US2591542A - Hardened photographic film of improved photographic properties - Google Patents

Hardened photographic film of improved photographic properties Download PDF

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Publication number
US2591542A
US2591542A US65568A US6556848A US2591542A US 2591542 A US2591542 A US 2591542A US 65568 A US65568 A US 65568A US 6556848 A US6556848 A US 6556848A US 2591542 A US2591542 A US 2591542A
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United States
Prior art keywords
layer
hardening
gelatin
photographic
halide emulsion
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US65568A
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English (en)
Inventor
Benjamin R Harriman
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GAF Chemicals Corp
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General Aniline and Film Corp
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Publication date
Priority to BE492746D priority Critical patent/BE492746A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US65568A priority patent/US2591542A/en
Priority to GB28615/49A priority patent/GB663457A/en
Priority to FR1000247D priority patent/FR1000247A/fr
Priority to DEG581A priority patent/DE837955C/de
Application granted granted Critical
Publication of US2591542A publication Critical patent/US2591542A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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

Definitions

  • This invention relates to photographic film, and especially to a photographic film in which the gelatino silver-halide emulsion layer is not subject to the deleterious efiects of hardening agents such as after-hardening.
  • Compounds which have been used for hardening gelatin as such or in silver-halide emulsions are formaldehyde, hydroxy aldehydes, acrolein, glyoxal, ketoaldehydes, aminoaldehydes, and derivatives thereof, and mixtures of an aliphatic aldehyde with an aromatic compound contain ing at least one nuclear hydroxy substituent group such as phenol, resorcinol, resorcylic aldehyde, and the like.
  • formaldehyde and hydroxy aldehydes are satisfactory as hardening agents, these compounds possess the undesirable property of producing excessive fog, desensitization, or flattening of gradation in the processed film.
  • any hardeners that function by the liberation of formaldehyde will also have these deleterious effects as well as that of after-hardening, i. e..- hardening continues over a period of time after the film has been coated, and may surpass in degree the initial hardening on first drying.
  • Another object is to provide a gelatino silverhalide emulsion which will be resistant to relatively high processing temperatures without reticulation, fogging, loss of speed, and loss of gradation.
  • a further object is to provide photographic films which are uniform throughout in hardness, aging characteristics, and photographic properties.
  • a still further object is to provide gelatino silver-halide emulsion layers, differentially hardened in. a direction perpendicular to its support, and which will swell uniformly in a direction perpendicular to the support when brought in contact with processing solutions.
  • ZA-dihydroxybenzaldehyde resorcylic aldehyde
  • an aromatic compound containing at least two nuclear hydroxy substituent groups hereinafter referred to as a polyhydroxybenzene, such as, 1,3-benzenediol (resorcinol), phloroglucinol, methylphloroglucinol, pyrogallol, 1.2,4 hvdroxybenzene (hydroxyhydroquinone), and the like or mixtures thereof.
  • the gelatino silver-halide emulsion layer is then coated on any suitable film base having a gelatin or colloidal layer integral therewith, or it may be coated over a gelatin'or colloidal layer, or a gelatin or colloidal layer may be coated over the emulsion layer.
  • the gelatin or other colloidal layer hereinafter referred to as colloid layer, contains an organic hardening agent of a low molecular weight, i. e., of not more than 6 carbon atoms, which is readily difiusible through the film support, or the gelatino silver-halide layer, or the colloidal layer superposed between the film base and silver-halide emulsion layer.
  • Organic hardening agents of low molecular weight are, for example, paraformaldehyde (polyoxymethylene), acetaldehyde (aldol), glyoxal, pyruvic aldehyde, nitromalonic aldehyde, mucochloric acid, trimethylolmelamine and the like.
  • Th latter labile compound or polymer which is an addition product of formaldehyde and melamine, and sold on the open market under the trade name Tanak MRX, behaves like a hardening agent.
  • the trimethylolmelamine may be coated upon the emulsion layer per s from an aqueous solution to leave a polymeric transparent film on the emulsion layer.
  • the organic hardening agent in the support, gelatin subbing or colloidal layer is only brought into contact with the gelatino silver-halide emulsion layer in a sufiiciently dilute state to prevent localized deleterious reactions with the gelatin and silver halide emulsion.
  • all coatings of a kettle or batch of th gelatino silver-halide are subjected to the same amount of hardening for the same period of time and at the same temperature thereby insuring uniform quality throughout the film.
