Alternative Formulations And Packaging To Reduce Use Of Chlorofluorocarbons

ALTERNATIVE FORMULATIONS AND PACKAGING TO REDUCE USE OF CHLOROFLUOROCARBONS (CFCs) Thomas P. Nelson and Sharon L. Wev...

Author: T.P. Nelson | S.L. Wevill

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ALTERNATIVE FORMULATIONS AND PACKAGING TO REDUCE USE OF

CHLOROFLUOROCARBONS (CFCs)

Thomas P. Nelson and Sharon L. Wevill Radian Corporation Austin, Texas

NOYES DATA CORPORATION Park Ridge, New Jersey, U.S.A.

Copyright @ 1990 by Noyes Data Corporation Library of Congress Catalog Card Number: 90-7746 ISBN: 0-8155-1257-0 ISSN: 0090-516X Printed i n the United States Published in the United States of America b y Noyes Data Corporation Mill Road, Park Ridge, New Jersay 07656 10987654321

Library of Congress Cataloging-in-Publication Data Nelson, T.P. Alternative formulations and packaging t o reduce use o f chlorofluorocarbons (CFCs) / by Thomas P. Nelson and Sharon L. Wevill. cm. (Pollution technology review, ISSN 0090-516X ;no. p. 194) Includes bibliographical references and index. ISBN 0-8155-1257-0 : 1. Pressure packaging. 2. Aerosol propellants. 3.Chlorofluorocarbons. I.Wevill, Sharon L. II. Title. I II.Series. 1990 TS198 .P7MN45 688.8-7dc20 90-7746 CIP

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Foreword

This book describes alternative formulations and packaging techniques for the reduction or elimination of chlorofluorocarbon (CFC) use as an aerosol propellant. Use of CFCs in specific categories of aerosols considered "nonessential" was banned by the U.S. in 1978. Recent renewed interest in further reducing worldwide production and consumption of CFCs, and other chemicals implicated in the depletion of the earth's stratospheric ozone layer, i s responsible for this study, which covers currently exempted and excluded CFC aerosol applications and their alternatives. The book i s presented in two parts. Part I gives background information on the issue and an overview of technically feasible methods for reducing CFCs in aerosol products without adverse effects on human life and health, military preparedness, and the economy. Part II discusses industry's experience in converting to alternative formulations. Detailed non-CFC formulations are provided for 28 categories of aerosol products. Special equipment may be needed to include these formulations in aerosol containers, and this i s discussed along with a variety of alternative dispensing devices. Advantages and drawbacks of these devices are discussed in detail, and examples of consumer products which have successfully utilized these alternatives are given. The information in the book i s from Alternative Formulations to Reduce CFC Use in U.S. Exempted and Excluded Aerosol Products, prepared by Thomas P. Nelson and Sharon L. Wevill of Radian Corporation for the U.S. Environmental Protection Agency, November 1989. Aerosol Industry Success in Reducing CFC Propellant Usage, prepared by Thomas P. Nelson and Sharon L. Wevill of Radian Corporation for the U.S. Environmental Protection Agency, November 1989. V

vi

Foreword

The table of contents i s organized in such a way as to serve as a subject index and provides easy access to the information contained in the book. Advanced composition and production methods developed by Noyes Data Corporation are employed to bring this durably bound book to you in a minimum of time. Special techniques are used to close the gap between "manuscript" and "completed book." I n order to keep the price of the book to a reasonable level, it has been partially reproduced by photo-offset directly from the original reports and the cost saving passed on to the reader. Due to this method of publishing, certain portions of the book may be less legible than desired.

NOTICE The materials in this book were prepared as accounts of work sponsored by the U.S. Environmental Protection Agency. They have been approved for publication as EPA documents. On this basis the Publisher assumes no responsibility nor liability for errors or any consequences arising from the use of the information contained herein. Mention of trade names or commercial products does not constitute endorsement or recommendation for use by the Agency or the Publisher. Final determination of the suitability of any information or procedure for use contemplated by any user, and the manner of that use, i s the sole responsibility of the user. The reader i s warned that caution must always be exercised when dealing with materials which might be hazardous, such as chlorofluorocarbons and their alternatives, and expert advice should be sought at all times. All information pertaining to law and regulations i s provided for background only. The reader must contact the appropriate legal sources and regulatory authorities for upto-date regulatory requirements, and their interpretation and implementation.

Contents and Subject Index

PART I BACKGROUND AND OVERVIEW

.

1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Historical Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Montreal Protocol Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . Objectives and Organization of the Report . . . . . . . . . . . . . . . . . . . . .

.

