Classifications

• • 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
  • G03C1/52—Compositions containing diazo compounds as photosensitive substances
  • G03C1/56—Diazo sulfonates

Definitions

• the aromatic diazo compound is incorporated into the light sensitive layer of thecar rier, which may be opaque or transparentized paper, films such as cellulose ester or cellulose ether film, regenerated cellulose bodies, ceram c surfaces, glass, metallic or wood surfaces, and after exposure under the orig nal pa tern. to be copied the undecomposed aromat c diazo compound is developed by contacting the exposed layer with a solut on of the coupling component necessary to produce the ultimately desired image.
• the developing solution containing the coupling component should be alkaline.
• diazo compounds which are 8 Claims. (Cl. 95-7) developable in acid solution and in such cases the solution of the coupler will be acid.
• the aromatic diazo compound and the coupling component necessary to 1 produce the dye image are both incorporated in the light sensitive layer on the carrier. In this case, development of the dye image is eifected after exposure by contacting the exposed light sensitive layer with ammonia fumes.
• diazo compounds For optimum results in the two-component process, it is necessary to limit the selection of diazo compounds to those which will be inert to reaction with the coupling component while in the coating solution and the light sensitive layer prior to development.
• the most satisfactory diazo compounds for this purpose have been found to be those which are derived from aromatic p-diamines and o-aminonaphthols; A few others have been found suitable, particularly when addition agents are employed which tend to retard the coupling function. For the most part, however, premature coupling of the dye components takes place when other types of diazo compounds are used.
• This class of compounds may be designated as the diazo sulfones. They are incapable of coupling with azo dye coupling components in the absence of the alkaline coupling medium and hence, like the N-nitroso-N-arylamides of Patent 2,411,811, two-component light sensitive layers produced from these diazo sultones can be stored indefinitely without danger oi precoupling of the dye components taking place under ordinary conditions of storage.
• the diazo sulfones of this invention will couple readily with azo dye coupling components in the presence of an alkaline medium, such as ammonia iumes, to produce an azo dye image in any desired color.
• R represents a radical derived from a compound having an aromatic character such as benzene, naphthalene, anthracene, quinoline, carbazole, indole and the like
• R represents a radical derived from a compound having an aromatic character as above or from a compound having an aliphatic character such as methane, ethane, butane, pentane, hexane, cyclohexane, methylcyclohexane, octane, decane, dodecane, hexadecane, octadecane and the like.
• the diazo sulfones may have certain substituents on the aromatic nuclei, R.
• benzylamino such as benzylamino; heterocyclic amino, such as and Z-pyridylamino; alkyl, such as methyl, ethyl, butyl, lauryl and octadecyl; alkoxy, such as methoxy and butoxy;
• aryioxy such as phenoxy
• aliphatic acylamino such as acetamido
• aromatic acylamino such as benzamido
• the diazo sulfones may be represented by the general formula wherein R and R represent radicals derived irmn compounds of an aromatic character as defined above, x has the same meaning as above and Y represents a member of the class consisting of allwlamino, such as methylamino, diethylamino, p,p'-dihydroxyethylamino and N-methyl- N-fl-hydroxyethylamino groups; arylamino, such as phenylamino; aralkylamino, such as benzylamino; heterocyclic amino, such as 2-benzothiazolylamino and 2-pyridylamino; alkyl, such as methyl, ethyl, butyl, lauryl and octadecyl; alkoxy, such as methoxy and butoxy; aryloxy, such as phenoxy; aliphatic acylamino, such as acetamido;
• X and Y may contain solubilizing groups such as sulfo, carboxy and polyoxyethylene groups.
• the diazo sulfones in general, are prepared by the reaction of a diazo compound with a sulilnic acid, oxidation of a fl-aryl sulfonhydrazide, condensation of a diazonium salt with a sulfonamide or decomposition of a diazo thiosulfate.
• Schematic reactions for these processes of preparing the diazo sulfones are as follows:
• RN N-SOzR'+HX 4.
• Decomposition of a diazothiosulionate RN N+X-+KSSO:R'
