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Stabilizers for Photographic SilverHalide Emulsions: Progress inChemistry and Application
TOPICS IN APPLIED CHEMISTRYSeries Editor: Alan R. Katritzky
University ofFloridaGainesville, Florida
Gebran J. Sabongi3M CompanySt. Paul. Minnesota
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Stabilizers for Photographic Silver Halide Emulsions: Progress in Chemistry and Application
Gunther Fischer Leipzig, Germany
Springer Science+Business Media, LLC
Library ofCongress Cataloging-in-Publication Data
Fischer, Gunther, 1932-Stabilizers for photographic silver halide emulsions: progress in chemistry and application I by Gunther Fischer.
p. cm.-(Topics in applied chemistry) Includes bibliographical references and index. ISBN 978-1-4613-4796-5 ISBN 978-1-4419-9108-9 (eBook) DOI 10.1007/978-1-4419-9108-9
1. Photographic emulsions. 2. Stabilizing agents. 3. Silver halide crystals. 1. Title. 11. Series.
TR395.F57 2003 772'.4--dc22
ISBN 978-1-4613-4796-5
© 2004 Springer Science+Business Media New York Originall~ I?ublished by. Kluwer I Plenum Publishers, New York in 2004
Softcover reprint ofthe hardcover Ist edition 2004
All rights reserved
2003060294
No par! of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher
Dedicated to the memory of Emil Joachim Birr, the Nestor of emulsionstabilization, on the occasion of his IOOth birthday
Contents
ForewordPrefaceAbbreviations
1. Emulsion Stability and Stabilization1.1. Aging and Fog Formation1.2. Stabilization and Fog Prevention
2. General Survey of Relevant Publications2.1. Scope and Limitations2.2. Reviews2.3. Original Articles2.4. Patents
3. Heterocyclic Stabilizers and Antifogging Agents3.1. Introduction3.2. Heterocyclic Structures
3.2.1. Tetraazaindenes and Related Compounds3.2.1.1. History, Nomenclature3.2.1.2. Photographic Studies3.2.1.3 . Patents
3.2.2. Other OH-NH-Acidic Compounds, Purines3.2.2.1. Tautomeric Hydroxyazoles and -azines3.2.2.2. Purines
3.2.3. NH-Acidic Compounds3.2.3 .1. General Aspects of Azoles3.2.3.2. Benzotriazoles3.2.3.3. Other Azoles3.2.3.4. Binuclear Heterocyclic Systems
3.2.4 . Nuclear-Nitrogen Substituted Compounds3.2.5. Mercapto Compounds
3.2.5.1. General Aspects3.2.5.2 . General and Partial Structures3.2.5.3. Tetrazoles3.2.5.4 . Other Mercaptoazoles
vii
xixxxi
xxiii
112
55577
131314141416171818191919212121212222232424
viii Contents
3.2.5.5. Azines 263.2.5.6. Binuclear Heterocyclic Systems 26
3.2.6. Thioxo Compounds 263.2.7. Thioethers 273.2.8. Quaternary Ammonium Salts 273.2.9. Various Heterocyclic Compounds 28
3.2.9.1 Amines and Hydroxylamines 283.2.9.2 Special Azole and Azine Derivatives 303.2.9.3 Binuclear Heterocyclic Systems 303.2.9.4 Sulfenamides and Sulfur-Containing
Heterocyclic Systems 313.3. Relevant Physico-Chemical and Physical Properties 32
3.3.1. Influence on Photographic Properties 323.3.2. Acidity 32
3.3.2.1. Dissociation and its Determination 323.3.2.2. Azaindenes and Benzazoles 343.3.2.3. Mercaptoazoles 353.3.2.4. Tautomerism 35
3.3.3. Reactivity against Silver Ions 353.3.3.1. Silver-Salt Solubilities and their Determination 353.3.3.2. Silver Salts of Azaindenes, Purines,
and Benzazoles 363.3.3.3. The Structures of TAl Silver Salts and
