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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/14—Dimensionally stable material
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/16—Blocked developers

Definitions

• This invention relates to photographic films having improved dimensional stability and freedom from curl. More particularly, the invention relates to a novel film support for photographic films which confers improvements in dimensional stability and curl resistance to photographic film structures.
• Photographic film comprises: a film support, generally glass, paper or polymeric film; a photosensitive emulsion containing one or more silver halides suspended in gelatin; and usually an intermediate gelatin layer generally termed subbing to insure adhesion of the emulsion to the film support.
• the most widely adopted film supports for photosensitive emulsions are those of organic esters of cellulose,
• Specialty film supports include polyethylene tenaciously to the film support before, during and after developing.
• a photographic film comprising a photosensitive emulsion adhered to a poly(hydroxyether) film support either through an intermediate layer of gelatin subbing or directly.
• the poly(hydroxyether) film supported photographic film is superior to photographic films heretofore made in:
• gelatin containing compositions can be adhered only with difiiculty to these film supports.
• Tests were conducted with various combinations of temperature and relative humidity. Film support samples 20" x 1" x 0.007 were placed in these environments for periods of from 24 to hours. The difference in the long dimension before and after the test is reported as percent change. A plus indicates an increase in the long dimension, and conversely a minus indicates a decrease.
• Table II Also given in Table II are the results of thermal embrittlement tests on a 0.003 inch thick section of both poly (hydroxyether) film support and celluloes triacetate. After aging for the indicated period the samples were folded and unfolded by hand. The number of times the film support could be folded on itself before the film split is reported in Table II. In the case of aged cellulose triacetate cracks appeared well before splitting occurred, as indicated in Table II. In all cases the poly(hydroxyether) Table II there are substituents exclusive of the hydroxyl groups on either or both of the aromatic divalent hydrocarbon PHYSICAL AND DIMENSIONAL STABILITY POLY(HYD ROXYETHER) VS.
• poly(hydroxyether) film supports of the present invention are prepared by extrusion, casting from solution,
• resins are reaction products of a dihydric polynuclear phenol and an epihalohydrin in about equimolar amounts such as are prepared in accordance with US. Patent 2,602,075, issued July 1, 1952, to A. S. Carpenter et al., which is herewith incorporated by reference.
• the film-forming poly(hydroxyethers) have reduced viscosities of from about 0.3 to 1.2 and preferably from 0.43 to 0.65 measured as a 0.2 gram sample in 100 milliliters of tetrahydrofuran at C.
• the poly(hy droxyethers) contain as the recurring units a residue of a dihydric polynuclear phenol having the general formula O--E-O wherein E is the nucleus of thesdihydric polynuclear phenol in which the hydroxyl groups are attached to different nuclei and a group having the general formula wherein Rand R which can be the same or different are hydrogen or methyl, with the recurring units having the E, R and R 'being as previously defined.
• dihydric polynuclear phenols which can I be reacted with epihalohydrins to produce the thermoplastic poly(hydroxyethers) of the present invention are the dihydric polynuclear phenols having the general formula like, preferably an alkoxy radical having a maximum of 4 carbon atoms.
• R is a divalent radical, as for example or O, or -S-, or-SO--, or SO or -S-S, or a divalent hydrocarbon radical as, for example, an alkylene radical such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexarnethylene, Z-ethyl hexamethylene, octamethylene, nonamethylene, decamethylene, and the like; an alkylidene radical such 'as ethylidene, propylidene, isopropylidene, isobutylidene, amylidene, isoamylidene, l
• alkyl substituted aromatic radicals such as 1,4-(2-methylphenyleue), 1,4- (2-ethylphenylene 1,4- (2-n-propylphenylene) 1,4- (2- n-butylphenylene), 1,4-(2-n-dodecylphenylene) and the like; or R can be a ring which is fused to one of the Ar groups as is the case, for example, in the compound having the formula:
• dihydric polynuclear phenols having the general formula:
• Y, Y; are as previously defined, m and z have values from 0 to 4 inclusive and R is an alkylene or alkylidene group, preferably having from 1 to 3 carbon atoms inclusive or R is a saturated group having the formula:-
• Exemplary of other specific dihydric phenols include among others the 2,2-bis- (Z-isopropyl-4-hydroxyphenyl) propane,
• Dihydroxy biphenyls such as 4,4'-dihydroxybiphenyl,
• Di(hydroxyphenyl)sulfones such as bis(4 hydroxvphenyl)-sulfone
• Di(hydroxyphenyl) ethers such as bis-(4-hydroxyphenyl)- ether, the 4,3'-, 4,2-, 2,2'-, 2,3'-dihydroxy-diphenyl ethers, 4,4'-dihydroxy-2,6-dimethyldiphenyl ether, bis- (4-hydroxy-3isobutylphenyl)ether, bis (4-hydroxy- 3-isopropylphenyl) ether, bis (4-hydroxy-3-chlorophenyl)-ether, bis (4-hydroxy-3-fluorophenyl)-ether, bis-(4-hydroxy-3bromophenyl) ether, bis (4-hydronaphthyl)-ether, bis (4-hydroxy-3-chloronaphthyl)- ether, bis-(Z- hydroxybiphenyl) ether, 4,4'-dihydroxy- 2,6-dimethoxy-diphenyl ether, 4,4'-dihydroxy-2,5-diethoxydiphenyl
• l,l-bis-(4-hydroxyphenyl)2-pl1enylethane 1,3,3-trimethyl 1 (4 hydroxyphenyl)-6- hydroxyindane, 2,4 bis-(p-hydroxyphenyl)4-methylpentane and the like.
