Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—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
  • G03C1/00—Photosensitive materials
  • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds

Definitions

• This invention relates to light-sensitive compositions which, upon exposure to a light image, may be developed to yield photographic image reproductions.
• the invention further relates to processes for preparing these compositions.
• photographic elements having lightsensitive compositions be capable of providing sharp photographic reproductions having dense images and having stable and clear backgrounds. Such photographic elements desirably are further capable of being conveniently and rapidly processed.
• the present invention relates to a light-sensitive composition
• a light-sensitive composition comprising a silver salt of a tetraazaindene having the formula:
• R is a hydrogen atom, or an alkyl (e.g., methyl,
• R and R which may be the same or different, are a hydrogen atom or a lower alkyl (e.g., methyl, ethyl, propyl, butyl, etc.) or substituted alkyl group such as a hydroxyalkyl group, or R and R together with the adjacent nitrogen atom may form a heterocyclic ring such as morpholine or pyridine ring; and Y represents a hydrogen atom or an alkyl, e.g., methyl, ethyl, propyl, alkylthio, aryl such as phenyl, naphthyl, etc., or amino such as --NH dimethylamino, etc. group;
• the present invention also relates to photographic elements comprising a base and at least one layer having a light-sensitive composition of the present invention and further relates to a method of producing such light-sensitive compositions.
• the light-sensitive compositions of the present invention may be produced by a method comprising reacting in aqueous media a water-soluble silver salt with a tetraazaindene having the general formula:
• Photographic elements prepared from light-sensitive compositions of the present invention may be rapidly developed and fixed by conventional wet processing techniques to yield excellent image reproductions which are characterized by very little fog. Considering the quantity of silver in the compositions, the images produced therefrom are unusually dense.
• the tetraazaindene-silver salt compounds of the present invention may conveniently be prepared by reacting in aqueous media the tetraazaindene compounds represented by the above formula, or a soluble salt of these tetraazaindene compounds adjusted to pH 6 to 8.5 with nitric acid, with from about 0.5 to 1.5 molecular equivalents of a soluble silver salt, such as, for example, silver nitrate.
• a soluble silver salt such as, for example, silver nitrate.
• the resulting tetraazaindeue-silver salts are soluble in water but may crystallize or precipitate out if the aqueous media is sufficiently concentrated.
• the soluble silver salt e.g., silver nitrate
• the preferred limits are from 0.5 to 0.95 molar proportions, since it appears that an excess of tetraazaindene acts as a stabilizer and antiioggant for the composition.
• the light-sensitivity of the compositions of the present invention is believed to be due to the presence therein of silver halide. It is believed that the tetraazaindene-silver salts are but slightly if at all light sensitive. Once a latent image has been formed in the silver halide, however, it appears that subsequent development utilizes the silver provided by the tetraazaindene-silver salt, since only very small amounts of silver halide need be present in the lightsensitive compositions of the present invention to yield sharp, dense images.
• Silver halide is present in the compositions of the present invention preferably in amounts sufiicient to yield a weight ratio of silver in the silver halide to total silver in the composition of from 0.001/1 to 0.5/ 1. The optimum ratio is best found by trial'and error, and is usually not greater than about 0.1/ 1.
• Silver halides which are suitable for use in the present invention include, for example, silver chloride, silver bromide, silver iodide or mixtures thereof.
• Light-sensitive compositions of the present invention may be produced by several methods.
• a tetraazaindene compound in aqueous media is treated with silver nitrate to form the tetraazaindenesilver salt.
• Soluble halide is then added which reacts in situ with silver from either an excess of the silver nitrate or from the soluble tetraazaindene-silver salt, to form silver halide.
• the media may then be coated onto a photographic substrate such as glass, film, or paper to form a tion, for example, by coating the composition from aqueous media onto a photographic substrate.
• the aqueous coating media preferably contains a suitable water-soluble binder material, such as gelatin or Gelvatol (polyvinylalcohol, a trademarked product of Monsanto Chemic'al Co.).
• aqueous media containing a tetraazaindene-silver salt and a water-soluble binder may be coated on a substrate which contains soluble halide, so that some of the halide is leached from the substrate to form silver halide in the coated media as explained above.
