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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/015—Apparatus or processes for the preparation of emulsions
• • 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
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances
  • G03C1/12—Methine and polymethine dyes

Definitions

• the present invention relates to a silver halide photographic light-sensitive material capable of providing a high quality image, and in particular to a silver halide photographic light-sensitive material comprising less fogging and a higher sensitivity, and capable of providing a high quality image that has good graininess and sharpness, even in rapid processing.
• the higher sensitivity is required in such fields as camera for higher shutter speed, color and black-and-white print paper for more rapid processing, printing for digitalization and rationalization, medical service for reduction of exposure to X-ray.
• ortho-type sensitive materials that are ortho-sensitized to a wavelength region of 540 - 550 nm are more commonly used instead of conventional regular type materials sensitive to a wavelength of 450 nm. These sensitized materials have a wider sensitive wavelength range as well as higher sensitivity, and therefore can contribute to reduction of adverse effects on a human body because of reduction of exposure to X-ray.
• sensitizing technique for a photographic sensitive emulsion
• spectral sensitization a method using a sensitizing dye, i.e. spectral sensitization.
• a spectral sensitization method is addition of a dye in formation of silver halide grains, as is disclosed in U.S. Patent Nos. 2,735,766, 3,628,960, and 4,225,666.
• the relevant methods are disclosed in further detail in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 184142/1983, 196278/1986, 103149/1986, and 205929/1986.
• a silver halide photographic light-sensitive material having a support and provided thereon, the hydrophilic colloid layers including at least one light-sensitive silver halide emulsion layer, wherein the light-sensitive material is characterized by that at least one emulsion layer comprises a silver halide emulsion prepared by removing excessive salts at pH of not higher than 6 after formation of silver halide grains and adding a sensitizing dye prior to chemical sensitization of the silver halide grains.
• the silver halide photographic light-sensitive material of the invention comprises a support having thereon the hydrophilic colloid layers including at least one light-sensitive silver halide emulsion layer.
• This material may be a two-sided light-sensitive material having each at least one silver halide emulsion layer on both sides of the support, or may be a single-sided light-sensitive material having at least one silver halide emulsion layer on only one side of the support.
• a backing layer comprising of a hydrophilic colloid layer may be provided on a side opposite to the side having the emulsion layer.
• silver halide may be any of silver bromide, silver bromoiodide, silver bromochloroiodide, silver bromochloride, and silver chloride.
• the preferred silver halide is silver bromoiodide or silver bromochloroiodide each having 30 molO/o or less of silver iodide.
• the particularly preferred is silver bromoiodide having 2 to 25 molO/o of silver iodide.
• the silver halide grains may have a regular crystal such as cube, octahedron, and tetradecahedron, or an irregular crystal such as sphere or twinned crystal.
• the silver halide grains may have either a uniform composition of silver halide or a multilayered construction in which a core and outer layers have different compositions of silver halide, and have preferably the multilayered construction consisting of the core having a higher silver iodide content and the outer layers having a lower silver iodide content.
• the silver halide emulsions used in the invention may be either monodispersed or multidispersed.
• the silver halide emulsions can be prepared by conventional methods.
• Two or more types of silver halide emulsions independently prepared may be blended to make an emulsion of the invention.
• the silver halide emulsion of the invention is preferably grown from a seed emulsion.
• the silver halide emulsion comprising of the regular grains is can be prepared by controlling pAg and pH during grain formation.
• the silver halide emulsion is subjected to desalination after completion of growth of the silver halide grains in order to remove excess salts.
• One typical method is a flocculation method where a flocculant is added to a silver halide emulsion for decantation of supernatant.
• the desalination process may be performed either only once or several times. When this process is repeated several times, a flocculant may be added either every time or only at first.
• pH of the emulsion in desalination is preferably not higher than 6, and more preferably 2 to 5. pH is controlled in the above range in flocculating and settling silver halide grains after adding a flocculant, and in repeating the same after the flocculated and settled silver halide grains are dispersed again. pH may be adjusted to not higher than 6 either before or after addition of a flocculant, preferably after addition thereof.
