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
  • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

• benzene diazonium compounds carrying in 4-position to the diazo group a tertiary amino group which is substituted by alkyl or aralkyl groups or whose nitrogen atom is a component of a heterocyclic radical.
• These compounds may contain further substituents at the benzene ring, e.g., alkyl or alkoxy groups, preferably in 2- or 5-position to the diazo group.
• the light-sensitivity is considerably increased by the presence of an alkoxy group in S-position to the diazo group, while the same group, when in 2-position, de creases the light-sensitivity, but improves the thermic stability of the compound concerned.
• a combination of one alkoxy group each in the 2- and in the 5-position of the benzene ring which results in highly light-sensitive and at the same time stable diazonium compounds, has proved particularly suitable for practical purposes.
• the light-sensitivity may also be influenced by the type of the tertiary amino group in the 4- position. It is increased, e.g., by the presence of a pyrrolidino radical in this position.
• the radicals attached to the nitrogen atom affect mainly the coupling speed of the diazo compounds.
• Lower alkyl groups cause a lower coupling speed than do those with longer carbon chains or aralkyl groups.
• Heterocyclic radicals instead of a tertiary amino group with aliphatic radicals also normally cause an increase in the coupling speed, but there are wide differences in this respect, e.g., between the readily coupling morpholino compounds and the relatively slow-coupling pyrrolidino compounds.
• the carbon chains of the alkoxy groups in the benzene nucleus may be extended.
• the readily coupling compounds are used mainly for one-component materials, while the United States Patent 0 See less rapidly coupling compounds are used for two-component materials.
• diazo compounds of greater coupling speed it is particularly desirable to replace the alkaline developer solutions normally used hitherto with solutions having a neutral or weakly acid reaction, because such solutions are considerably more stable than alkaline solutions.
• the coupling reaction proceeds considerably more slowly at lower pH-values, so that the choice of highly active diazo compounds available for this purpose is very limited.
• the invention employs a diazotype material with a light-sensitive one-or two-component layer containing a light-sensitive diazonium compound which is derived from unilaterally diazotized p-phenylene diamine.
• a material is provided which contains as the light-sensitive compound a diazonium compound corresponding to the general formula:
• R and R stand for unsubstituted or substituted alkyl, aralkyl or cycloalkyl groups, or form an unsubstituted or substituted heterocyclic radical with the nitrogen atom,
• R stands for hydrogen, an alkoxy group, or a fiuorinated alkoxy group
• R and R stand for hydrogen, halogen, alkyl, alkoxy, or
• X is the anion of the diazonium group
• radicals R and R are hydrogen, and at least one of the radicals R R and R is a fluorinated alkoxy group.
• the diazonium compounds of the present invention are distinguished by a coupling speed which is considerably 3 higher than that of compounds containing unsubstituted alkoxy groups instead of fiuorinated alkoxy groups.
• the coupling speed increases about equally when one of the groups R R or R is the fluorinated alkoxy group.
• Compounds having two fluorinated alkoxy groups possess an even higher coupling activity.
• the light sensitivity of the compounds with fluorinated alkoxy groups corresponds approximately to that of the corresponding compounds having unsubstituted alkoxy groups; it is, however, surprisingly increased when a fluorinated alkoxy group is in o-position to the diazo group.
• the fluorinated alkoxy radicals have not more than 5 carbon atoms, because the compounds become too difiicultly soluble or surface-active with longer carbon fluoride chains.
• the alkyl radicals in the tertiary amino group are such as have no more than 5 carbon atoms, and the radicals may contain further substituents in known manner, e.g., halides, hydroxy or amino groups, etc., or straight or branched chains.
• the cycloalkyl and arakyl groups contain not more than carbon atoms, benzyl and substituted benzyl groups or cyclohexyl and substituted cyclohexyl groups being preferred.
• R and R form a heterocyclic radical with the tertiary nitrogen atom
• this radical may be derived in known manner, e.g., from pyrrolidine, piperidine, piperazine, N-methyl-piperazine, thiomorpholine, morpholine, Z-methylmorpholine, 2,6-dimethyl-morpholine, hexamethyleneimine, etc.
• R and R are alkyl groups, they contain normally not more than 2 carbon atoms, methyl groups being preferred.
• the substituents at the benzene nucleus may also be the alkoxy radicals frequently used in the diazotype art. These radicals, which may carry further substituents, such as hydroxy groups, may contain up to about 5 carbon atoms in a straight or branched chain; methoxy, ethoxy, isopropoxy, n-butoxy, isobutoxy, hydroxyethoxy, ethoxyethoxy groups are exemplary.
• the new diazonium compounds provided in accordance with the present invention are separated in the normal manner in the form of their stable double salts or complex salts. Their compatibility with the usual stabilizers and other additives, such as citric acid, sulfosalicylic acid, thiourea, naphthalcne-1,3-trisulfonic acid, zinc chloride etc., is good.