• Photographic elements prepared from the light-sensitive compositions of the present invention may, after exposure, be developed with wet developers such as aqueous phenidone hydroquinone or meto hydroquinone developers. Fixing can thereafter be affected by methods which are commonly employed for silver halide photographicelements. For example, a thiosulfate fixer may be employed. Due to the water solubility of the tetraazaindene-silver salt, fixing is usually rapid.
• a solution of hydroquinone developer is coated onto an unexposed photographic element containing a composition of the present invention to yield a heat-developable photographic element. After exposure, the photographic element is heated to, for example 160 C. to develop the image.
• an unexposed photographic element comprising a composition of the present invention and a developer for silver halide, such as hydroquinone, may, after exposure, be developed and substantially fixed in one step by treating the element with an alkaline solution.
• a photographic element prepared from a light-sensitive composition of the present invention first developed by a Wet developer and is then fixed in a thiosulfate fixer as described above.
• Photographic elements prepared from the light-sensitive compositions of the present invention are particularly useful as masters in diazo reproductions. It has been found that such photographic elements can be used without fixing to produce many copies by this process. It has been further found that the photographic images produced by this process are unusually sharp. Line images of 1000 lines per millimeter can be accurately reproduced. Photographic elements containing the light-sensitive compositions of the present invention consequently are particularly useful for producing micro images.
• the light-sensitive compositions of the present invention are sensitive primarily to ultraviolet light and to light in the shorter wavelength region of the visible spectrum.
• the sensitivity of the compositions can be extended to longer wavelengths by the addition of spectral sensitizers which are commonly employed in silver halide emulsions, such as, for example, cyanine and merocyanine dyes.
• EXAMPLE 1 The diethylamine salt of 5-diethylaminomethyl-4-hydroxy 6 methyl 2 methylthio-l,3,3a,7-tetraazaindene (17.7 g.) was dissolved in water. Sufiicient 2 N nitric acid was added to give 100 ml. of solution of pH 8.0. This solution was stirred and warmed to 35 C. and 1 M silver nitrate (37.5 ml.) was added through a glass jet, followed by 1 M potassium bromide solution (3.75 ml.).
• EXAMPLE 2 To this mixture was then added 12% aqueous gelatin solution ml.), 4% aqueous chrome alum solution (6 ml.) and Teepol 610 (0.4 ml.) (a product of Shell Chemical Co.). The resulting emulsion was then coated at a wet thickness of 0.005 inch onto a clear polyester film base and dried.
• Example 1 After exposure through a photographic negative to 284x10 meter candle seconds of tungsten light, the film was developed for 15 seconds as in Example 1 to give a black and wln'te positive transparency of density 2.6 and contrast 1.1. The sensitivity of this film was found to have been extended into the green region of the spectrum by the sensitizing dye.
• EXAMPLE 3 The diethylamine salt of 5-diethylaminomethyl-4-hydroxy-6-methyl-2-methylthio-1,3,3a,7-tetraazaindene (17.7 g.) was dissolved in water. Sutficient 2 N nitric acid was added to give 100 ml. of solution of pH 8.0. This mixture was then stirred and warmed to 35 C. and a 12% aqueous solution of gelatin (100 ml.) added. 1 M silver nitrate solution (37.5 ml.) was added through a glass jet followed by 1 M potassium bromide solution (3.75 ml.).
• Example 1 After exposure through a photographic negative to 2.84 10 meter candle seconds of tungsten light the film was developed for 20 seconds as in Example 1 to give a black and white positive transparency of density 2.0 and contrast 2.0.
• EXAMPLE 4 The sodium salt of 5-diethylaminomethyl-4-hydroxy-6- methyl-2-methylthio-l,3,3a,7-tetraazaindene (15.2 g.) was dissolved in water. Sufiicient 2 N nitric acid was added to give 100 ml. of solution of pH 8.0. This solution was stirred and warmed to 35 C. and 12% aqueous gelatin solution was added (100 ml.). Then 1 M silver nitrate solution (37.5 ml.) was added through a glass jet followed by 1 M potassium chloride solution (3.75 ml.) and Teepol 610 (0.4 ml.) (a product of Shell Chemical Co.). The emulsion so prepared was coated at a wet thickness of 0.005 inch onto a clear polyester film base and dried.
