US3895948A - Silver halide light-sensitive material containing a heterocyclic thione and a polyalkylene oxide - Google Patents

Silver halide light-sensitive material containing a heterocyclic thione and a polyalkylene oxide Download PDF

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US3895948A
US3895948A US319815A US31981572A US3895948A US 3895948 A US3895948 A US 3895948A US 319815 A US319815 A US 319815A US 31981572 A US31981572 A US 31981572A US 3895948 A US3895948 A US 3895948A
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silver halide
ring
sensitive material
thione ring
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Keisuke Shiba
Seiiti Kubodera
Reiichi Ohi
Tadao Shishido
Nobuo Yamamoto
Takeo Sakai
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/28—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/58—Benzoxazoles; Hydrogenated benzoxazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/60—Naphthoxazoles; Hydrogenated naphthoxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/16—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/72—2-Mercaptobenzothiazole
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D293/00—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms
    • C07D293/10—Heterocyclic compounds containing rings having nitrogen and selenium or nitrogen and tellurium, with or without oxygen or sulfur atoms, as the ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D293/12—Selenazoles; Hydrogenated selenazoles
    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides
    • 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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • 0 represents the atoms neces- 2.772.164 11/1956 Allen ct 111. 96/109 sary to form heterocyclic ring and R represents an 2.956.876 1 1/
  • the present invention relates to a silver halide lightsensitive material and. more particularly. it relates to a lithographic light-sensitive material which provides an image of a high edge gradient.
  • the edge gradient In a photographic image when a blackened area and non-blackened area are contiguous to each other the ratio of change in optical density versus the distance in a direction at right angles to the tangent is referred to as the edge gradient. In general. the higher the edge gradient the sharper the image.
  • a lightsensitive material capable of providing an image having a high edge gradient is useful. e.g.. as a lithographic light-sensitive material for use in photographic platemaking processes wherein a dot image is prepared using a glass screen or a contact screen.
  • a special de derivative is used has the defect that prolonged development is required in order to obtain high contrast.
  • an emulsion containing a polyalkylene oxide derivative requires a long initial development before the start of infectious development, though such an initial development provides. once infectious development starts. high contrast by markedly strengthening the infectious development. Therefore. extremely low contrast gradation obtained in the initial development co-exists with high contrast gradation. which results in insufficient toe-gradation (see FIG. I, curve 11). This results from the fact that the polyalkylene oxide derivative makes the starting point of the infectious development irregular with respect to the individual silver halide grains contained in the emulsion.
  • a primary object of the present invention is. therefore. to provide an emulsion capable of providing high edge gradient with a comparatively short development time.
  • Another object of the present invention is to provide an emulsion capable of providing dots having good toegradation. i.e.. in the plot of Density vs. Exposure (log E the characteristic curve continues into the region of decreasing exposure with constantly decreasing gradient until at a point the gradient becomes Zero. that is, the curve becomes parallel to coincident with the log E axis. The region. where the curve starts to flatten. is referred to in the art as the toe of the characteristic curve.
  • a further object of the present invention is to improve the deterioration of toegradation caused by the use of certain sensitizing dyes without a reduction in light sensitivity and while providing a supersensitizing action.
  • Still a further object of the present invention is to render uniform the size and quality of individual dots in the density region wherein the (lot size is small.
  • 0 represents the atoms necessary to form a hetcrocyclic ring (which heterocyclic ring may be substituted) and R represents an alkyl group. an aryl group or a heterocyclic group.
  • FIG. is a characteristic curve with optical density (D) on the vertical axis and exposure amount (log E) horizontally.
  • FIGS. 25 are curves showing the relationship between the distance I L (unit:micron) )-optical density in the edge portion of a dot.
  • 0 represents the atoms necessary to complete a heterocyclic ring (which ring may be substituted).
  • benzothiazolin-2- thione ring 6-methyl-benzothiazolin-2-thione ring. 6- ethyl-benzothiazolin-2-thione ring. 6-methoxy-benzothiazolin-Z-thione ring.
  • thiazolidin-Z-thione ring e.g.. thiazolidin2-thione ring. 4-methylthiazolidin2-thione ring. etc.