• the flocculation method includes a sulfuric acid method, an organic solvent method, an organic gelatin flocculant method, a gelatin derivative method, and a high-molecular flocculant method.
• a gelatin derivative preferably used as a flocculant is a modified gelatin having substituted amino groups of not less than 50% (hereinafter referred to as a gelatin flocculant).
• the preferred gelatin flocculant comprises an amino group substituted by an acyl group (-COR 1 ) or a carbamoyl group wherein R 1 represents an aliphatic group such as an alkyl group having 1 to 18 carbon atoms or an allyl group, an aryl group or an aralkyl group such as phenethyl group; R 2 represents a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.
• R 1 represents an aliphatic group such as an alkyl group having 1 to 18 carbon atoms or an allyl group, an aryl group or an aralkyl group such as phenethyl group
• R 2 represents a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.
• R 1 is an aryl group and R 2 is a hydrogen atom.
• An addition amount of the gelatin flocculant is 0.3 to 10 parts (by weight) per part of a protective colloid, and preferably 1 to 5 parts.
• pH is adjusted to not higher than 6, and preferably to 2 to 5.
• An acid used for adjusting pH includes an organic acid such as acetic acid, citric acid, and salicylic acid; and an inorganic acid such as nitric acid, sulfuric acid, and phosphoric acid.
• heavy metal ions may be added, such as magnesium ion, cadmium ion, lead ion, and zirconium ion.
• the high-molecular flocculant used in the invention is represented by the following Formula (I).
• R 3 and R 4 independently represent a hydrogen atom, an aliphatic group, an aryl group and an aralkyl group
• Rs represents a hydrogen atom, an aliphatic group, an aryl group, an aralkyl group, or M
• X represents -0-, or -NH-
• M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, or a quaternary phosphonium group
• n is an integer of 10 to 10 4 ; either of two terminal beondages of Chain B may be linked to a tertiary carbon having R 3 and R 4 in Chain A;
• X may form a nitrogen-containing ring together with Rs, provided that X is -NH-.
• a molecular weight of these high molecular compounds is preferably 10 3 to 10 6 , and more preferably 3 x 10 3 to 2 x 10 5 .
• An addition amount thereof in a weight ratio to a protective colloid is preferably 1/50 to 1/4, and more preferably 1/40 to 1/10.
• An addition way thereof is the same as in the preceding gelatin flocculant.
• m represents a degree of polymerization, and a molecular weight of these flocculants ranges from 1,000 to 200,000.
• An addition amount thereof is 3 to 50 wt%, and preferably 3 to 20 wtOfo of gelatin in a silver halide emulsion.
• the silver halide emulsion of the invention is subjected to spectral sensitization and chemical sensitization.
• a spectral sensitizing dye is used.
• the preferred spectral sensitizing dyes are described in Japanese Patent O.P.I. Publication No. 80237/1986, and Japanese Patent O.P.I. Publication No. 257947/1987.
• the spectral sensitizing dye is added in formation of a silver halide grain or in desalination for removing excess salts; it is added prior to chemical sensitization, and preferably before completion of desalination. It is added more preferably while an addition of a silver ion is in a range of 70 to 1000/0 in forming a silver halide grain, or in desalination.
• the spectral sensitizing dye is not added in preparing the seed emulsion.
• the spectral sensitizing dye is added to the emulsion preferably at pH of 4 to 10 besides adding in desalination, and more preferably at pH of 6 to 9. It is added preferably at pAg of 5 to 11.
• Two or more of the spectral sensitizing dyes may be combinedly used. In this case, two or more spectral sensitizing dyes may be added either at once or independently and separately.
• It may be added in proportion to a surface area of the growing silver halide grains.
• An addition amount of the spectral sensitizing dye is 1 mg to 1 g, and preferably 5 to 500 mg per mol silver.
• potassium iodide prior to adding of the spectral sensitizing dye.
