EP0611109A1 - Silver halide light-sensitive photographic material - Google Patents

Silver halide light-sensitive photographic material Download PDF

Info

Publication number
EP0611109A1
EP0611109A1 EP94300819A EP94300819A EP0611109A1 EP 0611109 A1 EP0611109 A1 EP 0611109A1 EP 94300819 A EP94300819 A EP 94300819A EP 94300819 A EP94300819 A EP 94300819A EP 0611109 A1 EP0611109 A1 EP 0611109A1
Authority
EP
European Patent Office
Prior art keywords
group
silver halide
silver
emulsion
atom
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94300819A
Other languages
German (de)
French (fr)
Inventor
Yasuhiko C/O Konica Corporation Kawashima
Hirofumi C/O Konica Corporation Ohtani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0611109A1 publication Critical patent/EP0611109A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/12Methine and polymethine dyes
    • G03C1/24Styryl dyes

Definitions

  • the present invention is relates to a silver halide light-sensitive photographic material and, especially, to a silver halide light-sensitive photographic material which comprises silver halide emulsion containing silver halide grains of which storage stability is improved by incorporating therein a specific novel compound.
  • latent image is a microscopic change of state in silver halide crystal by exposure and the latent image itself is essentially unstable.
  • the latent image is liable to be decayed or intensified with the lapse of time between exposure and development.
  • latent image progression The decay of latent image is called, in the field of photographic industry, “latent-image fading” and the latter is called “latent image progression”.
  • the behavior of the latent image depends strongly upon the storage condition of the exposed light-sensitive material and, for example, the latent-image fading or the latent image intensification is remarkable in the preservation under high temperature.
  • the latent-image fading hardly be caused when the light-sensitive material is stored under low temperature.
  • One method to solve this problem is to carry out development process immediately after imagewise exposure. Another method is simply to store the exposed photographic material under cool condition.
  • the imagewise exposed photographic material is left as it is for a period of several months without undergoing development.
  • the latent image fading or the latent image intensification causes imbalanced photographic behavior between layers, which results in imbalanced color balance and deteriorates color reproduction.
  • the object of the present invention is, therefore, to provide a silver halide light-sensitive photographic material comprising a silver halide emulsion of which preservation stability and, especially, anti-latent- image fading property is improved.
  • a silver halide light-sensitive photographic material which comprises a compound represented by the following formula [I].
  • R1 and R2 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group
  • Z1 represents an oxygen atom, a selenium atom, a sulfur atom, a telurium atom, an organic group represented by -N(R7)- or -C(R8) (R9)-, provided that R1 and R2 may be bonded to each other to form a ring
  • R7, R8, and R9 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group
  • R3, R4, R5, and R6 independently represent a hydrogen atom or a substituent
  • Z2 represents a group of non-metal atoms necessary to form a 5- member
  • the alkyl group represented by R1 and R2 is, for example, methyl group, ethyl group, propyl group, iso-propyl group, n-butyl group, tert.-butyl group, n-pentyl group, a cyclopentyl group, n-hexyl group, a cyclohexyl group, n-octyl group, or n-dodecyl group.
  • alkyl groups may further be substituted by, for example, a halogen atom such as chlorine atom, bromine atom, fluorine atom, etc.; an alkoxy group, such as methoxy group, ethoxy group, 1,1-dimethylethoxy group, n-hexyloxy group, n-dodecyloxy group, etc.; an aryloxy group such as phenoxy group, naphthoxy group; an aryl group such as phenyl group, naphthyl group; an alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, 2-ethylhexyloxy- carbonyl group, etc.; an aryloxy carbonyl group such as phenoxycarbonyl group, naphthoxycarbonyl group, etc.; an alkenyl group such as vinyl group, allyl group, etc.; a heterocyclic group such as 2-pyridy
  • the alkenyl group represented by R1 and R2 is, for example, a vinyl group or an allyl group. These groups can further be substituted by the alkyl group represented by R1 and R2, and the groups as mentioned as the substituent for the alkyl group.
  • the alkynyl group is, for example, propagyl group.
  • the alkynyl group may be substituted by the alkyl group represented by R1 and R2, and the groups as mentioned as the substituent for the alkyl group.
  • the aryl group represented by R1 and R2 is, for example, a phenyl group, or a naphthyl group and these groups may also be substituted by the alkyl group represented by R1 and R2, and the groups mentioned as the substituent for the alkyl group.
  • the heterocyclic group represented by R1 and R2 is, for example, a pyridyl group such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc., a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrollyl group, a pyrradinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulforanyl, a pyperizinyl group, a pyrazolyl group, or a tetrazolyl group and these groups may be substituted by the alkyl group represented by R1 and R2 and the groups mentioned as the substituent for the alkyl group.
  • a pyridyl group such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc.
  • the substituent represented by R3, R4, R5 and R6 is, for example, an alkyl group such as methyl group, ethyl group, n-propyl 1 group, iso-propyl group, tert.-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, or n-dodecyl group; an alkenyl group such as vinyl group, or allyl group; an alkynyl group such as propargyl group; an aryl group such as a phenyl group, naphthyl group, etc.; a heterocyclic group such as a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrradinyl group, a pyrimidiny
  • the ring which can be formed with R1 and R2 is, for example, a benzene ring, a naphthalene ring, a thio- phen ring, a pyridine ring, a furane ring, a pyrimidine ring, a cyclohexane ring, a pyrane ring, a pyrrole ring, a pyradine ring, an indole ring, etc.
  • These groups may be substituted by the alkyl group represented by R1 and the groups as mentioned for the substituent for the alkyl group.
  • the methine group represented by substituted L1 and L2 can have a substituent.
  • the substituent is, for example, an alkyl group such as methyl group, ethyl group, propyl group, etc.; an aryl group such as phenyl group, etc.; an alkoxy group such as methoxy group, ethoxy group, etc.; an aryloxy group such as phenoxy group, etc.; a halogen atom such as chlorine atom, bromine atom, etc.
  • the 5-membered or 6-membered ring is, for example, a morphorine ring, a pyperidine ring, a pyperadine ring, a pyrroridine ring, etc. and these groups may be substituted by the alkyl group represented by R1 and R2, and the groups as mentioned for the substituent for the alkyl group.
  • the compound of the present invention is contained in an amount of 2x10- 8 to 1x10- 2 , preferably 2x10- 7 to 1 ⁇ 10 -4 mol per mol of silver halide.
  • the silver halide used for the photographic emulsion layer of the photographic light-sensitive material of the present invention any one or more selected from silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, and silver chloride can be used.
