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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
• • 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
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/30—Hardeners
  • G03C1/301—Aldehydes or derivatives thereof, e.g. bisulfite addition products
• • 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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/315—Tanning development

Definitions

• ABSTRACT OF THE DISCLOSURE T his invention relates to hardening of photographic gelatin layers by employing certain dialdehyde hardening agents or their bisulfite adducts in developing compositions or prehardener baths.
• This invention relates to the hardening of photographic gelatin coatings, that is of gelatin having a jelly strength of at least 150 g. Bloom, by treating those coatings with aqueous solutions containing a dialdehyde, the aldehyde groups of which are separated by 2-3 carbon atoms, or the bisulfite adduct of a dialdehyde, the aldehyde groups of which are separated by 3 carbon atoms.
• compositions containing said aldehydes or aldehyde derivatives and pH buffering materials which may or may not contain a solubilized anthraquinone, a polyhydroxy benzene such as resorcinol or phloroglucinol or some other additive useful in processing those gelatin layers.
• aldehydes have been mentioned previously as useful for the hardening of gelatin coatings. Probably the most widely mentioned material of this type is formaldehyde which is extremely active as a hardening agent for gelatin. Formaldehyde often exhibits undesirable photographic properties, in some situations may be toxic and has a detrimental effect upon certain photographic developing agents; hence, the desirability of replacing formaldehyde with some other effective hardening agent. Glyoxal has been mentioned in this connection but has not shown itself to be as effective as a gelatin hardener as formaldehyde and has poor keeping qualities. The presence of glyoxal in developing solutions is ordinarily undesirable. Various other hardening agents for gelatin have been mentioned, but up to the present time the search continues for such materials having desirable properties but free of undesirable properties exhibited by previous hardeners.
• One object of our invention is to provide a gelatin hardening material having active gelatin hardening properties and other characteristics which make it desirable for use in solutions employed for the treatment of photographic gelatin layers.
• Another object of our invention is to provide a hardening agent, for gelatin coatings, ef-
• a further object of our invention is to provide a gelatin hardening material which does not reduce the effectiveness of amino developing agents as found in some types of photographic developers.
• a still further object of our invention is to provide a solution, which hardens gelatin coatings, containing an aliphatic dialdehyde, the aldehyde groups of which are separated by a linear carbon chain of 2-3 carbon atoms or the alkali metal bisulfite derivative of a dialdehyde, the aldehyde groups of which are separated by 3 carbon atoms which solution may or may not contain a solubilized anthraquinone antifoggant or a polyhydroxy benzene.
• Other objects of our invention will appear herein.
• dialdehydes the aldehyde groups of which are separated by a linear chain of 2-3 carbon atoms, which chain has no more than three substituents thereon other than hydrogen being alkyl and/or alkoxy of l-4 carbon atoms when substituents are present (or the bisulfite addition compounds of a dialdehyde, the aldehyde groups of which are separated by 3 carbon atoms) are characterized by being active hardeners for gelatin of a jelly strength of at least g. Bloom but do not exhibit undesirable properties such as are found in many gelatin hardeners previously referred to.
• Some compounds of this type which are useful in hardening gelatin in accordance with our invention are: beta-methyl glutaraldehyde, glutaraldehyde, alpha-methyl glutaraldehyde, maleic dialdehyde, succinic dialdehyde, methoxy succinic dialdehyde, alpha-alpha-dimethyl glutaraldehyde, alpha-beta-dimethyl glutaraldehyde, beta-methyl glutaraldehyde bis-sodium bisulfite, maleic dialdehyde bis-sodium bisulfite, methyl maleic dialdehyde, methyl succinic dialdehyde, alpha-methyl-beta-ethoxy glutaraldehyde, alpha-n-butoxy glutaraldehyde, beta-n-butyl glutaraldehyde, beta-isopropoxy succinic dialdehyde, butyl maleic dialdehyde and the [bis
• the bisulfite derivatives may be those of alkali metal bisulfites, alkaline earth metal bisulfites, nitrogen base (ammonium, amines and the like) bisulfites, etc.
• the pH buffering agent used with the aldehyde in the solution with which the photographic emulsion layer is treated may be a compound supplying alkali metal ions or it may be an organic type of pH bulfering agent.