  • imidazolin-2-thione ring eg. l,3-dimethylimidazolin2-thione ring. l.3-diethylimidazolidin-2- thione ring. etc.
  • selenazolidin-Z-thione ring e.g... selenazolidin-Z-thione ring. 4-methylselenazolidin-2- thione ring, etc.
  • a l.3.4-thiadiazolin-2-thione ring e.g...
  • l.3.4-thiadiazolin-2-thione ring 5-methyl-l.3.4- thiadiazolin-Z-thione ring. S-ethylthio-l .3 .4- thiadiazolin-Z-thione ring. 5- ⁇ 2-(4-phenyl-5-thio l .3.4- thiadiazolin-2-yl J-mercaptoethylthio ⁇ l ,3.4- thiadiazolin-2-thione ring, etc.).
  • l.3.4-selenadiazolin- 2-thione ring e.g... l.3.4-selenadiazolin 2-thione ring, 5 ethyl l.3,4-selenadiazolin-Z-thione ring. etc.).
  • selenazolin-Z-thione ring e.g.. 4 -selenuzolin-2-thione ring, 4-methyl-4-selenuzolin-2-thi0nc ring, 4-phenyl-4- selenazolin-2-thione ring. etc).
  • l.2dihydropyridin-2- thione ring cg. l.2 dihydropyridin-Z-thione ring. 6- ethyl-l,Z-dihydropyridin-2-thione ring, etc).
  • benzoxuzolin-IZ-thione ring e.g.. benzoxazolin-Z-thione ring.
  • 6-ethylbcnz0xazolin-2-thione ring o-melhoxybenzoxazolin-Z-thione ring. S-methylhenzoxa2olin-2-lhione ring. etc).
  • benzimidazolin-Z-thione ring cg. 1.3- dimethylbenzimidazolin2-thione ring. 1.3-cli-npropylbenzimidazolin-Z-thione ring. l.3-di-ndecylbcnzimidazolin-Z-thione ring, l.3-di-benzlbenzimiduzoline-Z-thione ring.
  • the group R includes unsubstituted or hydroxy-. ur vl-, morpholinoor like group-substituted alkyl group having 1-13 carbon atoms. preferably. 1-6 carbon atoms. such as a methyl group. ethyl group. propyl group. hexyl group. decyl group. hydroxyethyl group. benzyl group and a morpholinoethyl group. etc; unsubstituted or alkyL. alkoxy-. halogen-. or the like groupsuhstituted uryl groups. such as a phenyl group. 2- methylphenyl group. 4-methoxyphenyl group, and a 4- chlorophenyl group. etc; heterocyclic ring group. such as Z-pyridyl group. a dipyridyl group and the like.
  • Synthesis Example 1 (Compounds l-l through l-8) These compounds can be synthesized according to the process described in the Journal of The Chemical Society. [939. pages 473 476, using Z-mercaptobenzonthiazole as a strating material.
  • Synthesis Example 2 (Compounds [-9 through l-l7) The compounds can be synthesized according to the H C 5 m. p. 0 process described in the Journal of The Chemical Soci- C S ty. I949, pages 1.503 L509, by reacting dithiocarbamate with an alpha-haloketone.
  • ⁇ N Compounds ll8-l-29 can be prepared by the proeedure of Synthesis Example I, in which the starting material is changed.
  • polyalkylene oxide derivatives used in the invention there are addition polymerization products between alkylene oxides such as ethylene oxide or propylene oxide and a compound such as water. an aliphatic alcohol. an aromatic alcohol. glycols. fatty acids. organic amines and a dehydrated compound of a hexitol derivative; condensates of a polyalkylene oxide with a compound such as just described: or block co-polymers of various alkylcne oxides such as ethylene oxidepropylene oxide block copolymers as described in US. Pat. No. 3.5lo.380 etc. Additional examples of such materials are described in. for example. US. Pat. Nos. 2.400.532; 3.294.537; and 3.294.540. French Pat. Nos. l.49l.805; 1.596.673. Japanese Patent Publication No. 23466/65. and the like.
