EP0363527A1 - Photographisches Element, das Benzoxazin- oder Benzthiazin-Derivate enthält - Google Patents

Photographisches Element, das Benzoxazin- oder Benzthiazin-Derivate enthält Download PDF

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Publication number
EP0363527A1
EP0363527A1 EP88202261A EP88202261A EP0363527A1 EP 0363527 A1 EP0363527 A1 EP 0363527A1 EP 88202261 A EP88202261 A EP 88202261A EP 88202261 A EP88202261 A EP 88202261A EP 0363527 A1 EP0363527 A1 EP 0363527A1
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EP
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Prior art keywords
group
speed
benzoxazine
photographic element
silver halide
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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.)
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EP88202261A
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English (en)
French (fr)
Inventor
Marcel Jacob Monbaliu
Ludovicus Pieter Joly
Erwin Charles Steeman
Christian Charles Van De Sande
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Agfa Gevaert NV
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Agfa Gevaert NV
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Priority to EP88202261A priority Critical patent/EP0363527A1/de
Publication of EP0363527A1 publication Critical patent/EP0363527A1/de
Ceased legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • 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
    • G03C1/295—Development accelerators

Definitions

  • the present invention relates to a photographic element comprising a support and at least one silver halide emulsion layer comprising benzoxazine or benzothiazine derivatives as compounds increasing the sensitivity of the silver halide emulsion, hereinafter called speed-increasing compounds or derivatives.
  • Another way of further increasing the sensitivity of photographic silver halide emulsions is by effecting the development in the presence of alkylene oxide polymers e.g. polyoxyethylene compounds, thioether compounds and/or onium or polyonium compounds of the ammonium, phosphonium, or sulphonium type.
  • alkylene oxide polymers e.g. polyoxyethylene compounds, thioether compounds and/or onium or polyonium compounds of the ammonium, phosphonium, or sulphonium type.
  • These classes of compounds sensitize the emulsion by development acceleration and can be used either in the emulsion or the developer.
  • US-A 4,038,075 a method has been described for developing an imagewise exposed photographic silver halide emulsion with a developing solution containing derivatives of polyethylene glycol having at one or both sides a terminal group containing a thioether linkage.
  • a photographic element comprising a support and coated thereon at least one silver halide emulsion layer, said emulsion layer or a non-photosensitive hydrophilic colloid layer in water-permeable relationship therewith comprising at least one dispersed compound in amounts increasing the sensitivity of the silver halide emulsion, characterized in that said at least one compound is chosen from the group of benzoxazine and benzothiazine derivatives corresponding to one of the following tautomeric general formulae I and II: wherein: X represents an oxygen or sulphur atom, R1 is a substituent selected from the group consisting of hydrogen, a branched or unbranched alkyl group e.g.
  • a substituted alkyl group e.g. carboxymethyl, an aryl group, a substituted aryl group, a heterocyclyl group, an acyl group e.g. acetyl, valeryl and benzoyl, a substituted acyl group e.g. 2-bromoacetyl and p-hexadecyloxy-benzoyl, a heterocyclylcarbonyl group, an alkylcarbamoyl group, a substituted alkylcarbamoyl group e.g.
  • methyl, butyl, tetradecyl, and pentadecyl a substituted alkyl group, an alkyloxy group e.g. hexadecyloxy, an aryl group e.g. phenyl, a substituted aryl group e.g.
  • R1 and R2 together can represent a group of atoms e.g.
  • each of R3 and R4 is a substituent selected from the group consisting of hydrogen, a halogen atom, a branched or unbranched alkyl group e.g. methyl and 1,1,3,3-tetramethylbutyl, a branched or unbranched alkyloxy group e.g. methoxy, an aralkyloxy group e.g.
  • benzyloxy an aryl group, an alkenyl group, an acylamido group, an alkylamino group, a hydroxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, an alkylthio group, an arylthio group, and a benzenesulphonyl group.