  • a preferable silver halide is a silver iodobromide of which silver iodide content is not more than 30 mol%, silver bromide or silver chlorobromide.
  • the silver halide grain crystals contained in the photographic emulsion may be regular shaped crystals such as cubic, octahedral or tetradecahedral shaped crystals; one with crystal imperfections such as one having twin planes; or irregular shaped crystals such as spherical shaped grains; and combined one thereof.
  • the silver halide emulsion used for the light-sensitive material of the present invention usually is subjected to, after physical ripening and chemical ripening, spectral sensitization.
  • Additives which can be used in these processes are illustrated in Research Disclosures No.17643, No.18716, and No.308119 (They are hereinafter referred to as RD 17643, RD18716, and RD 308119, respectively.
  • Couplers can be used for the light-sensitive material of the present invention according to the color- forming required in each of color-sensitive layers.
  • the specific example is illustrated in above-mentioned Research Disclosure. The related description place is shown as below.
  • Auxiliary layers such as a filter layer and a inter-layer, etc. described in the above-mentioned RD 308119 VII-K can be provided to the light-sensitive material of the present invention.
  • the light-sensitive material of the present invention can take various layer arrangements such as a conventional layer order, reverse-layer order, and the unit constitutions described in the above-mentioned RD 308119 VII-K.
  • the present invention can be applied to various color photographic materials such as the color negative film for general use or cine-use, the color reversal film for the slide or the televisions, the color paper, the color positive films, and the color reversal paper.
  • the light-sensitive material of the present invention can be subjected to the development processing by the usual method described at pages 28 - 29 of RD 17643, page 615 of RD 18716, and section XIX, RD 308119.
  • EmA-1 A method of preparing emulsion EmA-1 used in this example is shown below:
  • EmA-1 The manner of preparing emulsion EmA-1 is described.
  • Table 1 is a grain rowth condition of EmA-1.
  • Table 2 represents addition flowing rates of aqueous solutions (a-2) and (a-3) and Table 3 represents flowing rates of aqueous solution (a-4).
  • the grain emulsion was to be flocculated to perform desalinization washing.
  • EmA-1 Afteradjusting pAg of EmA-1 to 8.0 and adding 2.0 ⁇ 10 -6 mol/mol AgX of sodium thiosulfate to the emulsion, the emulsion was chemically ripened for a period of 60 minutes at a temperature of 55°C and pH of 5.8. Then, by adding a solution containing 4.4 ⁇ 10 -7 mol/mol AgX of chloroauric acid and ammonium thiocyanate, the emulsion was ripened furthermore for 60 minutes.
  • sensitizing dyes SD-A, SD-B and SD-C as shown below was made to adsorb together on the grains and the spectral sensitization was performed. Furthermore, magenta couplers M-A, M-B, and M-C were added thereto.
  • Comparative Compound-1 Comparative Compound-2 (Comp. 2) Comparative Compound-3 (Comp. 3) Comparative Compound-4 (Comp. 4) Comparative Compound-5 (Comp. 5)
  • composition of the processing solution used in the respective processing steps are given below:
  • sensitivity is defined by reciprocal of the exposure at which fog density +0.1 is given.
  • Sensitivity of the sample is represented as relative sensitivity when sensitivity of fresh Sample No.1 is assumed to be 100.
  • Em-1 to Em-8 The following emulsions Em-1 to Em-8 was prepared and a multi-layered light-sensitive material 101 was made.
  • the emulsion EmB-1 was prepared in the same manner as emulsion Em-2 disclosed in Japanese Patent O.P.I. Publication No. 3-241336(1991), as follows.
  • an aqueous solution containing 5% by weight of ossein gelatin was added into a reaction vessel. While stirring the solution at 40°C, a 3.5-N aqueous silver nitrate solution and a 3.5-N aqueous potassium iodide solution were added for 30 minutes at a fixed rate.
  • PAg was kept at 13.5 during the addition by a conventional pAg-controlling method.
  • the formed silver iodide was a mixture of ⁇ -Agl and y-Agl grains having the average size of 0.06 ⁇ m. This emulsion is called a silver iodide fine grain emulsion.
  • a mono-dispersion type silver halide seed emulsion containing spherical shaped twin crystals was prepared in the method as shown below:
  • solution C3 was added taking 20 seconds and ripening was carried out for five minutes.
  • concentration of potassium bromide during the ripening was 0.071 mols/literand that of ammonia was 0.63 mols/liter.
  • this seed emulsion was found to be a mono-dispersion type emulsion containing grains having average grain size of 0.36 ⁇ m and the distribution width of 18%. This emulsion is hereinafter refferred to a seed emulsion.
  • an emulsion of the present invention having an average grain size of 1.25 ⁇ m was prepared by using three kinds of aqueous solution shown as follows, the silver iodide fine grain emulsion and the seed emulsion.
  • the seed emulsion of 0.407 equivalent mols is added to aqueous solution A2 as above-mentioned, violently stirred at 60°C temperature and pH and pAg have been adjusted by using acetic acid and potassium bromide aqueous solution.
  • the mixed solution was flocculated to desalt by adding phenylcarbamyl gelatin aqueous solution to desalt and adjusting pH of the solution. Next, pH and pAg were each adjusted to 5.80 and 8.06 at 40°C.
  • EmB-1 This emulsion hereinafter is referred to as EmB-1.
  • Table 5 is a grain growth condition of EmB-1.
  • Table 6 is an addition pattern of B2, and Table 7 is an addition pattern of C2, and Table 8 is an addition pattern of D2.
  • sensitizing dyes S-5, S-6, S-7 and S-8 were added thereto and the the emulsion was allowed to stand for 30 minutes so that dyes were adsorbed on the silver halide grains. Then, 1.0 ⁇ x10 -6 mol/mol AgX of sodium thiosulfate was added. 10 minutes later, a solution mixture containing 2.2 ⁇ 10 -7 mol/mol AgX of chloroauric acid and thiocyanic acid ammonium salt was added to the emulsion, and it was further ripened for 60 minutes. Thereafter, inventive or comparative compounds as shown in Table are respectively added thereto.
  • the amount of the compound incorporated into the sample is given in terms of gram per m 2 unless otherwise noted.
  • the amount of silver halide and colloidal silver was expressed in terms of equivalent amount of silver and the added amount of the sensitizing dye is given in terms of mols per mol of AgX contained in the same layer.
  • coating aid (Su-1) dispersion aid (Su-2, Su-3), gelatin hardener (H-I, H-2), stabilizing agent (Stab-1), anti-foggant (AF-1, AF-2), and antiseptic (DI-1) were added to each layer.
  • the samples were exposed to yellow light through an optical wedge, and thereafter subjected to the following photographic processing.
  • compositions of the processing solutions used in each processing steps are the same as those used in Example 1.
  • sensitivity is defined in the same manner as in Eexample 1 and is represented as relative sensitivity by which sensitivity of Sample 101 is to be 100.
  • sensitivity is defined by the reciprocal of the exposure by which the density of fog +0.1 is given and was represented with a relative value, wherein a blue sensitivity of each fresh sample was assumed to be 100.
  • the compound of the present invention of samples 6 - 53 it is understood that the latent-image regression after exposure is small as compared with samples 1 - 5 in which the comparison compounds were added.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