Complexes 373.3.3.4. Silver Salts of Mercaptoazoles 383.3.3.5. Silver Complexes of Mercaptoazoles 383.3.3.6. Silver Complexes of Non-Acidic Compounds 383.3.3.7. Applications 38
3.3.4. Adsorption 393.3.4.1. The Adsorption State on Silver Halides 393.3.4.2. The Adsorption State on Silver and
Silver Sulfide 423.3.4.3. The Determination of the Adsorbability 423.3.4.4. Quantitative Results 443.3.4.5. Parameters Influencing Adsorbability 443.3.4.6. Adsorption of Azaindenes and Azoles 453.3.4.7. Adsorption ofMercaptoazoles 483.3.4.8. Applications 49
3.3.5. Influence on Physical Grain Properties 493.3.5.1. Electronic and Ionic Properties 493.3.5.2. Influence on Electronic Properties 493.3.5.3. Influence on Ionic Properties 503.3.5.4. Other Measuring Methods 50
Contents ix
3.3.6. Redox Properties 503.3.7. Hydrophilicity and Hydrophobicity 513.3.8. Diffusion 52
3.3.8.1. Diffusibility and Diffusion Resistance 523.3.8.2. Determination of Diffusibility 523.3.8.3. Rendering Stabilizers Diffusion-Resistant 533.3.8.4. Diffusion Rates 53
3.4. Analytics, Toxicology, and Environmental Behavior 553.4.1. Analytics 553.4.2. Toxicology 563.4.3. Environmental Behavior 56
3.5. Mechanisms of Stabilization 573.5.1. The State of Discussion around 1970 57
3.5.1.1. Birr 's Mechanistic Conclusions 573.5.1.2. Agreement and Contradiction 573.5.1.3. Subsequent Developments 58
3.5.2. Russian Studies on the Significance of Physico-ChemicalProperties 593.5.2.1. Acidity, Silver-Bonding, and Adsorption 593.5.2.2. Dipole Properties 60
3.5.3. Interactions of Stabilizers with Metallic Silver(Evva) 613.5.3.1. Influence on Metallic Silver Activity 613.5.3.2. Semiconductor Properties 613.5.3.3. Stabilizers and Colloidal Silver 62
3.5.4. The Oxidation Potential of Stabilizers (Tani) 623.5.5. The Complexation Theory (Cash) 63
3.5.5.1. The Silver Complex ofTetraazaindene 633.5.5.2. The Chelated Surface Complex 653.5.5.3. The Kinetic Analysis of Stabilization 653.5.5.4. The Molecular Mechanism of Stabilization 663.5.5.5. Discussion 66
3.5.6. Recent Developments: Interactions with InterstitialSilver Ions and Effects on Digestion 663.5.6.1. Bases 663.5.6.2. Interactions with Interstitial Silver Ions 673.5.6.3. Stabilization in Relation to Digestion 673.5.6.4. Further Contributions 67
3.6. Interactions of Stabilizers with Sensitization Processes 683.6.1. Main Topics 683.6.2. Stabilizers as Sulfur Sensitization Modifiers 683.6.3. Competitive Adsorption with Spectral Sensitizers 693.6.4. Potentiation 69
x Contents
3.6.5. Supersensitization by Non-Acidic Compounds 703.6.5.1. Definition 703.6.5.2. Mechanisms 713.6.5.3. Photographic Studies 723.6.5.4. Applications 72
3.6.6. Chemical Sensitization and Supersensitization byAcidic Compounds 723.6.6.1. Sensitizing Effects of Classic Stabilizers (Tani) 723.6.6.2. Tani's Proposed Mechanism 733.6.6.3. The InsulationTheory of Supersensitization (Shapiro) 763.6.6.4. Further Experimental Contributions 773.6.6.5. Applications 78
3.7. Other Uses 793.7.1. Photography 793.7.2. Corrosion Inhibition 80
4. Phenolic Species 814.1. Introduction 814.2. Structures 82
4.2.1. General and Partial Structures 824.2.2. Monohydric Phenols 834.2.3. Pyrocatechols 834.2.4. Resorcinols 844.2.5. Hydroquinones 84
4.2.5.1. Alkyl Derivatives 844.2.5.2. Hydrophilic and Amino Derivatives 864.2.5.3. Other Derivatives 87