  • the speed-increasing benzoxazine and benzothiazine derivatives for use according to the present invention can be incorporated successfully into a hydrophilic colloid layer by dissolving them first in at least one water-immiscible oil-type solvent or oil-former, adding the resulting solution to an aqueous phase containing a hydrophilic colloid e.g. gelatin and a dispersing agent e.g.
  • the speed-increasing benzoxazine and benzothiazine derivatives are generally added in amounts ranging from 0.005 g to 15 g, preferably 0.25 g to 8.0 g, per 1.5 mol of silver halide.
  • the speed-increasing benzoxazine and benzothiazine derivatives for use according to the present invention can be dispersed in hydrophilic colloid compositions preferably with the aid of at least one known oil-former such as an alkyl ester of phthalic acid, preferably di-n-butyl phthalate, or a phosphoric acid ester, preferably tricresyl phosphate, or any of the oil-formers listed in EP-A 0,176,628, EP-A 0,084,692, and EP-A 86-202066.6.
  • oil-former such as an alkyl ester of phthalic acid, preferably di-n-butyl phthalate, or a phosphoric acid ester, preferably tricresyl phosphate, or any of the oil-formers listed in EP-A 0,176,628, EP-A 0,084,692, and EP-A 86-202066.6.
  • the oil-formers can be used in widely varying concentrations e.g. in amounts ranging from about 0.1 to about 10 parts by weight and preferably from about 0.5 to about 2 parts by weight relative to the amount of the speed-increasing benzoxazine and benzothiazine derivatives dispersed therewith. Excellent results were accomplished with equal weights of oil-former and speed-increasing compound.
  • auxiliary solvent that is insoluble or almost insoluble in water and has a boiling point of at most 150°C, such as lower alkyl acetates e.g. ethyl acetate or any of the auxiliary solvents mentioned in EP-A 0,176,628.
  • the auxiliary solvent may also be a water-soluble organic solvent such as methanol, ethanol, isopropanol, di- methylsulphoxide, tetrahydrofuran, N-methylpyrrolidone, dioxan, acetone, butyrolactone, ethylene glycol, ethylene glycol monomethyl ether, ethy­ lene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, glycerol, acetonitrile, formamide, dimethylformamide, tetrahydrothiophene dioxide, or dimethoxyethane.
  • the auxiliary solvent may also be one described in i.a. US-A 2,801,170; 2,801,171; 2,949,360; 2,835,579.
  • the benzoxazine speed-increasing compounds according to the present invention can be prepared by reductive cyclization of 2-nitrophenoxyaceto compounds (method A) or by cyclocondensation of 2-aminophenols with Alpha-halogen-keto compounds (method B).
  • the benzothiazine speed-increasing compounds according to the present invention can be prepared by cyclocondensation of 2-aminothiophenols with Alpha-halogen-keto compounds (method C) or by oxidative cyclization of Beta-diketo compounds with o-aminothiophenols in dimethylsulphoxide (method D).
  • the speed-increasing benzoxazine and benzothiazine derivatives used in accordance with the present invention can be incorporated into any type of photographic element comprising a light-sensitive silver halide emulsion layer e.g. a spectrally sensitized silver halide emulsion layer, a non-spectrally sensitized silver halide emulsion layer, a silver halide emulsion layer of use in diffusion transfer reversal processes for the production of silver images, an X-ray silver halide emulsion layer, a silver halide emulsion layer for use in graphic arts e.g.
  • a light-sensitive silver halide emulsion layer e.g. a spectrally sensitized silver halide emulsion layer, a non-spectrally sensitized silver halide emulsion layer, a silver halide emulsion layer of use in diffusion transfer reversal processes for the production of silver images, an
  • a lith silver halide emulsion layer a silver halide emulsion layer sensitive to infra-red radiation, a silver halide emulsion layer used in a photographic element for so-called amateur or professional photography, in low-speed or high-speed photographic elements.
