US3900321A - Silver halide emulsion containing aromatic azocarbonamide antifog agent - Google Patents

Silver halide emulsion containing aromatic azocarbonamide antifog agent Download PDF

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US3900321A
US3900321A US293772A US29377272A US3900321A US 3900321 A US3900321 A US 3900321A US 293772 A US293772 A US 293772A US 29377272 A US29377272 A US 29377272A US 3900321 A US3900321 A US 3900321A
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azocarbonamide
emulsion
added
silver halide
group
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Alan Norman Ferguson
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3M Co
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Minnesota Mining and Manufacturing Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/40—Acylated substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
    • C07D295/215—Radicals derived from nitrogen analogues of carbonic acid
    • 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
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression

Definitions

  • This invention relates to photographic silver halide emulsions containing organic anti-fogging agents and to ring-substituted azocarbonamides for use as antifogging agents for photographic silver halide emulsions.
  • a photographic silver halide emulsion which has in fog inhibiting reactive association therewith an azocarbonamide.
  • azocarbonamides act as antifogging agents for photographic emulsions. It is believed that the desired anti-fogging effect is achieved because the azocarbonamide acts as an oxidizing agent for those silver halide crystals or grains in the emulsion which become accidentally developable, i.e., fogged, during production or handling of the emulsion, e.g., by accidental slight light exposure, chemical action or strain. Thus when a crystal or grain becomes fogged, it is oxidized by the azoearbonamide and so the crystal or grain does not therefore become developed as a fog speck when the emulsion is developed after normal light exposure.
  • the azocarbonamide is preferably added to the pho tographic emulsion. It can instead be present in a layer adjacent to an emulsion layer.
  • azocarbonamide to be added to a photographic emulsion to give the desired anti-fogging effect
  • good results will be given when from 0.025 to 1.0 millimole of an azocarbonamide, and preferably a ring-substituted azocarbonamide, is added per mole of silver in the emulsion.
  • the azocarbonamide does not seriously effect the other desirable properties of the emulsion such as film speed, and in addition we find that the azocarbonamide has comparable or better anti-fogging properties and also comparable or better gamma (contrast) and D-max when added to photographic emulsions as compared with azodicarbonamide.
  • these azocarbonamides act as antifogging agents for photographic emulsions because they can be readily reduced, i.e., they are oxidizing agents, and they oxidize developable silver halide specks to a non-developable form. This oxidation is illustrated for example, by the following reaction using phenylazocarbonamide:
  • Certain of the azocarbonamides of this invention, and particularly ring-substituted azocarbonamides, are unstable when in contact with the emulsion, e.g., hy drolytically unstable, and are decomposable in a rea sonable time at normal temperatures, e.g., days at 60F, to innocuous decomposition products.
  • these azocarbonamides can be added to photographic silver halide emulsions in relatively large amounts, i.e., in an amount which is at least sufficient to oxidize the silver in those silver halide crystals or grains which would otherwise become developable after the emulsion has been prepared and coated on a suitable substrate and dried, any excess azocarbonamide being capable of decomposing in a reasonable time at normal temperatures to leave insufficient azocarbonamide to interfere substantially with image exposure and development of the emulsion coating.
  • certain azocarbonamides and preferably ring-substituted azocarbonamides can be used as the oxidizing agent required to eliminate undesirable fog in photographic elements according to the inventions described in our copending US. patent application Ser. Nos. 243,463 and 244,276, filed Apr. 12, 1972 and Apr. 14, 1972 respectively. They are added to the emulsion in relatively large amounts, e.g., from 1.5 to 25 millimoles per mole of silver :in the emulsion and initially they almost completely desensitize the emulsion to light. However, they decompose in a reasonable time so that they protect the emulsion from fog formation during manufacture and coating of the emulsion and handling of the coated emulsion, and then the emulsion regains its speed before use.
  • the photographic emulsion to which the azocarbona mides can be added can be one which is suitable for black and white or for color photography, or for use in radiography. Also the emulsion can be a negative emulsion or a direct positive emulsion. Further the silver halide can be the bromide, iodide, a mixed halide or any of the silver halide materials useful in photographic techniques.
  • the preferred azocarbonamides used in photographic emulsion according to the invention are aryl azocarbonamides, preferably ring-substituted azocarbonamides represented by the formula:
  • Ar represents any aromatic group and R represents a carbonamide with the exception of the case where both Ar represents a phenyl group and R represents the group CON H
