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
  • G03C1/61—Compositions containing diazo compounds as photosensitive substances with non-macromolecular additives
• • 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
  • G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives

Definitions

• This invention relates to a process for the production of diazotype films, that is, positive copy films for photographic purposes, as well as to the diazotype films produced by this process.
• diazo salts suitable for diazotype processes are water-soluble and have good affinity to cellulose
• diazotype films were initially produced on substrata of unesterified cellulose. Such films, however, have insufiicient tensile strength and tear easily. Attempts have, therefore, been made to incorporate the diazo salt into a gelatin layer and to apply the latter to cellulose acetate substrata which, although they are of sufiicient tensile strength and do not tear, do not themselves absorb the diazo salts, in a similar manner as is employed in the production of motion picture films on the basis of the silver bromide process.
• cellulose acetate substrata it is conventional to hydrolyze a top layer at the surface of cellulose acetate substrata and to apply light-sensitive diazo salts to the cellulose hydrate top layers of these films. According to this process, the gradation of the diazotype layer is improved by prolonged ageing, e.g. during 2 to 3 months.
• cellulose acetate material preferably cellulose-2V2 acetate is used as it is more easily and much more rapidly hydrolyzed than cellulose triacetate.
• improved gradation means that the gradations of density obtained with films according to the invention approach the ideal photographic gamma of 1, i.e. corresponding to an angle of the curve of 45, more closely than hitherto known diazotype films, and thus approach and/ or attain that of a silver-gelatin film.
• a film base consisting essentially of cellulose ester, such as cellulose acetate, namely cellulose diacetate, cellulose tri-acetate or, preferably, cellulose 2 /2-acetate; cellulose nitrate, or mixed esters of cellulose such as cellulose acetate-propionate, cellulose acetate-butyrate and the like cellulose lower alkanoates,
• cellulose ester such as cellulose acetate, namely cellulose diacetate, cellulose tri-acetate or, preferably, cellulose 2 /2-acetate
• cellulose nitrate or mixed esters of cellulose such as cellulose acetate-propionate, cellulose acetate-butyrate and the like cellulose lower alkanoates
• top layer on and substantially integral with said film base which top layer consists at least in its major portion or entirely of cellulose hydrate and has a thickness of about 5 microns to, preferably, not more than 10 microns, and
• novel photographic diazotype films are produced according to the invention by a first process which comprises:
• a hydrolyzing bath which contains per liter preferably about 2 to g. of alkali metal hydroxide or alkaline earth metal hydroxide, particularly sodium hydroxide or potassium hydroxide, and preferably 0.5 to 5 g. of the above-described pure, concentrated fluorescent light-filtering compound which is substantive to cellulose hydrate as defined and, optionally, a wetting and dispersing agent which is stable to alkali, e.g. a fatty alcohol sulfate.
• the cellulose acetate substrate is continuously treated in this solution for from about 2 to 20 minutes at about 40 to 95 C., excess bath liquid is removed, and the film rinsed in cold water and dried.
• the former can also be applied in a separate bath following the formation of the hydrolyzed top layer.
• the contrast of the diazotype layers according to the invention is surprisingly satisfactorily but not excessively decreased i.e. their gradation is decisively improved by the treatment according to the invention, without requiring any previous ageing of the light-sensitive film.
• fluorescent compounds have been used in the past in order to brighten the substrate after the diazo compound had been incorporated therein and in developing the diazotype material.