• dihydric polynuclear phenols can also be employed and wherever the term dihydric polynuclear phenol is used herein, mixtures of these compounds are intended to be included.
• suitable epihalohydrins and mixtures thereof which can be reacted with dihydric polynuclear phenols to produce the thermoplastic poly(hydroxyethers) of this invention are those having the general formula wherein R and R which can be the same or different are hydrogen or methyl and X is a halogen atom, i.e., chlorine, bromine, and the like.
• Specific epihalohydrins are epichlorohydrin, epibromohydrin, 1,2-epoxy-l-methyl- 3 chloropropane and 1,2 epoxy-2-methyl-3-chloropropane.
• a clear film is cast from solution, suitably from a solution in tetrahydrofuran, dioxane, chloroform, dimethylform amide, Cellosolve or diacetone dialcohol, onto a glass plate or similar substrate, or extruded at the desired thickness.
• Film supports of poly(hydroxyether) are suitably of from 0.001 to 0.010 inch in thickness, with thickness of 0.003 to 0.07 being preferred for best combination of body and flexibility.
• a subbing generally a gelatin based composition
• the poly (hydroxyether) film supports described herein are uniquely advantageous in their wettability with photosensitive gelatin emulsion.
• This property permits use of a special photosensitive emulsion'which contains -a Water-soluble poly- (hydroxyether) solvent, e.g., tetrahydrofuran, dioxane, dimethylformamide, Cellosolve and diacetone dialcohol, and can be applied directly to the film support without use of an intermediate layer of subbing.
• a Water-soluble poly- (hydroxyether) solvent e.g., tetrahydrofuran, dioxane, dimethylformamide, Cellosolve and diacetone dialcohol
• the photosensitive emulsion is prepared by slowly adding a dilute solution of silver nitrate with vigorous stirring to a solution of gelatin and potassium chloride, iodide or bromide. Exceedingly fine silver halide crystals are thereby formed.
• the emulsion or, more properly, the suspension, of silver halide in the gelatin is ripened to make it more sensitive to light. Ripening is accomplished by maintaining theemulsion at an elevated temperature, e.g., 90 F. for several hours. After ripening the gelatin solution is cooled to a stiff 10 mass which is shredded to noodles. The noodles arewashed to free the emulsion of undesired salts, e.g., potassium salts. After washing, the noodles are melted and kept heated for a time to further sensitize the emulsion, then additives, such as hardening agents, solvents for the film support and sensitizers are incorporated.
• the emulsion is then coated onto the subbing on the film support or, if a water soluble solvent for poly(hydroxyether) such as are listed above was incorporated into the emulsion, directly onto the poly(hydroxyether) film support.
• Exposing the film to a light source causes an invisible latent image in the emulsion where the silver halides have been exposed to light.
• a developing agent is used to change the invisible latent image to a visible image.
• Developing agents comprise:
• a developer i.e., a compound which is capable of changing exposed silver halide crystals to metallic silver without any effect on unexposed silver halide crystals.
• Typical chemicals which can reduce AgCl, AgI and AgBr to elemental Ag are hydroquinone, p-aminophenol, pphenylenediamine and the like.
