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
  • G03C1/06—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
  • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
• • 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
  • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
  • G03C2001/7481—Coating simultaneously multiple layers

Definitions

• This invention relates to a light-sensitive silver halide photographic material feasible for high speed processing. Particularly, it relates to a light-sensitive silver halide photographic material having high sensitivity and also having excellent pressure resistance and graininess even when subjected to an ultra rapid processing.
• the ultra rapid processing causes problems such that (a) density is insufficient (i.e., decrease in sensitivity, contrast and maximum density), (b) fixing can not be sufficiently carried out, (c) water washing of films may become insufficient, (d) drying of films may become insufficient, and so forth. Moreover, the insufficient fixing and insufficient water washing may cause a change in tone during storage of films to lower image quality.
• a means for solving these problems is to decrease the amount of gelatin.
• decrease in the amount of gelatin tends to bring about troubles such as coating uneveness and coating streaks.
• films with less gelatin may produce problems such that, when films rub each other or films are rubbed by other materials, the so-called abrasion blackening may become liable to occur after the processing to form a portion having higher density than other portions, i.e., the so-called abrasion blackening.
• the ultra rapid processing is meant to be a processing for 20 seconds to 60 seconds in total of the time during which a top end of a film is first inserted to an automatic processor, and then passes through a developing tank, a gangway, a fixing tank, a gangway, a washing tank, a gangway and a drying spot, and thereafter the top end of the film comes out of the drying spot [in other words, the quotient (sec) obtained by dividing the total length (m) of a processing line by the line conveyor speed (m/sec)].
• the reason why the time for the gangways is included is, though well known in the present industrial field, that a processing solution used in a step preceding thereto may swell also at a gangway and a processing step is considered to substantially proceed thereat.
• the amount of coating solution and the viscosity are defined to be 2 to 12 g/m 2 and I to 8 cp, respectively (Japanese Unexamined Patent Publication No.
• Japanese Patent Publication No. 47045/1976 discloses the importance of the amount of gelatin in a rapid processing, in which, however, the processing time is 60 seconds to 120 seconds in total processing time including the time for gangways. Such a processing time, however, can not satisfy the demands in the ultra rapid processing recently practiced.
• orthochromatic light-sensitive materials which are made light-sensitive in the wavelength region of 540 to 550 nm by carrying out orthochromatic sensitization, rather than regular type materials conventionally having a light-sensitive region at 450 nm.
• the materials sensitized like this have wide light-sensitive wavelength region and also have a sensitivity made higher. Accordingly, they can decrease exposed X-ray doses and minimize the influence to be given to human bodies.
• dye sensitization is a very useful sensitizing means, but is still involved in unsolved problems. For example, there remains a problem that sufficient sensitivity can not be obtained depending on the kind of photographic emulsions to be used.
• Pressure desensitization i.e., desensitization seen at the time of development, caused by mechanical pressure applied before exposure
• film folding such as the so-called knick mark folding may sometimes occur, which is a phenomenon that a film is folded by its own weight at a portion where the film is held, whereby the pressure desensitization is liable to occur.
• automatic exposing and developing apparatus utilizing mechanical conveyance are widely used as medical X-ray photographic systems.
• a first object of this invention is to provide a light-sensitive silver halide photographic material that can eliminate the above problems in the prior arts even when a high speed processing is carried out, for example, even when the ultra rapid processing whose total processing time is 20 seconds to 60 seconds as mentioned above is carried out, and can be excellent in sensitivity, contrast, maximum density, fixing performance, dryness, and so forth.
• a second object of this invention is to provide a light-sensitive silver halide photographic material that may be involved in less troubles in coating even with less amount of gelatin, that may suffer less abrasion blackening or pressure desensitization, and that can also be excellent in graininess.
• a light-sensitive silver halide photographic material which comprises photographic layers applied under the condition that the surface tension of a coating solution for forming an outermost layer is 6 dyn/cm or more smaller than the surface tension of a solution for forming a layer adjacent to the outermost layer, and satisfying at least one of the conditions shown below:
• the above light-sensitive silver halide photographic material may preferably have at least one silver halide emulsion layer containing at least one compound selected from the group of the compounds represented respectively by Formulas (I), (II) and (III).
• Formulas (I), (II) and (III) are as follows: wherein R 1 , R 2 and R 3 each represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and at least one of Ri and R 3 represents a sulfoalkyl group or a carboxyalkyl group; X 1 - represents an anion; Z 1 and Z 2 represent a group of nonmetallic atoms necessary for the completion of a substituted or unsubstituted carbon ring; and n represents I or 2, provided, that n is I when an intramolecular salt is formed.
• R 4 and Rs each represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and at least one of R 4 and Rs represents a sulfoalkyl group or a carboxyalkyl group;
• R 6 represents a hydrogen atom, a lower alkyl group or an aryl group;
• X 2 - represents an anion, Zi and Z 2 represent a group of nonmetallic atoms necessary for the completion of a substituted or unsubstituted carbon ring; and
• n represents I or 2, provided, that n is I when an intramolecular salt is formed.
• R 7 and Rg each represent a substituted or unsubstituted lower alkyl group
• R 8 and R io each represent a lower alkyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group
• X 3 - represents an anion
• Zi and Z 2 represent a group of nonmetallic atoms necessary for the completion of a substituted or unsubstituted carbon ring
• n represents I or 2, provided, that n is I when an intramolecular salt is formed.
• photographic layers are applied under the conditions that the surface tension of a solution for forming an outermost layer is 6 dyn/cm or more smaller than the surface tension of a solution for forming a layer adjacent to the outermost layer.
• 6 dyn/cm or more the difference in the surface tension between the solutions used for the above outermost layer (which is usually an uppermost layer) and the adjacent layer (which is a layer directly under the uppermost layer)
• an embodiment may be taken wherein at least one kind of surface active agent is used in the uppermost layer and the surface active agent may be or may not be used in the layer directly under the uppermost layer.
• the surface active agents used in the uppermost layer and the layer directly under it may be the same or different.
• the difference in the surface tension between the solutions used for the uppermost layer and the layer directly under it is preferably controlled to be not less than 8 dyn/cm, more preferably not less than 10 dyn/cm, and most preferably not less than 12 dyn/cm.
• the "outermost layer” mentioned in this invention refers literally to a most outside layer, and, in general, it is formed as an uppermost layer as mentioned above, including, of course, in this invention a case where a coating called as a super coat or the like formed by spraying or coating is sometimes provided on such an outermost layer.
• the above surface active agent usable in this invention may include, for example, nonionic surface active agents such as saponin (steroid type), alkylene oxide derivatives (for example, polyethylene glycol, a polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, and addition products of silicone with polyethylene oxides), glycidol derivatives (for example, alkenylsuccinic acid polyglycerides, and alkylphenol polyglycerides), aliphatic acid esters of polyhydric alcohol and alkyl esters of sugar.
• nonionic surface active agents such as saponin (steroid type), alkylene oxide derivatives (for example, polyethylene glycol, a polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ether
• anionic surface active agents containing an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group and a phosphoric acid ester group, including alkyl carboxylates, alkyl sulfonates, alkyl benzenesulfonates, alkyl naphthalenesulfonates, alkylsulfuric acid esters, alkylphosphoric acid esters, N-acyl-N-alkyltaurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkylphosphoric acid esters, etc.