4.2.6. Trihydric Phenols 884.2.7. Monohydric Aminophenols 884.2.8. Non-Phenolic Antioxidants and ODS Compounds 89
4.2.8.1. Oxygen Containing Functionalities 894.2.8.2. Hydrazines and Related Compounds 894.2.8.3. Competing Couplers 91
4.3. Functions and Relevant Properties 924.3.1. Modes of Action 924.3.2. Mechanisms of Oxidized Developer Scavenging 934.3.3. Oxidation Potential, Reactivity, and Substance Stability 95
4.3.3.1. Oxidation Potentials 954.3.3.2. The Determination of the Scavenger Reactivity 954.3.3.3. Scavenger Stability 974.3.3.4. Influences of the Structure 974.3.3.5. Competition with Couplers 98
4.3.4. Diffusion Resistance and Dispersability 98
Contents xi
4.3.5. Further Properties 994.3.5.1. Physico-Chemical Properties 994.3.5.2. Toxicology and Environmental Behavior 99
4.4. Applications 994.4.1. Scavengers in Emulsion Layers and Non-Photosensitive
Layers 994.4.2. Combinations of Phenolic and Related Compounds 1004.4.3. Combinations with Other Additives 1014.4.4. Phenols in Color Image Stabilization Processes 10I
4.4.4.1. Color Image Stabilizers 1014.4.4.2. ODS-Type Compounds as Color Image
Stabilizers 10I4.4.4.3. Interactions of ODS with Color Image
Stabilization Processes 1024.4.5. Other Special Uses 102
5. Aliphatic and Non-Phenolic Aromatic Compounds 1035.1. Introduction 1035.2. Structures 103
5.2.1. Hydrocarbons and Halo Compounds 1035.2.2. Compounds Bearing Oxygen Functionalities lOS
5.2.2.1. Alkanols and Ethers lOS5.2.2.2. Carbonyl and Carboxyl Compounds 105
5.2.3. Nitrogen-Containing Species 1065.2.3.1. Amines 1065.2.3.2. Amino Acid and Carbamic Acid Derivatives 1075.2.3.3. Quaternary Ammonium Salts 1085.2.3.4. Other Nitrogen Functionalities 109
5.2.4. Phosphorus-Containing and Analogous Compounds 1105.2.5. Sulfur-Containing Species III
5.2.5.1. Mercaptanes, Thioethers, and RelatedCompounds III
5.2.5.2. Di- and Polysulfides 1135.2.5.3. Sulfur-Containing Amino Acid and Carbamic
Acid Derivatives 1145.2.5.4. Sulfur Oxygen Acid Derivatives and Related
Compounds lIS5.3. Relevant Properties and Mechanisms 118
5.3.1. Formation of Silver Salts and Complexes 1185.3.2. Transformations of Sulfur Compounds 1205.3.3. Redox and Sulfur-Acceptor Properties 121
5.3.3.1. Oxidants 1215.3.3.2. Sulfinic Acid Salts 122
xii
5.3.4. Further Properties5.3.4.1. Physico-Chemical Properties5.3.4.2. Analytics and Toxicology
5.4. Other Photographic Uses
6. Miscellaneous Compounds and Methods6.1. Species Containing Group VI Sulfur Analogs
6.1.1. Selenium Compounds6.1.2. Tellurium Compounds
6.2. Methine Dyes6.2.1. Blue Sensitizers6.2.2. Other Methine Dyes
6.3. Polymers6.3.1. Natural Polymers and Derivatives6.3.2. Synthetic Polymers
6.3.2.1. Vinyl-Type Polymers6.3.2.2. Acrylate-Type Polymers6.3.2.3. Other Polymeric Species
6.3.3. Polymers Bearing Specific Stabilizer Moieties6.3.3.1. Heterocyclic Stabilizer Species6.3.3.2. Phenolic and Related Species6.3.3.3. Syntheses of Polymer-Fixed Stabilizers6.3.3.4. Fixing Stabilizers to Gelatin
6.4. Inorganic Compounds6.4.1. Compounds of Subgroup Elements6.4.2. Compounds of Main-Group Elements
6.5. Coordination Compounds of Organic Ligands6.6. Other Stabilization Methods
6.6.1. Control of pH and pAg Values6.6.2. Miscellaneous Methods