  • the preferred carbonamide groups may be further characterized as in which R and R which may be the same or different, each represents a hydrogen atom, an alkyl, alkylene, alicyclic, aryl, aralkyl, alkaryl group or a grouping containing a center of positive charge and having associated with it one or more negatively charged moieties sufficient to impart electrical neutrality, or R and R together with the nitrogen atom to which they are linked represent the atoms required to complete a bet erocyclic ring which may itself be substituted or contain a center of positive charge having associated with it one or more negatively charged moieties sufficient to impart electrical neutrality, with the exception of the 5 case where Ar represents a phenyl group and R and R both represent hydrogen atoms.
  • oxidizing agents having an oxidizing potential of from 0.08 to +0.50. These compounds are hydrolytically unstable in that they decompose when in contact with an emulsion within about 60 days at 60F.
  • Illustrative of the types of groups which can be used for the aromatic group Ar are, for example, an aryl, aralkyl or alkaryl group such as a phenyl, naphthyl, or substituted phenyl group of the general formula:
  • heterocyclic group which can contain a quaternizable nitrogen atom such as one of the groups having the general formula:
  • R may be different from one another and are a hydrogen or halogen atom or an alkyl, alkylene, alicyclic, aryl, aralkyl, alkaryl, COOH, SO H, alkyl ammonium of fiuoroalkyl group.
  • the most preferred class of azocarbonamides which ace particularly well as excellent anti-fogging agents are those where Ar represents a phenyl or a naphthyl group. These may be substituted phenyl or naphthyl groups as well as unsubstituted. Also hetero-cyclic groups as set out above and R and R represent hydrogen atoms or lower alkyl groups, e.g., containing 1 to 4 carbon atoms may be used. In order to improve the water solubility of such compounds the grouping Ar may contain one or more water-solubilizing groups such as -COOH or -SO H. Substituents such as I JO tend to desensitize photographic emulsions and so are preferably not present.
  • azocarbonamides are relatively hydrolytically stable and so will generally be added in quite small amounts as noted above to photographic emulsions to act as anti-fogging agents. Generally the water solubility of these compounds is sufficient to enable them to be added in these relatively small amounts in aqueous solution which has the advantage of being compatible with the emuision and relatively inert to the emulsion.
  • azocarbonamides contain groupings hav ing centers of positive charge, e.g., quaternary ammonium groupings, they can have the general formula:
  • R represents a carbonamide wherein a substit uent in the nitrogen atom of the carbonamide group contains at least one quaternary ammonium
  • R represents a grouping containing at least one quaternary ammonium grouping
  • R represents a hydrogen atom or an aliphatic, alicyclic, aromatic or heterocyclic group, or R and it? together with the amide nitrogen atom cornwhile an example of a suitable grouping represented by R and R together with the amide nitrogen is where R represents a lower alkyl group.
  • the negatively charged moiety or moieties can be one or more separate anions associated with the amcarbonamide or the azocarbonamide can also contain one or more negatively charged substituents as part of its structure.
  • suitable anions include, for example, aryl sulphonates such as toluene-p-sulphonate, alkyl sulphites, boron tetrafluoride (BFf), iodide, iodate, chloride, chlorate, per chlorate and nitrate ions.
  • the negatively charged moiety forms part of the azocarbonamide
  • the negatively charged grouping can include, for example, a sulphobetain grouping.
  • ring-substituted az ocarbonamides of the invention can be prepared by oxidizing (e.g., with acid ified potassium permanganate), the corresponding ring-substituted hydrazocarbonamide.
  • this intermediate hydrazocarbonamide can be prepared in a number of ways.
  • a phenylazocarbonamide substituted or unsubstituted on the phenyl ring and unsubstituted on the amide nitrogen atom, can be prepared by reacting the corresponding phenylhydrazine, preferably as its hydrochloride salt, with a cyanate, e,g., KCNO, and then oxidizing the resulting phenyl hydrazocarbonamide.
  • a cyanate e,g., KCNO
  • a phenylazocarbonamide substituted or unsubstituted on the phenyl ring and monosubstituted on the amide nitrogen atom can be prepared by reacting the corresponding phenylhydrazine with the appropriate isocyanate followed by oxidation of this intermediate hydrazocarbonamide. This reaction is illustrated by the following scheme for preparing N- ethylphenylazocarbonamide:
  • a phenylazocarbonamide substituted or unsubsti tuted on the phenyl ring and di-substituted on the amide nitrogen atom can be prepared by reacting the corresponding phenylhydrazine with the appropriate di-substituted carbamyl chloride, e.g., a dialkyl chloride, followed by oxidation of the resulting intermediate hydrazocarbonamide. This reaction is illustrated by the following scheme for preparing N-dimethylphenylazocarbonamide:
  • a heterocyclic azocarbonamide unsubstituted on the amide nitrogen atom can be prepared by reacting the corresponding heterocyclic hydrazine, preferably in the form ofa salt with a cyanate, e.g., KCNO, and then oxidizing the resulting heterocyclic hydrazocarbonamide. This reaction can be illustrated by the following scheme for preparing 2-quinolineazocarbonamide:
  • KCNO b HEHCl NHNHCONH oxidation Another route for the preparation of the ring- Azocarbonamides containing a quaternary ammosubstituted azocarbonamides is to react the correnium group can be prepared from azocarbonamides sponding azo ester with a diamine. This route is particularly useful for the preparation of azocarbonamides which have tertiary amine substituents.