• an acidic group such as a carboxyl group, a sulfo group, a phospho group, a sulfuric acid ester group and a phosphoric acid ester group
• alkyl carboxylates alkyl sulfonates, alkyl
• amphoteric surface active agents such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, alkylbetaines and amine oxides. It may also include cationic surface active agents such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, phosphonium or sulfonium salts containing an aliphatic or a heterocyclic ring. There may be further used fluorine-containing surface active agents, fluorine-containing surface active agents having a polyoxyethylene group, etc.
• the surface active agents of alkylene oxide type are disclosed in Japanese Patent publication No. 9610/1976, DT-26 48 746, Japanese Unexamined Patent Publications No.129623/1978, No. 89624/1979, No. 98235/1979, 203435/1983, No. 208743/1983, No. 80848/1985 and No. 94126/1985, etc.
• Examples of combined use of the surface active agents of alkylene oxide type and other compounds are disclosed in Japanese Unexamined Patent Publications No. 89626/1979, No. 70837/1980, No. 11341/1982, No. 109947/1982, No. 74554/1984, No. 76741/1985, No. 76742/1985, No. 76743/1985, No. 80839/1985, No. 80846/1985, No. 80847/1985, No. 131293/1975, No. 29715/1978, etc.
• the anionic surface active agents may include those disclosed in Japanese Unexamined Patent Publication No. 21922/1978, GB-1,503,218, Japanese Patent Publication No. 1617/1981, and sulfates of higher alcohols, higher alkyl sulfonates, alkylbenzene sulfonates, dialkyl sulfosuccina tes, acylmethyltauride, N-acylsarcocinate, aliphatic monoglyceride sulfate, oc-sulfonic acid, etc.
• the fluorine-containing surface active agents may include the compounds disclosed in Japanese Patent Publications No. 9303/1972, No. 43130/1973, No. 25087/1977 and No. 1230/1982, Japanese Unexamined Patent Publications No. 46733/1974, No. 16525/1975, No. 34233/1975, No. 32322/1976, No. 14224/1979, No. 111330/1979, No. 557762/1980, No. 19042/1981, No. 41093/1981, No. 34856/1981, No. 11341/1982, No. 29691/1982, No. 64228/1982, No. 146248/1982, No. 114944/1981, No. 114945/1981, No. 196544/1983, No.
• the surface tension of the coating solutions regulated by the surface active agent can be determined by measurement according to the Wilhelm's conventional method at a prescribed liquid temperature.
• anionic surface active agents containing no polyalkylene oxide are shown below as I-I to 1-10.
• fluorine-containing surface active agents are shown below as 2-1 to 2-81.
• fluorine-containing surface active agents may include those which are commercially available in the trade name of UNIDAIN from Daikin Industries, Ltd., or in the trade name of FLOLARD from 3M (Sumitomo 3M Limited).
• polyoxyethylene surface active agents preferably usable in this invention are shown as 3-I to 3-44.
• Preferable quaternary ammonium salts may include the compounds shown below as 4-I to 4-20.
• Coating solutions for the outermost layer and the layer adjacent thereto which form the photographic constituent layers of the light-sensitive material of this invention will be described below.
• the coating solutions are controlled to have respectively a viscosity preferably of 20 cp or less, more preferably 15 cp or less. It is further preferable for both solutions to be controlled so that the difference in the viscosity therebetween may be in the range of ⁇ 2 cp.
• any thickening agent can be used if it has a thickening effect and, at the same time, may not particularly adversely affect the light-sensitive silver halide photographic material. In other words, if it is a thickening agent that may not inhibit any properties of the above light-sensitive material, it may not particularly limited to a particular substance.
• Those which are generally used as the thickening agent may include, for example, aqueous polymers having a sulfuric acid ester group (Japanese Patent Publication No. 21574/1961), dextran and sulfuric acid esters thereof (Japanese Patent Publications No. 11989/1960 and No. 12872/1970), polysaccharides (U.S. Patent No. 3,767,410), polymers having a sulfonic acid group, a carboxylic acid group or a phosphoric acid group (Japanese Unexamined Patent Publication No. 18687/1983) and colloid silica (Japanese Unexamined Patent Publication No. 36768/1983). Those which are particularly preferable in this invention are disclosed in Japanese Unexamined Patent Publication No. 109947/1982.
• one or more kinds of, for example, thickening agents other than colloidal silica can be used as the thickening agent.
• the amount of the thickening agents may be suitably selected depending on the layer(s) to which they are added or the kind of the compound. In summary, it is satisfactory if the viscosity has been controlled to 20 cp or less by using the thickening agent.
• the viscosity can be determined by measurement at a liquid temperature of 35 °C with use of a viscometer such as a B-type viscometer.
• the amount of gelatin contained in the photographic constituent layers formed on a support is 2.20 to 3.10 g/m 2 . If the amount of gelatin is in such a range, the sensitivity as a light-sensitive material and the resistance to abrasion blackening can be more improved than the case where gelatin is contained in an amount more than 3.10 g/m 2 . If it is less than 2.20 g/m 2 , gelatin can be applied to a support only with difficulty.
• Sensitizing dyes that can be used when working this invention will be described below.
• the sensitizing dyes may be any of substances having a desired absorption band in the visible light region, and a group of the organic compounds represented respectively by Formula (I), (II) and (Ill) shown below may be preferably used in this invention.
• R 1 , R 2 and R 3 each represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and at least one of Ri and R 3 takes a sulfoalkyl group or a carboxyalkyl group;
• Xi - represents an anion;
• Z 1 and Z 2 represent a group of nonmetallic atoms necessary for the completion of a substituted or unsubstituted carbon ring; and
• n represents I or 2, provided, however, that n is I when an intramolecular salt is formed.
• R 4 and Rs each represent a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and at least one of R 4 and Rs takes a sulfoalkyl group or a carboxyalkyl group;
• Rs represents a hydrogen atom, a lower alkyl group or an aryl group;
• X 2 - represents an anion, Zi and Z 2 represent a group of nonmetallic atoms necessary for the completion of a substituted or unsubstituted carbon ring; and
• n represents I or 2, provided, however, that n is I when an intramolecular salt is formed.
• R 7 and R 9 each represent a substituted or unsubstituted lower alkyl group
• R 8 and Rio each represent a lower alkyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group
• X 3 - represents an anion
• Z i and Z 2 represent a group of nonmetallic atoms necessary for the completion of a substituted or unsubstituted carbon ring
• n represents I or 2, provided, however, that n is I when an intramolecular salt is formed.
• the carbon ring containing Z i and Z 2 may preferably include an aromatic ring such as a substituted or unsubstituted benzene ring or naphthalene ring.
• the anion represented by Xi- may include, for example, a chloride ion, a bromide ion, an iodide ion, a thiocyanate ion, a sulfate ion, a perchlorate ion, a p-toluene sulfonate ion, an ethyl sulfate ion, etc.
• R 6 represents a hydrogen atom, a lower alkyl group or an aryl group
• the lower alkyl group may include groups such as methyl, ethyl, propyl and butyl.
• the aryl group may include, for example, a phenyl group.
• the groups represented by R 4 and Rs may include those exemplified for R 1 and R 3 in Formula (I) in the above description of Formula (I).
• the anions represented by X 2 - may also include those exemplified for Xi- Formula (I).
• the lower alkyl group represented by R 7 and Rg may include groups such as methyl, ethyl, propyl and butyl.
• the substituted alkyl group may include the groups exemplified for R 1 to R 3 in Formula (I).