7. The Moment of Incorporating Stabilizers7.1. Introduction7.2. Precipitation and Physical Ripening
7.2.1. Grain Growth Inhibition7.2.2. Grain Habit Modification7.2.3. Stabilization and Fog Prevention
7.3 Digestion7.3.1. Chemical Ripening Inhibition7.3.2. Stabilization and Fog Prevention
7.4. Coating7.4.1. Development Inhibition7.4.2. Stabilization and Fog Prevention
Contents
123123123124
127127127127129129130130130131131132133133133134136136137137138138140140141
143143143143144147147147148150150152
Contents xlii
7.5. Processing Solutions 1537.5.1. Development Inhibition 1537.5.2. Stabilizers (Tetraazaindenes) 1547.5.3. Antifoggants 155
8. Methods of Incorporation 1598.1. Solution 1598.2. Dispersion 159
8.2.1. Liquid-Liquid Dispersion 1598.2.2. Solid-Liquid Dispersion 161
8.3. Special Methods of Diffusion-Resistant Incorporation 1618.4. Other Incorporation Methods 1628.5. Addition to Non-Photosensitive Layers 163
9. Masked Antifoggants and Stabilizers 1659.1. General Structures and Effects 165
9.1.1. Structures 1659.1.2. Trends of the Patent Applications 1669.1.3. Modes of Action 167
9.2. Acyl Derivatives 1689.2.1. Hydrolyzable Heterocyclic Thiolesters and N-Acyl
Derivatives 1689.2.2. Hydrolysis Rate and Photographic Activity of Acyl
Derivatives 1719.2.3. Derivatives Cleavable by Intramolecular Nucleophilic
Displacement 1739.2.4. Aliphatic and Aromatic Thiolesters 175
9.3. Alkyl and Aryl Derivatives 1779.3.1. Survey 1779.3.2. Derivatives Cleavable by I3-Elimination 1779.3.3. Hydroxybenzyl Derivatives 1779.3.4. Heterocyclylmethyl Compounds 1799.3.5. Other Functionalized Methyl Derivatives 1829.3.6. Nitroaryl Derivatives 1839.3.7. Other Masked Heterocyclic Antifoggants 1859.3.8. Kinetics and Rate of Cleavage of Alkyl-TypeMasked
Antifoggants 1869.4. Heterocyclic Disulfides 189
9.4.1. Di-(l-phenyl-5-tetrazolyl) Disulfides 1899.4.2. Other Disu1fides 190
9.5. Benzothiazo1ium Salts 1919.5.1. Chemical Behavior 1919.5.2. Photographic Applications 1929.5.3. Use of Cleavage Products 193
xiv Contents
9.6. Demasking by Cyclization and Ring Transformation 1949.7. Salts and Adducts of Antifoggants 194
9.7.1. Ion Pairs formed with Inorganic and Organic Ions 1949.7.2. Heavy Metal Salts 1969.7.3. Adducts 197
9.8. Masked Phenolic and Non-Phenolic ODS Compounds 1979.9. Special Conditions and Applications 197
9.9.1. Influences on Cleavage Kinetics 1979.9.2. Incorporation 2009.9.3. Application 200
10. Imagewise Release from DIR Compounds 20310.1. Introduction 20310.2. DIR Compounds without Color Coupler Properties 204
10.2.1. Release by Coupling Reactions at ActiveMethylene or Methine Groups 204
10.2.2. Release by Redox Reactions 20610.2.2.1. DIR Hydroquinones and Other DIR
Phenols 20610.2.2.2. DIR Hydrazides 20810.2.2.3. Other DIR Compounds 209
10.2.3. Specific Properties and Applications 21110.3. DIR Couplers and Related Functional Couplers 212
10.3.1. Conventional DIR Couplers 21210.3.2. Timing-DIR (DIAR) Couplers 21410.3.3. Super-DIR Couplers 21710.3.4. DIRR Couplers 21710.3.5. ODSR Couplers 21710.3.6. UDIR Couplers 219
11. Stabilization of Special Emulsions, Materials,Processes,and Properties 22111.1. Materials Containing Little or No Gelatin 22111.2. Special Emulsions 222
