US3901708A - Process for hardening layers which contain gelatin within a silver halide photographic material with an aldehyde and an isonitrile - Google Patents

Process for hardening layers which contain gelatin within a silver halide photographic material with an aldehyde and an isonitrile Download PDF

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Publication number
US3901708A
US3901708A US349764A US34976473A US3901708A US 3901708 A US3901708 A US 3901708A US 349764 A US349764 A US 349764A US 34976473 A US34976473 A US 34976473A US 3901708 A US3901708 A US 3901708A
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layer
compound
layers
aldehyde
photographic material
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Ivar Ugi
Heinrich Seibert
Peter Hoffmann
Dieter Marquarding
Rintelen Harald Von
Erwin Ranz
Wolfgang Himmelmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • 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
    • G03C5/268—Processing baths not provided for elsewhere, e.g. pre-treatment, stop, intermediate or rinse baths

Definitions

  • N0.: 349,764 A process for hardening layers which contain protein in which the layer is treated with an aldehyde or an 1 Foreign Application Priority Data aldehyde-donor and wlth a water soluble, aliphatic or Apr. 14, 1972 Germany 2218009 araliphatic isonitrile compound.
  • cross-linking agents or hardeners for gelatin have already been described, for example metal salts such as salts of chromium, aluminium or zirconium, aldehydes or their derivatives, in particular formaldehyde, dialdehydes, mucochloric acid, diketones, quinones and chlorides of dibasic organic acids, dianhydrides and in general, compounds which contain several reactive vinyl groups, such as vinyl sulfones and acrylamides.
  • Compounds which contain at least two heterocyclic three membered rings which are easily split, such as ethylene oxide and ethylene imine, may also be used as hardeners for gelatin.
  • High molecular weight hardeners such as polyacrolein and its derivatives or copolymers of alginic acid derivatives have also become known in recent times. There are used particularly as diffusion resistant hardeners which are confined to a particular layer.
  • latent hardeners By latent hardening is meant a cross-linking reaction which is only fully effective after the material has been subjected to a certain treatment, e.g. the action of alkalies or other factors such as heat. Compounds which are predominantly latent in their action are of great practical importance because the photographic material should not undergo any change while it is stored before it is processed. The reason for this is that the maximum densities obtainable, the values and possibly also the light sensitivity of the photographic material decrease with an increasing degree of cross-linking of the layers.
  • hardeners are either too rapid or too slow in their action. If two reactive hardeners are used. eg. cyanuric acid chloride, the viscosity of the casting solution increases even while the solution is being prepared. before it is cast. In certain casting ma- 6g chines, this causes a constant change in the thickness of the layers. lf the hardeners are too slow in their action as is the case. for example. with trisacryloylhexahydrotriazine. the viscosities are not affected and the end points of hardening of the layers are reached only after a prolonged time in storage. All other types of hardeners have properties which are more or less intermediate between those extremes described above.
  • n an integer of from I to 6
  • 3-lsocyanosulpholan y COONa(K) Y -COONa(K) under vacuum.
  • the dark brown residue is dissolved in 1000 ml of methylene chloride and 252 g of triethylaminc. and 91 ml olphosgene are introduced into this solution at a temperature ofabout 35C with stirring. Stirring is then continued for 15 minutes ammonia is introduced at l()C until the solution is saturated with ammonia, and the precipitate is then filtered off. The filtrate is concentrated by evaporation under vacuum at a bath temperature of 35C. The residue is filtered over silica gel (benzene/ethyl acetate 1:1 and charcoal (methanol) and recrystallised from methanol.
  • 2-lsocyano- 1 -methoxy-ethane 94 g of Z-N-formylamino-l-methoxy-ethane are dissolved in 200 ml of methylene chloride and 200 ml of triethylamine. 100 g of phosgene are then introduced. After stirring for minutes, the solution is saturated with gaseous ammonia at. 10C, the precipitate is suction filtered and thefiltrate is concentrated by evaporation under vacuum (bath'temp'erature C) and the residue is distilled under vacuum. Yield: 29 g (37.5% of the theory) hp. 18 mm 50C..
  • N.l ⁇ l-Bis- 1 3-isocyanopropy1)-piperazine 343 g of N,N-Bis-l-(3-N-formylaminopropyl)- piperazine are dissolved in 1750 ml of methylene chloride and 870 ml of triethylamine. and 272 g of phosgene are introduced at 10 to 15C with vigorous stirring. Stirring is then continued for 10 minutes and the solution is then saturated with gaseous ammonia at 10C. The precipitate is suction filtered and washed thoroughly with methylene chloride. The filtrate is distilled off under vacuum at a bath temperature of 30-35C and the residue is recrystallised from methanol. Yield: 2.30 g (7571 of the theory). m.p. 8081C.