• the lower alkyl group represented by R 8 and R 10 may be exemplified by those same as for R 7 and R 9 .
• the hydroxyalkyl group, sulfoalkyl group and carboxyalkyl group represented by R 8 and Rio may include the groups exemplified for R 1 to R 3 in Formula (I).
• the anion represented by X 3 - may also include the ions exemplified for X 1 - in Formula (I).
• the compounds represented by the above Formulas (I), (II) and (III) may be used in an amount ranging between 10 mg and 900 mg in total per mole of silver halide. Particularly preferably, the amount ranges between 60 mg and 600 mg.
• the compounds represented by the above Formulas (I), (II) and (III) may be added at any position in the course of the production of the light-sensitive materials. For example, they may be added anywhere before chemical ripening, during chemical ripening, after termination of chemical ripening or before coating.
• the light-sensitive material of this invention is suitable for a high speed processing, and excellent photographs can be obtained without causing the problems mentioned above even when used, for example, in the ultra rapid processing mentioned above.
• the light-sensitive material of this invention can be processed by an automatic processor having a processing time of 20 to 60 seconds.
• Another preferred embodiment is to use a silver halide photographic emulsion comprising a silver halide grain substantially comprising silver iodobromide and having multi-layer structure, and to use light-sensitive silver halide grains such that the difference in average iodide contents between any two layers (between coats or between an inner nucleus and a coat) in the multi-layer silver halide grain, which are adjacent to each other and each have uniform iodide distribution, is 10 mole % or less.
• the most surface layer has an average iodide content of 10 mole % or less, and the silver halide grains are chemically sensitized.
• the grain having multi-layer structure is a grain provided outside an inner nucleus with a coat that may have any halogen composition.
• This coat may comprise only one layer or may be laminated to form two or more layers, for example, three layers or four layers, but preferably not more than five layers.
• silver bromide, silver iodobromide and silver iodide are used, but they may be a mixture with a small amount of silver chloride. Specifically, the mixture may contain about 10 mole % or less, preferably about 5 mole % or less of silver chloride.
• the most surface layer may preferably comprise substantially silver bromide or substantially silver iodobromide (iodide content: 10 % or less), and may contain less than several % of chloride.
• the average iodide content in total in the silver halide grains of this invention is preferably 10 mole % or less, more preferably 6 mole % or less.
• iodide may sometimes aggravate the problems such as development inhibition and infectious development, and, therefore, it is preferable to make the iodide content not more than a certain level in practical use.
• the method according to this invention is effective for decreasing fogging by pressure, and, for such a reason, the total iodide content in all of the grains is preferably 10 mole % or less, more preferably 7 mole % or less, and most preferably 5 mole % or less.
• the inner nucleus comprises silver iodobromide
• it is preferably of homogeneous phase of a solid solution.
• the conditions under which a diffractometer is used is such that, assuming the scanning speed of a goniometer as ⁇ (deg/min), the time constant as .(sec) and the receiving slit width as r(mm), ⁇ /r ⁇ 10.
• the halide composition of the inner nucleus may be such that the average iodide content is preferably 40 mole % or less, more preferably 0 to 20 mole %.
• the difference in the silver iodide content between the two layers adjacent to each other is preferably not less than 10 mole %, more preferably not less than 20 mole %, and particularly preferably not less than 25 mole %.
• the silver iodide content in a coat other than the most surface coat is preferably 10 mole % to 100 mole %.
• the silver halide grain comprises 3 or more layers and the coats comprise silver iodobromide, they may not necessarily be all homogeneous, but it is preferable for all layers to comprise homogeneous silver iodobromide.
• Such coats (or inner nucleus) having a high iodide content are preferably present below the most surface layer in the case of a negative type silver halide emulsion.
• a positive type silver halide emulsion they may be present either in the inside or at the surface.
• the silver iodide content in the most surface coat is preferably not more than I0 mole %, more preferably 0 to 5 mole %.
• the iodide content in the inner nucleus and the coats of the silver halide grain used in working this invention can be aiso determined according to the method disclosed in J.I. Goldstein and D.B. Williams, "X-ray Analysis in TEMIATEM", Scanning Electron Microscopy (1977), Vol. I, (I.I.T. Research Institute), p.651 (March, 1977).
• the inner nucleus may preferably have a higher iodide content than the most surface layer, and, when it comprises three layers, the coats other than the most surface layer or the inner nucleus may preferably have a higher iodide content than the most surface layer.
• This invention can be preferably applied in respect of silver halide grains chemically sensitized. This is because unsensitized grains may be very poor in the sensitivity itself, and neither abrasion blackening nor pressure desensitization may tend to occur in the first place.
• the silver halide grains used in this invention may be of positive type or of negative type.
• chemical sensitization is carried out preferably to such a degree that may give 60 % or more of the optimum sensitization degree when taking a sensitivity point of "fog + 0.1" in the optical density.
• chemical sensitization is applied in the inside of grains preferably to such a degree that may give 60 % or more of the optimum sensitization degree when taking a sensitivity point of "fog - 0.1" in the optical density.
• silver halide grains used in this invention there can be further used a combination of internal fog type silver halide grains with surface latent image type silver halide grains as disclosed in Japanese Patent Publication No. 2068/1966.
• Average grain size of the silver halide grains used in this invention is expressed in terms of an average value of the grain size determined by assuming as grain size the edge length to be found when converted into a cube having an equivalent volume.
• the silver halide emulsion grains used in the silver halide emulsion layers have an average grain size preferably of 0.30 to 1.50 um, more preferably 0.40 to 1.30 um, and most preferably 0.40 to 1.10 um.
• Grain size distribution of the grains used may be either narrow or wide.
• the silver halide grains contained in the photographic emulsion may have any grain size distribution, but may be of monodispersed one.
• the term "monodispersed” contemplates a dispersed system wherein 95 % of the grains is included in ⁇ 60 %, preferably in ⁇ 40 %, of the number average grain size.
• the number average grain size refers to the number average diameter of projected area size of silver halide grains.
• the silver halide grains in the photographic emulsion may have a regular crystal form such as a cube, an octahedron, a tetradecahedron and a dodecahedron, or may have an irregular crystal form such as a sphere and a plate, or may have a composite form of these crystal forms.
• the grains may comprise grains of various crystal forms.
• junction type silver halide crystals formed by combining crystals of oxides such as PbO with crystals of silver halides such as silver chloride, silver halide crystals formed by epitaxial growth (for example, silver chloride, silver iodobromide. silver iodide. etc. are epitaxially grown on silver bromide), hexagonal crystals. crysta!s formed by epitaxy of regular hexahedral silver chloride on regular octahedral silver iodide.
• an emulsion such that silver halide grains comprising an ultra flat plate having diameter 5 times or more of its thickness account for 50 % or more of the total projection area. Details thereof are disclosed in the specifications of Japanese Unexamined Patent Publications No. 127921/1983, No. 113927/1983. etc.
• the regular grains mentioned above refer to a silver halide emulsion wherein at least 80 % of the weight or number of silver halide grains are comprised of grains having a regular form.
• the silver haiide grains which are regular in the structure or form refer to grains all of which may isotropically grow without including any anisotropical growth of twin crystal face or the like. and have the shape of, for example, a cube, a tetradecahedron, a regular octahedron, a dodecahedron, a sphere, etc.
• Such regular silver halide grains can be obtained by controlling reaction conditions for allowing silver halide grains to grow with use of a simultaneous mixing method.
