging material include polyethylene resin, nylon resin, polypropylene resin, poly(ethylene terephthalate) resin, polyamido resin, ethylene-vinyl alcohol copolymer resin, ethylene-vinyl acetate copolymer resin, acrylonitrile-butadiene copolymer resin, cellophane resin, vinylon resin, vinylidene chloride resin, and the like.
• Polypropylene resin and nylon resin used for the packaging material may be stretched and further may be overcoated with vinylidene chloride resin thereon.
• Concerning polyethylene resin high density polyethylene resin or low density polyethylene resin can be used. Synthetic resin such as epoxy-phosphoric acid resin (polymers described in JP-A Nos. 63-63037 and 57-32952 ), and pulp can be also used.
• the packaging material preferably consists of a single material.
• the film When used as film, the film is laminated with adhesive, but may be a coated layer, or monolayered film may also be available. It is more preferred to use various gas barrier film such as aluminum foil or aluminum deposited synthetic resin, for example, between the above synthetic resin film.
• the total film thickness of the laminated film or the monolayered film is preferably in a range of from 1 ⁇ m to 3,000 ⁇ m, more preferably from 10 ⁇ m to 2,000 ⁇ m, and even more preferably from 50 ⁇ m to 1,000 ⁇ m.
• the raw material of the packaging material among the polymers described above, it is preferred to use polyethylene (PE), nylon (Ny), vinylidene chloride resin (PVDC) coated nylon (KNy), non-stretched polypropylene (CPP), stretched polypropylene (OPP), PVDC coated polypropylene (KOP), poly(ethylene terephthalate) (PET), PVDC coated cellophane (KPT), or polyethylene-vinyl alcohol copolymer (Eval).
• PE polyethylene
• nylon Ny
• PVDC vinylidene chloride resin
• KNy non-stretched polypropylene
• CPP non-stretched polypropylene
• OPP stretched polypropylene
• PVDC coated polypropylene KOP
• PET poly(ethylene terephthalate)
• KPT poly(ethylene terephthalate)
• KPT polyethylene-vinyl alcohol copolymer
• Eval polyethylene-vinyl alcohol copolymer
• an inorganic compound deposited polymer material can also be used where the polymer material may be the aforesaid or well-known material.
• the inorganic compounds used for vapor deposition include aluminum, aluminum oxide (Al 2 O 3 ), silicone oxide (SiOx), and the like.
• the film thickness of deposited film is in a range of from 50 ⁇ to 1,000 ⁇ .
• Well-known depositing methods such as a chemical vapor depositing method, a physical vapor depositing method, a vapor depositing method, a sputtering method, and the like can be employed.
• the film thickness of each layer may be properly adjusted depending on the demand for the light shielding ability, the oxygen permeability, the vapor permeability, the mechanical strength, and the like, but as the whole packaging material, the total thickness is fallen in 500 ⁇ m or less.
• the method of producing the multi-layered packaging material is not particularly limited, but for example, includes a method of combining a resin layer and the other resin layer with an adhesive, a method of combining a resin layer and the other resin layer with a melt-type resin, an extruding method, a laminating method, and the like.
• raw material of the packaging material include the following materials, but the invention is not limited to these.
• the layer constitution of (outermost portion)/ (intermediate portion)/ (contacted portion with the photothermographic material) is shown below.
• a solution was prepared by adding 4 g of sodium chloride, 4 g of potassium iodide, and 20 g of gelatin to 1 liter of water. The solution was kept at 70°C while stirring in a reaction vessel, and thereto were added 400 mL of an aqueous solution containing 83 g of silver nitrate and 190 mL of an aqueous solution containing 57 g of potassium bromide over 16 minutes by controlled double jet method.
• an aqueous solution containing from 0.1 mol to 0.85 mol of ammonia 250 mL of an aqueous solution containing 123 g of silver nitrate and 275 mL of an aqueous solution containing 82.5 g of potassium bromide were added over 20 minutes by controlled double jet method, and subjected to physical ripening for 18 minutes while keeping the temperature. Thereafter, the pH was neutralized using an aqueous solution of acetic acid and the mixture was cooled to 35°C followed by removing soluble salts by sedimentation method.