  • the polyalkylene oxide derivatives used in the pres ent invention are those having a molecular weight of from 500 to 12.000. most preferably from 800 to 6.000. Specific examples thereof include the following:
  • the compounds used in the invention and represented by the general formula (I) are characterized by the presence of a thioketone functional group. It is important in the invention that compound (I) has a thioketone functional group and the substituent R be a substituent other than a hydrogen atom.
  • R is not hydrogen the compounds cannot form a tautomeric isomer having a mercapto group. and no reduction in sensitivity is encountered upon the use of such compounds. On the contrary. these compounds supersensitive with most generally used simple merocyaninc dyes. dimcthine merocyanine dyes and carbocyanine dyes. and hence they raise the sensitivity without increasing the fog formation.
  • the silver halde photographic emulsions in accordance with the present invention can be spectrally sensitized. for example. by one or more sensitizing dyes represented by general formula (ll) or (III):
  • Z. represents the atoms necessary to form a tctrazole nucleus.
  • L represents a methine chain. such as an unsubstituted or a substituted methine group. for example. an alkyl( C,C..)-substituted methine group or a phenylsubstituted methine group.
  • Y represents an oxygen atom.
  • R represents an alkyl group having l 6 carbon atoms. c.g., methyl. ethyl. propyl. cyanoethyl. allyl. carboxycthyl. dimethylaminoethyl. benzyl group. etc.. an aryl group such a phenyl group or psulfophenyl group) n represents 0 or 1.
  • R and R represent an alkyl group (e.g.. methyl. ethyl. carboxyethyl. carhoxybutyl. sulfoethyl. sulfopropyl. allyl, morpholinoethyl. acetoxypropyl. benzyl group. etc), aryl group such as a phenyl group. a tolyl group. a pyridyl group or like group.
  • Y and Y represent an oxygen atom. sulfur atom. selenium atom. or NR;(R; being a (C,-C alkyl group. preferably a C,-C,; alkyl group such as methyl. ethyl. allyl. acetoxyethyl. cyanoethyl group. etc.).
  • R,-, and R represent an alkyl group having not more than 6 carbon atoms. such as methyl. ethyl. propenyl. hydroxyethyl. amidoethyl. carboxypropyl. sulfoethyl. 4-sulfobutyl.
  • the silver halide emulsion used in the present invention can be silver chloride. silver bromide. silver iodide or a mixture thereof. In particular, silver chlorobromoiodide emulsions comprising silver chlorobromide and less than 2 mole percent of iodide ions are preferred. Furthermore.
  • silver halide emulsions comprising grains whose mode size is less than 0.8 micron and which contain at least 50 mole percent chloride ions as grainforming ingredients are suitable.
  • the mode size is in the range (HM-0.8 microns. preferably 0.2-0.8 microns.
  • Preferred emulsions for use in the present invention have a silver halide grain size of 0. 1-1 micron. and contain 30-150 g per 1 mol of silver halide ofa hydrophilic collid material.
  • the most preferred hydrophilic colloid material is gelatin.
  • hydrophilic colloidal materials are used as a dispersingg agent. and the exact material selected is not overly critical. i.e.. materials such as gelatin. gelatin derivatives such as phthaloylated gelatin or malonylated gelatin. cellulose derivatives such as hydroxyethyl cellulose or carboxymethyl cellulose. soluble starches such as dextrin or alkalified starch. hydrophilic high molecular weight polymers such as polyvinyl alcohol. polyvinyl pyrrolidone. polyacrylamide or polystyrenesulfonic acid. and like materials may be used.
  • the emulsions can be chemically sensitized according to any process known to the art such as sulfur sensitization. reduction sensitization. sensitization with noble metal ions. e.g.. a gold compound. a platinum compound. etc.. or a combination of such processes.
  • noble metal ions e.g.. a gold compound. a platinum compound. etc.. or a combination of such processes.
  • metal ions other than silver ions such as group Vlll metal ions and group [I metal ions can be used to make the gradation more contrasty. to stabilize the emulsion. to control the formation of fog and to supersensitize the emulsion.
  • the emulsions can have added thereto a stabilizer (e.g.. a 4-hydroxy-l.3.3a-7-tetrazaindene derivative).
