US3645738A - Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup - Google Patents

Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup Download PDF

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Publication number
US3645738A
US3645738A US728321A US3645738DA US3645738A US 3645738 A US3645738 A US 3645738A US 728321 A US728321 A US 728321A US 3645738D A US3645738D A US 3645738DA US 3645738 A US3645738 A US 3645738A
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nucleus
thioxo
compound
heterocyclic
silver halide
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US728321A
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Jozef Frans Willems
Oskar Riester
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Agfa Gevaert NV
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Agfa Gevaert NV
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    • 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
    • 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
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • 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
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • 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
    • 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
    • C07D277/84—Naphthothiazoles
    • 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
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/164—Rapid access processing

Definitions

  • ABSTRACT heterocyclic thioxo compound showing thioxo-thiol tautomerism and corresponding to the formula wherein Z represents the atoms necessary to close a five or six member heterocyclic nucleus containing at least one sulfo group in acid or salt form.
  • Z represents the atoms necessary to close a five or six member heterocyclic nucleus containing at least one sulfo group in acid or salt form.
  • the residual unexposed and undeveloped silver halide which is left in the emulsion layer forms a light inert complex.
  • the thioxo-thiol compound improves the stability of the produced image to light, heat, and humidity.
  • the present invention relates to a process for stabilizing developed photographic images according to which the silver halides remaining after development in the unexposed areas are converted into compounds that are inert to heat, light and humidity, thereby eliminating normal processing operations of fixing and washing.
  • the normal processing of photographic materials involves the development of the exposed silver halide to a silver image, conversion of the unexposed silver halide to a soluble salt by fixation and removal of the soluble silver salt formed as well as of the fixing solution employed by washing with water.
  • ammonium thiocyanate is widely used as stabilizing agent although it has some disadvantages. indeed, ammonium thiocyanate produces a high rate of stabilization but the silver image has a great tendency to bleach out or fade upon storage, particularly at high humidity.
  • heterocyclic thioxo compounds such as 1-phenyl-2-tetrazoline-5-thione
  • these compounds are generally little soluble in acid stabilizing baths so that it is difficult to incorporate them therein in the appropriate concentration.
  • said compounds cannot be incorporated into the material itself in the required concentration because they inhibit development.
  • the stabilizing effect of the stabilizer can be improved i.e., that the loss of image density on storage of the stabilized image can be reduced or eliminated by carrying out the stabilizing treatment in the presence of at least one heterocyclic thioxo compound showing thioxo-thiol tautomerism and comprising in its molecule at least one sulpho group in acid or salt form.
  • a method for producing images that are stable to light, heat and humidity, and have much less propensity to fade or become stained on prolonged storage comprises exposing a photographic material comprising at least one light-sensitive silver halide emulsion layer, developing the exposed material and treating the material with a stabilizing composition, by which the residual unexposed silver halide is converted into a light-insensitive compound, wherein said treatment occurs in the presence of at least one heterocyclic thioxo compound showing thioxo-thiol tautomerism and comprising in its molecule at least one sulpho group in acid or salt form.
  • heterocyclic thioxo compounds of use according to the present invention can be represented by the following general formula:
  • Z represents the atoms necessary to close a 5- or 6- membered heterocyclic nucleus including a heterocyclic nucleus comprising a fused aromatic ring system for instance a fused benzene or naphthalene ring, preferably a benzoor naphtho-iniidazoline, -oxazoline or -thiazoline nucleus, a
  • heterocyclic thioxo compounds of use according to the present invention may be substituted in the aromatic or heterocyclic ring(s) in so far as these substituents do not adversely affect the image quality and the physical properties of the compounds.
  • suitable substituents are: alkyl of at most five carbon atoms including substituted alkyl e.g., hydroxyalkyl, aralkyl including substituted aralkyl, aryl including substituted aryl, alkoxy of at most five carbon atoms, halogen e.g., chlorine, alkoxy-carbonyl, nitro, amino including substituted amino e.g., acylarnino, carboxyl, etc.
  • the invention is of particular value in the processing where g (a) photographic developing agent(s) is (are) contained in the photographic material, the development is activated by means of an alkaline activator bath and the stabilizer is a solution containing known stabilizers; these known stabilizers or silvercomplexing agents include thiosulphates, thiocyanates, thioureas, thioglycollic acid, thiosalicylic acid, thiopyrimidines, etc.ammonium, potassium and sodium thiocyanate are preferably employed.
  • the compounds of use according to' the present invention are not only suitable for being incorporated into the stabilizing solution in which they dissolve readily but they are-also particularly suitable for being incorporated into at least one of the colloid layers of the photographic materiahpreferably into the silver halide emulsion layer, since they can be incorporated therein the required concentration without giving rise to a marked desensitization of the photographic material, which is the case, as already said above, with most known heterocyclic mercapto compounds comprising no solubilizing sulpho group.
  • the high water-solubility guarantees a homogeneous distribution of the compounds according to the invention in the coating composition of the layer into which they are intended to be incorporated.