  • the halide composition of the silver halide emulsions used according to the present invention is not specifically limited and may be any composition selected from i.a. silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, and silver chlorobromoiodide.
  • the photographic silver halide emulsions used according to the present invention can be prepared by mixing the halide and silver solutions in partially or fully controlled conditions of temperature, concentrations, sequence of addition, and rates of addition.
  • the silver halide can be precipitated according to the single-jet method, the double-jet method, or the conversion method.
  • the silver halide particles of the photographic emulsions used according to the present invention may have a regular crystalline form such as a cubic or octahedral form or they may have a transition form. They may also have an irregular crystalline form such as a spherical form or a tabular form, or may otherwise have a composite crystal form comprising a mixture of said regular and irregular crystalline forms.
  • the silver halide grains may have a multilayered grain structure. According to a simple embodiment the grains may comprise a core and a shell, which may have different halide compositions and/or may have undergone different modifications such as the addition of dopes. Besides having a differently composed core and shell the silver halide grains may also comprise different phases inbetween.
  • Two or more types of silver halide emulsions that have been prepared differently can be mixed for forming a photographic emulsion for use in accordance with the present invention.
  • the average size of the silver halide grains may range from 0.2 to 0.7 ⁇ m, preferably from 0.4 to 0.5 ⁇ m.
  • the size distribution of the silver halide particles of the photographic emulsions to be used according to the present invention can be homodisperse or heterodisperse.
  • a homodisperse size distribution is obtained when 95% of the grains have a size that does not deviate more than 30% from the average grain size.
  • the emulsions may also comprise organic silver salts such as e.g. silver benzotriazolate and silver behenate.
  • the silver halide crystals can be doped with Rh3+, Ir4+, Cd2+, Zn2+, Pb2+.
  • the photographic emulsions can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkides in "Chimie et Physique Photographique", Paul Montel, Paris (1967), by G.F. Duffin in “Photographic Emulsion Chemistry", The Focal Press, London (1966), and by V.L. Zelikman et al in “Making and Coating Photographic Emulsion", The Focal Press, London (1966).
  • iodide-converted silver bromoiodide emulsions comprising 5 mol% of silver iodide are prepared. It is, however, possible according to this method of emulsion preparation to increase the iodide content to as high as 15 mol% of silver iodide calculated on the total amount of silver halide.
  • the emulsions can be desalted in the usual ways e.g. by dialysis, by flocculation and re-dispersing, or by ultrafiltration.
  • the binder is a hydrophilic colloid, preferably gelatin.
  • Gelatin can, however, be replaced in part or integrallly by synthetic, semi-synthetic, or natural polymers.
  • Synthetic substitutes for gelatin are e.g. polyvinyl alcohol, poly-N-vinyl pyrrolidone, polyvinyl imidazole, polyvinyl pyrazole, polyacrylamide, polyacrylic acid, and derivatives thereof, in particular copolymers thereof.
  • Natural substitutes for gelatin are e.g. other proteins such as zein, albumin and casein, cellulose, saccharides, starch, and alginates.
  • the semi-synthetic substitutes for gelatin are modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin, and cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • modified natural products e.g. gelatin derivatives obtained by conversion of gelatin with alkylating or acylating agents or by grafting of polymerizable monomers on gelatin
  • cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose, phthaloyl cellulose, and cellulose sulphates.
  • the binder should dispose of an acceptably high number of functional groups, which by reaction with an appropriate hardening agent can provide a sufficiently resistant layer.
  • functional groups are especially the amino groups, but also carboxylic groups, hydroxy groups, and active methylene groups.
  • the gelatin can be lime-treated or acid-treated gelatin.
  • the preparation of such gelatin types has been described in e.g. "The Science and Technology of Gelatin", edited by A.G. Ward and A. Courts, Academic Press 1977, page 295 and next pages.