• a simultaneous mixing method silver halide grains can be obtained by adding to an aqueous solution of protective colloid a silver nitrate solution and a halide solution each in a substantially equimolar amount and with vigorous stirring.
• an emulsion should comprise at least about 60 to 70 0/ 0 by weight of the regular silver halide grains.
• silver ions and halide ions may be fed preferably by gradually increasing in a continuous manner or in a stepwise manner the growth rate at a critical growth rate, or within a tolerance scope thereof, for feeding the silver halide necessary and sufficient for the growth owing to existing grains only, without dissolving out the existing crystal grains, and without generation or growth of new grains on the contrary, accompanying with the growth of the crystal grains.
• the method of gradual increasing is disclosed in Japanese Patent Publications No. 36890/1973 and No. 16364/1977, and Japanese Unexamined Patent Publication No. 142329/1980.
• silver ions and halide ions are effectively fed at such a feed rate that the rate of growth of silver halide grains is 30 to 100 0 / 0 of the critical growth rate.
• This critical growth rate may vary depending on the temperature, the pH, the pAg, the degree of stirring, the composition of silver halide grains, the solubility, the grain size, the distance between grains, the crystal form, the kind and density of protective colloid, etc., but can be readily determined by an experimental approach according to the methods such as microscopic observation of emulsion grains suspended in a liquid phase, measurement of turbidity, etc.
• the silver halide grains used in the silver halide emulsion can be produced by applying a neutral method, an acidic method, an ammonia method, a regular mixing method, a reverse mixing method, a double jet method, a controlled double jet method, a conversion method, a core/shell method, etc. as disclosed in publications, for example, of T.H. James, The Theory of the Photographic Process, 4th Ed., published by Macmillan Publishing Co., Inc. (1977); P. Glfkides, Chemie et Physique Photographigue, published by Paul Montel Co., 1967; G.F. Duffin, Photographic Emulsion Chemistry, published by The Focal Press, 1966; V.L. Zelikman et al, Making and Coating Photographic Emulsion, published by The Forcal Press, 1964; etc.
• soluble halogen salts having different composition for example, a soluble silver salt, a soluble bromine salt and a soluble iodine salt
• soluble halogen salts having different composition for example, a soluble silver salt, a soluble bromine salt and a soluble iodine salt
• a silver halide solvent for example, ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds (see, for example, U.S. Patents No. 3,271,157, No. 3,574,628, No. 3,704,130, No. 4,297,439, No. 4,276,374, etc.), thion compounds (see, for example, Japanese Unexamined Patent Publications No. 144319/1978, No. 82408/1978, No. 77737/1980, etc.) and amine compounds (see, for example, Japanese Unexamined Patent Publication No. 100717/1979) can be used in order to control the growth of grains. Among them, ammonia is preferred.
• Two kinds or more of silver halide emulsions separately produced may be also used by mixing them.
• These silver halide grains or the silver halide emulsion may preferably contain at least one of salts (soluble salts) of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten and platinum. It may be contained preferably in an amount of 10- s to 10- 1 mole per mole of silver. It is particularly preferable to contain at least one of salts of thallium, palladium and iridium. These may be used alone or in combination, and any position (or time) of addition may be selected. Thus, there can be expected the effects such as improvement in flash light exposure performance, prevention of pressure desensitization, prevention of latent image fading, sensitization, and others.
• a mother liquor containing protective colloids is kept to have the pAg of at least 10.5 or more in the course of the grain growth effected before the chemical sensitization mentioned above.
• the grains should be allowed to pass at least once through an atmosphere of pAg 11.5 or more containing very excessive bromide ions.
• (III) face is increased and grains are rounded, whereby the effect of this invention can be increased.
• Such (III) face of a grain may preferably account for 5 % or more in the proportion to the total surface area thereof.
• the rate of increase in (III) face (the rate of increase relative to the grain having not yet been allowed to pass the above-mentioned atmosphere of pAg 10.5 or more) is preferably made to be not less than 10 %, more preferably 10 to 20 %.
• grains may be allowed to pass once through the atmosphere where a mother liquor containing protective colloids is kept to have the pAg of at least 10.5 or more, whereby it can be readily confirmed according to Hirata's measurement method to see whether the (III) face is increased to 5 % or more.
• the mother liquor may be made to have the above pAg preferably at the time after having added about 2/3 of the total amount of silver and before taking a step of the so-called desalting which is generally carried out before the chemical sensitization. This is because a monodispersed emulsion having wide grain size distribution can be readily obtained by doing so.
• the ripening in the atmosphere of pAg 10.5 or more is preferably effected for 2 minutes or more.
• the (III) face can be increased to 5 % or more and the grain can have roundish shape, whereby a preferable grain having 5 % or more of (III) face, relative to the total surface area of the grain, can be obtained.
• a noodle washing method which is carried out by gelation of gelatin may be used, or a sedimentation method (or a floculation method) utilizing inorganic salts, anionic surface active agents, anionic polymers (for example, polystyrene suff 3 nic acid) or gelatin derivatives (for example, acylated gelatin, carbamoylated gelatin, etc.) may also be used.
• the step of removing soluble salts may be omitted.
• the silver halide emulsion may be, or may not be, chemically sensitized, but may preferably be chemically sensitized.
• chemical sensitization the method disclosed in H. Frieser, Die Unen der Photo-graphischen Liste Sawe mit Silberhalogeniden, Akademische Verlagaeselischaft, 1968, pp.675-734 can be employed.
• a sulfur sensitization method using an active gelatin or a sulfur-containing compound capable of reacting with silver for example, thiosulfate, thioureas, mercapto compounds, rhodanines
• a reduction sensitization method using a reducible substance for example, a silver-tin salt, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds
• a noble metal sensitization method using a noble metal compound for example, gold complex salts, as well as complex salts of Group VIII metals in the periodic table such as Pt, Ir, Pd, etc.
• the photographic emulsion used in this invention may be spectrally sensitized by use of a methine dye or the like.
• the dye usable may include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolarcyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
• Particularly useful dyes are dyes belonging to cyanine dyes, merocyanine dyes and composite merocyanine dyes. In these dyes, any nuclei usually utilized in cyanine dyes as basic heterocyclic ring nuclei can be used.
• a pyrroline nucleus an oxazoline nucleus, a thiazoline nucleus, a pyrol nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc.; a nucleus wherein an aliphatic hydrocarbon nucleus is fused with any of the above nuclei; and a nucleus wherein an aromatic hydrocarbon is fused with any of the above nuclei, namely, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzosele
• 5- or 6-membered heterocyclic ring nuclei such as a pyrazolin-5-on nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dion nucleus, a thiazolidine-2,4-dion nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be used as nuclei having ketomethylene structure.
• spectral sensitizing dyes are disclosed in, for example, P. Glafkides, “Chemie Photographigue”, 2nd Ed.. 1957; Paul Montel, Paris, Articles 35 to 41; F.M. Hamer, "The Cyanine and Related Compounds', Interscience; and U.S. Patents No. 2,503,776, No. 3,459,553 and No. 3,117,210, Research Disclosure Vol. 176, 17643, published December, 1978, Paragraph 23-IV-J, etc.
• Sensitizing dyes may be used alone or may be used in combination, and a combination of sensitizing dye is frequently used particularly for the purpose of supersensitization.