  • the colloidal dispersing agent for the diffusibl hardening agent may be gelatin or other colloid such as water-soluble cellulose derivatives, e. g., hydroxyethyl cellulose, methyl cellulose, carboxyhydroxy cellulose, low acetyl value cellulose acetate, polyvinyl alcohol, partially hydrolyzed cellulose acetates and the like. If a dispersing medium other than gelatin is employed it may be coated over the gelatin subbing layer over which the usual gelatino silver-halide emulsion is coated or it may be coated directly on the gelatino silver-halide emulsion layer.
  • water-soluble cellulose derivatives e. g., hydroxyethyl cellulose, methyl cellulose, carboxyhydroxy cellulose, low acetyl value cellulose acetate, polyvinyl alcohol, partially hydrolyzed cellulose acetates and the like.
  • a dispersing medium other than gelatin it may be coated over the gelatin subbing layer over which
  • the 2,4-dihydroxybenzaldehyde in the gelatino silver-halide emulsion layer functions to boost or accelerate the hardening action of the hardening agent when it diffuses from the support or any layer and comes in contact with the gelatino silver-halide emulsion layer.
  • the 2,4-dihydroxybenzaldehyde is, in short, a necessary element in the photographic film since without it not only does the phenomenon of after-hardening" manifest itself, but in addition the photogfaphic characteristics are rendered inferior.
  • the contact of the diffusing organic hardening agent with the aforesaid benzaldehyde derivative is adequate where hardening without "after-hardening concomitant with retention of the desired photographic properties is desired.
  • the quantities of the ingredients may vary depending upon the degree of hardness desired, but it is recommended that the ratio of polyhydroxybenzene to the 2,4-dihydroxybenzaldehyde be from 1:20 to 120.2.
  • gelatinous silver-halide emulsion layers I prefer to use from 0.25% to 2.5% of total polyhydroxybenzenes based on the dry weight of the gelatin. In these concentrations efiective hardening of the gelatino silverhalide emulsion layer is obtained without afterhardening," i. e., the melting point of the gelatin in the silver-halide emulsion-layer does not vary with time or with long periods of storage prior to actual use and processing of the photographic material.
  • the amounts of the low molecular weight organic hardening agent in the gelatin subbing or separate colloidal layerand the amounts of 2,4-dihydroxybenzaldehyde employed in the gelatino silver-halide emulsion layer are the same as for the non-curling, anti-halation layer, etc., and the amount of a polyhydroxybenzene in the gelatino silver-halide emulsion layer may vary from 0.005% to 5% based on the weight of the dry gelatin in the emulsion.
  • resorcinol has a stabilizing effect all of its own, and if used alone in the gelatino silver-halide emulsion layer, it gives an appreciable hardening boost but not of the magnitude given by 2,4-dihydroxybenzaldehyde or in a mixture with 2,4-dihydroxybenzaldehyde.
  • Figs. 1 to 5 inclusive represent sectional views of a film provided with a gelatino silver-halide emulsion layer comprising 2,4-dihydroxybenzaldehyde and a separate layer or support containing a diffusing organic hardening agent in accordance with the present invention.
  • parent material such :as cellulose organieacetate, for example, cellulose acetate, cellulose .formate.
  • gelatin subbing-layer 4 is coated with the usual gelatin subbing-layer 4 layer, may be applied to a film base I opposite to that in the usual gelatin subbing-layer 4, and light-sensitive layer 3 as shown in Fig. 4.
  • the support I to which has been added one or a mixture of the diffusing organic hardening agents referred to above, is coated with the usual gelatin subbing-layer 4. Over this subbing-layer is .coated a light-sensitive emulsion layer 5 comprising ZA-dihydroxybenzaldehyde.
  • the diffusing low molecular weight organic hardening agent is incorporated into the film support during its manufacture, i. e., during the casting of the film support by dissolving the hardening agent in the cellulose ester solution.
  • the hardening agent need not be incorporated into any one of the separate colloid layers as such. Itmay for such purposes be introduced as a labile compound or complex which will slowly break down to liberate the hardening agent.
  • trimethylolmelamine may be applied as such to a film base opposite to that hearing the usual light-sensitive emulsion, in an anti-static surface layer as shown by 5 in Fig. 4, or over the light-sensitive emulsion layer as shown by 5 in Fig. 3.
  • the advantage in employing any one of the foregoing variations listed by Figs. 1-5 is the very low temperature at which the diffusion of the organic hardening ,agent to the gelatino silyer-halide emulsion layer takes place.
  • the hardening modifiers i. e., 2, i-dihydroxybenzaldehyde and polyhydroxybenzenes exhibit a synergistic effect with I the hardeners in obtaining greater, more rapid, and more complete hardening than was possible with the hardening agents alone.
  • a liquid or gaseous film may be applied to the gelatino silver-halide emulsion layer to effectumarked as Bl, B2 and B3.
  • Example I To 5 kilograms of a melted photographic silverhalide emulsion containing 8-10% gelatin there were added an aqueous solution of 0.5 gram of 2,4-dihydroxybenzaldehyde and 4.5 grams of resorcinol and the mixture heated to and held at C. for several hours. The emulsion was then coated on a cellulose acetate film base and divided into three sections marked Al, A2 and A3. A similar emulsion but containing no hardening modifiers was coated on a cellulose acetate film base and divided into three sections and The first sections of Al and BI were left untreated.