• At least one spectral sensitizing dye selected from the compounds represented by Formulas (II), (III) and (IV) is preferably added.
• R 1 , R 2 , and R 3 independently represent an alkyl group, an alkenyl group and an aryl group, provided that at least one of R 1 and R 3 is a sulfoalkyl or carboxyalkyl group
• X 1 - represents an anion
• Zi and Z 2 independently represent a non-metal atomic group needed for completing a carbon ring
• n represents 1 or 2, provided that n is 1 when an intramolecular salt is formed.
• R 4 and R 5 independently represent the same groups as those defined for R 1 , R 2 and R 3 in Formula (II), provided that at least one of R 4 and Rs is a sulfoalkyl or carboxyalkyl group;
• Re represents a hydrogen atom, a lower alkyl group, or an aryl group;
• X 2 - represents an anion;
• Z 1 and Z 2 independently represent the same as that defined for Z 1 and Z 2 in Formula (II);
• n represents 1 or 2, provided that n is 1 when an intramolecular salt is formed.
• R 7 and Rg independently represent a lower alkyl group
• Rs and R 10 independently represent a lower alkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group
• X 3 - represents an anion
• Z 1 and Z 2 independently represent the same as defined for Zi and Z 2 in Formula (II)
• n represents 1 or 2, provided that n is 1 when an intramolecular salt is formed.
• the carbon ring formed by each of Zi and Z 2 is preferably an aromatic ring such as a benzene and naphthalene ring;
• the alkyl group includes a lower alkyl group such as methyl, ethyl, n-propyl and butyl groups;
• the substituted alkyl group includes a vinylmethyl group;
• the hydroxyalkyl group includes 2-hydroxyethyl and 4-hydroxybutyl;
• the carboxyalkyl group includes 2-carboxyethyl, 3-carboxypropyl and 2-(2-carboxyethoxy)ethyl;
• the sulfoalkyl group includes 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, and 2-hydroxy-3-sulfopropyl;
• the alkenyl group includes allyl, butynyl, octenyl and oleyl;
• At least one selected from the compounds represented by Formula (V) is added preferably as a spectral sensitizing dye.
• Z 41 and 2 43 independently represent a non-metal atom group necessary for forming a benzothiazole, benzoxazole, naphtothiazole, and naphthooxazole nucleus each allowed to have a substituent including a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms;
• R 41 and R 42 independently represent a saturated or unsaturated aliphatic group such as methyl, 2-hydroxyethy, 2-methoxyethyl, carboxymethyl, 2-sulfoethyl, 3-sulfopropyl, vinylmethyl, benzyl, phenethyl, and p-sulfophene- thyl;
• Z 42 represents a five- or six-membered carbon ring; if Z 42 is a six-member
• A represents and R 44 represent independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms
• R 45 and R 46 represent independently an alkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl-alkyl group, and an aryl group
• R 47 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxycarbonyl group with an alkoxy group having 1 to 4 carbon atoms.
• Formula (V) is represented by following Formula (V-b), provided that Z 42 is a six-membered ring; wherein R 48 represents a hydrogen atom or a methyl group; R 49 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having a single ring; X 4 9 represents an anion such as a chloride ion, a perchlorate ion, a benzenesulfonate ion, a p-toluenesulfonate ion, a methylsulfate ion, an ethylsulfate ion, and a tetrafluoroborate ion; n represents 1 or 2, provided that n is 1 when an intramolecular salt is formed.
• a layer hardened with the vinylsulfone type hardener is arbitrarily selected; it may be a silver halide emulsion layer, or another hydrophilic colloid layers such as a protective layer, an intermediate layer and a subbing layer.
• a protective layer is hardened preferably with the vinylsulfone hardener.