• amounts of 0.1 to maximally 0.2% by weight calculated on the amount of entire film material were incorporated into the top layer, in the case of cellulose acetate films, or into the entire body of the substrate in the case of paper.
• the above-defined fluorescent compounds are used for an entirely different purpose, namely for effecting a filtration of ultraviolet light, thus avoiding the known use of separate filters.
• these filtering substances surprisingly increase the affinity of the cellulose hydrate of the top layers for the diazo compounds which must be incorporated thereinto, according to the process according to the invention, subsequent to the treatment of the substrate, whereby the top layer of the latter is hydrolyzed and the fluorescent compounds are incorporated into the hydrolyzed top layer.
• Particularly suitable as light-filtering compounds usable according to the invention which are substantive to cellulose hydrate are soluble salts of a compound having acid, salt-forming groups, which compound, in its free acid form, is of the formula in which formulas Q represents a radical of the formula a radical of the formula B1 A T I l -N N wherein A represents hydrogen or lower alkyl,
• B represents an arylamino radical wherein aryl is an unsubstituted mononuclear or dinuclear carbocyclic aryl radical or such radical substituted with non-color-imparting, non-water-decomposable substituents;
• substituents are, in particular, sulfo, carboxy, lower alkyl, lower alkoxy, chloro, bromo, fluoro, sulfamyl, carbamyl, sulfamyl which is Nsubstituted by lower alkyl, hydroxy-lower alkyl, lower alkoxy-lower alkyl, hydroxy-lower alkoxy-lower alkyl, sulfophenyl or carboxy-phenyl, or lower alkyl-sulfonyl-sulfamyl, carbamyl which is N-substituted by lower alkyl, hydroxylower alkyl, lower alkoxy-lower alkyl, hydroxy-lower alkoxy-lower alkyl, sulfophenyl or carboxyphenyl, lower alkyl-sulfonyl, hydroxy-lower alkyl-sulfonyl, lower alkanoylamino, N-lower alkan
• B represents hydrogen, lower alkyl, lower alkoxy, hydroxy-lower alkoxy, lower alkoxy-lower alkoxy, amino, lower alkyl-amino, hydroxy-lower alkylamino, lower alkoxy-lower alkylamino, carboxy-lower alkylamino, sulfo-lower alkylamino, pyrrolidino, piperidino, morpholino or sulfophenylamino;
• Z represents the above-described groupings represented by Q as well as hydrogen, chlorine, bromine, fluorine or lower alkyl;
• One of X X Y and Y represents an SO H group, And each of the other Xs and Ys represents hydrogen, a lower alkyl, a lower alkoxy or the --SO H group.
• both X and Y are SO H.
• phenyl-N-lower alkyl-sulfamyl, phenylamino, chlorophenfluorescent compounds which are substantive to cellulose ylamino, bromophenylamino and carboxyphenylamino, hydrate and usable in the photographic diazotype malower alkoxy-carbonyl-phenylamino, sulfo-phenylamino, terials according to the invention are benzidine and lower alkyl-sulfonyl-phenylamino, lower alkoxy-sulfonyldibenzyl derivatives falling under the formulas phenylamino, sulfamyl-phenylamino, N-lower alkyl-sul- 10 famyl-phenylamino, N,N-di-lower alkyl-sulfonyl-phenyl- Q Q amino, N-phenyl-s
• SO3H H038 The following non-limitative examples illustrate the SOSH HOBS (3:0 invention. The temperatures are given therein in degrees Centigrade. Percentages are given by Weight unless expressly stated otherwise; g stands for gram and ml (I for milliliter.
• n is an interger ranging from Example 1 l to 2; F or they are dihydro-p-toluidine derivatives falling under The f of a ceuumse'm/PacHate havmg a the formulas 52% acetic acid content 1s sapomfied for 4 mmutes at 65 with a solution which, per litre of Water, contains 50 ml. of sodium hydroxide solution of 40 B, 3 g. of sodium C 30 salt of oleyl polyglycol ether sulphate (with 3 to 4 CH3 CH CH O-- groups) and 1.5 g.
• Water-soluble salts in particular sodium, potassium or ammonium salts of the above-defined stilbene derivatives in which the terminal groupings Q and Z are identical are particularly readily available and are, therefore, preferred.