A silver halide photographic light-sensitive material improved in latent image stability is provided, comprising a support having thereon a silver halide emulsion layer which contains a compound represented by the following formula.

Description

    Field of the Invention
  • The present invention is relates to a silver halide light-sensitive photographic material and, especially, to a silver halide light-sensitive photographic material which comprises silver halide emulsion containing silver halide grains of which storage stability is improved by incorporating therein a specific novel compound.
  • Background of the Invention
  • Recently, the improvement in the preservation stability of the silver halide light-sensitive photographic materials has been a strong demand as well as the demand for high sensitivity and low fog.
  • In the image-forming technology using silver halide light-sensitive photographic materials, it is well known that two steps are necessary to form an image. That is; (a) a step of imagewise exposing a silver halide light-sensitive photographic material to light to form a latent image; and (b) a step of developing thus imagewise exposed photographic material to convert the formed latent image into a silver image or a dye image.
  • Concerning these processes, for instance, there is a detailed description in "The Theory of the Photographic Process", by James.
  • The formation of latent image is a microscopic change of state in silver halide crystal by exposure and the latent image itself is essentially unstable.
  • Therefore, the latent image is liable to be decayed or intensified with the lapse of time between exposure and development.
  • The decay of latent image is called, in the field of photographic industry, "latent-image fading" and the latter is called "latent image progression".
  • Generally, the behavior of the latent image depends strongly upon the storage condition of the exposed light-sensitive material and, for example, the latent-image fading or the latent image intensification is remarkable in the preservation under high temperature. On the other hand, the latent-image fading hardly be caused when the light-sensitive material is stored under low temperature.
  • One method to solve this problem is to carry out development process immediately after imagewise exposure. Another method is simply to store the exposed photographic material under cool condition.
  • These are the simplest methods from chemical point of view, but they are not necessarily welcomed to the customer.
  • In fact, for example, it is often the case that the imagewise exposed photographic material is left as it is for a period of several months without undergoing development.
  • In the case of multi-layered color photographic materials, the latent image fading or the latent image intensification causes imbalanced photographic behavior between layers, which results in imbalanced color balance and deteriorates color reproduction.
  • In order to prevent the latent image intensification, various attempts have been made. For example, there have been proposed a method of using a hardener which is capable of releasing an acid to lower pH of the emulsion layer, disclosed in Japanese Patent Publication No. 51-9 109(1976); a method of adding a rhodium compound and an iridium compound at the time of preparing of emulsion, which is disclosed in Japanese Patent 0.P.).Publication No. 48-6875(1973); a method of adding a heterocyclic mercapto compound to a silver halide emulsion prepared by using a rhodium compound, which is disclosed in Japanese Patent Publication No.57-23250(1982); a method of adding a hydroxy-aza-indorizine compound and a nitrogen-containing heterocyclic compound having a mercapto group to a silver halide emulsion containing a rhodium compound disclosed in Japanese Patent O.P.I. Publication No. 53-127714(1988).
  • However, these conventional methods were not necessarily satisfactory in view of its specific manner of preparation or insufficient effects, etc.
  • Summary of the Invention
  • The object of the present invention is, therefore, to provide a silver halide light-sensitive photographic material comprising a silver halide emulsion of which preservation stability and, especially, anti-latent- image fading property is improved.
  • The object of the present invention was found to be achieved by a silver halide light-sensitive photographic material which comprises a compound represented by the following formula [I].
    Figure imgb0001
    wherein R1 and R2 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Z1 represents an oxygen atom, a selenium atom, a sulfur atom, a telurium atom, an organic group represented by -N(R7)- or -C(R8) (R9)-, provided that R1 and R2 may be bonded to each other to form a ring; R7, R8, and R9 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group; R3, R4, R5, and R6 independently represent a hydrogen atom or a substituent; Z2 represents a group of non-metal atoms necessary to form a 5- membered or 6- membered heterocyclic ring; and each of L1 and L2 represents a methine group.
  • The alkyl group represented by R1 and R2 is, for example, methyl group, ethyl group, propyl group, iso-propyl group, n-butyl group, tert.-butyl group, n-pentyl group, a cyclopentyl group, n-hexyl group, a cyclohexyl group, n-octyl group, or n-dodecyl group. These alkyl groups may further be substituted by, for example, a halogen atom such as chlorine atom, bromine atom, fluorine atom, etc.; an alkoxy group, such as methoxy group, ethoxy group, 1,1-dimethylethoxy group, n-hexyloxy group, n-dodecyloxy group, etc.; an aryloxy group such as phenoxy group, naphthoxy group; an aryl group such as phenyl group, naphthyl group; an alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, 2-ethylhexyloxy- carbonyl group, etc.; an aryloxy carbonyl group such as phenoxycarbonyl group, naphthoxycarbonyl group, etc.; an alkenyl group such as vinyl group, allyl group, etc.; a heterocyclic group such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morphoryl group, pyperizyl group, pyperazyl group, furyl group; an alkynyl group such as propynyl group; an amino group such as amino group, N,N-di-methyl amino group, anilino group; hydroxy group, cyano group, sulfo group, carboxyl group, and a sulfonamide group such as methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-octylsulfonylamino group, phenylsulfonylamino group, etc.