• Paper, transparent paper, transparentized paper, cellulose ester films and plastic films capable of being sensitized with diazo compositions may be used as supports in the normal manner.
• the new compounds may be prepared analogously to known processes by one of the following procedures:
• (A) l-chloro-2-nitro-4-alkoxybenzene is reacted in a polar solvent and in the presence of an alkali with a fluorinated alcohol, e.g., with 2,2,2-trifluoro ethanol, 3,3,2,2- tetrafluoro propanol, or 5,5,4,4,3,3,2,2-octafluoro pentanol.
• a fluorinated alcohol e.g., with 2,2,2-trifluoro ethanol, 3,3,2,2- tetrafluoro propanol, or 5,5,4,4,3,3,2,2-octafluoro pentanol.
• the nitrohydroquinone diether thus obtained is reduced, diazotized, and then converted by the method of Sandmeyer into the corresponding chlorine compound. After nitration in p-position to the chlorine atom, this compound is then reacted with secondary amines, preferably with heterocyclic bases.
• heterocyclic bases examples include: pyrrolidine, morpholine, piperidine, piperazine, thiomorpholine, and the substitution products thereof.
• the basically substituted nitrohydroquinone ethers thus produced are reduced and then converted in the usual manner into the corresponding diazonium compounds.
• the new diazonium compounds may also be prepared by other methods, e.g., by reacting appropriately substituted phenolates with fluorinated alkyl bromides or alkyl iodides or with fiuorinated sulfonic acid or p-toluenesulfonic acid alkyl esters and processing further in the manner outlined above.
• Example 1 A photoprinting base paper normally used for diazotype purposes which was provided on one surface with a precoat of colloidal silica and polyvinyl acetate, was coated on the precoated side with an aqueous solution containing, per 100 ml. of solution:
• the finished photoprinting material was image-Wise exposed under an original and developed with ammonia. Images of a neutral blue were obtained on a clear white background.
• Example 2 A polyester film coated with a cellulose acetate lacquer was coated with a solution of the following composition and dried:
• the color shade of this material had a slightly cltl'lc redder tint 4.0 g of the sodium salt of naphthalene-1,3,6-tr1sulfon1c
• a material which has been prepared acld and according to the same recipe but with the known diazoof the dlazonlum p d r I-amm nium compound from 1-amino-4-morpholino-2,5-dieth- (N yl)' oxy-benzene, in the form of the Zinc chloride double trlfluoroethoxy)benzene: the form of the tetfafluosalt, the final point of coupling was reached distinctly borateearlier with the material according to the invention.
• the d d d v actinic opacity of the material according to the invention an me was also distinctly better.
• the fimshed photoprmtlng material was lmage-wlse exposed under a transparent original and then developed EXample 3 with a solution which contained, per 100 ml. of solution:
• a photoprinting base paper customarily used for diazotype purposes which was provided on one surface with 0330 phlorQgluclPol a precoat of colloidal silica and polyvinyl acetate, was 9-600 of ms?dlum curate coated on the precoated side with an aqueous solution g k fg which contained, per 100 ml.
• R is an alkyl group having 1-5 carbon atoms or an aralkyl group
• R is an alkyl group having 1-5 carbon atoms
• R and R together form a saturated 5, 6 or 7 membered heterocyclic radical with the nitrogen atom
• R is a hydrogen, an alkoxy group having l-S carbon atoms, or an alkoxy group having fluorine substitution to the carbon atoms of the alkoxy group wherein the alkoxy group has 1-5 carbon atoms,
• R is a hydrogen, a halogen, an alkoxy group having 1-5 carbon atoms, or an alkoxy group having fluorine substitution to the carbon atom of the alkoxy group wherein the alkoxy group has 1-5 carbon atoms and R is a hydrogen or a halogen, and
• X is the anion of the diazonium compound
• radicals R and R are hydrogen and at least one of the radicals R or R is an alkoxy group having flourine substitution to the carbon atoms of the alkoxy group.
• Diazotype material comprising a support and a light-sensitive composition coated thereon, said composition comprising a diazonium compound according to claim 1.
• Diazotype material according to claim 2 having an azo dye coupler compound capable of forming an azo dye with said diazonium compound in the light-sensitive composition.
• Diazotype material according to claim 2 wherein said compound is a zinc chloride double salt of a 4-dimethylamino 6 chloro-S-(2',2,2-trifluoroethoxy)-benzene diazonium compound.
• Diazotype material according to claim 2 wherein said compound is a tetrafluoborate salt of a 4-(N-methyl- N benzyl) amino 2 chloro-5-(3',3,2,2'-tetrafiuoropropoxy)-benzene diazonium compound.
• Diazotype material according to claim 2 wherein said compound is a tetrafiuoborate salt of a 4-[N-(2'- acetyloxyethyl)-N-benzyl]-amino-2-chloro 5 (2',2,2'- trifluoroethoxy)-benzene diazonium compound.
• Diazotype material according to claim 3 wherein said compound is a zinc chloride double salt of a 4-pyrrolidino 2-n1ethoxy-5-(2',2 ,2-trifluoroethoxy) -benzene diazonium compound.
• Diazotype material according to claim 3 wherein said compound is a zinc chloride double salt of a 4- morpholino-Z-methoxy-S-(2',2,2'-trifiuoroethoxy) benzene diazonium compound.
• Diazotype material according to claim 3 wherein said compound is a zinc chloride double salt of a 4- morpholino-2- 2',2',2'-trifiuoroethoxy -5-methoxy benzene diazonium compound.
• Diazotype material according to claim 3 wherein said compound is a zinc chloride double salt of a 4-piperidino-Z-methoxy-S-(2,2',2-trifluoroethoxy) benzene diazonium compound.