• the sensitizing dye when used in this invention, it can be used in the concentration same as used in ordinary negative type silver halide emulsions. It is particularly advantageously used in the dye concentration of a level that may not substantially lower the sensitivity inherent in a silver halide emulsion.
• the sensitizing dye may be preferably used in the concentration of about 1.0 x 10- 5 to about 5.0 x 10- 4 mole per mole of silver halide, particularly about 4.0 x 10- 5 to about 2.0 x 10- 4 mole per mole of silver halide.
• the emulsion may contain a dye having itself no action of spectral sensitization, or a substance substantially absorbing no visible light and showing supersensitization.
• it may contain an aminostilbene compound (for example, the compounds disclosed in U.S. Patents No. 3,533,590 and No. 3,638,721), an aromatic organic acid/formaldehyde condensate (for example, the compounds disclosed in U.S. Patent No. 3,743,510), a cadmium salt, an azaindene compound.
• aminostilbene compound for example, the compounds disclosed in U.S. Patents No. 3,533,590 and No. 3,638,721
• an aromatic organic acid/formaldehyde condensate for example, the compounds disclosed in U.S. Patent No. 3,743,510
• a cadmium salt for example, the compounds disclosed in U.S. Patent No. 3,615,641, No. 3,617,295 and No. 3,635,921.
• the photographic emulsion used in this invention may contain various compounds for the purpose of preventing fog during the production, storage or photographic processing of light-sensitive materials, or making photographic performances stable. That is, there can be added a variety of compounds known as antifoggants or stabilizers, including thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazsoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular, I-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotria- zines; thioketo compounds such as oxazoline thion; azaindenes, for example, tri
• Usable compounds may include, for example, thiazolium salts disclosed in U.S. Patents No. 2,131,038, No. 2,694,716, etc.; azaindenes disclosed in U.S. Patents No. 2,886,437, No. 2,444,605, etc.; urazoles disclosed in U.S. Patent No. 3,287,135; sulfocatechols disclosed in U.S. Patent No. 3,236,632; oxymes disclosed in British Patent No. 623,448; mercaptotetrazoles disclosed in U.S. Patents No. 2,403,927, No. 3,266,897, No.
• the light-sensitive material of this invention may contain a water soluble dye as a filter dye or for the purposes of preventing irradiation and halation and for any other various purposes.
• a dye may include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
• useful are oxonol dyes, hemioxonol dyes and merocyanine dyes.
• a dye or an ultraviolet absorbent when contained in a hydrophilic colloid layer, they may be mordanted by use of a cationic polymer or the like.
• Such a dye to be used may include the compounds disclosed in the paragraph of Absorbing and Filter Dyes in Research Disclosure Vol. 176, pp.23-26.
• the photographic emulsion layers of the light-sensitive photographic material of this invention may contain, for example, polyalkylene oxides, derivatives thereof such as ether, ester and amine thereof, thioether compounds, thiomorpholines, quaternary ammonium chloride compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, etc.
• gelatin as a binding material or a protective colloid which can be used in emulsion layers or intermediate layers of the light-sensitive material of this invention.
• hydrophilic colloid alone or in combination with gelatin.
• the gelatin When gelatin is used in working this invention, the gelatin may be either lime-treated or treated with use of an acid. Details of the method for producing gelatin are disclosed in Arther Davis, The Macromolecular Chemistry of Gelatin, Academic Press, published 1964).
• the above usable hydrophilic colloid may include, for example, proteins such as gelatin derivatives, graft polymers of gelatin with other macromolecules, albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfuric acid esters; sugar derivatives such as sodium alginate and starch derivatives; and various synthetic hydrophilic macromolecular substances such as homopolymers or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole or polyvinyl pyrazole.
• proteins such as gelatin derivatives, graft polymers of gelatin with other macromolecules, albumin and casein
• cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfuric acid esters
• sugar derivatives such as sodium alginate and starch derivatives
• the photographic emulsion layers and other hydrophilic colloid layers may contain an inorganic or organic hardening agent.
• an inorganic or organic hardening agent there can be used, alone or in combination, chromium salts (such as chrome alum and chromium acetate), aldehydes (such as formaldehyde, glyoxal and glutalaldehyde), N-methylol compounds (such as dimethylol urea and methyloldimethylhydantoin), dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-2-triazine and 1,3-vinylsulfonyl-2-propanol), active halogen compounds (such as 2,4-dichloro-6-hydroxy-3-triazine), mucohalogen acids (such as mucochloric acid and mucophenox- ychloric acid), etc.
• the photographic emulsion layers and other hydrophilic colloid layers may contain a dispersed product of a water soluble or slightly soluble synthetic polymer for the purpose of improving the dimensional stability.
• a water soluble or slightly soluble synthetic polymer for the purpose of improving the dimensional stability.
• alkyl acrylates or methacrylates alkoxyalkyl acrylates or methacrylates, glycidyl acrylates or methacrylates, acryl- or methacrylamide, vinyl esters (for example, vinyl acetate), acrylonitriles, olefins, styrenes, etc.
• a protective layer is preferably used in the light-sensitive silver halide photographic material of this invention.
• the Protective layer is a layer comprising a hydrophilic colloid, and, as the hydrophilic colloid to be used, there can be used those mentioned before. Also, the protective layer may comprise either a single layer or overlapped layers.
• a matte agent and/or a smoothing agent or the like may be added to the emulsion layers or the protective layer, preferably to the protective layers, of the light-sensitive silver halide photographic material of this invention.
• the matte agent preferably used may include organic compounds such as water dispersible vinyl polymers including polymethyl methacrylate having suitable grain size (preferably, grain size of 0.3 to 5 ⁇ m, or twice or more, particularly four times or more, of the thickness of a protective layer), or inorganic compounds such as silver halide and strontium or barium sulfate.
• the smoothing agent is useful for preventing an adhesion trouble as being similar to the matte agent, and also effective for improving the friction characteristics having a relation to the adaptability to cameras when taking photographs of motion picture films or projecting motion pictures.
• Specific examples thereof that can be preferably used may include waxes such as liquid paraffin and higher aliphatic acid esters; polyfluorinated hydrocarbons or derivatives thereof; and silicones such as polyalkyl polysiloxane, polyaryl polysiloxane, polyalkylaryl polysiloxane or alkylene oxide addition derivatives of these.
• additives can be used in the light-sensitive photographic material of this invention.
• they include a dye, a development accelerator, a brightening agent, a color fog preventive agent, an ultraviolet absorbent, etc.
• a dye for example, they include a dye, a development accelerator, a brightening agent, a color fog preventive agent, an ultraviolet absorbent, etc.
• a color fog preventive agent for example, those disclosed in Research Disclosure No. 176, pp.22-31 (RD-17643, 1978).
• the light-sensitive silver halide photographic material of this invention can be provided with an antihalation layer, an intermediate layer, a filter layer and the like.
• the photographic emulsion layers or other layers are applied to one side or both sides of a flexible support usually used in light-sensitive materials to embody a product.
• a flexible support usually used in light-sensitive materials to embody a product.
• films comprising semisynthesized or synthesized macromolecules such as cellulose nitrate, cellulose acetate, cellulose acetate butylate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.; paper coated or laminated with a baryta layer or an a-olefin polymer (for example, polyethylene, polypropylene, an ethylenelbutene copolymer), etc.
• the support may be colored by using a dye or a pigment.
• the surface of these supports are, in general, subbing-treated in order to improve the adhesion with a photographic emulsion.