• a plurality, e.g., three, layers of silver halide emulsion are used on the film support, and the developer is used with a coupler e.g., dimethyl-p-phenylenediamine, a-naphthol, indophenol blue, chloro-a-naphthol, 4-amin0-N-ethyl N (fl-methanesulfonamidoethyl) mtoluidine sesquisulfate rnonohydrate and the like, either embedded in the emulsion or present in the developing agent;
• a coupler e.g., dimethyl-p-phenylenediamine, a-naphthol, indophenol blue, chloro-a-naphthol, 4-amin0-N-ethyl N (fl-methanesulfonamidoethyl) mtoluidine sesquisulfate rnonohydrate and
• a preservative such as Na SO which combines chemically with oxidation products formed in the developing agent and so keeps the developer clear;
• An activator such as sodium hydroxide, sodium carbonate or borax which by alteration of the pH of the developing agent varies the activity of the developer;
• a restrainer e.g., potassium bromide, to inhibit fog formation (metallic silver produced by action of the developer on unexposed silver halide).
• Most commercial developing agents for silver halide photographic emulsion contain such ingredients.' The developing agents are not critical to this invention, however, and any combination of ingredients capable of producing visibleimages from photosensitive emulsion layers can be employed.-
• the development reaction is stopped either by use of running rinse water or by use of an acid rinse, a stop-bat such as acetic acid, which neutralizes the activator in the emulsion layer.
• a stop-bat such as acetic acid
• the unexposedsilver halides are removed from the emulsion by a fixing bath which is a'water solution of a compound which forms complexes with silver ions, e.g., sodium thiosulfate or ammonium thiosulfate.
• the fixing bath may contain acids, preservatives, hardeners, buffers and the like in order to fix the image and prevent further light sensitivity.
• a photosensitive film was prepared by dip-coating a 0.003 inch'thick uncoated film support of an extruded 8f poly-(hydroxyether) having a reduced viscosity of 0.46 measured as a 0.2 gram sample in milliliters of tetrahydrofuran and the recurring unit F 1L1 is ,1 r tHQ 1
• the dip-coated poly(hydroxyether) film support was air dried in complete darkness. The coating was exposed to light through a stencil. A transparency with a sharp brown image was obtained.
• Example 1 is illustrative of the use of poly(hydroxyether) as film support in applications where a gelatin emulsion of silver halides is not used to produce an image.
• Other useful image producing compositions readily adhere to the poly(hydroxyether) film support.
• dichromate process photosensitive coatings e.g., potassium dichromate in glues, gums or gelatins wherein exposure to light causes selective hardening of the gelatin, gum or glue to produce an image
• the inclusion of carbon black in the dichromate process coatings (the Carbon Process) provides black images
• diazo process coatings which upon exposure to light and treatment with alkali and phenolic compounds produce images byappearance of selectively formed dyes
• blueprint process coatings where ferric salts are adhered to the film support'and reduced to ferrous salts to produce an image, or where platinum and palladium salts are used for the same purpose and elfect.
• the present invention is not limitedto use of po1y(hydroxyether)' as film supports for gelatin emulsions of silver halides but rather extends to use of any photosensitive coating on poly(hydroxyether) film supports.
• EXAMPLE 2 A photographic film was prepared by first applying to the face of an extruded 0.003 inch thick film support of the same poly(hydroxyether) as used in Example 1, a subbing comprising Gelatin g 10 Acetic acid (glacial) cc 50 Water cc..- 50 Methanol cc 1000 and air drying. Then a photosensitive emulsion prepared in darkness using (1) Mixed silver halides (dehydrated iemulwas applied in darkness to the subbing layer on the poly (hydroxyether) film. support and the, assembly air dried. The photographic film was exposed to light through a negative. Developing, fixing and washing was by stand- 0 ard techniques using standard developers, stop baths and.
• Control 2A The procedure of Example 2 was followed but using a 0.003 inch thick sheet of cellulose triacetate as film support. The photosensitive emulsion and 9 the subbing layer lifted off the film support in the developer solution.
• Control ZB The procedure of Example 2 was followed but using a 0.003 inch thick sheet of polycarbonate as film support. The photosensitive emulsion and the subbing layer lifted off the film support in the developer solution.
• EXAMPLE 3 A photographic film was prepared without use of an intermediate subbing layer, by applying directly to the face of an extruded 0.003 inch thick film support of the same poly(hydroxyether) as used in Example 1 a photosensitive emulsion prepared as in Example 2 but containing 20% tetrahydrofuran. After drying the photographic film was exposed to light through a negative. After developing, fixing and washing by the technique of Example 2 a clear reverse image of the negative was obtained. The film support coating adhered tenaciously to the film support throughout developing. No curling occurred.