• Suitable water-soluble cationic, light sensitive aryldiazonium compounds for use in the process according to the invention are those wherein aryl represents from one to two six-membered carbocyclic aromatic rings, i.e. benzene, napthalene or diphenyl nuclei, bearing substituents selected from the group consisting of Hydrogen, N-lower alkyl-amino, N,N-di-lower alkylamino, N-(hydroxy-lower alkyl)-amino, morpholino, pi-
• the film is continuously developed for one second at 90 in a solution which contains 38 g. of monosodium phosphate, g. of disodium phosphate, 20 g. of sodium formate, 10 g. of sodium tartrate, 10 g. of phloroglucine, 4.5 g. of resorcinol and 4 g. of napththol in 1250 ml. of Water, and then rinsed cold and dried.
• a solution which contains 38 g. of monosodium phosphate, g. of disodium phosphate, 20 g. of sodium formate, 10 g. of sodium tartrate, 10 g. of phloroglucine, 4.5 g. of resorcinol and 4 g. of napththol in 1250 ml. of Water, and then rinsed cold and dried.
• the concentration of the diazo salt is increased to 100 g. per litre, then the maximal black density of the positive copies is only improved to an inconsiderable extent.
• the cellulose acetate substate is treated for 1-5 minutes at 65 therein instead of for 4 minutes and afterwards the substrate is coated with 100 g. of diazo salt per litre in the same way, then after exposure and development, similar black densities as mentioned in Example 1 are obtained.
• the cellulose acetate layer becomes thinner by the longer saponi fication time which becomes undesirably apparent in the reduction of its tensile strength:
• R represents lower alkyl or benzyl
• R represents'lower alkyl
• R and R represent alkyl of from 1 to 5 carbon atoms
• X represents an acid radical
• R and R together with a nitrogen atom to which they are linked also represent a S-membered or 6-membered heterocyclic ring.
• the fluorescent compounds which enable the excessively high contrast of the diazotype material to be reduced and so bring out the desirable half tones, can also be replaced by non-fluorescent UV-absorbers for polymeric plastics.
• the diazotype films for positive copies according to this second aspect of the invention are characterized by an acceptable reproduction of the half tones of the subject and by good wear in use, particularly by improved stability to yellowing of the copies.
• Non-coloring and non-fluorescent, light stable UV absorbers correspond, for example, to the formula VIII
• the ring A can be substituted by chlorine, lower alkyl and alkoxy groups, aryloxy groups as well as, in the 2'- and/or 4-position, by hydroxyl groups
• the ring B can be substituted by chlorine, lower alkyl groups, in the 4-position by alkoxy groups or the hydroxyl group and, in the 3- or S-position, by a benzoyl group.
• a third class of light stable, non-coloring UV absorbers corresponds to the formula In this formula X represents an optionally substituted alkoxy, alkylamino or dialkylamino group and the henzene rings A and B can be substituted, e.g., by chlorine, lower alkyl and alkoxy groups.
• a fourth class of non-coloring UV absorbers corresponds to the formula OH 9 H
• chlorine and alkyl groups can be substituents in the 2- to 9-positions and alkoxy and hydroxyl groups can be substituents in the 3-, 7- and 9-positions.
• Aonther class of light stable, non-coloring UV absorbers corresponds to the formula wherein the phenyl rings can be substituted by chlorine, alkyl and alkoxy groups.
• Example 32 /N (EH3 4 M l 1
• the film is then rinsed with cold, softened water, treated for 2 minutes at 35 with a solution of ml./1itre of formic acid, again rinsed and dried in a stream of 60-70 warm air.
• the film is then passed through a coating device which, by a rubber roller rotating in the diazo solution, applies a solution of 50 g. of 4-diazo-2-ethoxydiphenylamine which is free of nitrogen oxides, g. of thiourea, 5 g. of stearyl polyglycol ether (with 20 ethyleneoxy groups) and 5 g. of acetic acid per litre of water.
• a coating device which, by a rubber roller rotating in the diazo solution, applies a solution of 50 g. of 4-diazo-2-ethoxydiphenylamine which is free of nitrogen oxides, g. of thiourea, 5 g. of stearyl polyglycol ether (with 20 ethyleneoxy groups) and 5 g. of acetic acid per litre of water.