  • the second sections A2 and B2 were passed through a chamber containing gaseous formaldehyde and the third sections A3 and B3 were each passed through a 2% aqueoussolution of formaldehyde after the emulsion layer was chilled and set. After drying the sections of the film were compared photographically and physically.
  • the untreated sections of Al and Bi had melting points 5-10 0. lower than any of the other emulsions, but were equal to the others in speed and gradation. However, in comparing A2 with B2, and A3 with B3, all the A examples showed substantially less fog, greater hardness, gradation and speed.
  • Example II To 1 kilogram of a melted ammonia type photographic silver-halide emulsion containing 23-10% of gelatin there were added 0.9 gram of resorcinol and 0.1 gram of 2,4-dihydroxybenzaldehyde, and
  • a cellulose acetate-propionate sheet was coated with a thin layer'of this emulsion mixture and dried at room temperature. Immediately afterdrying, the emulsion layer was overcoated with a clear gelatin layer containing l5-gramsof formaldehyde per kilogram of gelatin.
  • the resulting film (1) was compared with one (2) prepared from the same ammonia type silverhalide emulsion containing no resorcinol and 2,4-dihydroxybenzaldehyde and over which was 7 coated a gelatin layer containing 15 grams of formaldehyde per kilogram of gelatin with the following results:
  • Example IV Example III was repeated with the exception that the formaldehyde in each of the gelatin layers of the two films was replaced by '15 grams each of glyoxal per kilogram of gelatin. The following results were obtained:
  • Example V To liters of the acid type emulsion of Example I there were added 1 gram of glyoxal, 1 gram of 2,4-dihydroxybenzaldehyde, and 9 grams of resorcinol, and the mixture kept at 45 C. for several hours. A cellulose acetate sheet was coated with a thin layer of this emulsion mixture, chilled and allowed to set. Immediately thereafter the moist emulsion layer was overcoated with a clear gelatin solution containing 1 kilogram of gelatin and 5 grams of glyoxal dissolved in 33 liters of water.
  • the resulting film (1) was compared with one (2) prepared from the same acid emulsion but containing no glyoxal and over which was coated a gelatin layer containing 19 grams of formaldehyde and 1 kilogram of gelatin dissolved in 33 liters of water.
  • Film (2) showed substantially less fog, greater speed and higher gradation in addition to improved storage stability.
  • film (2) which showed uniform photographic properties throughout its entire length could be processed at 43 C., whereas film (1) melted and separated from the film base at 33 C.
  • a photographic material comprising a support carrying a gelatino silver-halide emulsion layer containing at least one ofthe compounds of the group consisting of 2,4-dihydroxybenzaldehyde and a polyhydroxybenzene, said material having a layer integral therewith and adjacent to said silver-halide emulsion layer containing a low molecular weight organic hardening agent.
  • a photographic film containing a gelatino silver-halide emulsion layer having improved resistance to reticulation comprising a support, a gelatino silver-halide emulsion carried there by, said film having a colloid layer integral therewith and independent of said silver-halide emulsion layer, said gelatino silver-halide emulsion containing at least one of the compounds of the group consisting of 2,4-dihydroxybenzaldehyde and a polyhydroxybenzene and said colloid layer containing a low; molecular weight organic hardening agent.
  • a photographic film containing a gelatino silver-halide emulsion layer having improved resistance to reticulation comprising a support, and a gelatino silver-halide emulsion layer carried thereby, said emulsion layer containing at least one of the materials of the group consisting of 2,4-dihydroxybenzaldehyde and a polyhydroxybenzene and said support containing a low molecular weight organic hardening agent.
  • gelatino silver-halide emulsion layer contains 2,4-dihydroxybenzaldehyde and resorcinol and said adjacent layer contains formaldehyde.
  • gelatino silver-halide emulsion layer contains 2,4-dihydroxybenzaldehyde and resorcinol and said independent colloid layer contains glyoxal.
  • gelatino silver-halide emulsion layer contains 2,4-dihydroxybenzaldehyde and resorcinol and the support has dispersed therein trimethylolmelamine.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Materials For Photolithography (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Laminated Bodies (AREA)
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US65568A 1948-12-16 1948-12-16 Hardened photographic film of improved photographic properties Expired - Lifetime US2591542A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE492746D BE492746A (xx) 1948-12-16
US65568A US2591542A (en) 1948-12-16 1948-12-16 Hardened photographic film of improved photographic properties
GB28615/49A GB663457A (en) 1948-12-16 1949-11-08 Hardening photographic gelatino silver halide film of improved photographic properties
FR1000247D FR1000247A (fr) 1948-12-16 1949-11-22 Film photographique durci présentant des propriétés améliorées
DEG581A DE837955C (de) 1948-12-16 1949-12-11 Gehaertete photographische Filme mit verbesserten Eigenschaften