2 2 3 4

2 CFC AEROSOL APPLICATIONS EXEMPTED IN THE U.S . . . . . . . . . . . . 6 Rationale for Exempted Uses of CFC Aerosols . . . . . . . . . . . . . . . . . .9 Release Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 Lubricants. Cleaner.Solvents. Dusters and/or Coatings for 10 Electronics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mercaptan (Thiol) Stench-TypeWarning Devices . . . . . . . . . . . . . . 11 Other Warning Devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 12 Flying Insect Pesticides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Metered-Dose Inhalant Drugs (Steroids. Ergotamine Tartrate and Adrenergic Bronchodilator Types) . . . . . . . . . . . . . . . . . . . . 14 Contraceptive Vaginal Foams. . . . . . . . . . . . . . . . . . . . . . . . . . . 15 Hair Restorers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 Aerosols for Aircraft (Maintenance and Operation) . . . . . . . . . . . .16 Military Aerosols (For Continuing Military Preparedness) . . . . . . . . 17 Diamond Grit Sprays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18 CFC-115 for Puffed Food Product Aeration . . . . . . . . . . . . . . . . .18 Rationale for Excluded Uses of CFC Aerosols . . . . . . . . . . . . . . . . . . 20 Drain Openers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 Microscope Slide Cleaners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 Chewing Gum Removers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 21 Boat Horns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

viii

Contents and Subject Index Halon-Type Fire Extinguishers . . . . . . . . . . . . . . . . . . . . . . . . . . 22 Intruder Alarm Devices (for Cars. Trucks. and Homes) . . . . . . . . . .22 Skin Chillers (for Medical Purposes) . . . . . . . . . . . . . . . . . . . . . . 23 Polyurethane Blowing Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 24 Tire Inflators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Foams. Whips and Puffs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 Medical Solvents (Bandage Adhesive and Adhesive Remover) . . . . . . 25 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

3. CURRENT U.S. CONSUMPTION OF CFCs . . . . . . . . . . . . . . . . . . . . .

27 27 Discussion of the Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Source of the Data. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 Development of Numbers by Exact Product Type . . . . . . . . . . . . .33 33 Flying Insect Sprays. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 Aerosols for Military Use . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 Metered Dose Inhalant Drugs. . . . . . . . . . . . . . . . . . . . . . . . . . . Conversion of Pounds of CFCs Consumed to Aerosol Units Sold . . . 35 U.S. Marketers and Fillers of CFC Products . . . . . . . . . . . . . . . . . . .36

4. SUGGESTED ALTERNATIVE FORMULATIONS FOR EXEMPTED AND EXCLUDED CFC AEROSOLS . . . . . . . . . . . . . . . . . . . . . . . . . . 38 38 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Discussion of Alternative CFC Formulations . . . . . . . . . . . . . . . . . . . 40 Mold Release Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41 Lubricants for Electric and Electronic Equipment . . . . . . . . . . . . . 43 Lubricants for Pharmaceutical Pill and Tablet Manufacture . . . . . . . 45 Solvent.Cleaners. Dusters and Coatings for Electric/Electronic Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 Metered-Dose Oral and Nasal Inhalation Pharmaceutical Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48 Contraceptive Vaginal Foams. . . . . . . . . . . . . . . . . . . . . . . . . . . 60 Mercaptan (Thiol) Warning Devices . . . . . . . . . . . . . . . . . . . . . . . 62 Intruder Alarm Devices. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 Flying Insect Sprays for Food-Handling Areas . . . . . . . . . . . . . . . .64 65 Flying Insect Sprays for Aircraft . . . . . . . . . . . . . . . . . . . . . . . . Flying Insect Sprays for Tobacco Barns . . . . . . . . . . . . . . . . . . . . 66 Aircraft Maintenance and Operation Sprays . . . . . . . . . . . . . . . . . 67 Military Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68 Diamond Grit Sprays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 CFC-115 for Aeration of Puffed Food Products-Certain Limitations Applied . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 70 Tire Inflators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Polyurethane Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 71 Chewing Gum Removers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72 Drain Openers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chillers-Medical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72 Boat Horns. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -72 -73 Non-Electric/Electronic Dusters . . . . . . . . . . . . . . . . . . . . . . . .