• Suitable aryldlazosulfones include diphenylamine 4 diazo (p-aminophenyl) -sulione, 4--(N-ethyl-N-benzylamino) -benzenedlazo- (p-aminophenyl) -sulfone, 4-morpholinobenzenediazo- (p-aminophenyl) -sulfone, p- (N-methyl-N- fl-hydroxyethylamino) -benzenediazo (p-aminophenyl) -sulfone, 2,5-dimethoxy 4 benzamidobenzenediazo- (p-acetaminophenyl) -sulfone, 2,5- dimethoxy 4 benzamidobenzenediazo- (p-methtile amines or solutions of mild alkalis,
• Examples of coupling components which may be utilized with the diazo suliones in this process are 2,3-dihydroxynaphthalene, resorcinol, phloroglucinol, p-naphthol, a-naphthol, 3,5-dimethylphenol, 2,4-dihydroxybenzenesulfonamide, 1 phenyl-3-methylpyrazolone-5, acetoacetanilide, 5-methyl resorcinol, 1-dimethylaminomethyl-2- naphthol, 3-(fl-dimethylaminoethoxy) -naphthol- 2, esters of phloroglueinol monocarboxylic acid, and the couplers disclosed in United States Patents 1,822,065, 1,989,065, 2,150,565, 2,196,950, 2,212,959, 2,333,038, 2,245,628, 2,246,425 and 2,286,656.
• the process of this invention is carried out by coating a suitable base, such as paper, a cellulose ester, cellulose ether or regenerated cellulose film, a ceramic material, a textile material, a gelatinized surface or a metallic surface with a coating preparation containing the diazo sulfone compound.
• a suitable base such as paper, a cellulose ester, cellulose ether or regenerated cellulose film, a ceramic material, a textile material, a gelatinized surface or a metallic surface
• an azo dye coupling component such as one of the coupling components mentioned above, a mild acid such as citric, tartaric, acetic, oxalic, maleic acid or a strong acid such as sulfosalicylic acid and a solvent.
• the diazosulione unlike the corresponding diazonium salts, are soluble in water-miscible organic solvents such as acetone, methyl ethyl ketone, methanol, ethanol, isopropanol and the coating mixture can, therefore, be applied in the form of solutions in such solvents or aqueous mixtures thereof.
• the coating mixtures can also be applied to the base in the form of their water solutions if the diazo sulfone contains water solubilizing groups or if the coating mixture contains a hydrotropic reagent, such as sodium toluenesulfonate, potassium xylenesulfonate, sodium cymenesulfonate, sodium salicylate and the like.
• the coating of the selected support is efiected in the usual manner by applying the coating solution to the surface of the carrier with a trough and doctor blade or by spraying.
• the coated material is then dried and exposed under original positive or negative picture or drawing and developed by treatment with ammonia vapor or other suitable alkaline materials, such as v0 1 e coating medium or vehicle for the application of the light sensitive layer, in addition to water and organic solvents, may be an aqueous gelatin or a resinous material such as cellulose acetate hydrogen phthalate suitably liquefied by organic solvents or otherwise for coating purposes.
• the coupling reaction in the case of the diazo suli'ones is a direct action which takes place readily in the presence of proper alkaline coupling medium. The exact mechanism of the coupling reaction is not definitely known.
• Example 1 A diazotype paper stock was coated with a coating solution of the following composition 1.0 gram 2,5-diethoxy-4-benzamidobenzenediazo (p-acetamidophenyl) -sulfone O CzHe I c-mc ONHQNm-S OQNHC 0 on,
• the 2,5-diethoxy 4 benzamidobenzsnediazo- (p-acetamidophenyl) -sulfone may be obtained by diazotizing a suspension of 8.4 grams (0.025 mol) of 2,5-diethoxyi-benzamidoaniline hydrochloride in 2.0 cc. concentrated hydrochloric acid, 8.0 cc. formic acid and cc. water with a solution of 1.8 grams (0.026 mol) sodium nitrite in 10 cc. water.
• Example 2 A diazotype paper stock was coated with a resinous coating solution of the following composition:
• Example 3 A coating solution for a diazotype was made up as follows:
• the combined solution was coated on a diazotype paper stock and allowed to dry.
• the thus diazotype sensitized paper consisting of a resinous layer of the cellulose acetate butyrate carrying the diazosulfone and the coupling component on the paper support was exposed under a positive original pattern and the image developed after exposure by contacting the exposed surface with ammonia vapors. The image of the original was developed to a purple azo dye.