  • The alkenyl group represented by R1 and R2 is, for example, a vinyl group or an allyl group. These groups can further be substituted by the alkyl group represented by R1 and R2, and the groups as mentioned as the substituent for the alkyl group.
  • The alkynyl group is, for example, propagyl group. The alkynyl group may be substituted by the alkyl group represented by R1 and R2, and the groups as mentioned as the substituent for the alkyl group.
  • The aryl group represented by R1 and R2 is, for example, a phenyl group, or a naphthyl group and these groups may also be substituted by the alkyl group represented by R1 and R2, and the groups mentioned as the substituent for the alkyl group.
  • The heterocyclic group represented by R1 and R2 is, for example, a pyridyl group such as 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, etc., a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrollyl group, a pyrradinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulforanyl, a pyperizinyl group, a pyrazolyl group, or a tetrazolyl group and these groups may be substituted by the alkyl group represented by R1 and R2 and the groups mentioned as the substituent for the alkyl group.
  • The substituent represented by R3, R4, R5 and R6 is, for example, an alkyl group such as methyl group, ethyl group, n-propyl 1 group, iso-propyl group, tert.-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, or n-dodecyl group; an alkenyl group such as vinyl group, or allyl group; an alkynyl group such as propargyl group; an aryl group such as a phenyl group, naphthyl group, etc.; a heterocyclic group such as a pyridyl group, a thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrradinyl group, a pyrimidinyl group, a pyridazinyl group, a selenazolyl group, a sulforanyl group, a pyperidinyl group, a pyrazolyl group, tetrazolyl group, etc.; a halogen atom such as chlorine atom, bromine atom, fluorine atom, etc.; an alkoxy group such as methoxy group, ethoxy group, propyloxy group, n-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-octyloxy group, n-dodecyloxy group, etc.; an alkoxycarbonyl group such as methoxycarbonyl group, ethylethoxycabonyl group, n-butyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecyloxycabonyl group, etc.; an aryloxycarbonyl group such as phenyloxycarbonyl group, naphthoxycarbonyl group, etc.; a sulfonamide group such as methylsulfonylamino group, ethylsulfonylamino group, n-butylsulfonylamino group, n-hexylsulfonylamino group, cyclohex- ylsulfonylamino group, n-octylsulfonylamino group, n-dodecylsulfonylamino group, phenylsulfonylamino group, etc.; a sulfamoyl group such as aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, n-butylaminosulfony group, n-hexylaminosulfonyl group, cyclohexylaminosulfonyl group, n-octylamino- sulfonyl group, n-dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.; a ureido group such as methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, n-octylureido group, n-dodecylureido group, phenylureido group, naphthylur- eido group, 2-pyridylaminoureido group, etc.; an acyl group such as acetyl group, ethylcarbonyl group, propyl- carbonyl group, n-pentylcarbonyl group, cyclohexylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcar- bonyl group, n-dodecylcarbonyl group, phenylcarbonyl group, naphthoxycarbonyl group, pyridylcarbonyl group, etc.; a carbamoyl group such as aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylcarbonylamino group, n-pentylcarbonylamino group, cyclohexylcarbonylamino group, n-oc- tylcarbonylamino group, 2-ethylhexylcarbonylamino group, n-dodecylcarbonylamino group, phenylcarbonyla- mino group, naphthylcarbonylamino group, etc.; a sulfonyl group such as methylsulfonyl group, ethylsulfonyl group, n-butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.; an amino group such as amino group, ethylamino group, dimethylamino group, n-butylamino group, cyclopentylamino group, 2-ethylhexylamino group, n-dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.; a cyano group; a nitro group; a carboxyl group; and a hydroxyl group. These groups may be substituted by the alkyl group represented by R1 and the groups as mentioned for the substituent for the alkyl group.
  • The ring which can be formed with R1 and R2 is, for example, a benzene ring, a naphthalene ring, a thio- phen ring, a pyridine ring, a furane ring, a pyrimidine ring, a cyclohexane ring, a pyrane ring, a pyrrole ring, a pyradine ring, an indole ring, etc. These groups may be substituted by the alkyl group represented by R1 and the groups as mentioned for the substituent for the alkyl group.
  • The methine group represented by substituted L1 and L2 can have a substituent. The substituent is, for example, an alkyl group such as methyl group, ethyl group, propyl group, etc.; an aryl group such as phenyl group, etc.; an alkoxy group such as methoxy group, ethoxy group, etc.; an aryloxy group such as phenoxy group, etc.; a halogen atom such as chlorine atom, bromine atom, etc.
  • The 5-membered or 6-membered ring is, for example, a morphorine ring, a pyperidine ring, a pyperadine ring, a pyrroridine ring, etc. and these groups may be substituted by the alkyl group represented by R1 and R2, and the groups as mentioned for the substituent for the alkyl group.
  • Specific examples of the compounds of the present invention are given below, but the scope of the present invention is not limited by these.
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011
    Figure imgb0012
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    Figure imgb0019