• the examples of the vinylsulfone hardener used in the invention include an aromatic compound disclosed in West German Patent No. 1,100,942; an alkyl compound having a hetero-atom bond disclosed in Japanese Patent Examined Publication Nos. 29622/1969 and 25373/1972; sulfonamide and sulfonate disclosed in Japanese Patent Examined Publication No. 8736/1972; 1,3,5-tris[p-(vinylsulfonyl)-propionyl]-hexahydro-s-triazine disclosed in Japanese Patent O.P.I. Publication No. 24435/1974; and an alkyl compound disclosed in Japanese Patent O.P.I. Publication No. 44164/1976.
• the vinylsulfone hardener useful in the invention includes a compound prepared by reacting the exemplified compounds having at least three vinylsulfone groups in a molecular structure, such as example compounds H-12 to H-29, with a compound having a hydrophilic group and a group capable of reacting with a vinylsulfone group, such as diethanolamine, thioglycolic acid, sodium methylgiycinate, and sodium 2-aminoethanesulfonate.
• a chemical sensitization includes a gold sensitization, a sensitization with a VIII family metal ion, a sulfur sensitization, a reduction sensitization, a sensitization with a thioether compound, and a combination thereof.
• the useful chemical sensitizers include a sulfur sensitizer such as sodium thiosulfate, allylthiocarbamide, thiourea, thiosulfate, and cystine; a noble metal sensitizer such as potassium chloroaurate, aurathiosulfate, and potassium chloropalladate; and a reduction sensitizer such as tin chloride and phenyl hydrazine.
• the emulsion of the invention and the other emulsions that constitutes the light-sensitive material of the invention may incorporate conventional additives such as a whitening agent, an anti-fogging agent, an UV absorbent, and a surfactant.
• the light-sensitive material of the invention may have a non-light-sensitive layer such as a protective layer, an intermediate layer and an antihalation layer.
• the light-sensitive material of the invention is prepared by coating an emulsion with a conventional method on a conventional support such as a baryta paper, a polyethylene-coated paper, a polypropylene paper, a glass sheet and a cellulose acetate film, via a subbing layer and an intermediate layer.
• a conventional support such as a baryta paper, a polyethylene-coated paper, a polypropylene paper, a glass sheet and a cellulose acetate film
• the light-sensitive material of the invention can be used for black-and-white and color photograph, and for the various applications such as general purpose, printing and radiograph. Especially, it exhibits an optimum performance in a high-sensitivity light-sensitive material comprising silver bromoiodide.
• tofal processing time necessary for transporting a film from an inlet of an automatic processor to an exit of a drying unit thereof is 20 to 60 seconds.
• the excellent results can be achieved in processing time of 3 and a half minutes or less, and more excellent results in processing time of 90 seconds or less.
• a monodispersed seed emulsion containing silver bromoiodide grains having an average grain size of 0.3 ⁇ m and an iodide content of 2 mol% was prepared by a double jet method keeping a temperature at 60°C, pH and pAg at 60°C, 2 and 8, respectively.
• a twinned crystal of not more than 1% by number was observed therein with an electronmicroscope.
• the above seed emulsion dispersed in aqueous gelatin solution was cooled to 40°C, and then adjusted to pH of 9.5 with ammonia water and acetic acid. Then, it was further grown in the following manner.
• pH and pAg were adjusted to 9 and 9.0, respectively, with acetic acid and potassium bromide, and then an ammoniac silver ion solution and a potassium bromide solution were added simultaneously to grow silver halide grains up to 90% of a final size, wherein pH was gradually dropped from 9.0 to 8.2.
• pAg was adjusted to 11 by adding a potassium bromide solution, and then an ammoniac silver ion solution and a potassium bromide solution were added gradually lowering pH to 8 to grow the silver halide grains to prepare emulsion containing a silver bromoiodide grain having a silver iodide content of 2 mol% and an average size of 0.7 ⁇ m.
• pH of the emulsion was adjusted to 4.5, and 50 wt% aqueous magnesium sulfate solution of 15 g/mol of AgX was added. After standing, the suspension was subjected to decantation, and this decantation was repeated twice. Then, gelatin of 15 g/mol of AgX, and water were added to make total quantity 450 ml/mol of AgX. The emulsion was dispersed stirring further for 20 minutes at 55° C.