• EXAMPLE 4 A photographic film was prepared without use of an intermediate subbing layer by applying directly to the face of an extruded 0.003 inch thick film support of the same poly (hydroxyether) as used in Example 1, a photosensitive emulsion prepared as in Example 2 but which contained a total of 1500 cc. water.
• Example 2 To this emulsion was added 30% I tetrahydrofuran. Film supports were coated with this mixture at coating thicknesses of from 0.0003 inch to 0.001 inch. Exposure and development were carried out as in Example 2. All coatings gave good images after exposure to light through negatives. All coatings adhered firmly to the film support during developing.
• Control 4A The photosensitive emulsion used in Example 4 was solvent modified as in Example 4 but with 22% acetone in place of the 30% tetrahydrofuran in an attempt to obtain good bonding of the emulsion directly to cellulose triacetate. Photosensitive coatings 0.0003 inch-thick and thicker were applied to cellulose triacetate film support. After exposure the films were developed as in Example 4. Immersion in. the developer solution lifted each of the photosensitive coatings from the cellulose triacetate film support.
• Control 4B The photosensitive emulsion used in Example 4 was solvent modified as in Example 4 but with 17.8% dioxane in place of the 30% tetrahydrofuran in an attempt to obtain good bonding of the emulsion directly to polycarbonate.
• Photosensitive coatings 0.003 inch thick and thicker were applied to polycarbonate film support. The coatings were streaked and appeared not to wet the polycarbonate film support. After exposure the films were developed as in Example 4. Immersion in the developer solution lifted each of the photosensitive coatings from the polycarbonate film support.
• EXAMPLE 5 A photographic film was prepared using a 0.001 inch thick film support cast onto a glass plate from a 25% solution in tetrahydofuran of a poly(hydroxyether) having a reduced viscosity of 0.49 measured as above and the The cast film was aid dried at 68 F. and 50% relative humidity for 24 hours and at 110 F. for an additional 24 hours.
• a subbing having the formulation given in Example 2 was applied by brush tothe face of the cast film support and allowed to air dry.
• the photographic film was exposed to light as in the previous examples. Development was carried out as in Example 2. Adhesion of the gelatin and emulsion to the film support was good throughout developing. An excellent transparency was produced with no evidence of curling.
• EXAMPLE 6 A photographic film was prepared without use of a subbing layer by applying directly to the face of a 0.001 inch thick cast film support of the same poly(hydroxyether) as used in Example 5, a mixture of a photosensitive emulsion prepared as in Example 5 and a solvent, tetrahydrofuran, in a ratio 7 parts of the emulsion per 3 parts of the solvent.
• the poly(hydroxyether) film support was coated with the solvent modified photosensitive emulsion using a sponge as the applicator, care being taken to wet all spots of the film support.
• the coating was smooth.
• the photographic film was exposed to light and developed as in the previous examples. Adhesion of the emulsion to the film support was good throughout developing. An excellent transparency was obtained.
• EXAMPLE 7 A photographic film was prepared using a 0.001 inch thick film support cast onto a glass plate from a 25% solution in tetrahydrofuran of a poly-(hydroxyether) having a reduced viscosity of 0.44 measured as above and the recurring unit The cast film was air dried at 68 F. and 50% relative humidity for 24 hours and at F. for an additional 24 hours.
• a subbing having the formulation given in Example 2 was applied by brush to the face of the cast film support and allowed to air dry.
• a photosensitive emulsion prepared as in Example 5 was applied as a thin coating with a sponge to the subbing layer on the film support. A uniform and smooth coating was obtained.
• the photographic film was exposed to light and developed as in the previous examples. Adhesion of the gelatin layer and the photosensitive emulsion layer to the film support was good, throughout developing. A clear transparency having a good contrasting image was obtained. No curling occurred.
• EXAMPLE 8 A photographic film was prepared without use of a subbing coat by applying directly to the face of a 0.001 inch thick cast film support of the same poly(hydroxyether) as used in Example 7, a mixture of a photographic emulsion prepared as in Example 5 and a solvent, tetra- The poly(hydroxyether) film support was coated with I the solvent modified photosensitive emulsion using a sponge as the applicator. The coating was smooth and uniform over most of the film support. The photographic film was exposed to light and developed as in the previous examples. Adhesion of the photosensitive emulsion to the wetted film support was good throughout developing. An excellent transparency was obtained.
• EXAMPLE 9 A photographic film was prepared using a 0.001 inch thick .film support cast onto a glass plate from a 25% solution in tetrahydrofuran of a poly(hydroxyether) copolymer.