    Figure imgb0020
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
    Figure imgb0029
    Figure imgb0030
    Figure imgb0031
    Figure imgb0032
    Figure imgb0033
    Figure imgb0034
    Figure imgb0035
    Figure imgb0036
    Figure imgb0037
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
    Figure imgb0041
    Figure imgb0042
    Figure imgb0043
    Figure imgb0044
    Figure imgb0045
    Figure imgb0046
    Figure imgb0047
    Figure imgb0048
    Figure imgb0049
    the compound of the present invention is contained in an amount of 2x10-8 to 1x10-2, preferably 2x10-7 to 1×10-4 mol per mol of silver halide.
  • The examples of synthesizing the compounds of the present invention are given below. Other compounds may also be synthesized easily in the similar manner.
  • Synthesis Example 1. (synthesis of Exemplified Compound 39)
  • 5g of 2,5-dimethyl benzoxazole, 6.5g of morphorino benzaldehyde and 1.5g of sodium hydride (mineral oil 60%) were dissolved in 15ml of dimethyl formamide and the mixture was stirred for one hour in the room temperature. After the reaction was completed, the solution was added to 200ml of water and deposited solid was filtered. After drying solid ingredient, the object product was obtained by recrystallization using ethyl acetate. The amount obtained was 5.7g and the yield was 52%.
  • Synthesis Example 2. (synthesis of Eexemplified Compound 40)
  • 6.1g of 6-methoxy- 2-methyl benz thiazole, 6.5g of p-morphorino benzaldehyde, 1.5g of hydrogenated sodium hydride and 20mi of dimethylformamide were mixed under stirring for one hour at the room temperature. After the reaction was completed, the mixed solution was added to 200ml of water and deposited solid ingredient was filtered. After drying the solid ingredient, the objective product was obtained through recrystalliztion from ethyl acetate. The amount obtained was 7.2g and the yield was 60%.
  • The silver halide used for the photographic emulsion layer of the photographic light-sensitive material of the present invention, any one or more selected from silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, and silver chloride can be used. A preferable silver halide is a silver iodobromide of which silver iodide content is not more than 30 mol%, silver bromide or silver chlorobromide.
  • Moreover, the silver halide grain crystals contained in the photographic emulsion may be regular shaped crystals such as cubic, octahedral or tetradecahedral shaped crystals; one with crystal imperfections such as one having twin planes; or irregular shaped crystals such as spherical shaped grains; and combined one thereof.
  • The silver halide emulsion used for the light-sensitive material of the present invention usually is subjected to, after physical ripening and chemical ripening, spectral sensitization. Additives which can be used in these processes are illustrated in Research Disclosures No.17643, No.18716, and No.308119 (They are hereinafter referred to as RD 17643, RD18716, and RD 308119, respectively.
  • Page and column in RD 308119, RD 17643 and RD 18716, in which references are made, are given below:
    Figure imgb0050
  • Moreover, well-known photographic additives, which can be used in the present invention, are illustrated in above-mentioned Research Disclosure as shown below.
    Figure imgb0051
    Figure imgb0052
  • Various couplers can be used for the light-sensitive material of the present invention according to the color- forming required in each of color-sensitive layers. The specific example is illustrated in above-mentioned Research Disclosure. The related description place is shown as below.
    Figure imgb0053
  • When various additives are used for the light-sensitive material of the present invention, these may be added by using the dispersion method described in RD 308119 XIV.
  • In the present invention, the support described on page 28 of above-mentioned RD 17643, page 647-8 of RD 18716, and in XVIII of RD 308119 can be used.
  • Auxiliary layers such as a filter layer and a inter-layer, etc. described in the above-mentioned RD 308119 VII-K can be provided to the light-sensitive material of the present invention.
  • The light-sensitive material of the present invention can take various layer arrangements such as a conventional layer order, reverse-layer order, and the unit constitutions described in the above-mentioned RD 308119 VII-K.
  • The present invention can be applied to various color photographic materials such as the color negative film for general use or cine-use, the color reversal film for the slide or the televisions, the color paper, the color positive films, and the color reversal paper.
  • The light-sensitive material of the present invention can be subjected to the development processing by the usual method described at pages 28 - 29 of RD 17643, page 615 of RD 18716, and section XIX, RD 308119.
  • Examples
  • Next, the present invention is explained more specifically with reference to examples. However, the scope of the present invention is not limited by these.
  • Example 1
  • A method of preparing emulsion EmA-1 used in this example is shown below:
    • Preparation of Emulsion EmA-1:
  • The manner of preparing emulsion EmA-1 is described.
  • Following aqueous solutions (a-1) through (a-4) were used.
    Figure imgb0054
    Figure imgb0055
    Figure imgb0056
  • To the above-mentioned Solution (a-1), which was violently stirred at 60°C, 0.407 mol equivalent monodispersed silver iodobromide emulsion, of which average grain size is 0.27 µm and the silver iodide content of which is 2 mol%, was added as seed grains and pH and pAg of the solution was controlled by use of aqueous solutions of acetic acid and potassium bromide.
  • Thereafter, while controlling pH and pAg of the emulsion as shown in Table 1, aqueous solutions of (a-2), (a-3), and (a-4) were added at the flowing rates as shown in Table 2 and Table 3 by the simultaneous double- jet mixing method. Table 1 is a grain rowth condition of EmA-1.