  • a heterocyclic azocarbonamide which is monoor disubstituted on th amide nitrogen atom can, for example, be prepared by making the corresponding heterocyclic hydrazoester, oxidizing this to the azo ester followed by reaction with a diamine.
  • This diamine may form with the azo ester an azocarbonamide in which the amine nitrogen atom forms part of a heterocyclic ring containing a second tertiary nitrogen atom or an azocarbonamide in which one substituent on the amine nitrogen atom contains a tertiary nitrogen atom.
  • the following reaction scheme illustrates this procedure:
  • l-Chlorobenzotriazole (7.83 g, 0.05M) was dissolved in methylene dichloride ml) and added dropwise to a stirred solution of ethyl-2-quinolylhydrazocarboxylate (1 1.6 g, 0.05M) in methylene dichloride (150 ml). lce cooling was used to keep the temperature below 20C during the addition. The reaction mixture was then stirred for 1 hour at room temperature, filtered and the filtrate washed with 2 Normal NaOH (25 ml), then water (25 m1) and finally dried over sodium sulphate. Evaporation of the methylene dichloride gave ethyl-2-quinolylazocarboxylate: as a dark orange solid (melting point 57C).
  • R H requires:
  • 4,4-Dimethyl-l-phenylsemicarbazide 1 1.8 g; 0066M was dissolved in 600 ml of water at 90C and oxidized as described in Examples 10 to 18 to give an 9, can be prepared by preparing the appropriate azoester and then reacting this with the appropriate diamine. This is illustrated by the following preparation.
  • the azocarboxylate (8.8 g; 0.04 M) was dissolved in ether (50 ml) and stirred while a solution of 4- aminomethylpyridine (4.4g; 0.04 M) in ether (15 ml) was run in slowly. An orange-red precipitate was quickly formed. Stirring was continued for 1 hour, then ride and stirred while a solution of l-chlorobenzotriazole 15.4 g; 0.10 M) in methylene dichloride 100 ml) was added dropwise. External ice-cooling was used to keep the temperature below 20C during the addition. After addition was complete, a further 2 hours stirring at room temperature was given, then the reaction mixture was filtered.
  • EXAMPLE ammoniacal conditions the final emulsion having an 2 QumO1meazocarbonamldc iodide content 0 about 2 moles percent
  • the emulsion was digested with a sulphur and a gold sensitiser. After stabilization by the addition of 4-hydroxy-5-2- hydroxyethyl-o-methyll :3:3a:7-tetraazaindene 3- amino-5-methylthio-1:2:4-triazole salt (see Example 1 of our United Kingdom Pat. No. 1,022,872), the emulsion was divided into four parts.
  • the coated films were dried, exposed to a continuous wedge in a sensitometer, and processed at 104F in a standard, commercially-available developer of the type suitable for use in a modern X-ray film processing machine having a total dry-to-dry process time of 90 seconds.
  • the relative fog speeds, fog levels, gamma and D-max were measured and results were as shown in the following Table V.
  • the anti-fogging effects of the ring-substituted azocarbonamides in the emulsions according to the invention were excellent as compared with the Emulsion A without any addition, and also as good as or better than the anti-fogging effects of azodicarbonamide (Emulsion B), even though much smaller amounts of the ringsubstituted azocarbonamides were added to Emulsions C and D.
  • the other photographic properties of the emulsions according to the invention were similar to the emulsion without addition (Emulsion A).
  • EXAMPLE 32 Coarse-grain gelatine or silver bromoiodide emulsions, of cubic habit and having a mean grain size of approximately 2.0 microns, were prepared by ripening under ammoniacal conditions, the final emulsions having iodide contents of about 2 moles percent. The emulsions were digested with a sulphur and gold sensitizer.
  • the emulsions were coated on polyester bases to give a silver coating weight of 5.0 glmeter
  • Each emulsion layer was then coated with a protective gelatin super coat containing a gelatin cross-linking agent.
  • the coated films were then dried, exposed to a continuous wedge in a sensitometer and processed at 104F in a standard, commercially available developer of the type suitable for use in a modern X-ray film processing machine having a total dry-to-dry process time of 90 seconds.
  • the relative log speeds, fog levels, average contrast and D-max were measured and the results are shown in Tables V1 to X.
  • Table V11 Compound Relative added Quantity log (Example added speed Average No.) (mM/M) Fog (0.5) contrast D-max No addition 0.10 1.53 0.86 1.42 Azodicarbom amide 0.625 0.08 1.48 0.50 1.26 0.025 0.10 1.44 0.81 1.30 0.075 0.1 l 1.42 1.20 20 0.25 0.09 1.54 0.80 1.34 0.75 0.08 1.48 0.78 1.32 2.50 0.08 1.37 0.75 1.34 0.025 0.09 1.55 0.91 1.40 0.075 0.08 1.42 0.65 1.28 23 0.25 0.08 1.42 0.96 1.43 0.75 0.08 1.47 0.65 1.32 2.50 0.08 1.28 0.60 1.20
  • Table V111 Compound Relative added Quantity log (Example added speed Average No.) (mM/M) Fog (0.5) contrast D-max No addition 0.14 1.80 1.74 2.27 Azodicarbonamide 0.625 0.08 1.66 1.61 1.84 0.025 0.08 1.70 1.77 2.17 0.075 0.08 1.57 1.71 2.02 21 0.25 0.08 1.40 1.85 2.14 0.75 0.07 1.06 1.75 1.71 2.50 0.08 0.69 1.79 1.28 0.025 0.10 1.71 1.69 2.04 0.075 0.08 1.75 1.69 2.21 13 0.25 0.07 1.59 1.63 1.75 0.75 0.07 1.42 1.76 1.90 2.50 0.07 1.26 1.57 1.70
  • a silver halide photographic emulsion which has in fog inhibiting reactive association therewith at least a fog inhibiting amount of an azocarbonamide having one azo-carbonamide group.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Quinoline Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
US293772A 1971-10-08 1972-10-02 Silver halide emulsion containing aromatic azocarbonamide antifog agent Expired - Lifetime US3900321A (en)