  • N-Methyl-N-1-( 3-isocyano)-piperazine is prepared.
  • 3-lsocyano-1-(N-morpholino)-propane 1316 g of 3-Amino-l(N-morpholino)-propane are introduced dropwise into 1500 g of methyl formate with vigorous stirring and the mixture is then heated to boiling for 10 hours.
  • the volatile constituents are removed under vacuum (water pump) at a bath temperature of 75C.
  • the oily residue is dissolved in 4500 ml of methylene chloride and 2805 ml of triethylamine. and 877 g of phosgene are introduced at C with stirring.
  • the reaction mixture is cooled to 5C and 300 to 350 g of ammonia are introduced.
  • the reaction mixture is then filtered and the filtrate concentrated by evaporation under vacuum (water pump) at 50C.
  • Potassium salt of o-isocyano-caproie acid 98 g of the hydrochloride of ethyl 6-aminocaproate are suspended in 300 ml of methylene chloride and covered with a solution ofl06g of soda in 200 m1 of water.
  • a mixture of 75 mol of 98% formic acid and 63 ml of acetic anhydride which has previously been left to stand for one-half hour is introduced dropwise with vigorous stirring.
  • the reaction mixture is left to react for 1 hour and the aqueous phase is then separated off. Concentrated aqueous soda solution is added to the organic phase until the pH is 7.5 to 9 (controlled by pH meter) and the organic phase is cooled to 0 to 5C.
  • the potassium salts CN(CH. ,),,COOK (n 1,234.6) are prepared in analogous manner.
  • the hydrazides Cl ⁇ l(CH ),,CO-NHNH (n 2-6) are prepared in analogous manner Sodium salt of l-isocyano-cyclohexane carboxylic acid-( 1 46 g of N-formyl-l-amino-l-carbomethoxycyclohexane are dissolved in 250 ml of ethylene chloride and 83 ml of triethylamine, and g of phosgene are introduced at 40C. The reaction mixture is then stirred for l5 minutes and washed. first with a saturated sodium bicarbonate solution and then with water. The or ganic phase is dried and concentrated by evaporation under vacuum. The residue is distilled (b.p. 0.03 mm 50C) and dissolved in 1 l0 ml of 2N sodium hydroxide solution, the temperature rising to about C. After stirring this solution for 1 hour, it is concentrated by evaporation under vacuum.
  • the sodium salt of l-isocyano-cyclopentane carboxylic acid-( I is prepared in analogous manner.
  • the compounds are prepared from the methyl or ethyl esters COOR (R' -CH C H n 4,5) in analogous manner to the open chain compounds.
  • aldehydes or compounds which split off aldehydes used for the process according to the invention may be known compounds commonly used for hardening protein layers, e.g. monoaldehydes such as formaldehyde or aeetaldehyde or dialdehydes such as glyoxal, glyoxal-bisulfite, glyoxal tetraacetate, glyoxal tetracetal, glutaric dialdehyde and suecinic dialdehyde, tria'ldehydes, monoand dimethylolurea and homopolymers and copolymers of acrolein. Aldehydes and compounds which split off aldehydes will hereinafter be briefly referred to as aldehyde compounds.
  • the process according to the invention is suitable for hardening any protein layers for gelatin foils and in particular photographic layers.
  • photographic layers are meant layers which are used in photographic materials and especially also light sensitive silver halide-gelatin emulsion layers but also auxiliary layers such as protective layers, filter layers, antihalation layers, backcoating layers, NC layers, etc..
  • the light sensitive emulsion layers for which the hardening process according to the invention is particularly suitable are. for example. those layers which are based on non-sensitized emulsions, orthochromatic, panchromatic or infra-red emulsions, X-ray emulsions and other emulsions which are not spectrally sensitized.
  • the hardening process according to the invention has also proved suitable for hardening gelatin layers used for various black-and-white photographic processes and colour photographic processes.
  • the process according to the invention has proved particularly advantageous for hardening composite photographic layers used for colour photographic processes, e.g. those which contain emulsion layers with colour couplers or emulsion layers which are designed to be treated with solutions which contain colour couplers.
  • the aldehydes and isonitrile compounds may also be added at separate stages in the process according to the invention without the effect of the combination being thereby lost.
  • a gelatin layer having a melting point of 50 to 60C (to be defined hereinafter) may be prepared with the addition of isonitrile. and the aldehyde component may subsequently be added to this gelatin layer by bathing the layer in an aqueous solution of the component before the material is processed. The melting point of the layer then increases considerably, and hence also the degree of hardening.