11.2.1. Emulsions having Specific Grain Size 22211.2.2. Emulsions having Defined Crystal Habit 22211.2.3. Emulsions having Special Grain Composition 223
11.2.3.1. Silver Chloride and Silver ChlorobromideEmulsions 223
11.2.3.2. High-Silver Iodide Emulsions 22411.2.3.3. Core-Shell Emulsions 22511.2.3.4. Converted Emulsions 225
11.2.4. High-Speed Emulsions 225
Contents xv
11.3. Special Materials 22611.3.1. Reprographic and Related Materials 226
11.3.1.1. Lith Material 22611.3.1.2. Material with Incorporated Contrast
Promoters 22711.3.1.3. High-Speed Negative-Type Material 22811.3.1.4. High-Contrast Material for Low-pH
Development 22811.3.1.5. Material with Incorporated Inhibitors 22911.3.1.6. Scan Films 22911.3.1.7. Other Materials 230
11.3.2. Radiographic Materials 23011.3.3. Scientific and Technological Materials 23111.3.4. Other Black-and-White Materials 23211.3.5. Color Materials 23211.3.6. Direct-Positive Materials 234
11.4. Special Processes 23511.5. Stabilization of Speed and Gradient 236
12. Application in the Presence of Other Constituentsand Additives12.1. Introduction12.2. Support
12.2.1. Film12.2.1.1. Cellulose Esters12.2.1.2. Polyester
12.2.2. Paper12.3. Gelatin12.4. Speed-Increasing Additives
12.4.1. Chemical Sensitizers for Digestion12.4.2. Development Accelerators12.4.3. Spectral Sensitizers
12.5. Color Couplers12.6. Developing Agents12.7. Additives Influencing Physical and Mechanical
Properties12.7.1. Hardening Agents12.7.2. Other Relevant Additives and Layers
12.8. Influences of Stabilizers and Development Inhibitors
13. Applications under Certain EnvironmentalConditions13.1. Introduction
239239239239239239240241242242243244245247
248248249250
251251
xvi Contents
13.2. Physical Influences, Humidity, and Oxygen 25113.2.1. Pressure 251
13.2.1.1. Causes and Effects 25113.2.1.2. Agents Improving Pressure Resistance 25213.2.1.3. Agents Preventing Pressure
Desensitization or Pressure Fog 25413.2.2. Temperature, Humidity, and Oxygen Concentration 255
13.2.2.1. Test Conditions 25513.2.2.2. Temperature 25613.2.2.3. Humidity 25613.2.2.4. Temperature and Humidity 25813.2.2.5. Oxygen, Inert Gases, and Vacuum 260
13.2.3. Light and Ionizing Radiation 26013.3. Microorganisms 26113.4. Chemical Agents 263
13.4.1. Influences of Packaging 26313.4.2. Formaldehyde 26413.4.3. Other Gases and Vapors 26613.4.4. Nonvolatile Species 267
13.5. Influences of Processing 26813.5.1. High-Temperature, Rapid, and Machine Processing 268
13.5.1.1. General Conditions, Reports 26813.5.1.2. Patents 26913.5.1.3. Processing of Special Materials 27213.5.1.4. Exchangeable Processing 272
13.5.2. Processing under Safelight, Room-, and Daylight 27313.5.2.1. Safelight 27313.5.2.2. Room- and Daylight 274
13.5.3. Processing under Ecologically Safe Conditions 27413.5.3.1. Benzyl Alcohol-Free Processing 27413.5.3.2. Water-Saving Processing 27513.5.3.3. Low-Replenishment Processing 276
13.5.4. Processing Stability 27613.5.4.1. General Means 27613.5.4.2. Processing Parameter Latitude 27713.5.4.3. Processing Bath Quality 278
14. Applications to Prevent Special Kinds of Fog14.1. Yellow Fog, Aerial Fog
14.1.1. Yellow Fog14.1.2. Aerial Fog
14.2. Bleach Fog14.3. Contact Fog14.4. Other Kinds of Fog and Defects
281281281282282283283
Contents xvii