• the surface of the support may be applied with corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the subbing treatment. Entering into details, those disclosed in the paragraph of 'Supports' in Research Disclosure, Vol. 176, p.25 may be used.
• the photographic emulsion layers or other hydrophilic colloid layers can be applied on a support or other layers according to various coating methods.
• a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be employed. Entering into details, the method disclosed in the paragraph of 'Coating Procedures" in Research Disclosure, Vol. 176, pp.27-28.
• the light-sensitive silver halide photographic material of this invention can be used specifically in X-ray light-sensitive materials, lithographic light-sensitive materials, black and white photographing light-sensitive materials, color negative light-sensitive materials, color reversal light-sensitive materials, color photographic paper, a colloid transfer process, a silver salt diffusion transfer process, a dye transfer process, a silver dye bleaching method, print-out sensitive materials, heat development sensitive materials, and so forth.
• Exposure for obtaining a photographic image may be carried out by using conventional methods. Namely, there can be used any of various kinds of light sources containing ultraviolet light, including natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a cathode ray tube flying spot, a light-emitting diode, laser beams (for example, of a gas laser, a YAG laser, a dye laser, a semiconductor laser, etc.). Also, exposure may be carried out by use of light emitted from phosphors excited by electron rays, X-rays, gamma rays, alpha rays, etc.
• light sources containing ultraviolet light including natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, a ca
• Exposure may be carried out in the exposure time of 1/1000 second to I second used in ordinary cameras, as well as in exposure time shorter than 1/1000 second, for example, exposure time of 1/10 4 to 1/10 6 second using a xenon flash lamp or a cathode ray tube, or exposure longer than I second may also be used. If necessary, spectral composition of light used in exposure can be controlled by using a color filter.
• any of the various methods and various processing solutions as disclosed in, for example, Research Disclosure No. 176, pp.25-30 (RD-17643) can be used in the photographic processing of the light-sensitive material of this invention.
• This photographic processing may be either photographic processing for the formation of silver images (i.e., black and white photographic processing) or photographic processing for the formation of color images (i.e., color photographic processing).
• the processing temperature may be selected in the range between 18 0 C to 50° C in usual cases, but may be made lower than 18°C or higher than 50°C.
• a developing solution to be used when, for example, carrying out a black and white processing may contain known developing agents.
• the developing agents can be used as the developing agents, solely or in combination, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, I-phenyI-3-pyrazoIidone), aminophenols (for example, N-methyl-n-aminophenol), etc.
• the developing solution may contain a preservative, an alkali agent, a pH buffering agent, an antifoggant, etc., and may further contain, if necessary, a dissolution auxiliary, a color toning agent, a development accelerator, a surface active agent, an antifoaming agent, a hard water-softening agent, a hardening agent, a viscosity-imparting agent, etc.
• a development agent is incorporated in a light-sensitive material, for example, in emulsion layers, and the light-sensitive material is processed in an aqueous alkali solution to carry out the development.
• a hydrophobic development agent can be incorporated in the emulsion layers according to various methods as disclosed in Research Disclosure No. 169 (RD-16928), U.S. Patent No. 2,739,890, British Patent No. 813,253 and West German Patent No. 15 47 763.
• Such a developing processing may be combined with a silver salt stabilizing processing carried out by using thiocyanate.
• a fixing solution those having the formulation generally employed can be used.
• a fixing agent there can be used thiosulfate and thiocyanate, as well as organic sulfur compounds known to be effective as fixing agents.
• the fixing solution may contain a water soluble aluminum salt as a hardening agent.
• the photographic emulsion layer of the light-sensitive photographic material of the present invention may contain a color image-forming coupler, i.e., a compound capable of forming a dye by reacting with an oxidized product of an aromatic primary amine (for example, phenylenediamine derivative or aminophenol derivative) developing agent in color developing processing.
• a color image-forming coupler i.e., a compound capable of forming a dye by reacting with an oxidized product of an aromatic primary amine (for example, phenylenediamine derivative or aminophenol derivative) developing agent in color developing processing.
• magenta coupler there may be included 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, open chain acylacetonitrile couplers, etc.; as a yellow coupler, acylacetamide couplers (for example, benzoylacetanilides and pivaloylacetanirides); and as a cyan coupler, naphthol coupler, phenol coupler, etc.
• 5-pyrazolone couplers for example, pyrazolobenzimidazole couplers, cyanoacetylcumarone couplers, open chain acylacetonitrile couplers, etc.
• yellow coupler acylacetamide couplers (for example, benzoylacetanilides and pivaloylacetanirides)
• cyan coupler naphthol coupler, phenol coupler, etc.
• couplers are preferably non-diffusible couplers having a hydrophobic group called a ballast group In molecules.
• the couplers may be either of four equivalent type or two equivalent type relative to silver ion.
• DIR couplers there may be included colorless DIR coupling compounds that may form a colorless product by the coupling reaction and release a development restrainer.
• the light-sensitive silver halide photographic material of this invention may contain a color fog preventive agent including hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, etc.
• the light-sensitive silver halide photographic material of this invention may contain an ultraviolet absorbent in the hydrophilic colloid layer.
• an ultraviolet absorbent for example, there can be used benzotriazole compounds substituted with an aryl group (for example, those disclosed in U.S. Patent No. 3,533,794), 4-thiazolidone compounds (for example, those disclosed in No. 3,314,794 and No. 3,352,651), benzophenone compounds (for example, those disclosed in Japanese Unexamined Patent Publication No. 278411971), cinnamic acid ester compounds (for example, those disclosed in U.S. Patents No. 3,705,805 and No. 3,705,375), butadiene compounds (for example, those disclosed in U.S. Patent No.
• Couplers having ultraviolet absorbing properties for example, cyan dye-forming couplers of a-naphthol type
• polymers having ultraviolet absorbing properties may be also used. These ultraviolet absorbents may be mordanted in a particular layer.
• anti-color-fading agents shown below can be used in combination, and color image stabilizers used in this invention can be used alone or in combination of two or more of them.
• the anti-color-fading agents may include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivative, bisphenols, etc.
• a color developing solution may comprise an alkaline aqueous solution containing a color development agent.
• the color developing agent that can be used may include various primary aromatic amine developing agents such as phenylenediamines (for example, 4-amino-N,N-diethylamine, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyi-4-amino-N-ethyi-N-P-methanesuifoamide ethylaniline, 4-amino-3-methyI-N-ethyI-N- ⁇ -meth- oxyethylaniline, etc.).
• the color developing solution may further contain a pH buffering agent such as sulfite of alkali metals, carbonate, borate and phosphate, a development restrainer or antifoggant such as bromide, iodide and organic antifoggants, and so forth.
• a pH buffering agent such as sulfite of alkali metals, carbonate, borate and phosphate
• a development restrainer or antifoggant such as bromide, iodide and organic antifoggants, and so forth.
• it may also contain a hard water softening agent, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a development accelerator such as polyethylene glycol, quaternary ammonium salts and amines, a color dye-forming coupler, a competing coupler, a fogging agent such as sodium boron hydride, an auxiliary developing agent such as I-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid type chelating agent, an antioxidant, etc.
• a hard water softening agent such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol
• a development accelerator such as polyethylene glycol, quaternary ammonium salts and amines
• a color dye-forming coupler such as a competing coupler
• a fogging agent such as sodium boron hydride
• an auxiliary developing agent such as I-phenyl-3-pyrazolid
• the photographic emulsion layers are usually subjected to a bleaching processing.