• certain organic amines having the formula t N Ra in which R hydroxyalkyl of 1-4 carbon atoms
• R alkyl of l-4 carbon atoms
• these hardeners are employed in the form of aqueous solutions thereof and the gelatin coating may conveniently be treated during photographic processing or preliminary or subsequent thereto.
• Gelatin coatings hardened with these compounds are relatively free of excessive surface hardening as compared with formaldehyde hardened gelatin, and reticulation is less pronounced than with hardening with formaldehyde.
• the hardening agents are ordinarily employed in the solutions with which the gelatin layer is treated in a concentration of at least 1%, but the concentration of the hardener may be varied according to the amount of hardening desired and the duration of the time of treatment of the gelatin layer.
• the extent of hardening of the gelatin.layer is determined by taking its melting point when in contact with an aqueous bath. For instance, the melting point of a gelatin layer which has not been hardened in contact with water is ordinarily within the range of 3035 C. whereas gelatin coatings after hardening in accordance with our invention as a rule exhibit melting points greater than 97 C.
• the hardener is conveniently used in the form of the free aldehyde, while in alkaline solutions a bisulfite addition product of a glutaraldehyde is more conveniently employed, in which it is converted to the form of the free aldehyde.
• the invention here also includes as modifications the addition of either a solubilized anthraquinone or a polyhydroxy benzene, or both, to a dialdehyde hardener solution in accordance with the invention.
• the hardeners in accordance with our invention have in some cases shown advantages additional to the hardening of the gelatin.
• advantages additional to the hardening of the gelatin.
• reversal types of photographic emulsions such as described in US. Patent No. 2,563,785 of Ives are treated with alkaline developing solutions containing the bisulfite of an aldehyde as listed herein, a direct positive image may be produced whereas using the same developer without beta-methyl glutaraldehyde bis(sodium bisulfite) or the like, only a faint negative image may be obtained.
• the bisulfite addition compound is the preferred form of the aldehyde for use as a hardener in accordance with our invention in alkaline processing solutions, because of the unvarying stability of the bisulfite derivatives. Hydrolysis in this solution converts at least some of the material so as to present free aldehyde.
• the hardener be used in a concentration within the range of 1 gram per liter up to the limit of its solubility in the processing solution.
• Hardening of gelatin takes place readily at temperatures in the range of 60l20 F. at pH values of the hardening solution between 3 and 12 although other conditions may be employed and effective hardening will occur.
• Alkalies such as alkali metal carbonates, sodium sesquicarbonate, borax, sodium meta-borate, sodium meta-silicate, trisodium phosphate or an alkali metal hydroxide may be employed or an organic amine will many times be found useful in controlling the pH.
• An advantage which has been found of the use of hardeners in accordance with our invention is that when thin unhardened photographic emulsion layers having a minimum content of gelatin are developed in a developer containing as the hardener therein glutaraldehyde bisulfite EXAMPLE 1 Coatings of photographic gelatin having jelly strength of at least 150 g. Bloom were treated for times of 30 seconds to 5 minutes and at temperatures varying from 60 to F. with hardening baths of the composition given. In every case the melting point of the gelatin layer so treated in tests with water had greatly increased indicating substantial hardening.
• the composition used for treating the gelatin coating was as follows:
• the layers thus treated were found to be satisfactorily resistant to the efiects of the hot water used in testing the hardness of the gelatin.
• EXAMPLE 5 A reversal type photographic emulsion (of the type described in Ives U.S. Patent No. 2,563,785), the gelatin of Water to make 1 liter.
• the increase in thickness of the emulsion layer over the dry thickness after washing and the abrasion resistance after washing are recorded in the following table for various aldehydes used in the prehardener and in the developer.
• the emulsion layer was satisfactorily hardened by this treatment and a positive image was obtained. Without the use of beta-methylglutaraldehyde bis(sodium bisulfite) or the like in the developer only a faint negative image in the emulsion layer is obtained.
• Bloom were subjected after exposure to a processing cycle including 90 seconds prehardening at F., secconds development, 30 seconds acid rinse, 5 minutes fixing and 10 minutes washing in water.