  • the compounds of the invention form soluble silver complexes with the residual silver halide, less stain is produced in the highlight areas of the image on ageing because some of the silver complex diffuses from the material into the stabilizing solution. Moreover, in cases where a very high degree of stabilization is required the concentration of the soluble silver complexes formed in the material with the compounds of use according to the invention can be reduced by a post-stabilization treatment consisting of a short rinsing with water.
  • the amount of compound according to the above general formula to be used can vary within very wide limits and depends on the nature of the particular compound and on the photographic material for which it is used. The optimum amount can be readily determined for each particular material by simple tests.
  • said compounds are employed in the stabilizing bath in amounts from about 0.1 g. to about 10 g., preferably from about 0.5 to g., per litre of composition, and in the photographic material in amounts from about mg. to about 2 g. preferably from about 50 mg. to about 0.5 g. per mole of silver halide.
  • the photographic emulsions may be of any type, e.g., they may be spectrally sensitized or nonsensitized emulsions and 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, silver bromo-iodide andsilver chlorobromo-iodide.
  • the silver halides are dispersed in the common hydrophilic colloids e.g., gelatin, casein, polyvinyl alcohol, carboxymethyl cellulose, alginic acid etc., gelatin being however favoured.
  • the common hydrophilic colloids e.g., gelatin, casein, polyvinyl alcohol, carboxymethyl cellulose, 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 French Patent Specification 1,146,955 and in Belgian Patent Specification 568,687, imino-amino methane sulphinic acid compounds as described in British Patent Specification 789,823 and small amounts of noble metal compounds such as of gold, platinum, palladium, iridium, ruthenium and rhodium.
  • the light-sensitive emulsions may be sensitized by addition of development accelerators as for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in U.S. Pat. Nos. 2,531,832 and 2,533,990, in United Kingdom Pat. Nos. 920,637, 940,051, 945,340 and 991,608 and in Belgian Pat. No. 648,710 and onium derivatives of amino-N-oxides as described in published Dutch Patent Application 6612269.
  • the light-sensitive emulsions may also comprise one or more developing agents such as hydroquinone, l-phenyl-3- pyrazolidinone, p'aminophenol and p-phenylene diamine derivatives etc., antioxidantia for said developing agents such as potassium metabisulphite, matting agents, etc.
  • developing agents such as hydroquinone, l-phenyl-3- pyrazolidinone, p'aminophenol and p-phenylene diamine derivatives etc.
  • antioxidantia for said developing agents such as potassium metabisulphite, matting agents, etc.
  • the developer can be reduced to a mere aqueous alkaline activator bath, which by the absence of developing agent(s) is better keepable.
  • EXAMPLE 1 A gelatino silver chlorobromide emulsion (60 mole percent AgBr and 40 mole percent AgCl) containing hydroquinone and potassium metabisulphite as well as other common emulsion ingredients such as sensitizing agents, hardening agents and coating aids, is coated on a conventional film support and dried.
  • the photographic material obtained is exposed and developed e.g., in a developing bath comprising per litre 60 g. of sodium hydroxide, 40 g. of anhydrous sulphite, 2 g. of potassium bromide and 1 g. of l-phenyl-3-pyrazolidinone.
  • ammonium thiocyanate 250 g. potassium metabisulphite g. 30 formaldehyde [20 ml. 60 k acetic acid 25 ml. compound 22 l g.
  • the image treated with the above composition shows good stability against fading of the image silver and staining of the highlight areas. lndeed, even when having been kept for 18 days in an atmosphere of 20C. and 60 percent of relative humidity or exposed for 1 month to direct daylight the density of the image has faded less than that of an image treated with an analogous composition but without the compound according to the invention and the highlight areas are less stained.
  • EXAMPLE 2 added per mole of silver halide. This emulsion is then coated in the conventional manner on a baryta coated paper support and dried.
  • the material obtained is exposed and developed e.g., in a developing bath comprising per litre 40 g. of sodium hydroxide, 40 g. of anhydrous sodium sulphite, 2 g. of potassium bromide and l g. of l-phenyl-B-pyrazolidinone.
  • the image obtained shows as compared with a material comprising no compound-according to the invention, good stability against fading of the image silver and staining of the highlight areas on storage.
  • a rapid process for producing a stable photographic image which comprises developing an exposed silver halide emulsion layer of a photographic material and treating the developed emulsion layer with a stabilizing solution containing at least one stabilizing compound selected from the group consisting of alkali metal and ammonium thiocyanates and thiosulphates, thioureas, thioglycollic acid, thiosalicylic and thiopyrimidines as stabilizing agent to form with residual unexposed and undeveloped silver halide a light-inert complex which is left in the emulsion layer, the improvement which comprises treating the developed emulsion layer with the said stabilizing solution in the presence of at least one heterocyclic thioxo compound showing thioxo-thiol tautomerism and corresponding to the formula:
  • Z represents the atoms necessary to close a 5- or 6- membered heterocyclic nucleus selected from the group consisting of imidazoline, oxazoline, thiazoline, diazoline, triazoline, thiadiazoline, oxadiazoline, tetrazoline, thiadiazine, benzthiazolotriazine, pyridine, pyrimidine, pyridazine, and trian'ne; and said heterocyclic nuclei comprising a fused aromatic ring and on the molecule at least one sulpho group in acid or salt form.
  • Z represents the atoms necessary to close a benzoxazo line nucleus, a benzothiazoline nucleus, at benzoimidazoline nucleus, a naphtho-imidazoline nucleus, a naphthoxazoline nucleus, a naphtho-thiazoline nucleus, a diazoline nucleus, a triazoline nucleus, a thiadiazine nucleus, a benzthiazolotriazine nucleus, at pyridine nucleus, a pyrimidine nucleus, a pyridazine nucleus, or a triazine nucleus.
  • the stabilizing compound is an alkali metal or ammonium thiocyanate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Plural Heterocyclic Compounds (AREA)
US728321A 1967-05-18 1968-05-10 Stabilizing silver image in presence of heterocyclic thioxo compound containing sulphogroup Expired - Lifetime US3645738A (en)