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Microscope Slide Cleaners and Related Products . . . . . . . . . . . . . . 73 Solvents-Medical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74 Contingency Products. Including Unauthorized Uses . . . . . . . . . . . 75 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 5 . PROCEDURES FOR AND COSTS OF SUBSTITUTING ALTERNATIVE FORMULATIONS FOR CFC AEROSOLS . . . . . . . . . . 77 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 Cost of Converting Filling Lines . . . . . . . . . . . . . . . . . . . . . . . . . . . 80 Methods and Costs for Developing Alternative Formulations 83 for CFC Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mold Release Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 Lubricants-for Electric/Electronic Equipment . . . . . . . . . . . . . . . 86 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 Lubricants for Pharmaceutical Pill and Tablet Manufacture . . . . . . . 88 Solvent.Cleaners, Dusters, and Coatings for E'-ctric/Electronic 91 Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 Metered Dose Oral and Nasal Inhalation Pharmaceutical Drug Products (MDIDs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96 Contraceptive Vaginal Foams (Human Uses). . . . . . . . . . . . . . . . . 96 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 98 Mercaptan (Thiol) Warning Devices . . . . . . . . . . . . . . . . . . . . . . . 99 Intruder Alarm Device Canisters. . . . . . . . . . . . . . . . . . . . . . . . . Flying Insect Sprays for Food-Handling Areas . . . . . . . . . . . . . . . 100 Flying Insect Sprays for Aircraft . . . . . . . . . . . . . . . . . . . . . . . 101 Flying Insect Sprays for Tobacco Barns . . . . . . . . . . . . . . . . . . . 102 Aircraft Maintenance and Operation Sprays . . . . . . . . . . . . . . . . 102 103 Military Aerosols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . CFC-115 for Aeration of Food Products-Certain Limitations Applied . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 Excluded Products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 Tire Inflators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 Diamond Grit Spray . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105 105 Polyurethane Foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chewing Gum Removers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Drain Openers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Chi1lers-Med ical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 Non-Electric/Electronic Dusters . . . . . . . . . . . . . . . . . . . . . . . . 107 Microscope Slide Cleaners and Related Products . . . . . . . . . . . . . 108 Solvents-Medical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 110 Boat Horns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Contingency Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 111 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Procedures for Changing from CFC to Alternative Formulations. . . . . 114 114 Research Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .


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Manufacturing Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . Sales and Marketing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

114 115 115 115

.

6 CONCLUSIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117 Aerosol Uses for Which CFCs Are Difficult t o Eliminate (and 117 Possible Interim Reformulations) . . . . . . . . . . . . . . . . . . . . . . . . Mold Release Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119 Lubricants for Electric/Electronic Uses . . . . . . . . . . . . . . . . . . . 120 121 Lubricants for Pharmaceutical Pill and Tablet Manufacture Solvent.Cleaners. Dusters and Coatings for Electric/Electronic Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122 Metered-Dose Oral and Nasal Inhalation Pharmaceutical Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123 Contraceptive Vaginal Foams (Humans). . . . . . . . . . . . . . . . . . . 123 Solvents-Medical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 Potential for Reduction of CFC Use in Exempted and Excluded Aerosols. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 Scenario One . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 Scenario Two . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 Scenario Three . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 Scenario Four . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 Near-Term CFC Reductions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 Longer-Range CFC Reductions . . . . . . . . . . . . . . . . . . . . . . . . . . 132 133 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

......

REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

134

APPENDIX A-ADDITIONAL INFORMATION ON MDlDs . . . . . . . . . . . 135 APPENDIX B-DOT REGULATIONS FOR COMPRESSED GASES . . . . . . 142 APPENDIX C-METRIC

(SI) CONVERSION

FACTORS

. . . . . . . . . . . . . 148

PART II ALTERNATIVE FORMULATIONS AND AEROSOL DISPENSING SYSTEMS SECTION I: ALTERNATIVE AEROSOL FORMULATIONS . . . . . . . . . . 150

. ..................................... 2. FORMULATION GUIDELINES . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 INTRODUCTION

General considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Flammability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

151 162 162 165 167 170

Contents and Subject Index Materials Compatibility

.............................

xi

170

3. EXAMPLE NON-CFC ALTERNATIVE FORMULATIONS . . . . . . . . . . 173

Cosmetics. Toiletries. and Personal Care Products . . . . . . . . . . . . . . 173 Hair Sprays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173 Hair Lusterizers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177 Hair Mousse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179 Containers for Hair Setting and Conditioning Mousses 191 Other Mousse Products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193 Shave Creams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209 Underarm Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213 Colognes and Perfumes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226 Household Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230 General Comments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230 Window Cleaners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236 Spray Starch. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239 Heavy-Duty Hard-surfaceCleaners . . . . . . . . . . . . . . . . . . . . . . 243 Carpet and Rug Cleaner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249 Silica-Based Absorbent Fabric Cleaners . . . . . . . . . . . . . . . . . . . 253 Air Fresheners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254 Disinfectant/Deodorant Sprays . . . . . . . . . . . . . . . . . . . . . . . . 256 Disinfectant Cleaners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257 Paint Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261 Furniture Polishes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264 Car Windshield De-lcers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266 Pesticide Aerosol Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268 Insecticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268 Insect Repellents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271 Pharmaceutical Products. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 271 Industrial Aerosol Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 274 Adhesive Spray . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276

.........

SECTION II: ALTERNATIVE AEROSOL DISPENSING SYSTEMS

.

. . . . . 278

1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.

