Stabilizers for Photographic Silver Halide Emulsions: Progress in Chemistry and Application TOPICS INAPPLIED CHEMISTRY Series Editor: Alan R.Katritzky University ofFlorida Gainesville,Florida GebranJ. Sabongi 3MCompany St. Paul.Minnesota Currentvolumes intheseries: ANALYSISANDDEFORMATION OF POLYMERICMATERIALS Paints,Plastics,Adhesives,and Inks Jan W Gooch ELECTRON PARAMAGNETIC RESONANCE IN BIOCHEMISTRY ANDMEDICINE Lyudmila Ivanovna Larina, Rafik Galimzyanovich Sajfutdinov, Tamara II'inichnaVakul'skaya,and Mikhail Grigor'evichVoronkov FLUOROPOLYMERS 1:Synthesis FLUOROPOLYMERS 2:Properties Editedby Gareth Hougham,PatrickE.Cassidy, KenJohns,andTheodore Davidson FROM CHEMICALTOPOLOGYTO THREE-DIMENSIONAL GEOMETRY EditedbyAlexandruT.Balaban ORGANIC PHOTOCHROMICANDTHERMOCHROMIC COMPOUNDS Volume 1:Main Photochromic Families Volume2:PhysicochemicalStudies,BiologicalApplications, and Thermochromism Editedby John C.Crano and Robert1. Guglielmetti PHOSPHATE FIBERS Edward1. Griffith SURVEY OF INDUSTRIAL CHEMISTRY,Third Edition Philip 1. Chenier STABILIZERSFORPHOTOGRAPHIC SILVERHALIDE EMULSIONS: Progress in Chemistryand Application GuntherFischer AContinuationOrderPlanisavailableforthisseries.Acontinuationorderwillbringdeliveryofeach newvolumeimmediatelyuponpublication.Volumesarebilledonlyuponactualshipment.Forfurther informationpleasecontactthepublisher. Stabilizers for Photographic Silver Halide Emulsions: Progress in Chemistry and Application Gunther Fischer Leipzig, Germany Kluwer Academic / Plenum Publishers NewYork, Boston, Dordrecht, London, Moscow LibraryofCongress Cataloging-in-PublicationData Fischer,Gunther, 1932- Stabilizers forphotographic silverhalideemulsions: progress inchemistryand application /byGunther Fischer. p.cm.-(Topicsinappliedchemistry) Includesbibliographicalreferences andindex. ISBN0-306-47905-2 I. Photographicemulsions.2.Stabilizingagents.3.Silverhalidecrystals.I.Title.II.Series. TR395.F572003 772'.4-dc22 2003060294 ISBN:0-306-47905-2 ©2004KluwerAcademic/Plenum Publishers 233SpringStreet,NewYork,N.Y.10013 http://www.wkap.nl/ 10 9 8 7 6 5 4 3 2 Ac.I.P. recordforthisbookisavailablefromtheLibraryofCongress Allrightsreserved Nopartofthisbookmaybereproduced,storedinaretrievalsystem,ortransmittedinanyform orbyanymeans,electronic,mechanical,photocopying,microfilming,recording,orotherwise, without writtenpermission fromthePublisher Printed intheUnitedStatesofAmerica Dedicatedto the memory ofEmil Joachim Birr, theNestorofemulsion stabilization, onthe occasion ofhis IOOth birthday Contents Foreword xix Preface xxi Abbreviations xxiii 1. Emulsion Stability and Stabilization 1 1.1. Agingand Fog Formation 1 1.2. Stabilizationand Fog Prevention 2 2. General Survey of Relevant Publications 5 2.1. Scope and Limitations 5 2.2. Reviews 5 2.3. OriginalArticles 7 2.4. Patents 7 3. Heterocyclic Stabilizers and Antifogging Agents 13 3.1. Introduction 13 3.2. Heterocyclic Structures 14 3.2.1. Tetraazaindenes and RelatedCompounds 14 3.2.1.1. History,Nomenclature 14 3.2.1.2. Photographic Studies 16 3.2.1.3. Patents 17 3.2.2. OtherOH-NH-Acidic Compounds, Purines 18 3.2.2.1. Tautomeric Hydroxyazolesand -azines 18 3.2.2.2. Purines 19 3.2.3. NH-Acidic Compounds 19 3.2.3.1. GeneralAspects ofAzoles 19 3.2.3.2. Benzotriazoles 