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GB23050/67A GB1201621A (en) 1967-05-18 1967-05-18 Process for stabilizing developed photographic images

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US (1) US3645738A (en:Method)
BE (1) BE715410A (en:Method)
DE (1) DE1772451A1 (en:Method)
FR (1) FR1562731A (en:Method)
GB (1) GB1201621A (en:Method)
NL (1) NL6807018A (en:Method)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264721A (en) * 1978-10-30 1981-04-28 Konishiroku Photo Industry Co., Ltd. Color photographic materials
US4554242A (en) * 1984-01-12 1985-11-19 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
JPS63265241A (ja) * 1987-04-23 1988-11-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料の処理方法
US4906557A (en) * 1986-02-22 1990-03-06 Agfa-Gevaert Aktiengesellschaft Photographic recording material and process for the production of photographic images
US4960683A (en) * 1987-06-29 1990-10-02 Fuji Photo Film Co., Ltd. Method for processing a black-and-white photosensitive material
US5110716A (en) * 1989-04-28 1992-05-05 Konica Corporation Stabilizer for silver halide photographic light-sensitive material use and the method of processing the light-sensitive material with the stabilizer
US5141843A (en) * 1990-04-04 1992-08-25 Agfa-Gevaert N. V. Developer liquid for high contrast development

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2365571A1 (fr) * 1976-09-24 1978-04-21 Smithkline Corp Acides 7-acylamino-3-(sulfomethylthiadiazolyl- ou triazolyl-thiomethyl)-3-cepheme-4-carboxyliques, leur procede de preparation et leur application en therapeutique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137574A (en) * 1959-11-12 1964-06-16 Eastman Kodak Co Stability of rapid-processed photographic prints
US3305362A (en) * 1962-03-08 1967-02-21 Agfa Ag Process for developing silver halide and compositions therefor
US3326684A (en) * 1962-04-06 1967-06-20 Fuji Photo Film Co Ltd Method for stabilizing developed photosensitive materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137574A (en) * 1959-11-12 1964-06-16 Eastman Kodak Co Stability of rapid-processed photographic prints
US3305362A (en) * 1962-03-08 1967-02-21 Agfa Ag Process for developing silver halide and compositions therefor
US3326684A (en) * 1962-04-06 1967-06-20 Fuji Photo Film Co Ltd Method for stabilizing developed photosensitive materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264721A (en) * 1978-10-30 1981-04-28 Konishiroku Photo Industry Co., Ltd. Color photographic materials
US4554242A (en) * 1984-01-12 1985-11-19 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4906557A (en) * 1986-02-22 1990-03-06 Agfa-Gevaert Aktiengesellschaft Photographic recording material and process for the production of photographic images
JPS63265241A (ja) * 1987-04-23 1988-11-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料の処理方法
US4960683A (en) * 1987-06-29 1990-10-02 Fuji Photo Film Co., Ltd. Method for processing a black-and-white photosensitive material
US5110716A (en) * 1989-04-28 1992-05-05 Konica Corporation Stabilizer for silver halide photographic light-sensitive material use and the method of processing the light-sensitive material with the stabilizer
US5141843A (en) * 1990-04-04 1992-08-25 Agfa-Gevaert N. V. Developer liquid for high contrast development

Also Published As

Publication number Publication date
NL6807018A (en:Method) 1968-07-25
GB1201621A (en) 1970-08-12
FR1562731A (en:Method) 1969-04-04
BE715410A (en:Method) 1968-11-20
DE1772451A1 (de) 1971-04-08

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