279 279

2 DESCRIPTION OF AEROSOL PACKAGING ALTERNATIVES . . . . . . 285 Bag-in-CanTypes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 The Sepro Can . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285 Bi.Can . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303 Compack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .307 Alucompack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308 Micro.Compack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309 Lechner (Types I Through I V ) . . . . . . . . . . . . . . . . . . . . . . . . . 310 Presspack . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312 Other Bagin-Cans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312 Piston Cans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313

xii

Contents and Subject Index The Mira-Flo Can . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313 315 Other Piston Cans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Boxal Pump Dispenser . . . . . . . . . . . . . . . . . . . . . . . . . . . 317 Independent Bagin-Can Systems . . . . . . . . . . . . . . . . . . . . . . . . . 319 Pump Sprays-Aspirator Types. . . . . . . . . . . . . . . . . . . . . . . . . . . 325 Pump-Sprays-Standard Types . . . . . . . . . . . . . . . . . . . . . . . . . . . 327 327 The Finger-PumpSprayer . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trigger-Pump Sprayers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337 Finger-Pump Extruders. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 337 Trigger-Pump Extruders . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 338 338 Dispensing Closures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Pressurizing Dispensers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340 340 Twist-N-Mist II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The Exxel Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 344 The Mistlon System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 348 Airspray . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351 352 The Werding Nature Spray.Systems . . . . . . . . . . . . . . . . . . . . . . Miscellaneous Aerosol Alternatives . . . . . . . . . . . . . . . . . . . . . . . . 353 353 Insecticide Vaporizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Stick Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355

3. SUMMARY

.........................................

APPENDIX A-METRIC (SI) CONVERSION FACTORS

.............

359 361

Part I Background and Overview The information in Part I is from Alternative Formulations to Reduce CFC Use in U.S. Exempted and Excluded Aerosol Products, prepared by Thomas P. Nelson and Sharon L. Wevill of Radian Corporation for the U.S. Environmental Protection Agency, November 1989.

1

1. Introduction

The use of cblorofluorocrrbonr (CFCs) in specific categories of aerosol propollant use considered "aonessentirl' vas h n n e d in the U.S. by regulations p r o d g a t e d in 1978 (1). An aerosol v u defined as a package comprising a self-pressurized, non-recumable container constructed of metal, glass. or plastic that conuins a fluid product and that is fitted vlth a valve for expelling the product as a spray, Liquid. gas. foam. powder, or paste. bumad CFC propollants included the fully-halogenated types: CFC-113. CFC-114.

In view

rpd

The

CFC-11, CFC-12.

CFC-11.5.

of the recent renemd interest in reducing worldvide production

and consumption of CFCs and other c b o i c d r implicated in the depletion of the

Earth's stratospheric ozone layer, the U.S. Environmental Protection Agency (=A)

undertook chis study of currently exempted and excluded CFC aerosol

applications aad their alternatives. The EPA and the Food and Drug Administration (FDA) initiated and supervised the three-stage program from 1977 t o L978 to eliminate most uses of

f u l l y halogenated CFC propellanrs for aerosol propellant applications except for 'essential uses:

If the CFC in the product functioned as more than a

propellant or dispersant, it v u considered 'the product'

and excluded.

product" or "part of the

R m agencfes held the concepcr of "product" and

"propellant" to be outually exclusive.

Also. the EPA and FDA evaluated the

need for certain "essential' aerosol propellants.

These were products that.

for reasons of safety. health. or national security, required a CFC propellant.

The initid EPA evduation rmsulted in a list of approxirsacely 14

general applicatioru considered exempt.

2

Introduction

In th. years f o l l o v i n g u m p t i o n r were tendered.

3

the transition. a few a d d i t i o n a l p e t i t i o n s f o r

Sap. w e r e accepted.

In a d d i t i o n . agency c l a r i f i c a Some produces

tion of th. u c l u a i o n o f specific product types w a s requested.

were added t o the exempt list u the r e a u l t of these activities. Exemptions -re applied to th. product c a t e g o r y , rather thrn t o specific products o r brand

MUS.

This report 1d.ntifies technically f e u i b l e method. f o r reducing CECs i n

a e r o s o l products without m r s e e f f e c t s on human l i f e and health ( i n h a l a n c s . p h u n r c e u t i u l tablet p r e s s lubricants), military preparedness ( l u b r i c a n t s f o r

electronic g e a r ) . and the economy ( c l e a n e r s and c h i l l - t e s t e r s f o r compucer equipment).

The A u g u s t 1988 &PA r e g u l r t i o a r (2) implement the Honereal Protocol ( 3 )

The r e g u l a t o r y mechmirr t o Implement the Protocol is d i f f e r e n c from the 1978 a e r o s a l p r o p e l l a n t ban.

