US3600178A - Photographic emulsion containing a mercapto or thioxo group - Google Patents

Photographic emulsion containing a mercapto or thioxo group Download PDF

Info

Publication number
US3600178A
US3600178A US703572A US3600178DA US3600178A US 3600178 A US3600178 A US 3600178A US 703572 A US703572 A US 703572A US 3600178D A US3600178D A US 3600178DA US 3600178 A US3600178 A US 3600178A
Authority
US
United States
Prior art keywords
mole
group
compound
sensitive
water
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.)
Expired - Lifetime
Application number
US703572A
Other languages
English (en)
Inventor
Jozef Frans Willems
Robrecht Julius Thiers
Frans Clement Heugebaert
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.)
Agfa Gevaert NV
Original Assignee
Agfa Gevaert NV
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 Agfa Gevaert NV filed Critical Agfa Gevaert NV
Application granted granted Critical
Publication of US3600178A publication Critical patent/US3600178A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon 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
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • 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
    • 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
    • C07D285/15—Six-membered rings
    • C07D285/16—Thiadiazines; Hydrogenated thiadiazines
    • 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

  • Photographic light-sensitive silver halide materials including a non-light-sensitive water-permeable colloid layer and having incorporated therein at least one organic compound comprising a mercapto group or a thioxo group showing thioxo-thiol tautomerism, a group rendering the compound fast to diffusion in said colloid layer and a group rendering the molecule water-soluble or alkali-soluble.
  • the said organic compound prevents yellowing of the photographic material.
  • the present invention relates to improved photographic light-sensitive silver halide materials, more particularly to photographic materials comprising agents that protect said materials against yellowing and that have no detrimental effect on the sensitivity of the photographic materials.
  • photographic light-sensitive silver halide materials are subject to yellowing.
  • this yellowing is probably due to adsorption of finely divided silver particles, formed by reduction in more or less exhausted development baths, at the surface of processed photographic material where they are physically developed thus producing yellowing of the photographic material whereas in other cases this yellowing is most likely due to the deposition of finely divided silver in a non-light-sensitive colloid layer in water-permeable relationship with the emulsion layer resulting from the diffusion, during the coating process, of silver salts from the silver halide emulsion into the said water-permeable layer.
  • the diffused silver salts are reduced to silver and, on development, if the developer comprises silver halide solvents, the dissolved silver salts are reduced on the silver nuclei of the said non-light-sensitive Water-permeable colloid layer thus producing yellowing of the photographic materials.
  • yellowing of photographic light-sensitive silver halide materials can be prevented by incorporating into the non-light-sensitive water-permeable colloid layers wherein yellowing is produced at least one organic compound comprising a mercapto group or a thioxo group showing thioXo-thiol tautomerism, a group rendering the compound fast to diffusion in said colloid layers and a group rendering the molecule water-soluble or alkali-soluble.
  • a photographic light-sensitive silver halide material comprising in a non-light-sensitive water-permeable colloid layer an organic compound as defined above.
  • a water-solubilizing or alkali-solubilizing group such as a sulpho group or carboxyl group in acid or salt form e.g. as salt from an alkalimetal or alkaline earth metal, ammonium, an organic base such as an amine, etc.
  • a group rendering the molecule fast to diffusion e.g. a radical comprising or consisting of an aliphatic radical with 8 to 20 carbon atoms in straight chain.