• the bleaching processing may be carried out simultaneously with a fixing processing, or may be carried out separately.
• a bleaching agent there may be used polyvalent metal compounds such as iron (III), cobalt (111), chrome (VI) and copper (II), peracids, quinones, nitroso compounds, etc.
• ferricyanide dichromate
• organic complex salts of iron (Ill) or cobalt (III) for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and 1,3-diamino-2-propanoltetraacetic acid, or of organic acids such as citric acid, tartaric acid and malic acid; persulfate; permanganate; nitrosophenol; etc.
• potassium ferricyanide sodium ethylenediaminetetraacetic acid iron (III) and ammonium ethylenediaminetetraacetic acid iron (III).
• Ethylenediaminetetraacetic acid iron (III) complex salts are useful in both an independent bleaching solution and a combined bleach-fixing solution.
• a silver iodobromide emulsion E-I containing 2.0 mole % of silver iodide was first prepared according to regular mixing by a full ammonia method. This emulsion comprised grains having an average grain size of 1.10 ⁇ m. This silver iodobromide emulsion E-I was subjected to an optimum gold/sulfur sensitization by adding chloroauric acid, sodium thiosulfate and ammonium thiocyanate, and stabilized with use of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
• Both sides of a polyester film support having been subjected to subbing treatment were coated with the above stabilized emulsion and a protective layer to which a hardening agent was added, to provide layers in the order of the silver halide emulsion layer and the protective layer according to a slide hopper method at a coating rate of 100 m/min so that two layers may simultaneously overlap, thereby obtaining Samples No. I to No. 28 shown in Table I (Table I-a, -b, -c). Coated silver weight was 55 mg/dm 2 .
• the amount of hardening agent in each of the above samples was controlled to have a melting time of about 25 minutes.
• the melting time refers to the time by which an emulsion layer begins to melt out after a sample (a light-sensitive silver halide photographic material) cut into I cm x 2 cm was dipped in an aqueous solution of 1.5% sodium hydroxide kept at 50° C.
• measurement of sensitivity was carried out as follows. That is, a sample was interposed between two optical wedges wherein the density inclination was mirror-symmetrically adjusted, and exposed in equal quantity from both sides for 1/12.5 second with use of a light source of the color temperature of 5,400° K.
• Processing was carried out according to the following steps by using an automatic processor of roller conveyor type. Total processing time was 45 seconds.
• Developing solution and Fixing solution used were XD-90 and XF, respectively (both trade names; produced by Konishiroku Photo Industry Co., Ltd.).
• the exposure amount at base density + fog density + 1.0 was obtained to determine the relative sensitivity.
• drying characteristics were evaluated as follows. That is, after carrying out the above 45 second automatic processing, touch on the samples having passed through the drying area and degree of sticking to other samples were overall evaluated to indicate by the 5 rank system ranging I (poor) to 5 (excellent). There is no problem when it shows 3 to 5, but the rank of I to 2 means infeasibleness for practical use. Results obtained are shown together in Table I (Table I-c). At the right end column of the table, a sample according to this invention is indicated as “Yes", and a sample not according thereto as "No".
• the samples (light-sensitive silver halide photographic materials) of this invention have good coating properties and also excellent sensitivity and drying characteristics, and thus have the feasibility for ultra rapid processing. It is also seen from the comparison with the conventional 90 second processing that the processing time can be shortened to 1/2 to make twice the processing ability, retaining the sensitivity attained in the conventional system.
• octahedral silver iodobromide emulsions containing 5 mole %,10 mole %, 20 mole % and 30 mole % of silver iodide, respectively, were prepared employing substantially the same preparation method as that for E-2, except that the ratio of potassium iodide to potassium bromide was varied, that the core size was varied so as to make uniform the average silver content after the shell formation, and also that the rate of addition at the initial stage of mixing was controlled so as to give the same grain size.
• abrasion blackening was measured in the following manner: Samples were moisture-conditioned for 4 hours at 23°C and 55 % RH, and, thereafter, scratched with use of a sapphire stylus of 0.3 mil in radius while continuously varying the load, and developed to indicate the abrasion blackening by the load (g) at which the blackening began to occur. The smaller the value is, it means that the weaker the abrasion blackening is.
• Emulsions containing core grains were prepared in the same procedures as those for E-3 to E-6, whereby octahedral silver iodobromide emulsions containing 5 mole %, 10 mole %, 20 mole % and 30 mole % of silver iodide, respectively, were obtained.
• octahedral silver iodobromide emulsions containing 5 mole %, 10 mole %, 20 mole % and 30 mole % of silver iodide, respectively.
• 2.0 mole % of shell potassium iodide was contained in each of these emulsions
• there were prepared corresponding octahedral monodispersed core/shell emulsions comprising grains having an average grain size of 1.10 ⁇ m, which were designated as E-7, E-8, E-9 and E-10, respectively.
• a cubic monodispersed emulsion comprising silver iodobromide grains having an average grain size of 0.28 um and containing 2.5 mole % of silver iodide were prepared according to a double jet method. Part of this emulsion was used as cores, and allowed to grow in the following manner.
• an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added at 40° C, pAg 8.0 and pH 9.5 according to a double jet method to form a first coat each containing 5 mole %, 10 mole 0/0, 20 mole % or 30 mole % of silver iodide.
• Each of the emulsions was treated in the same procedures as those for E-2, except that the pAg was made to be 9.0, to form a second coat comprising silver bromide alone, thereby preparing core/shell emulsions comprising cubic monodispersed silver iodobromide grains having an average grain size of 1.0 um, which were designated as E-II, E-12, E-13 and E-14, respectively. All of these emulsions were made to have an average silver iodide content of 3.0 mole %.
• Example I was repeated to prepare emulsion E-15, except that the following thickening agents and surface active agents were used. Using this emulsion E-15, chemical sensitization and coating were carried out in the same procedures as in Example I to obtain samples No. 55 to No. 110. Subsequently, the experiments were carried out in the same manner as in Example I. Results are shown in Tables 6 and 7.
• Surface active agents used were surface active agents 1-10, 2-26, 2-80 and 3-3 of this invention, and the following compounds (I) to (3) .
• the samples (light-sensitive silver halide photographic materials) of this invention have good coating properties and also excellent sensitivity and drying characteristics, and thus have the feasibility for ultra rapid processing. It is also seen from the comparison with the conventional 90 second processing that the processing time can be shortened to 1/2 to make twice the processing ability, reataining the sensitivity attained in the conventional system.
• Example 5 was repeated except for employing dextran in place of the compound (A) as a thickening agent of the emulsion layer. The same result as in Example 5 was observed.
• Example 5 was repeated except for changing the menlting time to 20 minutes. The same result of relation was observed.
• Example 2 was repeated to prepare emulsions E-16 to E-20, except that the thickening agents and surface active agents used in Example 5 were used. Chemical sensitization and coating were carried out in the same procedures as in Example 2 to obtain samples No. III to No. 120 shown hereinbelow. Experiments were carried out on these samples in the same manner as in Example 2. Results obtained are shown in Table 8 (Table 8-a, -b, -c).
• Emulsions containing core grains were prepared in the same procedures as those for E-17 to E-20, whereby octahedral silver iodobromide emulsions containing 5 mole %,10 mole %, 20 mole % and 30 mole % of silver iodide, respectively, were obtained.
• octahedral silver iodobromide emulsions containing 5 mole %,10 mole %, 20 mole % and 30 mole % of silver iodide, respectively, were obtained.