Rather than develop t e y l a t i o n s s p e c i f i c t o each

fadustry a p p l i c a t i o n (such aa a e r o s o l p r o d u c t i o n ) , the e n t i r e supply of f u l l y halogenated chlorofluorocarbons u l l l be reduced. The Hontreal Protocol of 1987 and t h e corresponding EPA Final Rule co implement che Protocol r e q u i r e the following reductions i n c a l c u l a t e d l e v e l s of c o n a o l l e d CFCs: Beginning July 1. 1989. a f r e e z e a t 1986 consumption and production

levals of CFC-11. -12. -113, -114, and -115 on t h e b a s i s of t h e i r relative ozone d e p l e t i o n veights; Beginning mid-1993. a reduction of these CFCs eo 80% of 1986 l e v e l s ; and

-

Beginning mid-1998, a reduction of t h e s e CFCs eo 50% of 1986 levels.

4

Alternative Formulations and Packaging to Reduce Use of CFCs

In hy.1989, &legates o f the nations party to the Protocol met in He1rinLi and agreod on a fiva-point declaration t o strmgthen the Protocol. ‘zh. fiw polntr arm u follows: Phue

Ou+

later

ehrp tho y u r 2000.‘

&

coautmption and production of ozoru-depleting CFCs “not

soon u feuible, phase out halonr and concrol and reduce ocher

o+op.-&pleting substances th.t contribute significantly to ozone

dap letion. kcolorrto developmont of environmentally acceptable alternative

subetf~utingchemicals, producu‘. and technologies. H d p &v8loping countries by providing information, training, and POSSibly funding t o faCflitPt0 adoption of acceptable alternatives. Urgo all s u t e s &at

have not already done so to join the Protocol.

OBJECTIVES AND ORGANIZATION OF THE REPORT

The purposa of cha present report is 1) after reviewing the application. availability, and cost-effectiveness of CFC alternatives, to determine if suitable non-CTC alternatives or alternatives vith lover CFC content can be

substituted for thoae aerosol products in the U.S. that still use CFCs, and 2 ) to determine tho steps necessary to convert to the best alternatives.

Section 2 of ;his report &scribes

exempted and excluded CBC aerosol

applications in the U.S.. as well as thosa duplications not covered by the regulation.

Section 3 discusses the current U.S. consumption of exempted,

excluded, and nonregulated CFC products. formulations are discussed Ln Section

Suggested alternative aerosol

0 , and ,&a

m n c and application are explored in Saction 5.

economics of their develop-

Introduction

5

Section 6 presents the conclusions of the study and discusses the most promising alternative forarlations for CFC aerosols remaining in use in the

U.S.

Baaed om suggested scenarios for introducing the alternatives. the

following reductions Fn CFC aerosol usage in the U.S. are judged possible (see Sections 4

pad

61:

1990 Usage CFC Roducts

Present Connuptiop

1.50 Hold Roleases Lubtfcm+s 1.90 (electric/electr&c) Lubricants-Tablets 1.00 Solvents6.00 ( electric/electronic) ,%ID (Hetored-Dose 3.90 L n & l a t Drugs) Contraceptives 0.10 S o l ~ ~ - H . d i c r l 0.60 10.50 ALLOTAEBS

-

Units:

S c d o Orm

1990 Usage Scenario Tw

1995 Usage Scenario Three

2000 Usage Scenario Four

1.50 1.90

1.11 1.10

0.00

0.00

0.00

0.00

1.00

0.68

0.00

6.00

4.20

0.00

0.00 0.00

4.00

4.00

5.25

0.50

0.10

0.10 0.46 0.00

0.00 0.00 0.00

0.00

0.60 0.00

0.00

-

-

-

-

0.00 -

25.50

15-00

11.65

5.25

0.50

HH lbs/yr.' In addition, CFC control measures may need to be examined f o r certain

self-pressurized products not covered in c h i s report. €2.4

For example, in 1977. granted an exemption to flying insect sprays used in tobacco b a r n s . The

exemption was not limited by container size. Depending on the barn size and layout. one insecticide averaging 35% Vapona (2,2-dichlorovinyl dimethyl phosphate and r o l a t d corpormds) aad 6 5 % CFC-12 was used in sizes ranging from L2 Av.02. to 25 lbs.

For this product. considering density, the "aerosol"

containers are limited to n e t weights of approximately 24 Av.02. (1 lb. 8 or.) or less.

'Readers mro familiar v i t h metric units may in Appendix C.

us0

the conversion factors

2. CFC Aerosol Applications Exempted in the U.S. Table 1 lfsu CFC u r o r o l applications e x q t e d from E A ' S and FDA's 1970 replationr. =A's

final nrle-P.kin(l oxcludrd aerosols contafnfng propellant only,

aerosols that do

In such instances the Alro, vheu che CFC is an actfva ingredient. tho aerosol product assume. a nonregulrted s t a t u s . The concepts of "producc, active tngadient. and concentrate" and 'propellant' are held to be mutually i.0..