  • the compounds of use according to the present invention are fast to diffusion in the non-light-sensitive water-permeable colloid layers there is no risk at all of affecting the photographic characteristics of the silver halide emulsion layer.
  • the compounds of use according to the present invention may be illustrated by the following classes of compounds:
  • mercaptan acids comprising from 12 to 20 carbon atoms such as (1) a-mercapto-stearic acid, (2) a-mercapto-palmitic acid, etc.
  • aliphatic or aromatic thiols e.g. obtained by reaction of low molecular thiols carrying a functional group such as an amino group or hydroxyl group with compounds carrying a sulphonic acid group or latent sulphonic acid group e.g. a sulphofluoride group, a group rendering the compound fast to diffusion and a functional group such as an isocyanate group or chlorocarbonyl group which latter functional group reacts with the functional group of the low-molecular thiol to form a chemical bond.
  • a functional group such as an amino group or hydroxyl group
  • a functional group such as an isocyanate group or chlorocarbonyl group which latter functional group reacts with the functional group of the low-molecular thiol to form a chemical bond.
  • thiol is 3. s o Na HS-CH2CH O-(H1-NH OCI6H33
  • B Water-soluble or alkali-soluble heterocyclic nitrogen-containing thioxo-compounds showing thioxo-thiol tautomerism and having a group rendering the molecule fast to diffusion in the water-permeable colloid layers of the photographic material.
  • These compounds may belong to the most divergent kinds of heterocyclic ring systems, amongst which:
  • the latter two compounds can be prepared by reaction of the amino-substituted benzoxaline-Z-thione or benzthiazoline-2-thione with 2-hexadecyloxy-S-sulphofiuorophenyl isocyanate or 2-heXadecyloxy-5-sulphofluoro-benzoyl chloride followed by saponification of the sulphofluoride group.
  • N-(Z-hexadecyloxy 5 fluorosulphonylpheny1)-2- mercaptoethylurethane is prepared by allowing to react 22.05 g. (0.05 mole) of 2-hexadecyloxy-5-fluorosulphonylphenyl isocyanate with 40 ml. of fl-mercapto-ethanol while heating for 1 hour at C. The excess of ,B-mercaptoethanol is washed away with water and the residue is recrystallized from 100 m1. of ethanol. Yield: 23.5 g. (0.045 mole). Melting point: 5557 C.
  • anti-yellowing agents employed as additives to non-light-sensitive colloid layers depends on the particular material and the desired effect and can vary within very wide limits.
  • the optimum amount of anti-yellowing agent to be used can be readily determined by simple tests.
  • the compounds are employed in amounts comprised between about 2 mg. and about 500 mg. per sq. m. of non-light-sensitive water-permeable colloid-layer.
  • the anti-yellowing agents are particularly intended for the reduction of yellowing in photographic materials comprising lightsensitive silver halide X-ray emulsion layers
  • the compounds according to the present invention may be used to prevent yellowing of any kind of photographic material comprising any type of light-sensitive silver halide emulsion layer e.g. spectrally sensitized and non-sensitized emulsion layers, X-ray emulsion layers and emulsion layers sensitive to infra-red radiation.
  • the emulsions may be high-sensitive negative emulsions as well as rather low sensitive positive emulsions.
  • Various silver salts may be used as light-sensitive salt e.g. silver bromide, silver iodide, silver chloride or mixed silver halides e.g. silver chloro-bromide or silver bromo-iodide.
  • the silver halides are dispersed in the common hydrophilic colloids such as gelatin, casein, polyvinyl alcohol, carboxymethylcellulose, alginic acid, etc., gelatin being however favoured.
  • the light-sensitive emulsions may be chemically as well as optically sensitized. They may be chemically sensitized by effecting the ripening in the presence of small amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
  • the emulsions may also be sensitized by means of reductors for instance tin compounds as described in the French patent specification 1,146,955, filed Apr. 11, 1956 by Gevaert Photo-Producten N.V.