• Example 1 After exposure of the coating through a negative to 1.25 X 10' meter candle seconds of tungsten light the film was developed for 10 seconds as in Example 1 to give a black and white positive transparency of density 2.4 and contrast 4.0.
• EXAMPLE 5 The diethylamine salt of 5-diethylaminomethyl-4-hydroxy-6-methyl-Z-methylthio-l,3,3a,7-tetraaza.indene (17.7 g.) was dissolved in water. Sulfic-ient 2 N nitric acid was added to give 100 ml. of solution of pH 8.0. This solution was stirred and warmed to 35 C. and a 12% aqueous solution of gelatin (100 ml.) was added. Then 1 M silver nitrate solution (37.5 ml.) was added through a glass jet followed by 1 M potassium bromide solution (3.75 ml.). An aqueous solution ml.) of the following sensitizing dye was then added:
• Example 1 After exposure through a photographic negative to 284x10 meter candle seconds of tungsten light the film was developed for seconds as in Example 1. This gave a black and white positive transparency of density 2.9 and contrast 1.5. The sensitivity of this film was found to have been extended into the green region of the spec trum by the sensitizing dye.
• EXAMPLE 6 The diethylamine salt of S-diethylaminomethyl-4-hydroxy-6-mefihyl-2-methylthio-l,3,3a,7 tetraazaindene (l g.) was dissolved in water (10 ml.) and the pH was adjusted to 6.0 with nitric acid. 5 ml. of a aqueous solution of partially hydrolyzed polyvinyl acetate (Gelvatol, a trademarked prdouct of Monsanto Chemical Co.) was added and under red safe lights a solution of 0.3 g. silver nitrate dissolved in 2.5 ml. water was added. No crystals separated immediately and the solution was coated onto a paper which contained 0.1 mg. of soluble chloride per square decimeter and dried. During coating at least some of this soluble chloride became incorporated in the coating composition and it was calculated that the coating contained up to 4.3% by weight of silver chloride.
• the coated paper was exposed to light behind a negative image and developed in P.Q. Universal developer (a product of Ilford Ltd.) diluted 1 part of developer with 19 parts water. The paper was then washed in water at room temperature, and a black image with low background fog was obtained. The image processed in this manner was found to be stable against further light exposure.
• P.Q. Universal developer a product of Ilford Ltd.
• EXAMPLE 7 The diethylamine salt of 5 diethylaminomethyl-4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (0.85 g.) was dissolved in water (10 ml.) and the solution was adjusted to pH 2.5 with nitric acid. 5 ml. of a 12% gelatin solution were added, and under red safe lights a solution of 0.3 g. of silver nitrate dissolved in 2.5 ml. water was added. The resulting suspension of fine crystals was coated onto a paper base which contained 0.1 mg. of soluble chloride per square decimeter and dried. During coating at least some of this soluble chloride became incorporated in the coating and it has been calculated that the coated composition contained up to 4.3% by weight of silver chloride.
• the paper was exposed to light through a negative image and developed in the phenidone-hydroquinone developer of Example 6 and was subsequently washed in water at room temperature. A strong black image with low fog was obtained. The image processed in this manner was stable against further light exposure.
• EXAMPLE 8 The diethylamine salt of 5 diethylaminomethyl-4-hydroxy-6-methyl-2-methylthio-1,3,3a,7-tetraazaindene (0.85 g.) was dissolved in water, the pH adjusted to 8 and the volume adjusted to 3.75 ml. Silver nitrate (0.3 g.) was dissolved in 2.5 ml. of water and, under red safelights, the silver nitrate and tetraazaindene solutions were simultaneously jetted into a mixture of 6 ml.
• the coating was exposed to light through a negative image and was developed in the developer of Example 6. It was subsequently washed in water at room temperature and showed a strong black image with low fog. The image processed in this manner was stable against further light exposure.
• This coating showed a speed increase of fifty times over a corresponding coating having no sensitizing dye.