15. Other Special Use 28515.1. Stabilization of the Latent Image 28515.2. Spot Prevention 28915.3. Antibronzing 29115.4. Toning 292
16. Concluding Remarks 297
Appendix: Toxicity of Stabilizers and Related Addenda 299
References 301General Reviews of Stabilization and Other Photographic Topics 301References to Chapters 1-16 304Patents 324
Conference List 359
Indices 361Author Index 361Company and Institution Index 365Subject Index 367
Foreword
Stability is one of the most important performances required for silverhalide photographic materials. In 1935, Dr. E. 1. Birr introduced the concept ofthe stabilization of photographic emulsions for the first time by inventing a mosteffective stabilizer, 4-oxo-6-methyl-l ,3,3a,7-tetraazaindene (TAl). Dr. Birr 'smonograph Stabilization ofPhotographic Silver Halide Emulsions was publishedin 1974, and accepted as a reliable reference book by many photographic scientistsand engineers.
Since then, silver halide photographic materials have been greatlyimproved and expanded through active and continual development of variouskinds of technologies . Especially, extensive efforts have been made to developphotographic materials with high sensitivity and rapid processing, which relyupon the stability of photographic emulsions under various conditions. Thus, theconcept and technologie s of stabilization of photographic silver halide materialshave been expanded so extensively that many photographic scientists andengineers eagerly want a reliable, new reference book on the stabilization ofphotographic emulsions .
Dr. Gunther Fischer is one of the most experienced and eminent scientistsand engineers in the field of the stabilization of photographic materials withexpanded concept. He has been involved in research on the stabilization of photographic emulsions since 1964 when he joined the Technical ScientificLaboratory in the Research and Development Department of the Photo FilmCompany Agfa Wolfen formerly headed by Dr. Birr, whom he succeeded in thatposition. I was deeply impressed by his fruitful and elaborate achievements inthese fields. It was therefore quite fortunate for photographic scientists and engineers that Dr. Fischer made up his mind to write a monograph on Stabilizers ofPhotographic Silver Halide Emulsions, and has now completed it with greatefforts, for which I am sincerely grateful to him.
Knowledge of the stabilizers ofphotographic silver halide emulsions hasbeen widely distributed not only in scientific and technical papers but also inmany patents. It is worth of special mention that Dr. Fischer is quite knowledgeable about those patents as well as the literature owing to his deep experience inthis field for such a long time, and has managed to include them in this monographin good arrangement. This monograph is therefore unique in that it includes stabilizers, not only in conventional concept, but also expands on antioxidants, oxidized
xix
xx Foreword
developer scavengers, compounds for modifications of grain habit and growth,those for inhibitions of chemical ripening and development, and developmentinhibitor releasing compounds. I am sure that this monograph will be very usefulfor photographic scientists and engineers, and will greatly contribute to progressin photographic science and technology.