• the resulting mixture is warmed to 40°C, and thereto were added 23.7 mL of a 50% by weight solution of trimethylol propane, 42 mg of Proxel, 32.5 g of gelatin, and sodium polystyrenesulfonate (average molecular weight of 600,000) as a viscosity increasing agent and the pH was then adjusted to 6.6 using sodium hydroxide aqueous solution.
• the thus-prepared emulsion was warmed to 49°C and thereto were added 41 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 150 mg of sensitizing dye A-1, 0.93 mg of chloroauric acid, and 165 mg of potassium thiocyanate.
• the emulsion coating solution was prepared by adding the following agents in the amounts described below per 1 kg (1.52 mol of silver) of the above emulsion.
• Gelatin 38.2 g Sodium polystyrenesulfonate (weight-average molecular weight of 600,000) 1.4 g Polyacrylamide (weight-average molecular weight of 45,000) 27.2 g Compound A-3 24.3 mg Compound A-4 92.0 mg Compound A-5 73.5 mg Compound A-6 105.0 mg Compound A-7 (BFV) 73.5 mg Compound A-8 (KMF) 105.0 mg Palladium chloride 19.9 ⁇ mol 1,3-Dihydroxy benzene 1.2 g 1,2-Bis(vinylsulfonyl acetamido)ethane 1.2 g DV-759L manufactured by Dainippon Ink and Chemicals, Inc. (20% by weight aqueous solution) (mixed latex dispersion of acrylic ester polymer and SiO 2 ) 45.0 mL
• This coating solution was coated on both sides of a polyester support having a thickness of 0.18 mm so that the amount of coated silver became 2.2 g/m 2 per one side.
• the coating solutions for the surface protective layer were prepared by adding the surfactant of the invention or the comparative surfactant as described below. Then, samples were prepared by coating them on both emulsion layer sides at a coating speed of 160 m/second.
• repellency means a spot-like defect where the outermost surface protective layer is partially thin or is not coated partially.
• the obtained samples are evaluated and expressed by a relative value based on the comparative sample when the number of the defects occurred in the comparative sample is taken as 100.
• the coated samples each was cut into a sheet state and stored under an atmosphere of 25°C and 60%RH for a period of one hour, and thereafter contacted with the protection cardboard of the present invention or the comparative protection cardboard.
• the prepared set was sealed in a sack-shaped material and pressed with a load of 90 g/cm 2 , and left under a condition of 25°C for a period of 3 days while loaded.
• the samples were evaluated as follows. Hi-SCREEN B-2 (manufactured by Fuji Photo Film Co., Ltd.) was pasted inside of a cassette Fuji EC CASSETTEN (manufactured by Fuji Photo Film Co., Ltd.).
• the screen was rubbed with fibers under a condition of 25°C and 25%RH, and coated with a cleaner for X-ray intensifying screens manufactured by Fuji Photo Film Co., Ltd. (trade name: Fuji AS cleaner) and acetone or chloroform to remove the film, so that the surface electrostatic voltage of the screen surface was controlled within a range of from 3 kV to 4 kV measured by using an electrostatic voltage measuring apparatus M2 (trade name, available from Shishido Electrostatics Co., Ltd.). And then, the sample of the invention and the comparative sample were set in the cassette prepared above.
• test samples were taken out from the cassette, and developed by using an automatic developing apparatus CEPROS-M2 (trade name, manufactured by Fuji Photo Film Co., Ltd.) with Developer CED-1 (manufactured by Fuji Photo Film Co., Ltd) at 34°C for 25 seconds (total processing time of 90 seconds).
• an automatic developing apparatus CEPROS-M2 trade name, manufactured by Fuji Photo Film Co., Ltd.
• Developer CED-1 manufactured by Fuji Photo Film Co., Ltd
• total processing time of 90 seconds As the fixing solution, Fixer CEF-1 (manufactured by Fuji Photo Film Co., Ltd.) was used and water washing was carried out by using tap water.
• the following dye was dispersed using a ball mill by the method described in JP-A No. 68-197943 .
• the observation of the obtained dye dispersion revealed that the dispersion comprised pulverized dyes having a broad particle diameter distribution such as the diameter is from 0.05 ⁇ m to 1.15 ⁇ m and a mean particle diameter of 0.37 ⁇ m. Furthermore, the dye particles having a particle diameter of 0.9 ⁇ m or more were removed by centrifugal separation to obtain dispersion D-1.