• the prehardener used had the following formula:
• the abrasion resistance of nonhardened film is approximately 15-17 grams.
• EXAMPLE 7 A predevelopment hardening solution was prepared containing glutaraldehyde bis-sodium bisulfite as the hardening component according to the following formula:
• X-ray film the gelatin of which had a jelly strength of at least g. Bloom, after exposure was processed by treatment in the prehardener for 90 seconds at 80 F. followed by development for 90 seconds in a developer of the following composition:
• a control film was developed for the same time in this developer without the prehardening treatment. Both films were then rinsed for 15 seconds at 80 F., fixed for 90 seconds in a nonhardening sodium ammoinum thiosulfate fixer and washed for 90 seconds in water.
• the emulsion surface of the control scratched with a weight of l-l7 grams on the stylus.
• the hardened sample resisted abrasion up to 75 grams weight on the stylus.
• EXAMPLE 8 Photographic effects of glutaraldehyde bis(sodium bisulfite) on X-ray film Relative speed at a Contrast Density, density oi0.85 above Developer (gamma) base and log base and fog Control 2. 6 18 550 Hardening developer. 2. 3 26 500 The effect of the hardener on swelling, melting point, and abrasion resistance is shown in the following table:
• EXAMPLE 9 High speed type gelatin silver halide film, the gelatin of which had a jelly strength of at least 150 g. Bloom, after exposure was processed at 68 F. for 5 minutes with a developer having the following basic composition, the pH of which was adjusted to 9.8. In some cases, glutaraldehyde bisulfite or beta-methyl glutaraldehyde bisulfite were added, both with and without a solubilized anthraquinone antifoggant agent.
• the composition of the basic developer was as follows:
• a solubilized anthraquinone antifoggant also be included in the prehardener composition.
• EXAMPLE 10 An aqueous prehardening solution was prepared with a salt content as follows:
• Prehardener X Sodium metaphosphate g 1.5 Sodium bisulfite, anhydrous g 1.0 Tetrnsodium pyrophosphate, decahydrate g 33.5 Sodium bromide g 2.0 Sodium sulfate anhydrous g 155.0 Sodium hydroxide g 0.1 Formalln (40% formaldehyde) ml 16.33 Water to 1 liter.
• pH should be 9.5.
• a dialdehyde as described herein in the developing composition or in the prehardner employed before the development step.
• a meta-substituted hydroxy or amino aromatic compound as described, the life of the developer depending upon pyrogallol or pyrocatechol for the developing agent is appreciably extended.
• a useful developer containing hardening agents of the present invention has the following composition:
• Developers such as the above, containing 3-pyrazolidone developing agents in conjunction with the hardening agents of this invention have a tendency to produce a high level of fog on negative materials processed in them, e.g., at temperatures of 8090 F. It has been found that this tendency can be curbed to some extent by the addition of resorcinol as an antifoggant. It has been discovered furknown antifoggant S-methylbenzotriazole that the effectiveness of the combination exceeds that of either antifoggant alone.
• the addition of 8 grams per liter of resorcinol to the developer composition described above reduced the gross fog level from 0.34 to 0.23 when a fast gelatino-silver halide emulsion was developed for 2% minutes at F.; a relative emulsion speed of 132 being obtained in each case.
• the addition of 0.32 gram per liter of S-methylbenzotriazole to the basic developer reduced the gross fog level to 0.16 when the same emulsion was developed at 85 F. for 3% minutes to obtain a relative emulsion speed of 158.
• EXAMPLE 12 A photographic developer was prepared having the following ingredients incorporated in one liter of water:
• EXAMPLE 14 A developer was prepared containing therein a silver halide solvent having the following formula:
• This composition was used to process Kodak Verichrome Pan Film at 75 F. with no agitation. Clearing was acconiplished in 6 minutes and the quality of the resultant image compared favorably with that produced by conventional development processing in the same composition but with omission of the glutaraldehyde bis bisulfite resulted in severe reticulation.
• compositions in accordance with the invention one may if desired, employ a thickening agent such as would adapt the developing compositions to use for processing when in capsulated form.
• Thickening agents such as guar gum, carboxymethyl cellulose, hydroxyethyl cellulose or the like may be useful in this connection.