  • a stabilizer e.g.. a 4-hydroxy-l.3.3a-7-tetrazaindene derivative
  • an antifogging agent e.g.. a 4-hydroxy-l.3.3a-7-tetrazaindene derivative
  • a hardener e.g. a 4-hydroxy-l.3.3a-7-tetrazaindene derivative
  • a surfactant e.g. a hydrophilic synthetic polymer. a latex polymer and a dye for preventing irradiation. all of which materials are commonly used in the production of light-sensitive materials.
  • the compounds of general formula (I) used in the invention is preferably used at a level of from about It)" to about l0" moles per 1 mole of silver halide.
  • the polyalkylene oxide derivative is preferably added in an amount of from about ().0l to l g per l mole of silver halide. Optimum results are achieved within these ranges.
  • the amount of the compound is based on the silver halide contained in the silver halide emulsion layer into which the compound is diffused from the adjacent layer.
  • the compound of general formula (I) and the polyalkylene oxide derivatives can be added by dissolving them in water.
  • water-miscible alcohols e.g.. methanol. ethanol. methyl cellosolve. etc.
  • ketones e.g.. acetone. etc. and then either directly added to the emulsion or added to an adjacent layer to form a multi-layer structure.
  • a completed emulsion in accordance with the present invention is applied to a suitable support such as a glass plate.
  • a suitable support such as a glass plate.
  • An antihalation layer or a filter layer may be provided on or under the emulsion layer in accordance with the invention.
  • the silver halide high-sensitive material obtained by the present invention may be processed in any conventionally known manner.
  • an infectious developer fundamentally comprises dihydroxybenzene (developing agent). alkali. a small amount of sulfite. and sulfite ion buffer.
  • the developing agent. dihydroxybenzene can be selected from those known in the field of photography. Specific examples thereof include hydroquinone. chlorohydroquinone. bromohydroquinone. isopropylhydroquinone. toluhydroquinone. methylhydroquinone. 2.3-dichlorohydroquinone. 2.S-dimethylhydroquinone. etc. Hydroquinone is particularly preferred. These developing agent may be used singly or as combinations thereof.
  • a sulfite ion buffer is used in sufficient amount to effectively maintain the sulfite level in the developer low.
  • Illustrative of such materials are aldehyde-alkali hydrogen sulfite adducts such as a formalin-sodium hydrogen sulfite adduct. ketone-alkali hydrogen sulfite adducts such as acetone-sodium hydrogen sulfite adducts. carbonyl bisulfite-amine condensation products such as sodium bis( Z-hydroxyethyl )aminomethanesulfonate, and the like.
  • the developing agent. or agents. are used in amounts as are commonly used with prioir art infectious developers. e.g.. about 5 to about 50 g of developing agent or agents per 1 of developer. preferably l0 30 g per liter of developer.
  • the sulfite ion buffer and such materials are generally used in an amount of from about l3 to about 130. preferably 30-60. g per liter of developer.
  • alkali material is added so as to render the developer. alkaline. preferably to a pH above 9.
  • the type of alkali is not limited. and any of those commonly used in the photographic arts can be used for this purpose. e.g.. carbonates such as potassium. sodium or calcium carbonate, etc. borax. and secondary or tertiary phosphates such as disodium phosphate. trisodium phos phate. etc.
  • the developer may further contain various additives known to those skilled in the art.
  • an organic antifogging agent cg. benzotriazole. l-phenyl-S- mercaptotetrazole. etc.. polyalkylene oxides. amine compounds.
  • organic solvents e.g.. triethylene glycol. dimethylformamide. methanol. ethylene glycol monoalkyl ether. etc.. and the like.
  • EXAMPLE I A chemically ripened silver chlorobromoiodide gela tin emulsion l4 g gelatin/mole silver halide) was prepared in a conventional manner. i.e., by adding aqueous solutions of silver nitrate and potassium halide to an aqueous solution of gelatin. physically ripening it. and then adding a gold salt and sodium thiosulfate to the mixture.
  • the bromide ion content and the iodide ion content in the emulsion were 17 mole percent and 0.2 mole percent. respectively.
  • the amount of silver per 1 kg of the emulsion was about l.3 moles. and the mode size of the silver halide grains was 0.6 micron. 700 g portions of the resulting emulsion were weighed out in 20 pots.