• the copolymer was prepared by mixing 57 grams (0.25 mole) of 2,2-bis(p-hydroxyphenol)-propane and 74.1 grams (0.25 mole) of bisphenol of vinylcyclohexene, 46.3 grams of epichlorohyd-rin and 106.8 grams of ethyl alcohol together, and after the reaction mixture had been stirred for 15 minutes, adding 22 grams of sodium hydroxide in 69.7 grams of Water and then heating the mixture at reflux for five hours.
• the copolymer had a reduced viscosity of 0.54 measured as above.
• the cast film was air dried at 68 F. and 50% relative humidity for 24 hours and at 110 F. for an additional 24 hours.
• a subbing having the formulation given in Example 2 was applied by brush to the face of the cast film support and allowed to air dry.
• a photosensitive emulsion prepared as in Example was applied as a thin coating with a sponge to the subbing layer on the film support. A uniform and smooth coating was obtained.
• the photographic film was exposed to light and developed as in the previous examples. Adhesion of the gelatin layer and the photosensitive emulsion was good throughout developing. A transparency with a good contrasting image was obtained. No curling occurred.
• EXAMPLE A photographic film was prepared by applying directly to the face of a 0.001 inch thick cast film support of the same poly(hydroxyether) copolymer as used in Example 9, a mixture of a photographic emulsion prepared as in Example 5 and a.-solvent, tetrahydrofuran, in a ratio of 7 parts ofthe emulsion per -3 parts of the solvent.
• the poly(hydroxyether) film support was coated with the solvent modified photosensitive emulsion using a sponge as the applicator. A smooth and uniform coating was obtained over a major portion of the film support.
• the photographic film was exposed to light and developed as in the previous examples. Adhesion of the photosensitive emulsion to the wetted film support and the image produced were excellent. No curling occurred.
• a dimensionally stable and curl-free photosensitive film comprising a film support of a thermoplastic poly- (hydroxyether) containing recurring units having the formula wherein E is the nucleus of a dihydric polynuclear phenol in which the hydroxyl groups are attached to different nuclei and R and R are each selected from hydrogen and I. (hydroxyether) containing recurring units having. the formula R R1 laaaaaoa wherein E is the nucleus of a dihydric polynuclear phenol in which the 'hydroxyl groups are attached to different nuclei and R and R are each selected from hydrogen and methyl and having a reduced viscosity of from 0.3 to 1.2.
• a dimensionally stable and curl-free photographic film comprising a film support of a thermoplastic poly- (hydroxyether) containing recurring units having the formula o-u-o d-i om L. ll. 1.
• E is the nucleus of a dihydric polynuclear phenol in which the hydroxyl groups are attached to difierent nuclei and R and R are each selected from hydrogen and methyl and having a reduced viscosity of from 0.43 to 0.65 measured as a 0.2 gramsample-in 100 milliliters of tetrahydrofuran and, adhered to the film support.
• a dimensionally stable and curl-free photographic film comprising a film support of a thermoplastic poly- (hydroxyether) containing recurring units having the L teal wherein E is the nucleus of a dihydric polynuclear phenol in which the hydroxyl groups are attached to different nuclei and R and R are each selected from hydrogen and methyl and having a reduced viscosity of from 0.43 to 0.65 measured as a 0.2 gram sample in 100 milliliters of tetrahydrofuran at 25 C., a subbing layer containing gelatin adhered to the film support and an image producing photosensitive emulsion containing gelatin and a silver halide adhered to said subbing.
• the photographic film claimed in claim 10 wherein the poly(hydroxyether) has the recurring unit H H CH 12.
• the photographic film claimed in claim 10 wherein the poly(hydroxyether) has the recurring unit 13.
• the photographic film claimed in claim 10 Wherein the poly (hydroxyether) has the recurring unit 14.
• the photographic film claimed in claim 10 wherein the poly(hydroxyether) is a copolymer prepared by the condensation in an alkaline medium of 2,2-bis-(p-hydroxyphenyl) propane and 1,1-bis-(p hydroxyphenyl)-2- 25 phenylethane with epichlorohydrin.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (3)

• 0
  • GB GB26864D patent/GB26864A/en active Active
• 1964
  • 1964-02-28 BE BE653678A patent/BE653678A/xx unknown
  • 1964-08-26 GB GB35051/64A patent/GB1078074A/en not_active Expired
  • 1964-11-25 US US414001A patent/US3249439A/en not_active Expired - Lifetime

Non-Patent Citations (1)

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