    Figure imgb0057
  • Table 2 represents addition flowing rates of aqueous solutions (a-2) and (a-3) and Table 3 represents flowing rates of aqueous solution (a-4).
    Figure imgb0058
    Figure imgb0059
  • Next, by adding aqueous phenylcarbamyl gelatin solution and controlling pH of the solution, the grain emulsion was to be flocculated to perform desalinization washing.
  • Thus, a monodispersed emulsion EmA-1, of which silver iodide content is 8.0-mol % and the average grain size is 0.8 µm, was prepared.
  • Afteradjusting pAg of EmA-1 to 8.0 and adding 2.0×10-6 mol/mol AgX of sodium thiosulfate to the emulsion, the emulsion was chemically ripened for a period of 60 minutes at a temperature of 55°C and pH of 5.8. Then, by adding a solution containing 4.4×10-7 mol/mol AgX of chloroauric acid and ammonium thiocyanate, the emulsion was ripened furthermore for 60 minutes.
  • Afterwards, compounds of the present invention and comparison compounds 1-5 as shown in table 4 were added to this emulsion and the amount of 1/10 of all added amount of the sensitizing dye was added individually. Sensitizing dyes SD-A, SD-B and SD-C as shown below was made to adsorb together on the grains and the spectral sensitization was performed. Furthermore, magenta couplers M-A, M-B, and M-C were added thereto.
  • Then, after adding an appropriate amount of 2-hydroxy-4,6-dichrolotriazine sodium salt as a hardener to respective emulsions, they were respectively coated on a subbed triacetate support so that the coated amount of silver is 2.0 g/m2 and photographic material samples were obtained.
    Figure imgb0060
    Figure imgb0061
    Figure imgb0062
    Figure imgb0063
    Figure imgb0064
    Figure imgb0065
    Comparative Compound-1 (Comp. 1)
    Figure imgb0066
    Comparative Compound-2 (Comp. 2)
    Figure imgb0067
    Comparative Compound-3 (Comp. 3)
    Figure imgb0068
    Comparative Compound-4 (Comp. 4)
    Figure imgb0069
    Comparative Compound-5 (Comp. 5)
    Figure imgb0070
  • Each of these samples was exposed through an optical wedge to green light and then developed according to the following processing steps. Furtheremore, samples which were aged for one week after exposure were similarly developed. The photographic performance was comparatively evaluated. The results thereof are shown in Table 4. A green photosensitivity in Table 4 was represented by relative sensitivity wherein the sensitivity of the sample 1 (comparison) was represented as 100.
    Figure imgb0071
  • The composition of the processing solution used in the respective processing steps are given below:
    Figure imgb0072
  • (Bleaching Solution)
  • Ethylenediaminetetraacetic acid iron (III)
    Figure imgb0073
  • Add water to make the total vqlume 1000 ml and adjust the
  • pH of the solution to 6.0 using ammonia water.
    Figure imgb0074
    Figure imgb0075
    Figure imgb0076
  • Herein, sensitivity is defined by reciprocal of the exposure at which fog density +0.1 is given. Sensitivity of the sample is represented as relative sensitivity when sensitivity of fresh Sample No.1 is assumed to be 100.
  • It is understood from Table of 4 that the sensitivity of the samples of the present invention have achieved superior results in latent image-fading property comparing to the comparative samples.
  • Example 2
  • The following emulsions Em-1 to Em-8 was prepared and a multi-layered light-sensitive material 101 was made.
    • Em-1: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 0.8 µm and average silver iodide content is 8.0 mol% and which contain relatively low silver iodide content in the surface portion of the grain.
    • Em-2: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 0.38 µm and average silver iodide content is 8.0 mol % and which contain relatively low silver iodide content in the surface portion.
    • Em-3: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 0.65 µm and average silver iodide content is 8.0 mol% and which contain relatively low silver iodide content in the surface portion.
    • Em-4: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 0.85 µm and average silver iodide content is 8.0 mol% and which contain relatively low silver iodide content in the surface portion.
    • Em-5: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 1.20 µm and average silver iodide content is 6.0 mol% and which contain relatively low silver iodide content in the surface portion.
    • Em-6: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 0.70 µm and average silver iodide content is 8.0 mol% and which contain relatively low silver iodide content in the surface portion.
    • Em-7: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 1.40 µm and average silver iodide content is 8.0 mol% and which contain relatively low silver iodide content in the surface portion.
    • Em-8: A mono-dispersion type silver halide emulsion containing silver halide grains of which average grain size is 0.08 µm and average silver iodide content is 4.0 mol% and which contain relatively low silver iodide content in the surface portion.
    (EmB-1)
  • The emulsion EmB-1 was prepared in the same manner as emulsion Em-2 disclosed in Japanese Patent O.P.I. Publication No. 3-241336(1991), as follows.
  • Preparation of silver iodide fine grains
  • Into a reaction vessel, an aqueous solution containing 5% by weight of ossein gelatin was added. While stirring the solution at 40°C, a 3.5-N aqueous silver nitrate solution and a 3.5-N aqueous potassium iodide solution were added for 30 minutes at a fixed rate.
  • PAg was kept at 13.5 during the addition by a conventional pAg-controlling method. The formed silver iodide was a mixture of β-Agl and y-Agl grains having the average size of 0.06 µm. This emulsion is called a silver iodide fine grain emulsion.
  • Preparation of silver halide seed emulsion containing spherical shaped twin crystal grains
  • A mono-dispersion type silver halide seed emulsion containing spherical shaped twin crystals was prepared in the method as shown below:
    Figure imgb0077
    Figure imgb0078
    Figure imgb0079
    Figure imgb0080
  • While stirring A3 solution, solution B3 and the solution C3 were added to solution A3 by double jet mixing method for 30 seconds and silver halide nucleii were formed. pBr over this period of time was 1.09 - 1.15.
  • 1 minute 30 seconds later, solution C3 was added taking 20 seconds and ripening was carried out for five minutes. The concentration of potassium bromide during the ripening was 0.071 mols/literand that of ammonia was 0.63 mols/liter.
  • Then PH of the emulsion was was adjusted to 6.0 and the emulsion was desalted and washed. After observation using an electron microscope, this seed emulsion was found to be a mono-dispersion type emulsion containing grains having average grain size of 0.36 µm and the distribution width of 18%. This emulsion is hereinafter refferred to a seed emulsion.
  • Next, an emulsion of the present invention having an average grain size of 1.25 µm was prepared by using three kinds of aqueous solution shown as follows, the silver iodide fine grain emulsion and the seed emulsion.
    Figure imgb0081
    Figure imgb0082
    Figure imgb0083
    Figure imgb0084
  • The seed emulsion of 0.407 equivalent mols is added to aqueous solution A2 as above-mentioned, violently stirred at 60°C temperature and pH and pAg have been adjusted by using acetic acid and potassium bromide aqueous solution.
  • Thereafter, while controlling pH and pAg as shown in Table 5, solutions B2 and C2, and solution D2 were each added, by the triple jet method, at flowing rates as shown in Tables 6 to 8.
  • After addition, the mixed solution was flocculated to desalt by adding phenylcarbamyl gelatin aqueous solution to desalt and adjusting pH of the solution. Next, pH and pAg were each adjusted to 5.80 and 8.06 at 40°C.
  • Thus, there was obtained monodispersed silver bromoiodide emulsion having average grain size of 1.25 µm, an average silver iodide content of 8.0 mol% and the grain size distribution width of 13.2%.
  • This emulsion hereinafter is referred to as EmB-1.
  • From the emulsion formula, the grain structure of EmB-1 and the volume ratio of each phase are shown in Table 9.
  • Table 5 is a grain growth condition of EmB-1.
    Figure imgb0085
  • Table 6 is an addition pattern of B2, and Table 7 is an addition pattern of C2, and Table 8 is an addition pattern of D2.
    Figure imgb0086
    Figure imgb0087
    Figure imgb0088
    Figure imgb0089
    Figure imgb0090
  • After adjusting PAg, pH and temperature of the emulsion EmB-1 at 8.5, 5.8 and 55°C, respectively, sensitizing dyes S-5, S-6, S-7 and S-8 were added thereto and the the emulsion was allowed to stand for 30 minutes so that dyes were adsorbed on the silver halide grains. Then, 1.0×x10-6 mol/mol AgX of sodium thiosulfate was added. 10 minutes later, a solution mixture containing 2.2×10-7 mol/mol AgX of chloroauric acid and thiocyanic acid ammonium salt was added to the emulsion, and it was further ripened for 60 minutes. Thereafter, inventive or comparative compounds as shown in Table are respectively added thereto.
  • Basic structure of the multi-layered photographic material(Sample101) is shown below:
  • In the following descriptions, the amount of the compound incorporated into the sample is given in terms of gram per m2 unless otherwise noted. Moreover, the amount of silver halide and colloidal silverwas expressed in terms of equivalent amount of silver and the added amount of the sensitizing dye is given in terms of mols per mol of AgX contained in the same layer.
  • Sample-101
  • Figure imgb0091
    Figure imgb0092
    Figure imgb0093
    Figure imgb0094
    Figure imgb0095
    Figure imgb0096
    Figure imgb0097
    Figure imgb0098
    Figure imgb0099
    Figure imgb0100
    Figure imgb0101
    Figure imgb0102
    Figure imgb0103
    Figure imgb0104
    Figure imgb0105
    Figure imgb0106
    Figure imgb0107
    Figure imgb0108
    Figure imgb0109
    Figure imgb0110
  • Besides the above-mentioned composition, coating aid (Su-1) dispersion aid (Su-2, Su-3), gelatin hardener (H-I, H-2), stabilizing agent (Stab-1), anti-foggant (AF-1, AF-2), and antiseptic (DI-1) were added to each layer.
    Figure imgb0111
    Figure imgb0112
    Figure imgb0113
    Figure imgb0114
    Figure imgb0115
    Figure imgb0116
    Figure imgb0117
    Figure imgb0118
    Figure imgb0119
    Figure imgb0120
    Figure imgb0121
    Figure imgb0122
    Figure imgb0123
    Figure imgb0124
    Figure imgb0125
    Figure imgb0126
    Figure imgb0127
    Figure imgb0128
    Figure imgb0129
    Figure imgb0130
    Figure imgb0131
    Figure imgb0132
    Figure imgb0133
    Figure imgb0134
    Figure imgb0135
    Figure imgb0136
    Figure imgb0137
    Figure imgb0138
    Figure imgb0139
    Figure imgb0140
    Figure imgb0141
    Figure imgb0142
    Figure imgb0143
    Figure imgb0144
  • The samples were exposed to yellow light through an optical wedge, and thereafter subjected to the following photographic processing.
    Figure imgb0145
    Figure imgb0146
  • Compositions of the processing solutions used in each processing steps are the same as those used in Example 1.
  • Relative sensitivity of the respective samples were measured by using green light. Resaults thereof are given in Table 9.
  • In the table, sensitivity is defined in the same manner as in Eexample 1 and is represented as relative sensitivity by which sensitivity of Sample 101 is to be 100.
    Figure imgb0147
    Figure imgb0148
  • Herein sensitivity is defined by the reciprocal of the exposure by which the density of fog +0.1 is given and was represented with a relative value, wherein a blue sensitivity of each fresh sample was assumed to be 100. As for the compound of the present invention of samples 6 - 53, it is understood that the latent-image regression after exposure is small as compared with samples 1 - 5 in which the comparison compounds were added.