  • Each emulsion was prepared according to the prescription given in Table l. Preparation was as follows: first. each pot was heated to 45C with stirring;
  • polyethylene oxide derivative containing about ethylene oxide chains per oleylphenoxy group. molecular weight about 2,600.
  • polyethylene oxide derivative containing about 30 ethylene oxide chains per oleyl alcohol group. molecular weight about [.500.
  • polyalkylene oxide derivative of a block copolymer having a molecular weight of about 2.000 and comprising polypropylene oxide chains and polyethylene oxide chains. the number ratio of propylene oxide groups to ethylene oxide groups in the molecule being about 30 8,
  • ethylene oxide derivative containing about ethylene oxide chains per oleylphenoxy group. molecular weight about 3.500.
  • the coated film was cut into strips. and the resulting strips were wedge exposed using a 2.854K light source by means of a sensitometer for one section (250 lux).
  • the exposed strips were developed with the use of the following developer as is commonly employed in the development of lithographic light-sensitive materials at 20C for 1.5 minutes. 3 minutes or 4 minutes. and then fixed.
  • composition of the developer is composition of the developer:
  • Curve 31 In the Table 2. the relative sensitivity is shown in Curve 51 i F
  • FIGS. 2 4 curves showing the relationship between distance and optical density with respect to the edge portions are given. the relationship being based on the average of six dots.
  • a silver halide lightsensitive material which comprises in a silver halide emulsion layer or a layer adja Cent thereto at least one heterocyclic thioketone comcellent, high contrast light-sensitive material having 5 pound which does not form a mercapto group through higher sensitivity than that of any of the conventional tautnmerism, said compound being represented by the materials which provided good dot quality.
  • a silver halide lightsensitive material which comprises in a silver halide emulsion layer or a layer adja Cent thereto at least one heterocyclic thioketone comcellent, high contrast light-sensitive material having 5 pound which does not form a mercapto group through higher sensitivity than that of any of the conventional tautnmerism, said compound being represented by the materials which provided good dot quality.
  • Example zoselenazolin 2 thione ring, benzoxazolin-Lthione l The results shown in Table 3 were obtained. ring, imidazolin-lthione ring, benzimidazolin-Z-thione The terms in Table 3 have the same meaning as in T21 ring. selenazolidin-2-thione ring. 4'selenazolin-2- bles l and 2. thione ring. l.3.4-thiodiazolin-2-thione ring. l,3.4-
  • Preferred embodiments of the present invention are as follows.
  • a silver halide emulsion spectrally sensitized with a sensitizing dye represented by the general formula (ll) or (Ill) is used.
  • an emulsion containing silver halide grains ofless than 0.8 micron in grain mode size and comprising at least 50 mole percent silver chloride are used.
  • the silver halide light-sensitive material of claim I wherein the silver halide has a mode grain size of 0.2 to 0.8 microns.
  • the silver halide lightsensitive material of claim I wherein the comound of general formula (I) is present in an amount of from about l() to about moles and the poly-alkylene oxide derivative is present in an amount of from about 0.01 to about 1 g per mole of silver halide in the silver halide emulsion layer.
  • R is a 2-pyridyl group or a dipyridyl group.
  • R is selected from group consisting of a methyl group. ethyl group. propyl group. hexyl group. decyl group. and a benzyl group.
  • R is selected from the group consisting of a phenyl group. Imethylphenyl group. 4-methoxyphenyl group and a 4-chlorophenyl group.