  • the gelatin can also be an enzyme-treated gelatin as described in Bull. Soc. Sci. Phot. Japan, N° 16, page 30 (1966).
  • the light-sensitive silver halide emulsion can be a so-called primitive emulsion, in other words an emulsion that has not been chemically sensitized.
  • the light-sensitive silver halide emulsion can be chemically sensitized as described i.a. in the above-mentioned "Chimie et Physique Photographique” by P. Glafkides, in the above-mentioned “Photographic Emulsion Chemistry" by G.F. Duffin, in the above-mentioned “Making and Coating Photographic Emulsion” by V.L. Zelikman et al, and in "Die Grundlagen der Photographischen mit Silberhalogeniden” edited by H.
  • chemical sensitization can be carried out by effecting the ripening in the presence of small amounts of compounds containing sulphur e.g. thiosulphate, thiocyanate, thioureas, sulphites, mercapto compounds, and rhodamines.
  • the emulsions can be sensitized also by means of gold-sulphur ripeners or by means of reductors e.g. tin compounds as described in GB-A 789,823, amines, hydrazine derivatives, formamidine-sulphinic acids, and silane compounds.
  • Chemical sensitization can also be performed with small amounts of Ir, Rh, Ru, Pb, Cd, Hg, Tl, Pd, Pt, or Au.
  • One of these chemical sensitization methods or a combination thereof can be used.
  • the light-sensitive silver halide emulsions can be spectrally sensitized with methine dyes such as those described by F.M. Hamer in "The Cyanine Dyes and Related Compounds", 1964, John Wiley & Sons.
  • Dyes that can be used for the purpose of spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
  • Suitable supersensitizers are i.a. heterocyclic mercapto compounds containing at least one electronegative substituent as described e.g. in US-A 3,457,078, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds as described e.g. in US-A 2,933,390 and US-A 3,635,721, aromatic organic acid/formaldehyde condensation products as described e.g. in US-A 3,743,510, cadmium salts, and azaindene compounds.
  • the silver halide emulsion for use in accordance with the present invention may comprise compounds preventing the formation of fog or stabilizing the photographic characteristics during the production or storage of photographic elements or during the photographic treatment thereof.
  • Many known compounds can be added as fog-inhibiting agent or stabilizer to the silver halide emulsion. Suitable examples are i.a.
  • heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptotetrazoles, in particular 1-phenyl-5-mercapto-tetrazole, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione, 1-phenyl-Delta-2-tetrazoline-5-thione, oxazoline-thione, triazaindenes, tetrazaindenes and pentazaindenes, especially those described by Birr in Z.
  • benzothiazolium salts such as benzothia
  • the fog-inhibiting agents or stabilizers can be added to the silver halide emulsion prior to, during, or after the ripening thereof and mixtures of two or more of these compounds can be used.
  • the binders of the photographic element can be hardened with appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and chromium alum, aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, dioxan derivatives e.g.
  • appropriate hardening agents such as those of the epoxide type, those of the ethylenimine type, those of the vinylsulfone type e.g. 1,3-vinylsulphonyl-2-propanol, chromium salts e.g. chromium acetate and
  • 2,3-dihydroxy-dioxan active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • active vinyl compounds e.g. 1,3,5-triacryloyl-hexahydro-s-triazine
  • active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid.
  • the photographic element of the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer.
  • Suitable surface-active agents include non-ionic agents such as saponins, alkylene oxides e.g.
  • polyethylene glycol polyethylene glycol/polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or alkylamides, silicone-polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; anionic agents comprising an acid group such as a carboxy, sulpho, phospho, sulphuric or phosphoric ester group; ampholytic agents such as aminoacids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkyl betaines, and amine-N-oxides; and cationic agents such as alkylamine salts, aliphatic, aromatic, or heterocyclic quaternary ammonium salts, aliphatic or heterocyclic ring
  • Such surface-active agents can be used for various purposes e.g. as coating aids, as compounds preventing electric charges, as compounds improving slidability, as compounds facilitating dispersive emulsification, as compounds preventing or reducing adhesion, and as compounds improving the photographic characteristics e.g higher contrast, sensitization, and development acceleration.