• the surfaces of the biaxially tentered poly(ethylene terephthalate) film having a thickness of 183 ⁇ m were subjected to corona discharge treatment. Thereafter, the first undercoat solution comprising the following composition was coated on one surface with a wire bar coater so that the coating amount became 5.1 mL/m 2 , and dried at 175°C for one minutes. Then, the first undercoat layer was disposed on the opposite side in a similar manner.
• Poly(ethylene terephthalate) film including 0.04% by weight of dye D-2 having the following structure was used.
• the amount of coating solution was 4.9 mL per 1 m 2 of one side of the support.
• the coating amount of each additive per 1 m 2 of one side of the support is as follows.
• a second undercoat solution comprising the following composition was overcoated with a wire bar coater so that the coating amount became the amount described below, and dried at 150°C.
• each compound per 1 m 2 on one side is shown below.
• Gelatin 81 mg C 12 H 25 O(CH 2 CH 2 O) 10 H 3.8 mg
• Matting agent poly(methyl methacrylate) particles, mean particle diameter of 2.5 ⁇ m
• Dye dispersion D-1 8.2 mg Acetic acid 0.6 mg
• a solution was prepared by adding 6 g of potassium bromide and 7 g of gelatin to 1 liter of water. The solution was kept at 55°C while stirring in a vessel, and thereto were added 37 mL of an aqueous solution containing 4.00 g of silver nitrate and 38 mL of an aqueous solution containing 5.9 g of potassium bromide over 37 seconds by controlled double jet method. After adding 18.6 g of gelatin, the mixture was heated to 70°C and then 89 mL of an aqueous solution containing 9.8 g of silver nitrate was added over 22 minutes.
• fine silver iodide grains were added in an amount of 0.05 mol% per 1 mol of monodispersed pure silver bromide tabular grain.
• 0.043 mg of thiourea dioxide was added followed by subjecting to reduction sensitization while keeping the state for 22 minutes.
• 20 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 400 mg of sensitizing dye A-13, and 2 mg of A-14 were added. Further, 0.83 mg of calcium chloride was added.
• Silver halide emulsion T-2 was prepared in a similar manner to the process in the preparation of silver halide emulsion T-1 except that the addition amount of fine silver iodide grains prior to and during the chemical sensitization was changed to 0.5 mol% respectively. Silver halide grains in the obtained silver halide emulsion T-2 had an average iodide content of 1.0 mol%.
• the coating solution for emulsion layer T-1 was prepared by adding the following compounds to give the coating amount as follows.
• Emulsion T-1 (on the basis of Ag content) 1.09 g/m 2 Dextran (average molecular weight of 39,000) 0.21 g/m 2
• Sodium polystyrenesufonate (average molecular weight of 600,000) 19 mg/m 2
• Hardener (1,2-bis(vinylsulfonyl acetamido)ethane) 26 mg/m 2 A-3 0.2 mg/m 2 A-4 1.1 mg /m 2 A-15 4.1 mg/m 2 A-16 0.1 g/m 2 A-17 0.02 g/m 2
• the coating solution for emulsion layer T-2 was prepared by adding the following compounds to give the coating amount as follows.
• Emulsion T-2 (on the basis of Ag content) 0.66 g/m 2 Dextran (average molecular weight of 39,000) 0.13 g/m 2
• Sodium polystyrenesulfonate (average molecular weight of 600,000) 11 mg/m 2
• Hardener (1,2-bis(vinylsulfonyl acetamido)ethane) 27 mg/m 2 A-3 0.1 mg/ m 2 A-4 0.6 mg/ m 2 A-5 0.45 mg/ m 2 A-7 0.34 g/ m 2 A-15 1.2 mg/ m 2 A-16 0.06 g/ m 2 A-17 C 16 H 33 (CH 2 CH 2 O) 10 H
• composition of coating solution for surface protective layer comprising: Gelatin 0.966 g/ m 2 Sodium polyacrylate 0.023 g/ m 2 4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene 0.015 g/ m 2 Poly(methyl methacrylate) particles (mean particle diameter of 3.7 ⁇ m) 0.087 g/m 2 Proxel (the pH being adjusted to 7.4 with sodium hydroxide) 0.5 mg/m 2 Surfactant of the invention or comparative surfactant (See Table 2) A-17 0.045 g/ m 2 A-18 6.5 mg/ m 2 A-19 1.7 mg/ m 2
• the coating solutions T-1 and T-2 for the emulsion layer, and the coating solution for the surface protective layer were coated by a simultaneous extruding method at a coating speed of 160 m/second to form emulsion layers and a surface protective layer thereby.
