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
• • 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

Definitions

• This invention relates to photosensitive material and more particularly to light sensitive photographic material containing diazo and tetrazo compounds of the diphenylamine group as light sensitive compound, and to a process of making same.
• Diazo compounds of bases of the diphenylamine series stabilized by means of aluminium or magnesium salts, and their coupling or, developing with 2,3-hydroxy naphthoic acid arylides and other coupling components of the naphthol AS group are known. It is furthermore known that said diazo and tetrazo salts of bases of the diphenylamine series are unstable in aqueous solution, for instance, in the dyeing bath, and on carriers. Such compositions, in the undeveloped state, can be stored, at the most, for 2-3 days only.
• Another object of the present invention is to provide a process of making such light sensitive photographic material and of substantially increasing the sensitivity to light of such material.
• Said ripening process furthermore imparts to the light sensitive layer more uniform gradation than is exhibited by such layer directly after applying said diazo and tetrazo salts to the cellulose hydrate layer.
• Such a more uniform gradation is of great advantage in the production of satisfactory photographic pictures.
• the optimum gradation being obtained after a ripening period of about 14 days. The higher the initial gradation the lesser its reduction on ripening. When starting with initial gradations of 1.5, 2 and 3 these are reduced to 0.8, 1.6 and 2.4 respectively.
• the sensitivity to light of said diazo and tetrazo salts can be further improved by using said salts in their 2,893,866 Patented July 7, 1959 purest form, i.e., without any addition of filler salts as they were present in the diazo compounds heretofore known in the dyestulf industry.
• Gradation of the finished color picture can readily be affected and adjusted and can be considerably varied from soft to hard, i.e., from semitone for lavender prints to high contrasts for outline drawings.
• gradation depends to a considerable extent upon the size of the dyestuif molecules.
• the molecular size is to be understood as particle size.
• Optimum gradation is achieved with compounds of the smallest molecular size. This is probably due to the fact that larger particles tend to form colloidal particles in solution.
• the salts used in accordance with the present invention are salts e.g. chlorides or sulphates of diazonium compounds, which in an aqueous medium form true molecular solutions, which obey to the laws of electrolytic dissociation, the development of the particle size is in close relationship to azeocomponents used in the coupling reaction (e.g. derivatives of beta-hydroxynaphthoic acid) which in turn form colloidal solutions in aqueous media.
• azeocomponents used in the coupling reaction e.g. derivatives of beta-hydroxynaphthoic acid
• the diazo and tetrazo compounds of the diphenylamine series are charged in aqueous solution with such a strongly positively polar-charge that the strongly negatively polar cellulose hydrate surface as it is obtained, for instance, on superficially saponifying acetyl cellulose by means of alkali hydroxide, binds so many dyestuff molecules that satisfactory depth of color is combined with sufiicient gradation and is achieved even on sensitizing said cellulose hydrate foil only on one side.
• diazo and tetrazo salts of the I diphenylamine series can be employed for making photographic light sensitive materials, since it was known that said salts are unstable in aqueous solution. Their combination with a cellulose hydrate carrier is surprisingly stable. A further increase in stability is achieved by adding acetic acid to the dye bath.
• the pH-value of the layer should, however, not exceed 7. Any other suitable aliphatic carboxylic acid like citric acid or tartaric acid may also be used.
• the diazo and tetrazo salts of the diphenylamine series are suitable not only for producing so-called black-andwhite pictures but also for producing colored pictures.
• Example 1 An acetyl cellulose film is superficially saponified by a treatment with 5% sodium hydroxide solution at a temperature of 65 C. during 12-18 minutes and is thereby partly reconverted into cellulose hydrate on its surface.
• Said alkaline bath contains 60 ml. of a suitable leveling agent per liter, preferably an addition product of ethylene oxide to alkyl phenols having 12-14 carbon atoms 2;sas,see s as their alkyl chain.
• Such addition compounds correspond, in general, to the formula wherein Ris an alkyl radical having from 12-14 C-atoms and. nan integer from 3-19,.preferably 11-13.
• Thepreferred thickness of the hydrolised layer being about 0.01 mm., but may vary between 0006-0012.
• An. aqueous solution of the. tetrazo. compound of p aminodiphenylamino-p azo-4-amino 5-ethoxy-2-toluene instabilizedform is appliedtosaidsuperficiallysaponified acetyl celluloseby means of rubber rollers.
• Example 2 An. aqueous solution of the stabilized diazo compound of 4t-amino diphenylaminesulfateon chloride which contains 20 cc. of acetic acid and 100 g. of said diazo compound perlitenis applied to superficiallysaponified cellulose acetate foil, asdescribedin Example. 1.
• Example 4 An aqueous solution of the stabliized diazo compound of 4-amino 3-methoxy diphenylamine which contains 12 cc. of acetic, acid and 100 g. of said diazo compound per liter, is appliedtto a superficially saponifiedcellulose acee tate'foil, as described in Example 1.
• Example 5 A cellulose hydrate-film prepared asin- Example 1 is treated with a solution containing 100 gms. of the diazo compound of 4-amino-4rethoxydiphenylamine in one liter-of water containing 16 ml acetic acid. After exposure under a pattern and development with 2.3-hydroxyanthracene carboxylie acid-ortho-toluidide a green picture is obtained.