• a convenient method for preparing succinaldehyde for use in hardening photographic gelatin is by hydrolyzing 2,S-diethoxytetrahydrofuran accompanied by refluxing in the presence of acetic acid or the like. Where the purity of product is important, it may be desirable to first refine the diethoxytetrahydrofuran such as by dissolving it in a petroleum distillate (such as hexane) and treating with activated alumina.
• a petroleum distillate such as hexane
• succinaldehyde As an example of a procedure by which succinaldehyde may be prepared, a mixture of 600 parts of 2,S-diethoxytetrahydrofuran, 300 parts of distilled water, 1 part of acetic acid and 0.5 part of hydroquinone was heated under a slow stream of nitrogen, the alcohol-water azeotrope being removed continuously through a 12-inch column packed with 5 inch helices, fitted with a variable reflux head. Regulating the rate of takeoff to maintain a distillate temperature of less than C., the pot temperature reached a temperature of 101 C. after 3 /2 hours when reaction is considered complete.
• the mass is cooled, the water is removed by azeotropic distillation using benzene, the benzene is then boiled off and the product is recovercd by distillation into a well-cooled receiver.
• the succinaldehyde is dissolved in water or other solvent to inhibit polymerization of the succinaldehyde.
• the step which comprises treating the emulsion layer with a bath including a considerable concentration of pH buffering agent and a gelatin hardening agent selected from the group consisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than three swbstituents thereon other than hydrogen being alkyl and/or alkoxy of 1-4 carbon atoms when substituents are present, and their bisulfite adducts, the aldehyde groups of which are separated by 3 carbon atoms.
• a gelatin hardening agent selected from the group consisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than three swbstituents thereon other than hydrogen being alkyl and/or alkoxy of 1-4 carbon atoms when substituents are present, and their bisulfite adducts, the al
• a method of hardening a gelatin containing photographic emulsion layer which comprises treating said layer with an aqueous solution containing a considerable concentration of pH buffering agent and a gelatin hardening agent selected from the group consisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than three substituents thereon other than hydrogen being dlkyl and/or alkoxy of 1-4 carbon atoms when substituents are present, and their bisulfite adducts, the aldehyde groups of which are separated by 3 carbon atoms.
• a gelatin hardening agent selected from the group consisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than three substituents thereon other than hydrogen being dlkyl and/or alkoxy of 1-4 carbon atoms when substituents are present, and their bisulfite
• a method of hardening a gelatin containing photographic emulsion layer which comprises treating said layer with an aqueous solution having a considerable concentration of alkali metal ion therein and a gelatin hardening agent selected from the group consisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than three substitu'ents thereon other than hydrogen being alkyl and/or alkoxy of 1-4 carbon atoms when substituents are present, and their bisulfite adducts, the aldehyde groups of which are separated by 3 carbon atoms.
• a method of hardening a gelatin containing photographic emulsion layer which comprises treating said layer with an aqueous solution having a considerable concentration of an organic amine buffering agent therein and a gelatin hardening agent selected from the group cosisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than there sub stituents thereon other than hydrogen being alkyl and! or alkoxy of I-4 carbon atoms when substituents are present, and their bisulfite adducts, the aldehyde groups of which are separated by 3 carbon atoms.
• step 5 which comprises treating the emulsion layer with a bath including a considerable concentration of pH bufiering agent and as a hardening agent therein beta-methyl glutaraldehyde bisulfite.
• the stcp which comprises treating the emulsion layer with a bath including a considerable concentration of pH buffering agent and as a hardening agent therein glutaraldehyde bisulfite.
• R alkyl of 1-4 carbon atoms
• R is selected from R and R and S adducts thereof
• a gelatin hardening agent selected from the group consisting of succinaldehyde, glutaraldehyde and beta-methyl glutaraldehyde and the bisulfite derivatives of glutaraldehyde and beta-methyl glutaraldehyde.
• R1 NqRz in which R hydroxyalkyl of l-4 carbon atoms
• R alkyl of 1-4 carbon atoms is selected from R and R and S0 adducts thereof, plus as a gelatin hardener therein glutaraldehyde.