MI:

propol another material.

p r o p e l l a a ~ & c ~ the s pboduct.

exclusive. and regrlrtlonr only deal with aerosol propellants.

Table 2 lists

t h m CFC aerosol applfcrtioar that are exc1ud.d from the ragulatton.

The rationale applfed in 1978 and 1979 by EPA and the FDA vhen considerfn8 proposed exemptions inc1ud.d the following: %.

need for a n o n f l d l e product;

The five years often taken by the Drug Division of the FDA co

approve an Amended New Drug Application (applies to bronchodilacors and other inhalants, and vaginal contraceptive foams for human =e) ;

Required solvency and purity profiles. e . g . , CFC-113: Doctrine of cquivalency--dut highly similar products cannot reasonably be treated differently;

6

CFC Aerosol Applications Exempted in the U.S.

TABLE 1. SPECIFIC

=SOL

PROPELLANT APPLICATIONS

-

7

1978

1.

h l e u e a g e n u f o r molds used t o producm p l u t i c and d a r t o m e r i c materials;

2.

Lubricants f o r r o w - q p a presr-prmch.s f o r the production of pharu c o u t l d tablets:

5.

krbricaau. c l u u o r - s o l v e n u . dusters o r coatings f o r i n d u s t r i a l / institutional applicaciana t o e l e c ~ r o a f co r e l m c t r i c a l aqufpmont ;

4.

m r u p t a n stench varning d.ofcms f o r minor;

5.

Ocher varning -cas, horns, e t c . ;

6,

Flying insect p e s t i c i d e s f o r uae in c o v r c i a l food handling a r e a s , u c e p t vhen applied by t o t a l rmlease o r metered valve aerosol devices;

7.

Propellaata f o r flying insect p e s t i c i d e s f o r the fumigation of a i r c r a f r ;

a.

Flying h a a c t spray f o r tobacco barns;

9.

m.ter.d

----

_-

such

M

L n W r alarms. boat horns. bicycle

dose inhalant drugs, as follovs:

Steroid drugs f o r hrnmr, ( o r a l and nasal) Ergotmine t a r t r a t e drugs, and Adrenergic bronchodilator drugs ( o r a l ) ;

LO.

Conttaceptivm vaginal foams f o r human use;

11.

Aerosols f o r the maintenance and operation of a i r c r a f t ;

12.

Aerosols necessary f o r the military preparedness of chc United Staces o f America;

13.

Diamond g r i t sprays; and

14.

CFC-115 (CCIFz-CF,) f o r t h m a e r a t i o n of puffed food products.

8


TABLE 2. CFC as Active or

1. 2.

3. 4. 5. 6. 7.

a.

9.

LO. 11. 12.

EXCLUDED CFC AEROSOL APPLICATIONS

Sole Inuredient

CFC-12 used as a polyurethana blowing agent (insulation foams); CFC-12 apd CFC-lN mixtures wad in tire inflators: Corrrin spacialty f-, vhips, and puffs h d l d solvmts such as sFlicop.-bued badage adhesive (CFC-113) and W g a &rlva r.I.0y.r (CFC-113, vith 5% a,): CFC-12 and CFC-114 refrigoration .ab air-conditioniaq system refill unit* : Drain opanars: Microscop. slid. cleumrs : Colprter damars a d dusters (equivalent to numbor 3 in Table 1); Boat horns; Halon fire ertinguishars (tha typos containing 952 Halon-1211 and 5% CO, may not ba oxcludad); Intruder dun sonic devices for homas and card; and Sldn chillers--for medical purposes.

'The aerosol indurtq recognizer thase products as .aerosols" in surveys and closo irmolvemant u i t h tha iurketing firms.


9

Limited availabilirjr of rubstitute propellants or products; Srnatospheric

BATIOUALE

mx

XDXPTED

OZON

impact, e . & ,

production tormrge Per year; and

USES OF CFC AEROSOLS

This section vi11 s p e e i f f d l y ezaminm the rationale for exempting certain aerosol products from the 1978 baa on CFC use. m e r e possible, produces in siailar groupings vi11 be treated u a unit.

w

J

&(For ool&

to produce plutics and elastomers for medical rpplicationa. Also, for mold ch.nbers in punch presses used t o produce pharmaceutical pills a d tablets.)

CFC-11 and CFC-12 are w e d . sometimas vi&

CFC-113. in an industrial

environment. The solvent propellant system must be extremely pure to prevent product contamination.

The system must also be compatible vith the item being

formed to minimize such effects u colorant bleed, distortion, and filler micro-crgstalliration.