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  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Quinoline Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Pyridine Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US319815A 1971-12-28 1972-12-29 Silver halide light-sensitive material containing a heterocyclic thione and a polyalkylene oxide Expired - Lifetime US3895948A (en)

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001020A (en) * 1971-03-04 1977-01-04 Fuji Photo Film Co., Ltd. Developing a silver ha1ide emulsion in contact with a heterocyclic thione and a polyalkylene oxide
US4001021A (en) * 1972-06-30 1977-01-04 Konishiroku Photo Industry Co., Ltd. Lithographic development of a lith-type silver halide emulsions containing a benzimidazole
US4011082A (en) * 1974-06-06 1977-03-08 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4038081A (en) * 1975-02-28 1977-07-26 Konishiroku Photo Industry Co., Ltd. Development method
US4097284A (en) * 1974-11-26 1978-06-27 Fuji Photo Film Co., Ltd. Method for supersensitizing silver halide photographic emulsions
US4121935A (en) * 1974-09-17 1978-10-24 Konishiroku Photo Industry Co., Ltd. Lith-type silver halide photographic light-sensitive material
US4144070A (en) * 1976-11-22 1979-03-13 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4207108A (en) * 1976-11-04 1980-06-10 Eastman Kodak Company Silver halide photothermographic element, composition and process
US4216284A (en) * 1974-12-27 1980-08-05 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4221863A (en) * 1978-03-31 1980-09-09 E. I. Du Pont De Nemours And Company Formation of silver halide grains in the presence of thioureas
US4724196A (en) * 1984-04-12 1988-02-09 Tadao Shoji Silver halide photographic lith material
US4994350A (en) * 1988-09-07 1991-02-19 Konica Corporation Method for forming a color proof having a specified toe gradation
US5217842A (en) * 1990-09-19 1993-06-08 Dainippon Ink And Chemical, Inc. Superhigh contrast negative image forming process
US5955249A (en) * 1998-03-09 1999-09-21 Eastman Kodak Company Radiographic elements exhibiting increased speed and covering power
US6303284B1 (en) 2000-08-24 2001-10-16 Eastman Kodak Company Process for manufacture of photographic emulsion
US6326134B1 (en) 2000-08-24 2001-12-04 Eastman Kodak Company Process for manufacture of photographic emulsion

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62113138A (ja) * 1985-11-12 1987-05-25 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS62210458A (ja) * 1986-03-11 1987-09-16 Fuji Photo Film Co Ltd 画像形成方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772164A (en) * 1955-01-03 1956-11-27 Eastman Kodak Co Photographic silver halide emulsions containing 1-thia-3, 5, 7-triazaindenes
US2956876A (en) * 1957-09-09 1960-10-18 Eastman Kodak Co Mercapto heterocyclic addenda for reversal color development
US3081170A (en) * 1958-10-06 1963-03-12 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3161520A (en) * 1962-12-11 1964-12-15 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3294540A (en) * 1963-12-17 1966-12-27 Eastman Kodak Co Lith-type emulsions with block co-polymers
US3345175A (en) * 1963-05-17 1967-10-03 Fuji Photo Film Co Ltd High edge-gradient photosensitive material
US3397987A (en) * 1965-05-24 1968-08-20 Eastman Kodak Co Photographic emulsion containing mercapto development anti-foggants
US3433640A (en) * 1964-11-13 1969-03-18 Fuji Photo Film Co Ltd Photographic silver halide light-sensitive material
US3518085A (en) * 1965-09-23 1970-06-30 Eastman Kodak Co Lith-type emulsions containing a polyalkyleneoxy polymer and a 3-pyrazolidone developing agent
US3692527A (en) * 1969-12-13 1972-09-19 Agfa Gevaert Ag Silver halide emulsion containing a mercapto pyrimidine derivative antifoggant
US3708303A (en) * 1971-01-12 1973-01-02 Eastman Kodak Co Photographic elements and processes lithographic silver halide element containing a 1-(amidophenyl)-5-mercaptotetrazole sensitizing agent and development process of using same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US30172A (en) * 1860-09-25 whitwell
BE553031A (xx) * 1955-12-01
BE577256A (xx) * 1958-03-31
US3026201A (en) * 1959-02-02 1962-03-20 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