• the emulsion prepared in Process 5 was subjected to chemical sensitization with chloroauric acid and hypo at 55°C, and then 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to prepare a light-sensitive emulsion.
• process 5 was subdevided into I, II and III; the sensitizing dyes were added during addition of an exemplified compound A-3 in case of I, during addition of MgS0 4 in case of II, and during second addition of MgS0 4 in case of III.
• the emulsion was uniformly coated on both faces of a subbed and blue-colored polyethylene terephthalate film base of thickness 180w, and dried to prepare Sample Nos. 1 through 44, each of which was evaluated as follows.
• a sample was sandwiched between two sheets of KS for radiography made by Konica Corporation and was exposed to X-ray via Penetrometer Model B made by Konica Medical. Then, the sample was processed in a developer XD-90 in 90 seconds with an automatic developer Model KX-500 made by Konica Corporation. The sensitivities of the processed samples were evaluated. The sensitivity is expressed by a reciprocal of an exposure necessary for giving a fog + 1.0 density, and by a value relative to that of Sample 1, which is set at 100.
• roller marks pressure marks caused by rollers of an automatic developer
• resistance for roller marks was evaluated as follows; an unexposed sample was processed in 45 or 90 seconds by an X-ray automatic developer having opposed type rollers with heavily roughened surfaces, and the developed sample was observed visually and classified to five grades: 5: no roller marks; 4: only a few roller marks; 3: some roller marks; 2: many roller marks; 1: heavy roller marks.
• a sample uniformly exposed to light and developed was observed visually in an area of 20 cm x 20 cm having a black density of 0.6 to 0.8, and classified to five grades: 5: very excellent; 4: good; 3: practicable; 2: roughened within practicability; 1: no practicable due to roughness.
• MTF is a value in a spatial frequency of 20 lines/mm.
• compositions of the developer and fixer used for processing a light-sensitive material were as follows:
• the emulsions were prepared in the same manner as Example 1, except that the following sensitizing dye (C) was used instead of sensitizing dyes (A) and (B) used in Example 1.
• the emulsions were prepared in the same manner as Example 1, except that the following sensitizing dye (D) was used instead of sensitizing. dyes (A) and (B).
• This sensitizing dye was 300 mg per mol silver.
• the emulsions E1 and E2 each having a different average grain size were prepared by processes 1 through 6 in Example 1.
• E1 and E2 had. the same Agl content of 2 mol% and the average silver halide grain sizes of 0.55 ⁇ m and 0.80 ⁇ m, respectively.
• Sensitizing dye (A) of 300 mg per mol silver and sensitizing dye (B) of 15 mg per mol silver were added to the emulsions in the processes as shown in Table IV.
• Sample Nos. 191 through 227 were prepared and evaluated in the same manners as Example 1, except that formalin used in Example 1 was replaced with a hardener specified in Table V. Desalination was carried out by process (a). The evaluation results are summarized in Table V.
• the emulsions were prepared in the same manner as Example 1, except that the sensitizing dyes used in Example 1 was replaced with an exemplified compound 31 of 20 mg per mol Ag.
• a protective layer solution containing gelatin, matting agent, sodium dodecylbenzenesulfonate and the like was prepared. Further, the following compounds were added thereto.
• Samples 228 to 248 were prepared in the same manner as Example 1.
• each of the samples was slit into 3.5 cm strips, and each strip was subjected to wedgewise exposure via an 820 nm interference filter in 10- 5 second with a a xenon flash. Next, it was processed at 35°C in a developer XD-SR in 45 seconds with an automatic developer for radiograph Model SRX-501 made by Konica Corporation.
• the sensitivities of the developed samples were evaluated.
• the sensitivity of each sample is expressed by a reciprocal of an exposure necessary for giving fog + 1.0 density, and by a value relative to that of Sample 228, which is set at 100.
• the evaluation results are summarized in Table VI.
• the samples of the invention comprise less fogging and high sensitivity.

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