• the 4 -diethylaminobenzenediazo (p-amlnophenyl) -sulfone of this example may be obtained as follows. A solution of 20.0 grams (0.1 mol) p-diethylaminoaniline hydrochloride in 75.0 00. water and 20.0 cc. concentrated hydrochloric acid is diazotized with a solution of 6.9 grams (0.1 mol) sodium nitrite in 75.0 cc. water. This solution is then poured into a solution of 15.7 grams (0.1 mol) 4-aminobenzene sulflnic acid, 6.2 grams (0.05 mol) sodium carbonate monohydrate, 41.0 grams (0.3 mol) sodium acetate dihydrate and 250.0 cc. water. The resulting mixture is allowed to remain overnight in a refrigerator and the following day the orange color precipitate is removed by filtration,
• a diazotype coating solution was prepared in the following manner:
• the combined solution was coated on a sheet of diazotype paper stock and dried.
• the image of the original was reproduced in a brown azo dye.
• Example 6 A diazotype coating solution was prepared as follows:
• the combined solution was coated on a sheet of diazotype paper stock and dried.
• the thus sensitized diazotype was exposed under a positive original design and processed in the same manner as in the case of Example 4.
• a redorange azo dye image was produced.
• Example 7 A diazotype coating solution was prepared as follows:
• the combined solution was coated on a sheet of diazotype paper stock and dried.
• the thus sensitized diazotype was exposed under a positive original design and processed in the same manner as in Example 4.
• a yellow azo dye image was produced.
• Example 8 A diazotype coating solution was made up in the following manner:
• the combined solution was coated on a sheet of diazotype paper stock and dried. It was then exposed under a positive original design to ultraviolet radiations and developed by passing the exposed surface through a chamber containing ammonia fumes with which the exposed surface was brought into contact. The image of the original was reproduced in a reddish-purple azo dye.
• Dlaaotype photoprinting materials compris- 10 ing as the light sensitive element a light sensitive diazo sulfone of the following formula wherein R is an aromatic radical and R is a member of the group consisting of aromatic and aliphatic radicals.
• Diazotype photoprinting materials comprising as the light sensitive element a light sensitive diazo sulfone of the following formula wherein R and R are aromatic radicals.
• Diazotype photoprinting materials comprising as the light sensitive element a light sensitive diazo sulfone of the following formula wherein R and R are aromatic radicals and an azo dye coupling component.
• Diazotype photoprinting materials comprising a light sensitive layer on a suitable carrier, said light sensitive layer containing as the light sensitive element a diazo sulfone of the following formula wherein R and R are aromatic radicals and an azo dye coupling component.
• Diazotype photoprinting materials comprising a resinous layer on a paper carrier, said resinous layer containing as a light sensitive element a diazo sulfone of the following formula wherein R and R are aromatic radicals together with an azo dye coupling component.
• Diazotype photoprinting materials comprising a light sensitive layer on a. suitable carrier, said light sensitive layer containing 2,5- diethoxy- 4-benzamidodiazo-(p-acetamidophenyl) sulfone as the light sensitive element and an azo dye coupling component.
• Diazotype photoprinting materials comprising a light sensitive layer on a suitable carrier. said light sensitive layer containing 4-diethylaminobenzenediazo-(p-aminophenyl)-sulfone as the light sensitive element and an azo dye coupling component.
• Dlaaotype photoprinting materials comprising a light sensitive layer on a suitable carrier, said light sensitive layer containing d-morpholinobenzenediaso-(p-aminophenyll-sulfone as the light sensitive element and an azo dye coupling component.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Heat Sensitive Colour Forming Recording (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Thiazole And Isothizaole Compounds (AREA)

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Cited By (5)

Citations (2)

• 0
  • BE BE483794D patent/BE483794A/xx unknown
  • NL NL66139D patent/NL66139C/xx active
  • NL NL686816496A patent/NL141017B/xx unknown
• 1947
  • 1947-07-02 US US758702A patent/US2465760A/en not_active Expired - Lifetime
• 1948
  • 1948-06-04 GB GB15165/48A patent/GB649604A/en not_active Expired
  • 1948-06-28 FR FR988484D patent/FR988484A/fr not_active Expired
  • 1948-07-02 CH CH279648D patent/CH279648A/fr unknown
• 1949
  • 1949-01-01 DE DEP29262D patent/DE815301C/de not_active Expired

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