• Example 6 A11- acetyl cellulose film treated according to one of the foregoing Examples 1-5 with a diazo compound after exposure is treated at a temperature of '20 C. with an aqueous solution of the coupling component 2.3-hydroxy-.
• Example 7 An acetyl cellulose filmpretreated according to one of the foregoing Examples 1-5 with a diazo compound, after exposure is treated-with an aqueous solution of the coupling component 2,-3-hydroxynaphthoic acid-orthoanisidide at any desired temperature.
• the particle size of the dye will in any casebe larger than in Example 6, the chemical structure of this coupling component being such that it can-be adapted to the molecule of the-diazonium salt neither by choice of the temperature nor by controlling the pH value.
• Example 8 The acetyl cellulosefilm pretreated with a diazo-compound asdescribed in any of the Examples, 1-5, after, exposure is treated with an aqueous solution of'the coupling component 2-acetosacetlyaminor6-ethoxybenzothiazoleat any-desired temperature.
• the. particle size of thev dyeformed will be larger than; inExample 8.
• the control of the .pH-value will notadapt-the molecule ofthis component .to the molecule of thediazonium compound.
• the most preferred diazo compounds to be used in the process of this invention are 4-aminodiphenylamine and its substitution products having at least one lower alkyl or lower alkoxy group in one of the phenyl rings of said amino diphenylamine amino compound.
• the tretrazo compounds used in this invention are derived from-p,p'-diphenylamine and its subst'itution'productsas. indicated. above; Especially suitable compounds are apparently compounds obtained. byncoupling diazotized 4:amino..dia phenylamine with iaromatic amino compounds, such as, 7 lower; allroxy substituted.
• Stabilization of said compounds is effected, for instance, by the addition of alurniniumsulphate-or-magnesiumsul p phate. Stabilization may also be effected by removing the oxidation-products from .the diazo compounds and, precipitating the latter-with neutral salts which do. not. undergo hydrolytic cleavage at room temperature ,inthe p s qe f a dhav n a-s l pH- u ,.,l lre bor acid. Anad dition of materials which, like urea bindthe free nitrous acid is favourable.
• the material After. applying the solutionof said diazo and tetrazo. compounds-s to the .cellulose hydrate .base, the material is subjected to a dryipggprocess at-a temperature between. 9-1451 nipreferah y 40f C.
• acetyl cellulose In place of superficially saponified acetyl cellulose, there may be used other types of regenerated cellulose or cellulose hydrate for micro films, whereas a cellulose hydrate derived from acetyl cellulose has proved to be the preferred starting material for movie films.
• Superficial saponification of said cellulose acetate material may be carried out with sodium or potassium hydroxide solutions of a concentration between about 2% and about 5%. The temperature is preferably between about 62 C. and 68 C.
• leveling agent added to the alkali hydroxide solution of Example 1 there may be used other leveling and emulsifying agents such as wetting agents known in the art, for example Turkey red oil, alcohols, etc.
• acetic acid there may be added other organic acids to the aqueous solution of diazo and tetrazo salts of bases of the diphenylamine series such as the aliphatic carboxylic acids having 1-4 carbon atoms, provided that the pH does not exceed 7. Consequently it is of advantage to said solution to impart a pH of between about 5 and about 7.
• Ripening of the new photosensitive material and increase of its sensitivity to light is elfected by simply storing the said material while excluding excess of air and light at a preferred temperature of 20 C. maximum light sensitivity and gradation being achieved within 3-4 months and 2 Weeks respectively.
• cellulose hydrate as used herein and the claims annexed hereto indicates any regenerated cellulose which is obtained by alkaline saponification of cellulose esters.
• the preparation of the carrier used in this invention is more fully disclosed in my copending application Ser.No. 408,037.
• a process of making light sensitive cinematographic and photographic material comprising in combination, the steps of embedding the light sensitive substance consisting of a chloride of nitroso-free diazo compound of 4-methoxy-4-amino-diphenylamine having the formula in a superfically saponified cellulose hydrate layer, said layer having been saponified by caustic sodawith an equalizing agent having the formula wherein R is an alkyl radical having from 12-14 C-atoms and 11 an integer from 3-19, and ripening the embedded diazo compound by storage during a period of one to three months, whereby film of constant low contrast characteristics is produced.
• the cellulose hydrate layer is formed by superficially saponifying an acetyl cellulose foil with a 5 to 10% NaOH solution containing an equalizing agent having the formula at a temperature of 62 C. to 68 C., wherein R is an alkyl radical having from 12-14 carbon atoms and n is an integer from 3-19, the chloride of nitroso-free diazo compound of 4-methoxy-4-aminodiphenylamine being strongly positively charged.

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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)
• Heat Sensitive Colour Forming Recording (AREA)

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Cited By (7)

Citations (2)

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  • BE BE536396D patent/BE536396A/xx unknown
• 1954
  • 1954-03-15 DE DES38160A patent/DE959613C/de not_active Expired
• 1955
  • 1955-02-21 CH CH333208D patent/CH333208A/de unknown
  • 1955-03-08 FR FR1120765D patent/FR1120765A/fr not_active Expired
  • 1955-03-14 GB GB9415/55D patent/GB777281A/en not_active Expired
  • 1955-03-15 US US494547A patent/US2893866A/en not_active Expired - Lifetime

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