  • the hardening of photographic gelatin layers by the process according to the invention can therefore be achieved either by using the aldehyde and isonitrile compound in the same or different layers of a photographic material or by adding the compounds to preliminary and/or after-hardening baths.
  • the photographic material may be treated either before or after the photographic process either with separate baths for the aldehyde compounds and for the isonitrile compound or with baths which contain the two compounds together.
  • the aldehydes are used in quantities of0.l to 8% by weight, based on gelatin, and preferably in quantities of 0.5 to 7% by weight, and the isonitrile compounds are used in quantities of 005 to 1571 by weight and preferably in quantities of 0.1 to 10% by weight.
  • the usual silver halide emulsions are suitable for the hardening process described here,
  • the silver halide contained in them may be silver chloride, silver bromide or mixtures thereof, optionally with a small silver iodide content, i.c. up to mols percent.
  • Photographic materials prepared with these emulsions may contain the emulsion layers either as single layers, e.g. in the case of simple black-and-white materials, or as several layers arranged above one another, e.g. in the case of colour photographic materials. Each of the individual layers of these layer combinations may contain the usual additives.
  • the binders used for the photographic layers are protein layers. preferably gelatin although gelatin may be partly replaced by other natural or synthetic binders.
  • Suitable natural binders are e.g. alginic acid and its derivatives such as salts. esters or amides, cellulose derivatives such as carboxymethyl cellulose, alkyl cellulose such as hydroxyethyl cellulose, starch or derivatives of starch such as others or esters or carrageenates.
  • Suitable synthetic binders are: polyvinyl alcohol, partly saponified polyvinyl acetate, polyvinyl pyrrolidone and the like.
  • the emulsions may also be chemically sensitized, e.g. by the addition ofsulphur compounds during the stage of chemical ripening. for example allyl isothiocyanate, allyl thiourea, sodium thiosulfate, etc..
  • the chemical sensitizers used may also be reducing agents. e.g. the tin compounds described in Belgian Pat. Nos. 493,464 and 568,687, polyamines such as diethylene triamine or aminomethylsulfinic acid derivatives, e.g. according to Belgian Patv No. 547.323.
  • the emulsions may also be sensitized with polyalkylene oxide derivatives, e.g. with polyethylene oxide having a molecular weight of between l()()() and 20,000, or with condensation products of alkylene oxides and aliphatic alcohols. glycols, cyclic dehydration products of hexitols, alkyl substituted phenyls, aliphatic carboxylic acid, aliphatic amines, aliphatic diamines and amides.
  • polyalkylene oxide derivatives e.g. with polyethylene oxide having a molecular weight of between l()()() and 20,000, or with condensation products of alkylene oxides and aliphatic alcohols. glycols, cyclic dehydration products of hexitols, alkyl substituted phenyls, aliphatic carboxylic acid, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700 and preferably more than 1000. These sen sitizers may, of course, also be combined to achieve special effects, as described in Belgian Pat. No. 537,278 and in British Pat. No. 727,982.
  • the emulsions may also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanine, basic or acid carbocyanines, rhodacyanines, hemieyanines, styryl dyes, oxonoles and the like. Sensitizers of this kind have been described in the work by F. M. Hammer The Cyanine Dyes and related Compounds, (1964).
  • the emulsions may contain the usual stabilizers, e.g. homopolar or salt-type compounds of mercury which contain aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • mercaptotriazoles simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • Azaindenes especially tetraor penta-azaindenes and particularly those which are substituted with hydroxyl or amino groups are also suitable stabilizers. Compounds of this type have been described in the article by Birr, Z. Wiss, Phot. 47, 2-58 1952).
  • Other suitable stabilizers are inter alia heterocyclic mercapto compounds, e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
  • the emulsions may also contain the usual additives used for colour photographic materials, e.g. colour couplers.
  • the activity of the hardener combination according to the invention may be demonstrated in known manner by measuring the melting point of the layers or degree of swelling of the layers.
  • the melting point of the layers is determined as follows: The layer cast on a support is half dipped into water which is continuously heated to l00C. The temperature at which the layer runs off the support (formation of streaks) is taken as the melting point or melting off point. If no melting occurs at temperatures up to 100C, the layer is again kept at l00C for a maximum of 30 minutes. The measure of the hardening in that case is the length of time after which the layer runs off the support. Under the conditions of measurement, pure gelatin layers without hardener show a melting off point of 30 35C.