I would like to congratulate Dr. Gunther Fischer for completing thisexcellent monograph that offers important knowledge of stabilizers of photographic silver halide emulsions.
October 31, 2003Tadaaki TaniThe PresidentThe International Committee for Imaging Science and Technology (lCIS)Ashigara Research Laboratories, Fuji Photo Film Co., Ltd.
Preface
For more than 150 years silver halide photography has played a dominantrole in image recording. The maintenance of an important position in competitionwith non-silver halide methods is dependent on a high quality standard. Stabilityof silver halide photographic materials is regarded as one of the parametersgoverning the quality of this imaging medium.
The main steps for producing silver halide photographic material areprecipitation, physical and chemical ripening of the emulsion , and coating asupport with an emulsion. Especially after the chemical ripening step or beforecoating, each emulsion has to be stabilized to maintain its photographic properties, primarily sensitivity and absence of fog (an unwanted image density developed in unexposed areas), during storage .
In 1935 Emil-Joachim Birr was the first to find an effective, generallyapplicable stabilizer. Later on, in 1974, Birr's monograph Stabilization ofPhotographic Silver Halide Emulsions was posthumously published, comprising hislifelong experience and knowledge and reviewing other worldwide activities inthis field .
In the meantime, the sphere of emulsion stabilization has markedlyextended. Topics, nearly unknown or less important during Birr's days, have come tothe fore, for example, oxidized developer scavenging, masking of antifoggants, orhigh temperature processing. To meet requirements for higher sensitivity and higherimage quality, remarkable progress in stabilization had also to be made. The steadyefforts are documented in more than 800 articles and 3,260 patents published since1969.
The aim of this book is to give a comprehensive view on the resultsobtained during the last 35 years, with special emphasis being laid on the chemical properties and the applications of stabilizing additives .
After remarks on emulsion stability and fog and a survey of recentpublications, the different classes of stabilizing and antifogging agents are treatedaccording to their chemical structures; physico-chemical properties, modemideas of the stabilization mechanism, and other applications are included . Thenext chapters cover the moment and the methods of incorporation as well as theuse of masked compounds and DIR compounds. The final parts comprise applications in certain emulsions and materials or in the presence of other additives,
xxi
xxii Preface
applications under certain environmental conditions , applications to preventspecial kinds of fog, and other special use.
Such a work does not materialize without the support of manycommitted persons . Thus, I was glad to get advice and help from colleaguesand friends, and I am grateful to all of them. My colleagues Dr. Horst Engelmann,Dr. Siegfried Gahler, Gunter Hubner, and Axel Schulze-Jorgensen were alwaysready to discuss topics in their fields. Syntec AG in Wolfen, especially represented by Dr. Jorg Marx and Thomas Seele, provided me with working facilities.
A number of recent conference proceedings were made available byDr. Gunther Israel, Rainer Redmann, Dr. Andreas M. Richter, Dr. Werner Walther,and Dr. Achim Winzer as well as Katrin Hamburg (Consulate General of the USA,Leipzig). Countless literary sources were rendered accessible to me with the helpof scientific librarians in Leipzig (especially Johanna Zander, Jiirgen Posselt,and Marlies Frenkler), Wolfen (Gunda Romling and Eva Poppe), and Berlin.Furthermore, I could read hundreds of patents provided by the staff of DeutschesPatentamt Berlin, and Manfred Gill (Wolfen) led me to archives material. FinallyWerner Daniel read the entire manuscript. The staff of Kluwer Academic/PlenumPublishers , especially Kenneth Howell and Felix Portnoy, helpfully accompaniedthe writing of the manuscript and reliably produced the book.
On composing the work, I got valuable technical advice and aid fromWalter Wilke and Roland Schneider. My children, Stefan, Susanne, and SilviaFischer, and my son-in-law Ingo Grundmann likewise shared their computerexperience with their father. My wife Ingrid gave me help and advice and showedinfinite patience. It is a pleasure for me to thank all of them.