• the amount of coated silver was 1.75 g/m 2 per one side.
• Example 2 The obtained samples were evaluated similar to Example 1. Results of the evaluation including the results obtained in other Examples are shown in Table 2.
• the use of the protection cardboard of the present invention stabilizes the electrostatic characteristics.
• a liquid was prepared by adding 21 g of gelatin, 10.7 g of ammonium nitrate, 0.3 g of potassium bromide, and 0.07g of silver nitrate to 1 liter of water.
• the liquid was kept at 42°C while stirring in a reaction vessel, and thereto were added: an aqueous solution containing 85.7 g of silver nitrate and 0.71 g of ammonium nitrate; and an aqueous solution containing potassium bromide over 19 minutes and 10 seconds by controlled double jet method.
• 2.4 mL of a 25% by weight aqueous solution of ammonium was added, and after t minutes, the mixture was neutralized using 0.71 g of glacial acetic acid.
• an aqueous solution containing 85.7 g of silver nitrate and 0.71 g of ammonium nitrate; and an aqueous solution containing 39.6 g of potassium bromide, 1.17 g of potassium iodide, and 0.52 mg of K 3 IrCl 6 were added over 8 minutes and 40 seconds by controlled double jet method.
• the time t was adjusted so that the obtained grains had a mean equivalent spherical diameter of 0.21 ⁇ m.
• the mixture was cooled to 35°C and soluble salts were removed by sedimentation method. Thereafter, the resulting mixture was heated to 60°C, and thereto were added 156 g of gelatin and 5 g of 2-phenoxyethanol.
• the pH was adjusted to 6.70 with sodium hydroxide and sulfuric acid. Thereafter, 56 mg of 1-phenyl-mercaptotetrazole, 4.79 mg of sodium thiosulfate, 124 mg of 4,7-dithia-1,10-decanediol, 49.57 mg of HAuCl, and 43.4 mg of potassium thiocyanate were added thereto. After T minutes, 0.91 g of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to the mixture. Then the mixture was cooled down quickly and solidified.
• the prepared solution was coated on a blue colored poly(ethylene terephthalate) support having a thickness of 175 ⁇ m, which is biaxially tentered and thereafter on which the first undercoat comprising styrene-butadiene (0.3 g/m 2 ) and the second undercoat comprising gelatin (0.1 g/m 2 ) were conducted, to provide 109 mL/m 2 , and dried.
• the obtained grains had a crystal habit of cubic form and a mean equivalent spherical diameter of 0.21 ⁇ m.
• Concerning the prepared sample an amount of coated silver was 7.35 g/m 2 and an amount of coated gelatin was 12.0 g/m 2 .
• the above emulsion layer and surface protective layer were coated on both sides of the support at a coating speed of 40 m/second so that the amount of coated silver became 7.35 g/m 2 per one side and an amount of coated gelatin became 14.2 g/m 2 per one side.
• the layer described below was coated on the side having no emulsion layer.
• the coating solution for back surface protective layer was prepared using the same additives as those used in the surface protective layer on the emulsion layer side except that the matting agent having a mean particle diameter of 8 ⁇ m was used and Snowtex C was added so that the coating amount thereof became 0 g/m 2 to 0.6 g/m 2 on the basis of solid content.
• the prepared solution was coated to form a single layer or multilayer, so that the amount of coated gelatin became of 1.7 g /m 2 , and dried.
• Example 2 The obtained samples were evaluated similar to Example 1. Results including the results obtained in other Examples are shown in Table 2. It can be seen from the results that the use of compounds of the present invention is very effective with respect to decreasing the repelling trouble. Moreover, the use of the protection cardboard of the present invention stabilizes the electrostatic characteristics.
• sodium polystyrenesulfonate having an average molecular weight of 50,000 was added, and after desalting treatment, 48 g of gelatin, 0.14 g of nucleic acid base mixture, 0.16 g of potassium bromide, and 2.2 g of phenoxyethanol were added and the pH was adjusted to 6.0. Then, 4.1 mg of sodium thiosulfate and 7.4 mg of chloroauric acid were added followed by subjecting to chemical sensitization at 60°C. After adding 0.37 g of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, the mixture was cooled down quickly and solidified.