  • Swelling is determined gravimetrically after 10 minutes treatment in distilled water at 22C and is indicated in percent.
  • EXAMPLE 1 A gelatin-containing silver chlorobromide emulsion which is composed of g of gelatin, 38 g of silver nitrate in the form of the halides and 0.571 of glyoxal (based on the quantity of gelatin) per kg of solution is cast on a layer support of triacetyl cellulose at pH 6.2 and dried. The material is then divided into 3 parts A, B and C. Part B is coated with the following mixture:
  • Part C is coated with a mixture of 500 ml of a 271 aqueous gelatin solution and 4 ml ofa l 71 solution of compound I in a 1:3 mixture of dimethylformamidelH O.
  • Table l The samples are adjusted to pH 6.2 and cast on a layer support of cellulose acetate. The melting points of the layers are determined immediately after drying Sample Melting point after storage of the layers 111 lsmiwmwrh and after 1,234 and 5 hours storage. The following rel 3 3 5 sults are obtained: A 58 5s 5x 5x Table 3 B 62 65 69 74 C 57 72 73 78 Sample Melting points after storage at room temperature with exclusion of moisture in C l 2 3 4 5 hrs. The figures show that the hardening effect of the Q 23 ix 7 combination of aldehyde and isonitrile compound is C D 37 37 37 37 37 37 37 greater than that of aldehyde alone.
  • An emulsion layer ofthe following composition is apbathed for 2 minutes in a 1% aqueous solution of complied to a layer support of baryta paper: pound ii and washed f0! 10 minutes.
  • the melting point of the layer has risen to 75C. 35 ing 0
  • EXAMPLE 3 3 /:ltl;Z Wlght ofsilver halide and 671 by weight of gel
  • An aqueous silver chlorobromide emulsion which 4.4 ml of a l()% aqueous solution of saponin.
  • v of mixture (pH 6.2) is east on a layer support of ethyl- 200 ml of a 2% aqueous gelatin solution, enc terephthalate (Sample A).
  • the addition 50 l y om in ion i no destroy d by keeping it in boilof compound I also reduces the swelling of the layer as g Water for 30 minutes a Whole If the top layer contains formalin instead of compound lll, the resulting melting point is 96C.
  • the top EXAMPLE 4 layer is in that case applied from a casting solution of s the following composition: 100 ml portions of gelatine-containing silver chloro- 2()() f a 27, aqueous gelatin solutionbromide emulsions which contain 100 g of gelatine and 9 i f u 30% aqueous Solution f f ld h d 40 g of silver nitrate in the form of the halides pere kg 4 ml of a 10% aqueous solution of saponin. of emulsion are treated with the following additives:
  • Sample A 0.3% of formalin, based on the gelatin EXAMPLE 6 content (in the form of a 1% solution), 60 Sump: 83 0317! of Compound I (in the form of a 1% An isonitrile-containing silver halide emulsion layer solution), of the following composition is applied to a layer sup- Sample C: 0.3% of formalin and 0.3% of compound 1 of hurytu paper:
  • EXAMPLE 7 A black-and-white photog been only slightly hardened and is not sufficiently resistant for drying on a drying dru with a hath of the following composition after the developed and fixed image has 90 ml of water. 5 ml of compound IV 2.5 ml of a 30% aqueous s A material which is very resistant on the drying drum is obtained in this Way.
  • Emulsion layers which have not been hardened and which contain 80 g of gelatin and 38 g of silver nitrate 30 in the form of the halides are treated with the following freshly prepared prehardening baths (3 minutes, to
  • Prehardening bath ll A 550 ml of water I54 g of sodium sulfate 20 g of sodium acetate 16.6 ml of 3091' aqueous so 5 g of compound I made up to 1000 ml with water B. the same as A. but
  • a process for hardening a photographic material comprising photographically processing a photoaphic material containing on a support a layer containing a protein compound and a silver halide emul- Sit lution of formaldehyde m layer. or a layer ofa silver halide emulsion containing a protein compound wherein the improvement comprises treating the photographic material in a step which contains an aldehyde or an aldehyde-donor compound and an isonitrile compound selected from the group consisting of a watersoluble, isonitrile compound for 10 minutes and dried ielting point.
  • n is an integer of from 1 to 6
  • n 4 or 5.
  • a process as claimed in claim 1 in which the protein -containing layer to be hardened contains one of the treating agents and the other agent is contained in a treatment bath.
  • a process as claimed in claim 1 in which the protein-containing layer to be hardened contains both of said treating agents.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US349764A 1972-04-14 1973-04-10 Process for hardening layers which contain gelatin within a silver halide photographic material with an aldehyde and an isonitrile Expired - Lifetime US3901708A (en)