May 28, 2003 GUNTHER FISCHER
Abbreviations
Af+
Ar-(Ag, Au)SAg(Br, I)Ag(Cl , Br)AgStAgXAlkArarBALLBEBTBuCACACHClog PCMICNCoucp(s).CSDDDEder(s) .DIRo-:DOHDPDRIFTEEoEDP
Antifoggant cationAntifoggant anionSilver/gold sulfide (specks)Silver bromide/iodide (emulsion)Silver chloridelbromide (emulsion)Stabilizer silver saltSilver halideAlkylArylSubstituted at the aromatic (benzene) ringBallast groupBelgian PatentBenzotriazole (2)ButylCanadian PatentChemical AbstractsSwiss Patent (or Priority)Calculated log partition coefficientColor-mixing inhibitorChinese PatentCoupler (in formulas)CompoundsCzecho-Slovak PatentGerman Patent (DDR)German PatentDerivative(s)Development inhibitor releasingMinimum densityDi-t-octylhydroquinone (1l6c)Direct positiveInfrared diffuse reflectanceExtinction coefficientOxidation potentialElectron donor precursor
xxiii
xxiv
EDTAEMFEPEq(s)ESCAFDFRGBgem .hHAfHetHStHTPHU
IRDITJEJPLtc.,LDsoLDLoMMMBIMBOMBTMeminmsMWANnNBIn.d.NHEODSp.a.pAgPE
Ethylene diamine tetraacetic acidElectromotive forceEuropean PatentEquation(s)Electron spectroscopy for chemical analysisFrench Demand (patent)French PatentBritish PatentGeminateHourAntifoggant (acidic, undissociated)HeterocyclylStabilizer (acidic, undissociated)High-temperature processingHungarian PatentIso (alkyl)Inhibitor releasing developerItalian Patent (or Priority)Japanese Patent (examined)Japanese PatentLiterLethal concentration for 50% of experimental animalsLethal dose for 50% of experimental animalsMinimal lethal dose ever reportedMolar (concentration)Metal (in formulas)2-Mercaptobenzimidazole (31a)2-Mercaptobenzoxazole (31b)2-Mercaptobenzothiazole (31c)MethylMinuteMesoMicrowave absorptionNormal (concentration)Normal (alkyl)5-NitrobenzimidazoleNo date (books)Normal hydrogen electrodeOxidized developer scavengerPer annumNegative logarithm of silver ion concentrationPolyethylene
Abbreviations
Abbreviations xxv
PEaPhpKa
pKspPLPMTPrProceed.PTPUGPVPQDIR,R',R"R' , R2, ...
Rct(s)ref.r.h.RTECSRUsSSCEsecSERSUp
Sre'SCSUt
TAlTsUSUS-DPvisWOX-Y,Z100111
Polyethylene oxidePhenylNegative logarithm of K, (acid dissociation constant)Negative logarithm ofKsp (solubility product constant)Polish Patentl-Phenyl-5-mercaptotetrazole (3)PropylProceedingsl-Phenyltetrazol-5-ylPhotographically useful groupPolyphenylpyrrolidoneQuinone diimineSubstituentsSubstituentsReactionsReferenceRelative humidityRegistry of toxic effects of chemical substancesRussian PatentSecond (time)Sensitivity, speedSaturated calomel electrodeSecondary (alkyl)Surface-enhanced Raman scatteringHammett substituent constantRelative sensitivity (speed)Stabilizer anionSoviet PatentTertiary (alkyl)4-oxo-6-methyl-l ,3,3a,7-tetraazaindene (1)p-ToluenesulfonylUSA PatentUSA Defensive Publication (patent)Visible spectrumWorld PatentAnionRing and chain atoms or groupsCubic crystal habitOctahedral crystal habit