• the coating solution was prepared by mixing the emulsion (O) and the emulsion (P) to give a silver halide molar ratio of 1/ 2.1 and adding the following additives in the amount described below per 1 mol of silver halide.
• Spectral sensitizing dye (D-1) 3.6 ⁇ 10 -5 mol
• Super sensitizer (Compound D) 1.5 ⁇ 10 -4 mol 3-Allyl-2,6-dimethylbenzothiazolium bromide 5.7 ⁇ 10 -4 mol
• Compound E 2.5 ⁇ 10 -4 mol
• Polyacrylamide (molecular weight of 40,000 to 50,000) 9.3 g
• Poly(ethylacrylate/ methacrylic acid) latex 1.8 g 1,2-Bis(vinylsulfonyl acetamido)ethane 1.8 g 1,3-Bis(vinylsulfonyl acetamido)propane 0.59 g
• the vessel was warmed to 65°C and the coating solution for the emulsion surface protective layer was prepared by adding the following additives according to the following composition.
• the vessel for preparing the coating solution for back layer was heated to 65°C and the following additives according to the following composition were added thereto, to obtain the coating solution for the back layer.
• the vessel for preparing the coating solution for back surface protective layer was warmed to 65°C and the following additives according to the following composition were added thereto, to obtain the coating solution for the back surface protective layer.
• the coating solution for the back layer and the back surface protective layer prepared above were coated on one side of the poly(ethylene terephthalate) support at a coating speed of 160 m/second so that: the coating solution for the back layer gave the coating amount of gelatin of 2.4 g/m 2 ; the coating solution for the back surface protective layer gave the coating amount of gelatin of 1.4 g/m 2 ; and so that the total amount of gelatin became 3.8 g/m 2 .
• the coating solution for the emulsion layer and the surface protective layer were coated on the opposite side of the support so that the coating solution for the emulsion layer gave the coating amount of silver of 2.8 g/m 2 and so that the coating solution for the surface protective layer gave the coating amount of gelatin of 1.2 g/m 2 .
• Example 2 The obtained samples were evaluated similar to Example 1. Results including the results obtained in other Examples are shown in Table 2. It can be seen from the results that the use of compounds of the present invention is very effective with regard to decreasing the repelling trouble. Moreover, the use of the protection cardboard of the present invention stabilizes the electrostatic characteristics.
• the mixture was heated to 75°C over 20 minutes, and 26 g of gelatin having an average molecular weight of 100,000 was added thereto. Then, an aqueous solution containing 209 g of silver nitrate and an aqueous solution comprising 99.9 mol% of potassium bromide and 0.1 mol% of potassium iodide were added by controlled double jet method in an accelerated flow rate over 75 minutes while keeping the pAg at 8.5. After adding gelatin having an average molecular weight of 100,000, the mixture was subjected to desalting treatment by the conventional way.
• the mixture was dispersed by adding gelatin having an average molecular weight of 100,000, and the pH and pAg was adjusted to 5.8 and 8.0 at 40°C respectively, to obtain an emulsion.
• the obtained emulsion contained 1 mol of silver and 60 g of gelatin, per 1 kg of the emulsion.
• Grains in thus prepared silver halide emulsion were tabular grains having a mean equivalent circular diameter of 1.5 ⁇ m, a variation coefficient of an equivalent circular diameter distribution of 22%, a mean grain thickness of 0.10 ⁇ m, and a mean aspect ratio of 15.
• 1,178 mL of an aqueous solution containing 0.8 g of potassium bromide and 1 g of gelatin having an average molecular weight of 20,000 were stirred while keeping the temperature at 35°C. Thereafter, an aqueous solution containing 0.74 g of silver nitrate and an aqueous solution containing 0.54 g of potassium bromide were added thereto by controlled double jet method over 45 seconds. The concentration of the silver nitrate solution was 0.2 mol/L. Thereafter, the mixture was heated to 68°C over 30 minutes and 13 g of succinated gelatin having an average molecular weight of 100,000 was added thereto.
• an aqueous solution containing 237 g of silver nitrate and an aqueous solution of potassium bromide were added by controlled double jet method in an accelerated flow rate over 45 minutes while keeping the pAg at 8.5.
• the mixture was subjected to desalting treatment by the conventional way.