21 3.2.3.3. OtherAzoles 21 3.2.3.4. BinuclearHeterocyclic Systems 21 3.2.4. Nuclear-Nitrogen Substituted Compounds 21 3.2.5. Mercapto Compounds 22 3.2.5.1. GeneralAspects 22 3.2.5.2. General and Partial Structures 23 3.2.5.3. Tetrazoles 24 3.2.5.4. OtherMercaptoazoles 24 vii viii Contents 3.2.5.5. Azines 26 3.2.5.6. BinuclearHeterocyclicSystems 26 3.2.6. ThioxoCompounds 26 3.2.7. Thioethers 27 3.2.8. QuaternaryAmmoniumSalts 27 3.2.9. VariousHeterocyclicCompounds 28 3.2.9.1 AminesandHydroxylamines 28 3.2.9.2 SpecialAzoleandAzineDerivatives 30 3.2.9.3 BinuclearHeterocyclicSystems 30 3.2.9.4 Sulfenamidesand Sulfur-Containing HeterocyclicSystems 31 3.3. RelevantPhysico-ChemicalandPhysicalProperties 32 3.3.1. InfluenceonPhotographicProperties 32 3.3.2. Acidity 32 3.3.2.1. DissociationanditsDetermination 32 3.3.2.2. AzaindenesandBenzazoles 34 3.3.2.3. Mercaptoazoles 35 3.3.2.4. Tautomerism 35 3.3.3. ReactivityagainstSilverIons 35 3.3.3.1. Silver-SaltSolubilitiesandtheirDetermination 35 3.3.3.2. SilverSaltsofAzaindenes,Purines, andBenzazoles 36 3.3.3.3. TheStructuresofTAlSilverSaltsand Complexes 37 3.3.3.4. SilverSaltsofMercaptoazoles 38 3.3.3.5. SilverComplexesofMercaptoazoles 38 3.3.3.6. SilverComplexesofNon-AcidicCompounds 38 3.3.3.7. Applications 38 3.3.4. Adsorption 39 3.3.4.1. TheAdsorptionStateonSilverHalides 39 3.3.4.2. TheAdsorptionStateonSilverand SilverSulfide 42 3.3.4.3. TheDeterminationoftheAdsorbability 42 3.3.4.4. QuantitativeResults 44 3.3.4.5. ParametersInfluencingAdsorbability 44 3.3.4.6. AdsorptionofAzaindenesandAzoles 45 3.3.4.7. AdsorptionofMercaptoazoles 48 3.3.4.8. Applications 49 3.3.5. InfluenceonPhysicalGrainProperties 49 3.3.5.1. ElectronicandIonicProperties 49 3.3.5.2. InfluenceonElectronicProperties 49 3.3.5.3. InfluenceonIonicProperties 50 3.3.5.4. OtherMeasuringMethods 50 Contents ix 3.3.6. RedoxProperties 50 3.3.7. HydrophilicityandHydrophobicity 51 3.3.8. Diffusion 52 3.3.8.1. DiffusibilityandDiffusionResistance 52 3.3.8.2. Determination ofDiffusibility 52 3.3.8.3. Rendering StabilizersDiffusion-Resistant 53 3.3.8.4. DiffusionRates 53 3.4. Analytics,Toxicology, andEnvironmentalBehavior 55 3.4.1. Analytics 55 3.4.2. Toxicology 56 3.4.3. EnvironmentalBehavior 56 3.5. MechanismsofStabilization 57 3.5.1. The StateofDiscussionaround 1970 57 3.5.1.1. Birr'sMechanisticConclusions 57 3.5.1.2. Agreement andContradiction 57 3.5.1.3. SubsequentDevelopments 58 3.5.2. RussianStudiesonthe Significance ofPhysico-Chemical Properties 59 3.5.2.1. Acidity,Silver-Bonding,andAdsorption 59 3.5.2.2. Dipole Properties 60 3.5.3. InteractionsofStabilizerswithMetallic Silver (Evva) 61 3.5.3.1. InfluenceonMetallic SilverActivity 61 3.5.3.2. SemiconductorProperties 61 3.5.3.3. StabilizersandColloidalSilver 62 3.5.4. TheOxidation PotentialofStabilizers(Tani) 62 3.5.5. TheComplexationTheory (Cash) 63 3.5.5.1. The SilverComplexofTetraazaindene 63 3.5.5.2. The Chelated SurfaceComplex 65 3.5.5.3. TheKineticAnalysisof Stabilization 65 3.5.5.4. TheMolecular MechanismofStabilization 66 3.5.5.5. Discussion 66 3.5.6. RecentDevelopments:Interactionswith Interstitial SilverIonsandEffectsonDigestion 66 3.5.6.1. Bases 66 3.5.6.2. Interactionswith InterstitialSilverIons 67 3.5.6.3. StabilizationinRelationto