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GB4705671A GB1411373A (en) 1971-10-08 1971-10-08 Azomonocarbonamides and their use in photographic silver halide emulsions

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US (1) US3900321A (cs)
JP (1) JPS5539823B2 (cs)
AR (1) AR204307A1 (cs)
BE (1) BE789780A (cs)
CA (1) CA980341A (cs)
CH (1) CH601195A5 (cs)
DE (1) DE2248958A1 (cs)
FR (1) FR2155631A5 (cs)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731141A (en) * 1995-06-16 1998-03-24 Imation Corp. Light-sensitive photographic materials comprising tabular silver halide grains and azodicarbonamide derivatives
US11559404B2 (en) 2017-02-14 2023-01-24 Onkos Surgical, Inc. Acetabular surgical implant for segmental pelvic defect and methods of use and manufacture

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL171968B1 (pl) * 1991-11-22 1997-07-31 Uniroyal Chem Co Inc Srodek szkodnikobójczy PL PL PL PL PL PL
FR2754254B1 (fr) * 1996-10-09 1998-10-30 Rhone Poulenc Agrochimie Fongicides a groupes hydroximiques et hydrazoniques

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3655391A (en) * 1969-05-16 1972-04-11 Paoli Merli Azodicarbonamide fog inhibitors
US3732104A (en) * 1969-11-03 1973-05-08 Agfa Gevaert Nv Silver halide emulsions containing azaindene and amide stabilizing agents

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3655391A (en) * 1969-05-16 1972-04-11 Paoli Merli Azodicarbonamide fog inhibitors
US3732104A (en) * 1969-11-03 1973-05-08 Agfa Gevaert Nv Silver halide emulsions containing azaindene and amide stabilizing agents

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731141A (en) * 1995-06-16 1998-03-24 Imation Corp. Light-sensitive photographic materials comprising tabular silver halide grains and azodicarbonamide derivatives
US11559404B2 (en) 2017-02-14 2023-01-24 Onkos Surgical, Inc. Acetabular surgical implant for segmental pelvic defect and methods of use and manufacture

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JPS5539823B2 (cs) 1980-10-14
JPS496919A (cs) 1974-01-22
DE2248958A1 (de) 1973-04-12
AR204307A1 (es) 1975-12-22
GB1411373A (en) 1975-10-22
CH601195A5 (cs) 1978-06-30
FR2155631A5 (cs) 1973-05-18
BE789780A (fr) 1973-02-01
CA980341A (en) 1975-12-23

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