  • the light-sensitive silver halide emulsion layers may comprise compounds which sensitize the emulsion by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pats. 2,531,832 of William Alexander Stanton issued Nov. 28, 1950 and 2,533,990 of Ralph Kingsly Blake, issued Dec. 12, 1950, in UK. Pats. 920,637, 940,051, 945,340, filed May 7, 1959, Nov. 1, 1961, Oct. 23, 1961 all by Gevaert Photo- Producten N.V. and 991,608, filed June 14, 1961 by Kodak and in Belgian Pat. 648,710, filed June 2, 1964 by Gevaert Photo-Producten N.V. and onium derivatives of amino- N-oxides as described in French patent specification 1,498,724, filed Oct. 3, 1966 by Gevaert-Agfa N.V.
  • the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S.
  • these emulsion layers also comprise stabilizers for instance heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and l-phenyl- Z-tetrazoline-S-thione and particularly compounds of the hydroxy-triazolopyrimidine type (azaindolizines).
  • They may also comprise mercury compounds as stabilizers, particularly in the case of high-sensitive emulsions comprising development accelerators of the polyoxyalkylene type.
  • Suitable mercury compounds are, e.g. mercury oxide, the mercury compounds described in Belgian patent specifications 524,121, filed July 9, 1953 by Kodak and 677,337, filed Mr. 4, 1966 by Gevaert-Agfa N.V. and in UK patent application No. 55,445/66, filed Dec. 12, 1966 by Gevaert-Agfa N.V., basic salts of mercury corresponding to the formula:
  • X represents an aryl radical, a heterocyclic radical, a hydroxyl group or an acid residue e.g. thiophene-mercury(Il) hydroxide and the compounds with formulae molecular addition compounds of mercury salts and organic sulphides such as the compound with formula:
  • Example 1 A coarse-grain gelatin brornoiodide (1.8 mole percent of iodide) emulsion of the X-ray type is prepared comas moistening agent. Two analogous X-ray materials are prepared with the difference however, that the protective layer also comprises an amount of compound 11 and compound 17, respectively as mentioned in the table below.
  • Example 2 A series of X-ray materials is prepared as described in Example 1, comprising, however, in the silver bromoiodide emulsion layer 2.0 mole percent of silver iodide and comprising in the gelatin antistress layer either no anti-yellowing agent or an anti-yellowing agent as listed in the following table. The materials are further treated as described in Example 1 giving the following results.
  • a photographic material comprising a support and at least one light-sensitive silver halide emulsion layer, characterized in that a non-light-sensitive water-permeable colloid layer of said photographic material contains at least one organic compound comprising a mercapto group or a thioxo group showing thioxo-thiol tautomerism, an aliphatic radical comprising from 8-20 carbon atoms rendering the compound fast to diffusion in said colloid layer and a carboxyl or sulpho radical in acid or salt form rendering the compound water-soluble or alkali-soluble.
  • a photographic material according to claim 1, wherein said organic compound is a heterocyclic nitrogen containing thioxo compound selected from a 1,2,4- triazoline-S-thione, a benzimidazoline-2-thione, a benzoX- azoline-Z-thione, a benzthiazoline-Z-thione, a 1,3,4-oxadiazoline-Z-thione, a tetrazoline-S-thione, a pyrimidinethioue, a triazine-thione and a 1,3,4-thiadiazine-2-thione.
  • a heterocyclic nitrogen containing thioxo compound selected from a 1,2,4- triazoline-S-thione, a benzimidazoline-2-thione, a benzoX- azoline-Z-thione, a benzthiazoline-Z-thione, a 1,3,4-oxadiazoline-Z-thione, a tetrazoline-S-thi
  • a photographic material according to claim 1, wherein said non-light-sensitive water-permeable colloid layer is a gelatin protective layer coated over the silver halide emulsion layer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
US703572A 1967-02-15 1968-02-07 Photographic emulsion containing a mercapto or thioxo group Expired - Lifetime US3600178A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7252/67A GB1203051A (en) 1967-02-15 1967-02-15 Improvements in or relating to photographic light-sensitive silver halide materials