• EXAMPLE 9 4 hydroxy-6-methyl-5-piperidinomethyl-l,3,3a,7-tetraazaindene (0.7 g.) was dissolved in 10 ml. of water and the solution adjusted to pH 2.5 with nitric acid. 5 ml. of 20% Gelvatol (a trademarked product of Monsanto Chemical Co.) was added, and under red safelights a solution of 0.3 g. of silver nitrate dissolved in 2.5 ml. of water was added. The resulting suspension of fine crystals was coated onto a paper base containing 0.1 mg. of soluble chloride per square decimeter and dried. During coating at least some of this soluble chloride became incorporated in the coating, and it was calculated that the coated composition contained up to 4.3 by weight of silver chloride.
• Gelvatol a trademarked product of Monsanto Chemical Co.
• the paper was exposed to light through a negative image and was developed in the developer of Example 6. It was subsequently washed at room temperature and showed a strong black image with low fog.
• EXAMPLE 10 5 diethylaminomethyl 4-hydroxy-2-methyl-6-methylthio-l,3,3a,7-tetraazaidene (2.81 g.) was dissolved in water (15 ml.). This solution was stirred, warmed to 45 C., and 10% gelatin solution (35 ml.) was added. 1 M silver nitrate solution (10 ml.) was added slowly with efiicient stirring and after stirring for 10 minutes a 1 M potassium bromide/iodide solution containing 3% iodide (1.0 ml.) was added slowly. After stirring for a further 10 minutes 7 chrome alum solution (2 ml.) was added and the emulsion so prepared was coated at a wet thickness of 0.003 inch onto baryta paper and dried.
• Example 1 After exposure of the coating through a negative image to 1.14 meter candle seconds of tungsten light, the paper was developed for 13 seconds by the method of Example 1 to give a black and white positive of density 1.66 and contrast 1.84.
• Example 1 After exposure of the coating through a negative to 1.36 10 meter candle seconds of tungsten light the paper was developed for seconds by the method of Example 1 to give a black and white positive of density 1.97 and contrast 1.9.
• EXAMPLE 12 4-hydroxy-6-methyl-2-methylthio 5 piperidinomethyl- 1,3,3a,7-tetraazaindene (2.93 g.) and sodium hydroxide (0.4 g.) were dissolved in water (15 ml.). This solution was stirred, warmed to 45 C., and 10% gelatin solution ml.) was added. 1 M silver nitrate solution (10 ml.) was added slowly with efiicient stirring, and after stirring for 10 minutes 1 M potassium bromide/iodide solution containing 3% iodide (1.0 ml.) was added slowly. After stirring for a further 10' minutes, 5% chrome alum solu tion (2 ml.) was added and the emulsion so prepared was coated at a wet thickness of 0.03 inch on baryta. paper and dried.
• the paper After exposure of the coating through a negative to 1.136 10 meter candle seconds of tungsten light, the paper was developed for 20 seconds by the method of EX- ample 1 to yield a black and white positive of density 1.56 and contrast 1.5.
• EXAMPLE 13 4 hydroxy-S-hydroxyethylethylaminomethyl-6-methyl- 1,3,3a,7-tetraazaindene (2.51 g.) and sodium hydroxide (0.35 g.) were dissolved in water (15 ml.) This solution was stirred, warmed to C., and 10% gelatin solution (35 ml.) was added. 1 M silver nitrate solution (10 ml.) was added slowly with efficient stirring and after stirring for 10 minutes 1 M potassium bromide/iodide solution containing 3% iodide (1.0 ml.) was added slowly. After stirring for a further 10 minutes, 5% chrome alum solution (2 ml.) was added and the emulsion so prepared was coated at a wet thickness of 0.003 inch on baryta paper and dried.
• Example 1 After exposure of the coating through a negative to 1.137 10 meter candle seconds of tungsten light, the paper was developed for 45 seconds by the method of Example 1 to yield a black and white positiveof density 1.3 and contrast 0.75.
• EXAMPLE 14 S-diethylaminomethyl-4-hydroxy 2 methylthio-l,3,3a, 7-tetraazaindene (2.67 g.) was dissolved in water (15 ml.). This solution was stirred, warmed to 45 C., and 10% gelatin solution (35 ml.) was added. 1 M silver'nitrate solution (10 ml.) was added slowly with efficient stirring and after stirring for 10 minutes, 1 M potassium bromide/ iodide containing 3% iodide (1.0 ml. was'added slowly. After stirring for a further 10 minutes, 5% chrome alum solution (2 ml.) was added and the emulsion so prepared was coated at a wet thickness of 0.003 inch on baryta paper and dried.