Since the solvent/propellant system may be used

repeatedly. and u u a l l y i n a controlled environment vich negative-pressure settings, minimum f l d i l i c y , preferably n o d - b i l i c y .

is an important

attribute. The solvent must be volatile so that all buc ppb traces arc gone by che time che product is packaged and possibly radioisotopically sterilized. CFC-11 and CFC-113 provide this volatilicy. vhile also modifying the particle size distribution of the spray to achieve opt%en

the application v u

M&

surface coating efficacy.

for CFC-11. CFC-12. and CFC-113 to be

exempted from che regulacion. che only available nod-ble propellant vas HCFC-22. The possible nonflammable chlorinated solvent alternatives vere methylene chloride and 1,l.l-crichloroechane ( 0 ) . Boch contain considerable amounts of mixed inhibitors (free-radical chain stoppers), such as 1.4-dioxane and nltxome-. The effect of these high-solvent substances on molded

10


u d l c a l p r o d u c u v u s o a o t i m s d o l e t e r i o u r ; choy s o m a t h o r v o l a t i l i z e d from

th.r w i t h d i f f i c u l t y , and the c o n d z m t i o n e f f e c u of the v a r i o u s i n h i b i t o r s d d have c u u a d tho FDA t o r e q u i r e a peru+rrting o v a l r u t i o n of product putty and toxicology.

E.+r.wly pure CFC-12 and CIC-113 u e used t o luk. sprays' o f varying p u t i c l o sire distribution f o r t r e a t i n g f i n f s h a d e l e c t r i c o r e l e c t r o n i c

circuit boards, cuwrs. computer lay-mu. and r i m f l u "hi-tech' a r t i c l e s . U h r e l u b r i c a n t a p p l i c a t i o n o r solvene-bued cleming is r e q u i r e d , a mixture of about 25Q CFC-12 and 75% CFC-113 is tho choice.

Coating s p r a y s ( o t h e r than

l u b r i c a n u - - r u c h u a n t i - s t a t i c ) MY us0 30-35% CFC-12; t h e remainder is CFC113.

Duster sprays o f t o n use 100% CFC-U. Vapor-phase defluxers use v a r i o u s

blonds of CFC-12/113, dopending on the s p o c i f i c a p p l i c a t i o n . CFC-113 is p r e f e r r e d because of its e x t r . ~p u r i t y vhen purchased i n grades s p e c i f i c f o r tho purpose and because o f its c o m p a t i b i l i t y v i t h mater-

ials of conseruction.

It can e f f e c t i v o l y r e w v o o i l s . s o l d o r by-products,

g r e u o s . inorganic d u s t s , and o t h e r dotritus vithout adversely a f f e c t i n g e l a s t o w r s , p l a s t i c s , and weals.

Any more c r i t i c a l treatment of the s u b j e c c

vould hiwe t o consider individual a p p l i c a t i o n s .

The firms soaking an exemption claimed that t h e r e vas no s u b s t i t u t e chemical v i t h the e x t r e w p u r i t y , n o n f l d i l i t y . m a t e r i a l s c o m p a t i b i l i t y , and the v o l a t i l i t y of CFC-113.

Ono manufacturer of personal computer boards LO t o 15 o p e r a t o r s sprayed residue m a t e r i a l s from f i n i s h e d boards a t the r a t e of t w o t o f i v e b a u d s per minute. Besides Leaving t r a c e s of petroleum o i l s on the boards, the use of hydrocarbon g a s e s , such as i s o bucane. would have caused a f i r e h a r d in an a r e a h e r e t e s t i n g equipment vas needed that could not be purchased i n explosion-proof designs.

c i t e d a room & r e


11

Typically. t h s e &vices a r e w e d in mine tuamels to varn of the buildThe devices are

up of seeping mch.ru and/or carbon a o n o x i b n h l e gases.

operated by airand

small, parubla miffel-tarter that continuowly monitors the

& t ~ -leu

Bridge circuit.

g a s u by tho dffierentiating a c t i o n of a Wheatstone The s t m c h M c e is preferred to siren. since some miners

may be operating air d r s or drills and MY also h v e hearing deficiencies because of their long exposure to the 110-docibel noise of these cools. The typical aerosol container, equipped v i t h a piseon-operated actuational device, COPUIM an ethyl mercaptan (ethylthiol) stenching agent in a m i x w e such as one

of the following: 3% 17% 8Q*

Ethyl Karcapcau

2r

E t h y l Mercaptan

1.1,l-Trichloroethme (6)

CFC-12 or

9aa

-

CFC 12

Uining companies seeking the exemption reported the life-saving actribute of the product, also pointing out that a nonflammable composition v u necessary, since 1) the entire can w a a discharged quite rapidly and 2) there v u already a buildup of €lamable gases; deliberately releasing more

would seme to exacerbate an already hazardous situation.

Other self-pressurized varning devices include home and car intruder alarms, boat horns, etc. They generally consist of 100% CFC-12. Since large quancitier of gas are released at one time--often the entire can contents-under a variecy of closed or open environmental conditions. the use of a

f l d l e propellant seemed w i s e .