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• Chemical & Material Sciences (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)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
• Pyrrole Compounds (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

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Cited By (3)

Citations (8)

• 0
  • ZA ZA6801453D patent/ZA6801453B/xx unknown
• 1967
  • 1967-03-08 DE DE1797615A patent/DE1797615C2/de not_active Expired
  • 1967-03-08 DE DE1967K0061652 patent/DE1572098B2/de active Granted
• 1968
  • 1968-02-27 NL NL6802734A patent/NL6802734A/xx not_active Application Discontinuation
  • 1968-03-04 BR BR197370/68A patent/BR6897370D0/pt unknown
  • 1968-03-05 BE BE711687A patent/BE711687A/fr unknown
  • 1968-03-05 AT AT215568A patent/AT282345B/de not_active IP Right Cessation
  • 1968-03-06 CH CH331568A patent/CH489823A/de not_active IP Right Cessation
  • 1968-03-06 ES ES351305A patent/ES351305A1/es not_active Expired
  • 1968-03-06 SE SE2954/68A patent/SE342703B/xx unknown
  • 1968-03-06 GB GB10909/68A patent/GB1197376A/en not_active Expired
  • 1968-03-07 FI FI0623/68A patent/FI44089B/fi active
  • 1968-03-07 DK DK93968AA patent/DK116489B/da unknown
  • 1968-03-08 FR FR142869A patent/FR1559274A/fr not_active Expired
  • 1968-04-24 US US723931A patent/US3539347A/en not_active Expired - Lifetime

Patent Citations (8)

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