• Example 1 After exposure of the coating through a negative to 1.5l6 l0 meter candle seconds of tungsten light, the paper was developed for 40 seconds by the method of Example 1 to give a black and white positive of density 1.6 and contrast 1.6.
• a light-sensitive composition comprising,
• a silver salt of a tetraazaindene having the general formula wherein R is a hydrogen atom, an alkyl group, an aralkyl group, or an alkylthio group; R and R are a hydrogen atom, a lower alkyl group, or a substituted alkyl group, or R and R together with the adjacent nitrogen atom form a heterocyclic ring; and Y is a hydrogen atom, an alkyl group, an alkylthio group, an aryl group or an amino group; and an intimately associated portion of a silver halide of amount sufi'icient to provide a weight ratio of silver in the silver halide to silver in the light-sensitive composition of from 0.001/ 1 to 0.5/ 1. 2.
• the composition of claim 1 wherein said weight ratio is not greater than about 0.1/1.
• composition of claim 1 additionally comprising a water-soluble binder.
• composition of claim 3 wherein said binder is gelatin.
• composition of claim 3 wherein said binder is polyvinylalcohol.
• composition of claim 1 additionally comprising a spectral sensitizer for silver halide.
• a photographic element comprising a base and at least one layer having a light-sensitive composition comprising a silver salt of a tetraazaindene having the general formula:
• R is a hydrogen atom, an alkyl group, an
• aralkyl group, or an alkylthio group R and R are a hydrogen atom, a lower alkyl group, or a substituted alkyl group, or R and R together with the adjacent nitrogen atom form a heterocyclic ring; and Y is a hydrogen atom, an alkyl group, an alkylthio group, an aryl group or an amino group; and an intimately associated portion of a silver salide such that the weight ratio of silver in the silver halide to silver in the light-sensitive composition is from 0.001/1 to 0. 5/ 1. 8. The photographic element of claim 7 wherein said weight ratio is not greater than about 0.1/1.
• said at least one layer additionally comprises a water-soluble binder.
• the photographic element of claim 7 additionally comprising a spectral sensitizer for silver halide.
• said spectral sensitizer is a cyanine or merocyanine dye.
• the photographic element of claim 7 additionally comprising a layer containing a developer for silver halide.
• Method of producing a photographic element comprising reacting in aqueous media a tetraazaindene having the 16. The method of claim 15 wherein said developer is general formula a hydroquinone developer.
• N N 17 A photographic image reproduction produced from El R Y Y the photographic element of claim 7.
• N-CH2 5 References Cited R2 H UNITED STATES PATENTS 2,835,581 5/1958 Tinker et al 96-107 wherein R is a hydrogen atom, an alkyl group, an 3 418 130 12/1968 Stevens et a1 aralkyl group, or an alkylthio group with from 0.5 to 10 3462272 8/1969 Duflin et a1 1.5 molecular equivalents of a water-soluble silver 3375114 8/1968 Hayakawa 5 96 94 salt; R and R are a hydrogen atom, a lower alkyl 3519426 7/1970 Halwig group, or a substituted alkyl group, or R and R together with the adjacent nitrogen atom form a hetero- FOREIGN PATENTS cyclic ring; and Y is a hydrogen atom, an alkyl group, 15 751,867 1/1967 Canada 9 6-
• R R N N R R N N Y Y should be k Y Y m-cll k l /N-CH R R s OH Column 8, line 57 "salide" should be -halide-.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (6)

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• 1968
  • 1968-01-08 GB GB114668A patent/GB1230642A/en not_active Expired
• 1969
  • 1969-01-03 US US788933A patent/US3689270A/en not_active Expired - Lifetime
  • 1969-01-07 CA CA039497A patent/CA918989A/en not_active Expired
  • 1969-01-07 FR FR6900075A patent/FR2000052A1/fr active Pending
  • 1969-01-08 DE DE19691900780 patent/DE1900780A1/de active Pending
  • 1969-01-08 JP JP691369A patent/JPS53296B1/ja active Pending
  • 1969-01-08 BE BE726623D patent/BE726623A/xx not_active IP Right Cessation

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