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US65568A US2591542A (en) 1948-12-16 1948-12-16 Hardened photographic film of improved photographic properties

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US (1) US2591542A (xx)
BE (1) BE492746A (xx)
DE (1) DE837955C (xx)
FR (1) FR1000247A (xx)
GB (1) GB663457A (xx)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3128185A (en) * 1960-01-25 1964-04-07 Eastman Kodak Co Antifoggants for formaldehydehardened photographic layers
US3143421A (en) * 1960-03-17 1964-08-04 Eastman Kodak Co Adhering photographic subbing layers to polyester film
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
US3277041A (en) * 1963-05-15 1966-10-04 Eastman Kodak Co Water resistant polyvinyl alcohol coatings
US3506445A (en) * 1964-12-09 1970-04-14 Bexford Ltd Synthetic film materials
US3958050A (en) * 1973-04-12 1976-05-18 Ciba-Geigy Ag Process for crosslinking hydrophilic colloids
US4241171A (en) * 1979-02-21 1980-12-23 Polaroid Corporation Hardener in carrier layer
US4510237A (en) * 1983-10-11 1985-04-09 E. I. Du Pont De Nemours And Company In situ film hardening with aldehyde bisulfite and nonhardening aldehyde

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1112282B (de) * 1959-01-30 1961-08-03 Wolfen Filmfab Veb Verfahren zum Haerten von Gelatineschichten, insbesondere photographischen Emulsionen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2165421A (en) * 1936-09-25 1939-07-11 Eastman Kodak Co Hardening photographic emulsions
US2169513A (en) * 1936-07-28 1939-08-15 Agfa Ansco Corp Process for hardening albuminous substances
US2309492A (en) * 1939-07-14 1943-01-26 Gen Aniline & Film Corp Process for avoiding color fog on photographic color material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2169513A (en) * 1936-07-28 1939-08-15 Agfa Ansco Corp Process for hardening albuminous substances
US2165421A (en) * 1936-09-25 1939-07-11 Eastman Kodak Co Hardening photographic emulsions
US2309492A (en) * 1939-07-14 1943-01-26 Gen Aniline & Film Corp Process for avoiding color fog on photographic color material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3128185A (en) * 1960-01-25 1964-04-07 Eastman Kodak Co Antifoggants for formaldehydehardened photographic layers
US3143421A (en) * 1960-03-17 1964-08-04 Eastman Kodak Co Adhering photographic subbing layers to polyester film
US3236652A (en) * 1963-01-10 1966-02-22 Eastman Kodak Co Stabilized silver halide emulsions
US3277041A (en) * 1963-05-15 1966-10-04 Eastman Kodak Co Water resistant polyvinyl alcohol coatings
US3506445A (en) * 1964-12-09 1970-04-14 Bexford Ltd Synthetic film materials
US3958050A (en) * 1973-04-12 1976-05-18 Ciba-Geigy Ag Process for crosslinking hydrophilic colloids
US4241171A (en) * 1979-02-21 1980-12-23 Polaroid Corporation Hardener in carrier layer
US4510237A (en) * 1983-10-11 1985-04-09 E. I. Du Pont De Nemours And Company In situ film hardening with aldehyde bisulfite and nonhardening aldehyde

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Publication number Publication date
GB663457A (en) 1951-12-19
FR1000247A (fr) 1952-02-11
DE837955C (de) 1952-05-05
BE492746A (xx)

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