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DE2218009A DE2218009A1 (de) 1972-04-14 1972-04-14 Verfahren zur haertung gelatinehaltiger schichten

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JP (1) JPS4919825A (forum.php)
BE (1) BE797784A (forum.php)
CA (1) CA1002806A (forum.php)
CH (1) CH602833A5 (forum.php)
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4078932A (en) * 1975-05-01 1978-03-14 Agfa-Gevaert, N.V. Hardening developers for silver halide photography
US20070077274A1 (en) * 2004-05-12 2007-04-05 Gelita Ag Method for producing shaped bodies based on crosslinked gelatine
CN110062782A (zh) * 2016-12-19 2019-07-26 科思创德国股份有限公司 降低聚氨酯泡沫的释放的方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098600A (en) 1976-05-24 1978-07-04 Monsanto Company Isocyanoacylamides
DE2751783A1 (de) * 1977-11-19 1979-05-23 Bayer Ag Alpha-isocyanocarbonsaeure-salze, verfahren zu ihrer herstellung und ihre verwendung als pflanzenwachstumsregulatoren
DE2842639A1 (de) 1978-09-29 1980-04-10 Bayer Ag Alpha -isocyano-carbonsaeureamide, verfahren zu ihrer herstellung und ihre verwendung als pflanzenwachstumsregulatoren
GB2039095B (en) 1978-12-07 1982-11-24 Hansen J S Electric motors speed regulation
DE4428292A1 (de) 1994-08-10 1996-02-15 Agfa Gevaert Ag Lichtempfindliches fotografisches Aufzeichnungsmaterial mit lichtabsorbierendem Farbstoff
US5773078A (en) * 1996-06-24 1998-06-30 General Electric Company Method for depositing zirconium oxide on a substrate
WO2003045928A1 (en) * 2001-11-26 2003-06-05 Genzyme Corporation Diastereoselective synthesis of udp-glucose : n-acylsphingosine glucosyltransferase inhibitors

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2766247A (en) * 1955-04-15 1956-10-09 Du Pont Acyclic, polynitrile-containing, unsaturated compounds and preparation thereof
US3295976A (en) * 1964-09-01 1967-01-03 Eastman Kodak Co Novel inhibitors for use in the black and white development of color reversal film
US3554987A (en) * 1965-12-20 1971-01-12 Eastman Kodak Co Novel compounds and photographic materials containing said compounds
US3701664A (en) * 1968-02-09 1972-10-31 Ciba Geigy Ag Process for hardening light-sensitive photographic layers containing gelatine

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2766247A (en) * 1955-04-15 1956-10-09 Du Pont Acyclic, polynitrile-containing, unsaturated compounds and preparation thereof
US3295976A (en) * 1964-09-01 1967-01-03 Eastman Kodak Co Novel inhibitors for use in the black and white development of color reversal film
US3554987A (en) * 1965-12-20 1971-01-12 Eastman Kodak Co Novel compounds and photographic materials containing said compounds
US3701664A (en) * 1968-02-09 1972-10-31 Ciba Geigy Ag Process for hardening light-sensitive photographic layers containing gelatine

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4078932A (en) * 1975-05-01 1978-03-14 Agfa-Gevaert, N.V. Hardening developers for silver halide photography
US20070077274A1 (en) * 2004-05-12 2007-04-05 Gelita Ag Method for producing shaped bodies based on crosslinked gelatine
CN110062782A (zh) * 2016-12-19 2019-07-26 科思创德国股份有限公司 降低聚氨酯泡沫的释放的方法

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FR2180100B1 (forum.php) 1976-11-12
CH602833A5 (forum.php) 1978-08-15
IT980173B (it) 1974-09-30
JPS4919825A (forum.php) 1974-02-21
CA1002806A (en) 1977-01-04
BE797784A (nl) 1973-10-05
GB1379196A (en) 1975-01-02
DE2218009A1 (de) 1973-11-08

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