  • Development acceleration can be accomplished with the aid of various compounds, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. US-A 3,038,805 - 4,038,075 - 4,292,400.
  • the photographic element of the present invention may further comprise various other additives such as e.g. developing agents, compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers.
  • various other additives such as e.g. developing agents, compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents, hardeners, and plasticizers.
  • the photographic element is a cadmium-free highly sensitive orthochromatic silver halide element comprising developing agents in the light-sensitive hydrophilic colloid silver halide emulsion layer or in an adjacent hydrophilic colloid layer in water-permeable relationship therewith e.g. in a subbing layer or adhesive layer.
  • the exposed photographic element is developed by processing it merely with an alkaline activating liquid. Development can then be followed by stabilization as described in e.g. US-A 4,030,924.
  • the hydrophilic colloid binder preferably gelatin
  • the hydrophilic colloid binder preferably gelatin
  • the covering power of the silver image formed in the developed photographic element can be enhanced substantially.
  • This enhanced covering power can also be profitable in that less silver coverage is needed in the preparation of the silver halide emulsion.
  • the use of dextran or derivatives thereof in the photographic element also offers the advantage that a higher resistance to abrasion in wet condition before and after development can be obtained. Furthermore, the stability during storage of the photographic element comprising dextran or derivatives thereof is improved substantially.
  • Suitable additives for improving the dimensional stability of the photographic element are i.a. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins , and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, Alpha-Beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
  • a water-soluble or soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters,
  • Suitable UV-absorbers are i.a. aryl-substituted benzotriazole compounds as described in US-A 3,533,794, 4-thiazolidone compounds as described in US-A 3,314,794 and 3,352,681, benzophenone compounds as described in JP-A 2784/71, cinnamic ester compounds as described in US-A 3,705,805 and 3,707,375, butadiene compounds as described in US-A 4,045,229, and benzoxazole compounds as described in US-A 3,700,455.
  • the average particle size of spacing agents is comprised between 0.2 and 10 ⁇ m.
  • Spacing agents can be soluble or insoluble in alkali. Alkali-insoluble spacing agents usually remain permanently in the photographic element, whereas alkali-soluble spacing agents usually are removed therefrom in an alkaline processing bath.
  • Suitable spacing agents can be made i.a. of polymethyl methacrylate, of copolymers of acrylic acid and methyl methacrylate, and of hydroxypropylmethyl cellulose hexahydrophthalate. Other suitable spacing agents have been described in US-A 4,614,708.
  • benzoxazine and benzothiazine structures according to the general formulae I and II can be used advantageously in colour photographic silver halide elements as coupling off groups that constitute an integral part of colour couplers incorporated therein, which colour couplers during reaction with an oxidized primary amino developing agent form a coloured image dye e.g. a cyan, magenta, or yellow image dye and at the same time release the speed-increasing benzoxazine or benzothiazine moiety.
  • a coloured image dye e.g. a cyan, magenta, or yellow image dye
  • Coupler Y01 Yellow-forming couplers according to the following formula: Coupler Y01 , R5 representing methyl (method E) melting at 94-96°C Coupler Y02 , R5 representing hydrogen (method E) melting at 80-90°C Yellow-forming couplers according to the following formula: Coupler Y03 , R6 representing bromo (method F) melting at 85°C Coupler Y04 , R6 representing chloro (method E or F) melting at 90-97°C Coupler Y05 , R6 representing hydrogen (method F) melting at 85°C Coupler Y06 according to the following formula: (method F) (melting 168°C) Cyan-forming Coupler C01 according to the following formula: (melting at 153°C:
  • the above colour couplers can be prepared by synthesizing the benzoxazine or benzothiazine moiety and then making it react with a colour coupler that has been chlorinated first at the coupling off position (method E).