• the film is immediately dried with 30 warm air and packed while excluding light.
• This film is well suited for copying positive cin films in a usual copying machine with a mercury vapour or xenon lamp.
• the film After exposure, the film is continuously developed for 5 seconds at in a solution which contains, per litre of water,
• Example 33 the formula I SOaH SOQH 15 Afterwards, the film is finished in the same way as described in Example 32. A diazotype film having similar properties is obtained. Instead of the 2-(2-hydroxyphenyl)-benzotriazole compound mentioned above, one of the other compounds listed in Example 32 can be used.
• Example 34 (a) A cellulose acetate film is continuously saponified at 70 in a solution of the composition described in Example 32 but which, instead of the benzotriazole compound, contains 2 g. of the following compound I OH On emergence of the film from the saponification bath it is squeezed out and, without rinsing, passed through a second tank containing a 50 Warm solution of 20 mL/Iitre of formic acid. Afterwards, the film is thoroughly rinsed with cold water, dried and, as described in Example 32 treated with a light-sensitive diazonium compound.
• a diazotype film is obtained which, on exposure and coupling, satisfactorily reproduces the half tones of the subject.
• a diazotype photographic positive copy film comprising (a) a film base consisting essentially of cellulose alkanoate,
• top layer on and substantially integral with said film base which top layer consists in its major portion of partially hydrolyzed cellulose acetate and has a thickness of from about 5 to microns and contains in fine dispersion therein (i) a cationic light-sensitive aryl diazonium compound suitable as diazotype developable component, and
• non-color-imparting greenish-blue to violet fluorescing compound selected from the group consisting of the sulfonated stilbenes, sulfonated dehydrothiotoluidines, sulfonated diphenyls and sulfonated dibenzyls which are capable of decreasing the contarst of the said aryl diazonium compound sufficiently to adjust the photographic gamma of said film material closer to l, and have a maximum light-absorptivity in the ultraviolet range between about 300 and 390 millimicrons.
• component (i) is present in amounts ranging from about 0.02 to 0.2 grams per square meter, and component (ii) is present in amounts rangcellulose hydrate-substantive,
• said fluorescing compound (ii) is a sulfonated stilbene possessing, per molecule, from one to not more than two stilbene nuclei and from one to not more than two s-triazinyl-(2)-amino radicals linked to the stilbene nucleus via said amino grouping, the 4- position of which s-triazinyl grouping is occupied by a mononuclear carbocyclic arylamino substituent and the 6-position of which s-triazinyl ring is free from arylcontaining substituents.
• said fluorescing compound (ii) is a sulfonatecl stilbene possessing, per molecule, from one to not more than two stilbene nuclei and from one to not more than two s-triazinyl-(2)-amino radicals linked to the stilbene nucleus via said amino grouping, at least one of the positions 4 and 6 of which s-triazinyl grouping is occupied by a mononuclear carbocyclic arylamino substituent.

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• Engineering & Computer Science (AREA)
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• General Physics & Mathematics (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Luminescent Compositions (AREA)

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Citations (17)

• 0
  • US US510379A patent/US3365293A/en not_active Expired - Lifetime
• 1963
  • 1963-06-06 CH CH712063A patent/CH433006A/de unknown
  • 1963-06-24 AT AT505663A patent/AT244754B/de active
• 1964
  • 1964-06-05 DE DEG40773A patent/DE1297986B/de active Pending
  • 1964-06-05 GB GB23445/64A patent/GB1059856A/en not_active Expired
  • 1964-06-05 BE BE648911D patent/BE648911A/xx unknown
  • 1964-06-05 FR FR977190A patent/FR1403153A/fr not_active Expired

Patent Citations (17)

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