• a photographic developer especially adapted for processing gelatin containing high speed photographic emulsions, the gelatin of which has a jelly strength of at least 150 g. Bloom which developer contains alkali metal salts, a silver halide developer, as the gelatin hardener therein beta-methyl glutaraldehyde bis-sodium bisulfite and solubilized anthraquinone antifoggant.
• a photographic developer especially adapted for procesing gelatin containing high speed photographic emulsions, the gelatin of which has a jelly strength of at least 150 g. Bloom which developer contains alkali metal salts, a silver halide developer, as the gelatin hardener therein beta-methyl glutaraldehyde bis-sodium bisulfite and sodium anthraquinone sulfonate antifoggant.
• a photographic prehardener processing solution which comprises an aqueous solution with a considerable concentration of alkali metal ions and a gelatin hardener selected from the group consisting of the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms, which chain has no more than three substituents thereon other than hydrogen being alkyl and/ or alkoxy of 1-4 carbon atoms when substituents are present, and their bisulfite adducts, the aldehyde groups of which are separated by 3 carbon atoms, and a polyhydroxybenzene selected from the group consisting of resorcinol and phloroglucinol.
• a photographic developer especially adapted for processing high speed photographic emulsions which developer contains a considerable concentration of alkali metal ions therein including those of sodium sulfite, a silver halide developer, as a gelatin hardener therein betarnethyl glutaraldehyde bis-sodium bisulfite and resorcinol antifoggant.
• a photographic developer especially adapted for processing high speed photographic emulsions which developer contains a silver halide developer, a considerable concentration of alkali metal ion including that of sodium sulfite, bissulfite adduct of a dialdehyde, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of [2-3] 3 carbon atoms, which chain has no more than three substituents thereon other than hydrogen being alkyl and/ or alkoxy of 1-4 carbon atoms when substituents are present, and a mixture of resorcinol and phloroglucinol.
• a prehardener solution comprising an aqueous solution of sodium metaphosphate, sodium bisulfite, and sodium sulfate containing as a hardener therein succinaldehyde.
• a photographic developer comprising an aqueous solution of beta-methyl glutaraldehyde bis alkali metal bisulfite, phenyl pyrazolidone, hydroquinone, sodium sulfite, sodium metaborate, sodium hydroxide, potassium bromide and a sequestering agent.
• a developing solution for gelatin-silver halide photographic emulsions comprising (1) an alkali metal salt to adjust the hydrogen ion, (2) a preservative, (3) an alkali metal bromide, (4) a silver halide developer agent, and (5) beta-methyl glutaraldehyde bis alkali metal bisulfite.
• a photographic developer especially adapted for processing gelatin containing high speed photographic emulsions the gelatin of which has a jelly strength of at least g. Bloom which developer contains a silver halide developing agent, a considerable concentration of pH buffering agent, and a gelatin hardening agent selected from the group consisting of glutaraldehyde [the dialdehydes, the aldehyde groups of which are joined by an uninterrupted linear carbon chain of 2-3 carbon atoms] and [their] its bisulfite adduct[s].
• a solution for hardening photographic gelatin layers which comprises an aqueous solution containing a hardener and a considerable proportion of an alkaline pH buffering agent in an amount sufiicient to maintain the pH of the solution upon treating photographic gelatin layers therewith,
• the hardener being a dialdehyde in which the aldehyde groups are joined by an uninterrupted carbon chain of 2-3 carbon atoms, which chain has no more than three substituents thereon other than hydrogen being alkyl and/ or alkoxy of 1-4 carbon atoms when substitnents are present, or a bisulfite adduct thereof, the aldehyde groups of which are separated by 3 carbon atoms
• the buffering agent being at least one of an alkali metal carbonate, an alkali metal borate, an alkali metal phosphate, or an organic amine.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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Cited By (5)

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• 1956
  • 1956-12-28 FR FR1169616D patent/FR1169616A/fr not_active Expired
  • 1956-12-31 GB GB39589/56A patent/GB825544A/en not_active Expired
• 1967
  • 1967-02-13 BE BE694020D patent/BE694020A/xx unknown
• 1968
  • 1968-10-16 US US26601D patent/USRE26601E/en not_active Expired

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