  • Coupler Y02 A description of the synthesis of Coupler Y02 according to this method is given hereinafter by way of example.
  • the precipitate is stirred for 10 min in a mixture of 100 ml of ethanol and 20 ml of saturated aqueous solution of sodium carbonate. After neutralization with acetic acid the precipitate is separated, dried, and recrystallized from ethyl acetate. Yield: 2.3 g (30%). Melting point: 85°C.
  • Step 1 A solution of 61.2 g (0.3 mol) of dihydroxynaphthoic acid in 300 ml of dimethylformamide is added dropwise to a suspension of 28.8 g (0.6 mol) of sodium hydride in 450 ml of dimethylformamide. The mixture is stirred for 1 h and then chilled to 5°C. A solution of 77.1 g (0.3 mol) of the above bromide in 250 ml of dimethylformamide is added in 30 min, while the temperature is maintained under 10°C. Next, the reaction mixture is stirred at room temperature for 4 h.
  • Step 2 A solution of 38 g (0.1 mol) of the intermediate product (aa), 30.5 g (0.1 mol) of the amino compound represented in the above reaction scheme , and 22.7 g (0.11 mol) of dicyclohexyl carbodiimide (DCC) in methylene chloride is stirred for 24 h at room temperature.
  • DCC dicyclohexyl carbodiimide
  • Step 3 A solution of 3.2 g (0.02 mol) of bromine in 30 ml of methylene chloride is added to a solution of 13.34 g (0.02 mol) of the intermediate product (bb) in 30 min at approximately 10°C. The mixture is stirred for 2 h at room temperature and added to a 10% aqueous sodium hydrogen carbonate solution. The methylene chloride is removed by evaporation and the residue is concentrated by evaporation and purified by column chromatography.
  • Step 4 A mixture of 5.22 g (0.007 mol) of the intermediate product (cc), 0.875 g of o-aminothiophenol and 40 ml of acetonitrile is first stirred for 6 h at room temperature and next for 15 min at 75°C. A volume of 50 ml of hot water is added to the orange mixture. A tacky precipitate settles and converts into a grainy product upon cooling. The product is filtered and extracted with methylene chloride. The residue is concentrated by evaporation and purified by column chromatography. Yield: 1.7 g of Coupler C01 melting at 153°C.
  • a volume of 100 ml of 5% aqueous gelatin is mixed with 5 to 10% of sodium salt of dodedylbenzenesulphonic acid (calculated on the weight of the gelatin) as dispersing agent.
  • the resulting mixture is dispersed at 40°C.
  • a solution of 1 g of speed-increasing benzoxazine or benzothiazine derivative according to the present invention and 1 g of dibutyl phthalate in 5 ml of ethyl acetate is added in 30 s with stirring to the dispersion.
  • the ethyl acetate is removed by heating the mixture to 60°C in a rotating thin-layer evaporator at about 5 kPa.
  • the emulsion was coated on both sides of a polyethylene-coated paper support at a ratio of 4.25 g per m2 per side.
  • the coated emulsion layers were dried.
  • a photographic Comparison element was made in exactly the same way as described above for the photographic element according to the present invention, except for the fact that no dispersion of speed-increasing compound was added to the silver bromoiodide emulsion of the photographic Comparison element.
  • a dispersion of yellow-forming coupler was made by dissolving 0.006 mol of coupler corresponding to the following structural formula: in 16 ml of ethyl acetate and 2 g of dibutyl phthalate, dispersing the resulting solution in 100 ml of a 5 % by volume aqueous solution of gelatin containing 0.4 g of the sodium salt of dodecylbenzene sulphonic acid by means of an ultrasonic power generator, and eliminating the ethyl acetate by evaporation under reduced pressure.
  • the resulting dispersion was added to the blue-sensitive emulsion.