Claims (3)

1. A silver halide photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer, wherein said silver halide emulsion layer contains a compound represented by the following formula [I]
Figure imgb0149
wherein R1 and R2 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, provided that R1 and R2 may combine with each other to form a ring; R3, R4, R5 and R6 each represent a hydrogen atom or a substituent; Z1 represents a oxygen atom, a selenium atom, a sulfur atom, a tellurium atom, -N(R7)- or-C(R8)(R9)-, where R7, R8 and R9 each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; Z2 represents a group of non-metal atoms necessary to form a 5- or 6-membered heterocyclic ring; L1 and L2 each represent a methine group.
2. The photographic material of claim 1, wherein said silver halide emulsion layer comprises silver iodobromide, silver bromide or silver chlorobromide grains.
3. The photographic material of claim 1, wherein said compound is contained in an amount of 2 x 10-8 to 1 x 10-2 moles per mole of silver halide.
EP94300819A 1993-02-08 1994-02-04 Silver halide light-sensitive photographic material Withdrawn EP0611109A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP20273/93 1993-02-08
JP02027393A JP3240530B2 (en) 1993-02-08 1993-02-08 Silver halide photographic materials

Publications (1)

Publication Number Publication Date
EP0611109A1 true EP0611109A1 (en) 1994-08-17

Family

ID=12022578

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94300819A Withdrawn EP0611109A1 (en) 1993-02-08 1994-02-04 Silver halide light-sensitive photographic material

Country Status (2)

Country Link
EP (1) EP0611109A1 (en)
JP (1) JP3240530B2 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2147586A1 (en) * 1970-09-24 1972-04-13 Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa (Japan) Photographic silver halide emulsion
JPH03219233A (en) * 1990-01-24 1991-09-26 Konica Corp Silver halide color photographic sensitive material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2147586A1 (en) * 1970-09-24 1972-04-13 Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa (Japan) Photographic silver halide emulsion
JPH03219233A (en) * 1990-01-24 1991-09-26 Konica Corp Silver halide color photographic sensitive material

Also Published As

Publication number Publication date
JP3240530B2 (en) 2001-12-17
JPH06235999A (en) 1994-08-23

Similar Documents

Publication Publication Date Title
CA1086546A (en) Silver halide photographic emulsion containing 2 sensitizing dyes having heterocyclic quaternary nitrogen
US3769024A (en) Light-sensitive silver halide photographic material with sensitizing dye combination
US5759760A (en) Aqueous solid particle dispersions in chemical sensitization
JPS61165751A (en) Preparation of silver halide photographic emulsion
US5418126A (en) Furan or pyrrole substituted dye compounds and silver halide photographic elements containing such dyes
EP0611109A1 (en) Silver halide light-sensitive photographic material
JPH06194780A (en) Silver halide photographic emulsion
JPS6232444A (en) Silver halide photographic sensitive material
US5849470A (en) Mixed grain emulsions of the same grains having different speed properties for photographic elements
US5989795A (en) Performance of photographic emulsions at high silver ion concentrations
JPS5847703B2 (en) Halogen Kagin Color - Shashinzairiyo
JP2890055B2 (en) Silver halide photographic material
JPH06235997A (en) Silver halide photosensitive material
JPH063770A (en) Silver halide photographic sensitive material
JPH0743848A (en) Photograph recording material whose spectrum is sensitized
JP2632398B2 (en) Silver halide photographic material
US4810627A (en) Photographic recording material
JPS58139138A (en) Two-equivalent yellow coupler for photography
JPH10268461A (en) Silver halide photographic emulsion
JP2000239547A (en) Cyanine dye
JPS599900B2 (en) Halogen Kagin Color - Shashin Kanko Zairiyou
JPH1069040A (en) Silver halide photographic sensitive material
JPS63231445A (en) Silver halide photographic sensitive material containing oxonol dye
JPH07253626A (en) Silver halide photographic emulsion, its production and silver halide photographic sensitive material
JPH07281374A (en) Silver halide color photographic sensitive material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE FR GB NL

17P Request for examination filed

Effective date: 19950119

17Q First examination report despatched

Effective date: 19981117

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19990601