• the mixture was dispersed by adding gelatin having an average molecular weight of 100,000, and the pH and pAg was adjusted to 5.8 and 8.0 at 40°C respectively, to obtain an emulsion.
• the obtained emulsion contained 1 mol of silver and 60 g of gelatin per 1 kg of the emulsion.
• Grains in thus prepared silver halide emulsion were tabular grains having a mean equivalent circular diameter of 2.0 ⁇ m, a variation coefficient of an equivalent circular diameter distribution of 30%, a mean grain thickness of 0.09 ⁇ m, and a mean aspect ratio of 22.
• potassium thiocyanate was added in an amount of 6 ⁇ 10 -4 mol equivalent per 1 mol of silver halide, and then A-13 in an amount of 1 ⁇ 10 -3 mol equivalent per 1 mol of silver halide and A-14 solution in an amount of 3 ⁇ 10 -6 mol equivalent per 1 mol of silver halide were added, and further, calcium chloride was added thereto. Thereafter, a solution of A-15 described below was added in an amount of 2 ⁇ 10 -4 mol equivalent per 1 mol of silver halide.
• aurochloric acid in an amount of 2 ⁇ 10 -5 mol equivalent per 1 mol of silver halide and potassium thiocyanate in an amount of 6 ⁇ 10 -4 mol equivalent per 1 mol of silver halide were added, and then, sodium thiosulfate in an amount of 1 ⁇ 10 -5 mol equivalent per 1 mol of silver halide and selenium sensitizer A-2 in an amount of 4 ⁇ 10 -6 mol equivalent per 1 mol of silver halide were added thereto. 60 minutes later, the resulting mixture was cooled to 35°C and thereby the chemical sensitization of the emulsion was finished.
• Thiosulfonic acid compound-1 C 2 H 5 SOSNa
• Each compound was added to the emulsion to give the following coating amount.
• the amount of the coating solution was 50.5 mL per 1 m 2 of one side.
• the pH of the coating solution for surface protective layer was adjusted to 6.6 using a small quantity of sodium hydroxide.
• the amount of the coating solution was 9.4 mL per 1 m 2 of one side.
• Example 2 The obtained samples were evaluated similar to Example 1. Results including the results obtained in other Example are shown in Table 2. It can be seen from the results that the use of compounds of the present invention is very effective with respect to decreasing the repelling trouble. Moreover, the use of the protection cardboard of the present invention stabilizes the electrostatic characteristics.
• Silver halide photosensitive material Nos. 6-1 to 6-7 were prepared similar to Example 2 except that the surfactants added in the surface protective layer were changed to the compound shown in the following Table
• NBKP Naadelholz Bleached Kraft Pulp
• LBKP Longbholz Bleached Kraft Pulp
• An acrylamido type paper power enhancer was added to the virgin pulp prepared above and then alkylketene dimer and cationic starch were added thereto and mixed to form a paper having triple-layered structure.
• prepared paper was dewatered by a press roller and dried so that the surface temperature became from 120°C to 150°C and the moisture content became from 2% by weight to 3% by weight.
• the comparative protection cardboard having a moisture content of from 7% by weight to 8% by weight without any overcoat was prepared.
• the prepared photosensitive materials each were stored under an atmosphere of 25°C and 60%RH for a period of 1 hour, and then samples for measurement were prepared as follows.
• Sample a Simple photosensitive material
• Sample b the photosensitive material was contacted with the protection cardboard A of the present invention. And then the combined set was sealed in a sack-shaped material and left at 25°C for 3 days with a load of 90 g/cm 2 . Thereafter, the photosensitive material was taken out;
• Sample c the photosensitive material was contacted with the comparative protection cardboard C. And then the combined set was sealed in a sack-shaped material and left at 25°C for 3 days with a load of 90 g/cm 2 . Thereafter, the photosensitive material was taken out.
• the above samples were conditioned at 25°C and 25%RH for 1 hour.
• the surface resistance (log SR) of the sample was measured by using R12704 (trade name, available from Advantest Co. Ltd.) while loading voltage thereon for 50 seconds.
• Results are shown in Table 1. The smaller is the log SR value, the shorter is the time period for electric leakage, and namely the slower is the discharge.
• the coating amount of each compound described in Table 2 is as follows.

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• 2005
  • 2005-08-04 JP JP2005226621A patent/JP2007041376A/ja active Pending
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