  • the emulsion was coated on a film support at a ratio of 150 g per m2.
  • the emulsion layer was dried and covered with a gelatin layer.
  • the resulting element was used for comparison and is called Blank A hereinafter.
  • a colour photographic element A was made in exactly the same way as described above for the Blank A, except for the fact that a dispersion (prepared as described in Example 1) of speed-increasing compound 15 of Table 1 was added to the silver bromoiodide emulsion in a ratio of 10 % by weight calculated on the weight of the yellow-forming coupler.
  • the Blank A and colour photographic Element A were exposed in a Herrnfeld sensitometer for 1/20 s through a continuous wedge with a constant of 0.30.
  • the exposed samples were colour processed in the usual way, which includes colour development, bleaching, and fixing.
  • the developing agent was 4-amino-N-ethyl-N-(Beta-methanesulphonamidoethyl)-m-toluidine sesquisulphate monohydrate, the development time being 15 min and the temperature of development being 21°C.
  • a dispersion of cyan-forming coupler was made by dissolving 0.0015 mol of the coupler disclosed as Colour coupler II in Example 3 of US-A 3,980,481, in 16 ml of ethyl acetate and 2 g of dibutyl phthalate, dispersing the resulting solution in 100 ml of a 5 % by volume aqueous solution of gelatin containing 0.4 g of the sodium salt of dodecylbenzene sulphonic acid by means of an ultrasonic power generator, and eliminating the ethyl acetate by evaporation under reduced pressure.
  • the resulting dispersion was added to the red-sensitized emulsion.
  • a colour photographic element B was made in exactly the same way as described above for the Blank B, except for the fact that a dispersion of speed-increasing compound 16 of Table 1, prepared as described in Example 1, was added to the silver bromoiodide emulsion in a ratio of 0.1 mol% of compound 16 in respect of the amount of cyan-forming coupler added.
  • Blank Element C was fully identical to that of Blank Element B.
  • a colour photographic element C was made in exactly the same way as described above for the Blank C, except for the fact that a dispersion (prepared as described in Example 1) of speed-increasing compound 13 of Table 1 was added to the silver bromoiodide emulsion in a ratio of 10 mol% of compound 13 in respect of the amount of cyan-forming coupler added.

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  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
EP88202261A 1988-10-11 1988-10-11 Photographisches Element, das Benzoxazin- oder Benzthiazin-Derivate enthält Ceased EP0363527A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP88202261A EP0363527A1 (de) 1988-10-11 1988-10-11 Photographisches Element, das Benzoxazin- oder Benzthiazin-Derivate enthält

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Application Number Priority Date Filing Date Title
EP88202261A EP0363527A1 (de) 1988-10-11 1988-10-11 Photographisches Element, das Benzoxazin- oder Benzthiazin-Derivate enthält

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EP0363527A1 true EP0363527A1 (de) 1990-04-18

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002522421A (ja) * 1998-08-04 2002-07-23 アストラゼネカ アクチボラグ サイトカイン産生の阻害剤として有用なアミド誘導体

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2013284A1 (de) * 1968-07-19 1970-03-27 Agfa Gevaert Ag
DE3529934A1 (de) * 1984-08-22 1986-03-06 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Waermeentwickelbares lichtempfindliches material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2013284A1 (de) * 1968-07-19 1970-03-27 Agfa Gevaert Ag
DE3529934A1 (de) * 1984-08-22 1986-03-06 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Waermeentwickelbares lichtempfindliches material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RESEARCH DISCLOSURE BULLETIN, PRODUCT LICENSING INDEX, no. 98, June 1972, pages 31,32, disclosure no. 9806, Havant, Hampshire, GB; "Photographic compositions and processes" *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002522421A (ja) * 1998-08-04 2002-07-23 アストラゼネカ アクチボラグ サイトカイン産生の阻害剤として有用なアミド誘導体

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