BE595325A (xx) * 1960-09-23
DE1522432C3 (de) * 1967-03-11 1975-01-30 Agfa-Gevaert Ag, 5090 Leverkusen Spektral sensibilisiertes photographisches Material
US3567458A (en) * 1967-11-15 1971-03-02 Eastman Kodak Co Photographic emulsion containing a water-soluble alkylene oxide block copolymer and a merocyanine dye
US3598598A (en) * 1968-10-01 1971-08-10 Eastman Kodak Co Fog stabilizers for photographic emulsions

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2772164A (en) * 1955-01-03 1956-11-27 Eastman Kodak Co Photographic silver halide emulsions containing 1-thia-3, 5, 7-triazaindenes
US2956876A (en) * 1957-09-09 1960-10-18 Eastman Kodak Co Mercapto heterocyclic addenda for reversal color development
US3081170A (en) * 1958-10-06 1963-03-12 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3161520A (en) * 1962-12-11 1964-12-15 Gen Aniline & Film Corp Fog reduction in photographic silver halide emulsions
US3345175A (en) * 1963-05-17 1967-10-03 Fuji Photo Film Co Ltd High edge-gradient photosensitive material
US3294540A (en) * 1963-12-17 1966-12-27 Eastman Kodak Co Lith-type emulsions with block co-polymers
US3433640A (en) * 1964-11-13 1969-03-18 Fuji Photo Film Co Ltd Photographic silver halide light-sensitive material
US3397987A (en) * 1965-05-24 1968-08-20 Eastman Kodak Co Photographic emulsion containing mercapto development anti-foggants
US3518085A (en) * 1965-09-23 1970-06-30 Eastman Kodak Co Lith-type emulsions containing a polyalkyleneoxy polymer and a 3-pyrazolidone developing agent
US3692527A (en) * 1969-12-13 1972-09-19 Agfa Gevaert Ag Silver halide emulsion containing a mercapto pyrimidine derivative antifoggant
US3708303A (en) * 1971-01-12 1973-01-02 Eastman Kodak Co Photographic elements and processes lithographic silver halide element containing a 1-(amidophenyl)-5-mercaptotetrazole sensitizing agent and development process of using same

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4001020A (en) * 1971-03-04 1977-01-04 Fuji Photo Film Co., Ltd. Developing a silver ha1ide emulsion in contact with a heterocyclic thione and a polyalkylene oxide
US4001021A (en) * 1972-06-30 1977-01-04 Konishiroku Photo Industry Co., Ltd. Lithographic development of a lith-type silver halide emulsions containing a benzimidazole
US4011082A (en) * 1974-06-06 1977-03-08 Fuji Photo Film Co., Ltd. Silver halide photographic material
US4121935A (en) * 1974-09-17 1978-10-24 Konishiroku Photo Industry Co., Ltd. Lith-type silver halide photographic light-sensitive material
US4097284A (en) * 1974-11-26 1978-06-27 Fuji Photo Film Co., Ltd. Method for supersensitizing silver halide photographic emulsions
US4216284A (en) * 1974-12-27 1980-08-05 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
US4038081A (en) * 1975-02-28 1977-07-26 Konishiroku Photo Industry Co., Ltd. Development method
US4207108A (en) * 1976-11-04 1980-06-10 Eastman Kodak Company Silver halide photothermographic element, composition and process
US4144070A (en) * 1976-11-22 1979-03-13 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic materials
US4221863A (en) * 1978-03-31 1980-09-09 E. I. Du Pont De Nemours And Company Formation of silver halide grains in the presence of thioureas
US4724196A (en) * 1984-04-12 1988-02-09 Tadao Shoji Silver halide photographic lith material
US4994350A (en) * 1988-09-07 1991-02-19 Konica Corporation Method for forming a color proof having a specified toe gradation
US5217842A (en) * 1990-09-19 1993-06-08 Dainippon Ink And Chemical, Inc. Superhigh contrast negative image forming process
US5955249A (en) * 1998-03-09 1999-09-21 Eastman Kodak Company Radiographic elements exhibiting increased speed and covering power
US6303284B1 (en) 2000-08-24 2001-10-16 Eastman Kodak Company Process for manufacture of photographic emulsion
US6326134B1 (en) 2000-08-24 2001-12-04 Eastman Kodak Company Process for manufacture of photographic emulsion

Also Published As

Publication number Publication date
FR2166144B1 (xx) 1976-10-29
JPS4873135A (xx) 1973-10-02
JPS576092B2 (xx) 1982-02-03
GB1415010A (en) 1975-11-26
DE2263808A1 (de) 1973-07-05
DE2263808C2 (de) 1987-04-16
FR2166144A1 (xx) 1973-08-10

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