Digestion 67 3.5.6.4. Further Contributions 67 3.6. InteractionsofStabilizerswith SensitizationProcesses 68 3.6.1. MainTopics 68 3.6.2. Stabilizersas Sulfur SensitizationModifiers 68 3.6.3. CompetitiveAdsorption withSpectralSensitizers 69 3.6.4. Potentiation 69 x Contents 3.6.5. SupersensitizationbyNon-AcidicCompounds 70 3.6.5.1. Definition 70 3.6.5.2. Mechanisms 71 3.6.5.3. PhotographicStudies 72 3.6.5.4. Applications 72 3.6.6. ChemicalSensitizationandSupersensitizationby AcidicCompounds 72 3.6.6.1. SensitizingEffectsofClassicStabilizers(Tani) 72 3.6.6.2. Tani'sProposedMechanism 73 3.6.6.3. TheInsulationTheoryofSupersensitization(Shapiro) 76 3.6.6.4. FurtherExperimentalContributions 77 3.6.6.5. Applications 78 3.7. OtherUses 79 3.7.1. Photography 79 3.7.2. CorrosionInhibition 80 4. PhenolicSpecies 81 4.1. Introduction 81 4.2. Structures 82 4.2.1. GeneralandPartialStructures 82 4.2.2. MonohydricPhenols 83 4.2.3. Pyrocatechols 83 4.2.4. Resorcinols 84 4.2.5. Hydroquinones 84 4.2.5.1. AlkylDerivatives 84 4.2.5.2. HydrophilicandAminoDerivatives 86 4.2.5.3. OtherDerivatives 87 4.2.6. TrihydricPhenols 88 4.2.7. MonohydricAminophenols 88 4.2.8. Non-PhenolicAntioxidantsandODSCompounds 89 4.2.8.1. OxygenContainingFunctionalities 89 4.2.8.2. HydrazinesandRelatedCompounds 89 4.2.8.3. CompetingCouplers 91 4.3. FunctionsandRelevantProperties 92 4.3.1. ModesofAction 92 4.3.2. MechanismsofOxidizedDeveloperScavenging 93 4.3.3. OxidationPotential,Reactivity,andSubstanceStability 95 4.3.3.1. OxidationPotentials 95 4.3.3.2. TheDeterminationoftheScavengerReactivity 95 4.3.3.3. ScavengerStability 97 4.3.3.4. Influencesofthe Structure 97 4.3.3.5. CompetitionwithCouplers 98 4.3.4. DiffusionResistanceandDispersability 98 Contents xi 4.3.5. Further Properties 99 4.3.5.1. Physico-ChemicalProperties 99 4.3.5.2. ToxicologyandEnvironmentalBehavior 99 4.4. Applications 99 4.4.1. ScavengersinEmulsionLayersandNon-Photosensitive Layers 99 4.4.2. Combinations ofPhenolicandRelatedCompounds 100 4.4.3. Combinations withOtherAdditives 101 4.4.4. PhenolsinColor ImageStabilizationProcesses 10I 4.4.4.1. ColorImageStabilizers 101 4.4.4.2. ODS-TypeCompoundsasColorImage Stabilizers 10I 4.4.4.3. InteractionsofODSwithColorImage StabilizationProcesses 102 4.4.5. OtherSpecialUses 102 5. Aliphatic andNon-Phenolic Aromatic Compounds 103 5.1. Introduction 103 5.2. Structures 103 5.2.1. Hydrocarbonsand HaloCompounds 103 5.2.2. CompoundsBearingOxygenFunctionalities lOS 5.2.2.1. AlkanolsandEthers lOS 5.2.2.2. CarbonylandCarboxylCompounds 105 5.2.3. Nitrogen-Containing Species 106 5.2.3.1. Amines 106 5.2.3.2. AminoAcid andCarbamicAcidDerivatives 107 5.2.3.3. QuaternaryAmmoniumSalts 108 5.2.3.4. OtherNitrogenFunctionalities 109 5.2.4. Phosphorus-ContainingandAnalogousCompounds 110 5.2.5. Sulfur-ContainingSpecies III 5.2.5.1. Mercaptanes,Thioethers,andRelated Compounds III 5.2.5.2. Di-andPolysulfides 113 5.2.5.3. Sulfur-ContainingAminoAcidand Carbamic AcidDerivatives 114 5.2.5.4. SulfurOxygenAcidDerivativesandRelated Compounds lIS 5.3. RelevantProperties andMechanisms 118 5.3.1. FormationofSilverSaltsand Complexes 118 5.3.2. Transformations ofSulfurCompounds 120 5.3.3. Redoxand Sulfur-AcceptorProperties 121 5.3.3.1. Oxidants 121 5.3.3.2. SulfinicAcidSalts 122