Publications (1)

Publication Number Publication Date
US3600178A true US3600178A (en) 1971-08-17

Family

ID=9829552

Family Applications (1)

Application Number Title Priority Date Filing Date
US703572A Expired - Lifetime US3600178A (en) 1967-02-15 1968-02-07 Photographic emulsion containing a mercapto or thioxo group

Country Status (6)

Country Link
US (1) US3600178A (en, 2012)
BE (1) BE710798A (en, 2012)
DE (1) DE1622259C2 (en, 2012)
FR (1) FR1556514A (en, 2012)
GB (1) GB1203051A (en, 2012)
NL (1) NL6802016A (en, 2012)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0002763A3 (en) * 1977-12-29 1979-07-25 Agfa-Gevaert Aktiengesellschaft Photographic material with stabilisers and process for forming photographic images
US4784938A (en) * 1985-10-22 1988-11-15 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3051570A (en) * 1958-10-01 1962-08-28 Gen Aniline & Film Corp Antifoggants and stabilizers for photographic silver halide emulsions
BE595325A (en, 2012) * 1960-09-23
BE624110A (en, 2012) * 1961-11-02
BE612311A (en, 2012) * 1962-01-05
BE630297A (en, 2012) * 1963-03-29
US3226231A (en) * 1963-05-16 1965-12-28 Gen Aniline & Film Corp Fog reduction in silver halide emulsions with 3-mercaptobenzoic acid

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0002763A3 (en) * 1977-12-29 1979-07-25 Agfa-Gevaert Aktiengesellschaft Photographic material with stabilisers and process for forming photographic images
US4282313A (en) * 1977-12-29 1981-08-04 Agfa-Gevaert Aktiengesellschaft Photographic material with stabilizers
US4784938A (en) * 1985-10-22 1988-11-15 Konishiroku Photo Industry Co., Ltd. Silver halide photographic light-sensitive material

Also Published As

Publication number Publication date
FR1556514A (en, 2012) 1969-02-07
NL6802016A (en, 2012) 1968-07-25
BE710798A (en, 2012) 1968-08-16
GB1203051A (en) 1970-08-26
DE1622259A1 (de) 1970-10-29
DE1622259C2 (de) 1983-05-19

Similar Documents

Publication Publication Date Title
US3503749A (en) Light-sensitive silver halide emulsions containing soluble gold salts
US3397987A (en) Photographic emulsion containing mercapto development anti-foggants
US2886437A (en) Photographic emulsions sensitized with alkylene oxide polymers and quaternary ammonium compounds
US3501313A (en) Photographic silver halide emulsions which include high efficiency sulfurcontaining sensitizers
US3397986A (en) Photographic emulsion stabilized with bis (p-acylamidophenyl) disulfides
US3650749A (en) Photographic development
US3499761A (en) Silver halide emulsions containing alkyl esters of benzimidazole carbamic acid antifogging agents
US3071465A (en) Fog reduction in silver halide emulsions by 2h-tetrazolium halides
US2948614A (en) Stabilized photographic silver halede
US3576638A (en) High molecular weight, long chain tetrazole-containing polymers for antifogging use in photographic elements
US3271154A (en) Antifogging and stabilizing agents for photography
US3765901A (en) Spectral sensitization of light-sensitive silver halide emulsions
US3598600A (en) Photographic compositions and elements containing polymeric imidazoles
US3060028A (en) Stabilized photographic silver halide emulsions containing iodine complexes of poly-n-vinyl-2-oxazolidinones
JPS5943728B2 (ja) ハロゲン化銀写真材料
US2939789A (en) Fog reduction in photographic silver halide emulsions
US3600178A (en) Photographic emulsion containing a mercapto or thioxo group
US3051570A (en) Antifoggants and stabilizers for photographic silver halide emulsions
US2728667A (en) Molecular compounds of mercury salts with benzothiazoles as fog inhibitors in a silver halide emulsion
US3622339A (en) Polymeric antifoggant containing at least four triazine rings
US2860985A (en) Stabilization of photographic silver halide emulsions and means of increasing contrast
US2887378A (en) Photographic silver halide emulsions containing thiol compounds
US3645738A (en) Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup
US3857711A (en) Silver halide photographic emulsion sensitized with a heterocyclic compound containing 4-sulfur atoms
US3764339A (en) Silver halide emulsions stabilized with n-(1,3,4-thiadiazol-2-yl)-dithiocarbamic acid esters