• 2.0 mole % of shell potassium iodide was contained in each of these emulsions
• there were prepared corresponding tetrahedral monodispersed core/shell emulsions comprising grains having an average grain size of 1.10 ⁇ m, which were designated as E-21, E-22, E-23 and E-24, respectively.
• Example 4 was repeated to prepare emulsions E-25 to E-28, except that the thickening agents and surface active agents used in Example 5 were used. Chemical sensitization and coating were carried out on these samples in the same procedures as in Example 4 to obtain samples No. 129 to No. 136 as shown in Table 10 (Table 10-a, -b, -c). Experiments were carried out in the same manner as in Example 4 to obtain the results shown in Table 10 (Table 10-c).
• Example 5 using the emulsion used in Example 5, the sensitizing dyes shown as the examples of the compounds of Formulas (I) to (III) or control dyes (a) to (c) shown below were added to the respective samples. Thereafter, chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to carry out optimum gold and sulfur sensitization, followed by stablization with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. Coating weight of silver was 45 mg/dm 2 , and other conditions same as in the procedures in Example 5 were used to obtain samples No. 137 to No. 197 as in Table II (Table II-a, -b, -c) shown below. On these samples, coating troubles, sensitivities and drying characteristics were evaluated in the same manner as in Example 5 to obtain the results as shown in Table 12 shown below.
• Table II-a, -b, -c Table II-a, -b, -c
• R.M.S. granularity was also measured in the following manner.
• each sample was inserted to an orthochromatic sensitizing screen KS (produced by Konishiroku Photo Industry Co., Ltd.), and irradiated with X-rays for 0.10 second at a tube voltage of 90 KVP and a tube current of 100 mA with use of an aluminum wedge, followed by the above 45 second processing.
• an emulsion layer of the sample was peeled off at a portion of the density 1.0 and at the front side facing to an X-ray generator, and, using Sakura one-touch type RMS measuring machine (produced by Konishiroku Photo Industry Co., Ltd.), the other side emulsion face was measured under an aperture size of 50 x 200 ⁇ m. The smaller the measured value is, the better the granularity is.
• the samples according to this invention have good coating properties and also excellent sensitivity and drying characteristics, and thus have the feasibility for ultra rapid processing. It is also seen from the comparison with the conventional 90 second processing that the processing time can be shortened to 1/2 to make twice the processing ability, retaining the sensitivity attained in the conventional system.
• Example 6 Using the emulsion used in Example 6, the sensitizing dyes (2) were added, and thereafter, chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to carry out optimum gold and sulfur sensitization, followed by stabilization with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. Coating weight of silver was 45 mg/dm 2 , and other conditions same as in the procedures in Example 5 were used to obtain the samples as shown in Table 14 (Table 14-a, -b, -c) shown below.
• Two kinds of silver iodobromide emulsions containing 3.0 mole % of silver iodide were prepared according to regular mixing by a full ammonia method. They comprised grains having an average grain size of 1.10 ⁇ m and 0.80 ⁇ m, respectively, which are designated as emulsions E-29 and E-30, respectively. To these emulsions E-29 and E-30, the sensitizing dyes as shown in Table 16 (Table 16-c) were added. Thereafter, chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to carry out optimum gold and sulfur sensitization, followed by stabilization with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene.
• Silver weight was 45 mg/dm2.
• the amount of hardening agent in each of the above samples was controlled to have a melting time of about 30 minutes.
• Measurement of pressure desensitization was also carried out in the following manner. That is, each sample was moisture-conditioned at 23°C, 35 % R.H. for 5 hours, and, under such conditions, folded about 280° with a curvature radius of 2 cm. Three (3) minutes after folded, with use of an optical wedge, the sample was exposed for 1/10 second using a tungsten lamp as a light source to carry out development. The difference in density between the portion with a blackening density of 1.0 where desensitization occurred due to the folding and the density of 1.0 at the portion where the sample was not folded, was indicated by ⁇ 7. It follows that, the smaller this value is, the smaller the pressure desensitization is.
• the samples according to this invention have good coating properties and also totally excellent sensitivity, granularity, pressure desensitization, abrasion blackening and drying characteristics, and thus have the feasibility for ultra rapid processing. It is also seen from the comparison with the conventional 90 second processing that the sensitivity is higher than the conventional system, and yet the processing time can be shortened to 1/2 to make twice the processing ability.
• the samples according to this invention are excellent in sensitivity, granularity, pressure desensitization, and abrasion blackening as a whole, and it is also seen from the comparison with the conventional 90 second processing that the sensitivity is higher than the conventional system (samples No. 231 and No. 235), and yet the processing time can be shortened to I/2 to make twice the processing ability.
• Formation of core grains was carried out in the same procedures as those for E-32 to E-35 to prepare octahedral silver iodobromide emulsions containing 5 mole %, 10 mole %, 25 mole % and 40 mole 0/ 0 , respectively, of silver iodide.
• shells were made to contain 1.0 mole % of potassium iodide, octahedral monodispersed emulsions comprising grains having an average grain size of 0.75 ⁇ m were prepared, which were respectively designated as E-36, E-37, E-38 and E-39.
• the samples according to this invention are excellent in sensitivity, granularity, pressure desensitization, and abrasion blackening as a whole, and it is also seen from the comparison with the conventional 90 second processing that the sensitivity is higher than the conventional system (samples No. 240 and No. 243), and yet the processing time can be shortened to 1/2 to make twice the processing ability.
• a cubic monodispersed emulsion comprising silver iodobromide grains having an average grain size of 0.28 ⁇ m and containing 2.0 mole % of silver iodide were prepared according to a double jet method. Part of this emulsion was used as cores, and allowed to grow in the following manner.
• an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added at 40° C, pAg 8.0 and pH 9.5 according to a double jet method to form a first coat each containing 5 mole %, 10 mole 0/ 0 , 25 mole % or 40 mole % of silver iodide.
• each of the emulsions was treated in the quite same procedures as those for E-2, except that the pAg was made to be 9.0, to form a second coat comprising silver bromide alone, thereby preparing core/shell emulsions comprising cubic monodispersed silver iodobromide grains having an average grain size of 0.65 ⁇ m, which were designated as E-40, E-41, E-42 and E-43, respectively. All of these emulsions were made to have an average silver iodide content of 3.0 mole %.
• the samples according to this invention are excellent in sensitivity, granularity, pressure desensitization, and abrasion blackening as a whole, and it is also seen from the comparison with the conventional 90 second processing that the sensitivity is higher than the conventional system (samples No. 248 and No. 251), and yet the processing time can be shortened to 1/2 to make twice the processing ability.
• this invention can give a light-sensitive silver halide photographic material excellent in sensitivity, contrast, maximum density, fixing performance and drying characteristics even when an ultra rapid processing of total processing time of 20 seconds to 60 seconds is carried out.
• This invention can also give a light-sensitive silver halide photographic material being involved in less trouble in coating even with a small amount of gelatin, suffering less abrasion blackening or pressure desensitization, and also having excellent graininess.

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• 1987
  • 1987-03-24 EP EP87302526A patent/EP0239363B1/fr not_active Expired - Lifetime
  • 1987-03-24 DE DE8787302526T patent/DE3782351T2/de not_active Expired - Lifetime
• 1990
  • 1990-03-21 US US07/502,371 patent/USH899H/en not_active Abandoned

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