(At the time the exemption vas sought, no

12


toxicologically s a f e . liquid honflanaable altemrcive propellant had been identified.)

The firms seokiry an exemption pointed out that products designed for +h. preservation of life and property should MC.

S u l l (though pa+entirllp dangerous) m

to . s u

and chore -re

110

of themaelver, be hazardous t

s were released each time,

available substitutes. Also, the production volume was

fairly lov.

w

(For use in c o m n r c i d food-handling areas. except for total-releaso and mater-sprays; also for killing

LNecu in and on aircraft and in tobacco vuehoures

.)

The produces for comercial food-handling areas have the following typical formula:

2r 1ar

Pyrethrins 6 Piperonyl Butoxide Toxicants

368

m-11 CFC 12

bb8

Petroleum Distillates (Food Grade)

-

Minor amounts of methylene chloride and/or iso-butane have also been included in some products as less costly alternatives.

Two other approaches were proposed but rejected. The petitioning marketers vere .not interested in providing total release

or macarspray products to these food-handling establishments and suggested that EPA exclude those forms from the exemption they vere seeking. Aircraft fumigacion 1s used co prevent the antry of unwanted insects inco che United States.

In some instances, the products also contain a disinfeccanc ingredient to reduce surface-contact bacteria. molds, mildew. yeasts. rickettsia. virus, and other micro-flora.


13

Regulations v q among coun+ries, b u t many r e q u i r e fumigation v i c h n o n f l d l e f o r n u l a t i o a r in a e r o s o l d i s p e n s e r s . both a t their home p o r t s of mcry and in aircraft of their r e g i s t e r . In the U.S., the American P i l o t s Association hu esublished

coda. 8ccepted by the c u r i e r s , that only

a e r o s o l s shall ba rued for fuelgation.

-la Of

8

th. c1-1

h.rOMUdC8

This is a l s o a r e g u l a t i o n

hUd.

Alrcraft are not eade explosion-proof, and the p o s s i b i l i t y e x i s t s chat Ln a sensitive area by a poorly informed person could lead to a fire, although not t o an explosion ( 9 . 6 g of hydrocarbon p r o p e l l a n t is capable of b r i n g i n g 55 U.S. Gallons of a i r to t h e flammable

ucess, localized spraylug

rauge).

In the p e t i t i o n for exempting these p e s t i c i d e s from the r e g u l a t i o n , che option of a water-brred product v u considered, b u t it w a s r e j e c t e d f o r t h r e e rerrons: v u

1) ic still contained 30 t o 32% hydrocarbon p r o p e l l a n t . although i t

technicdly n o n f l h l e by strndnrd t e s t m t h o b then f n use; 2) t h e

h e a v i e r p a r t i c l o s e e caused fall-out t o ' a f f e c t the passengers and polished s u r f a c e s ; and 3) because of t h e f a l l - o u t , the odor o f the t o x i c a n t s vas more p a r s i s t e n t than vith true space sprays.

The exemption allowed f o r tobacco barns and warehouses has a p p a r e n t l y been l i b e r a l i z e d t o cover tobacco vareho-.ses and food warehouses if they c o n u i n tobacco products.

Nevertheless, this is a

.

a p p l i c a t i o n . and

s o u users have converted. because of economic incencives.

The p e t i t i o n claimed chat tobacco l e a v e s , dusts, and granules a r e boch c o s t l y and v e r y flrPuble; thus, n a m a b l e sprays should n o t be used i n b u i l d i n g s chat c o n t a i n these materials.

Tobacco i n che d r i e d s t a t e is a l s o

highly absorbent and would p i c k up a c e r t a i n amount o f t h e e m u l s i f i e r s . f n h i b i t o r s . and o t h e r i n g r e d i e n t s of water-based f l y i n g insect s p r a y s , a d u l t e r a t i n g the tobacco.

14


(Steroida, ergotamine tartrate and adrenergic bronchodilator types.) This category rapreseuts about 4C of the U.S.

d o M S t f C aerosol u n i t in size. The usual range is from about 0.5 Av.02. (14 g or 10 rt) eo about 0.75 Av.02. (21 g or 15 A). The CFC cmtmt la 07 t o 96 percent. In general. 70 to 801 of the CFC content is CFC-12. Tho 0tb.r CFCI a r m CFC-11 and CFC-114. A typical formulation

volm, although th. products a r e vary -11

folious: 1.51

Solid Drug (hamrally povdered to 2-10 microns)

1.5C

excipieuu

12.01

CFC-11

10.01

CFC-114

75.01

CFC-12

The leas cop.(m solution typer use about LO* anhydrous ethanol as a corolvanc; h u t 8% or more CFC-12 is used in such producer to achieve the desired break-up of the spray. Unless the particles are within 0.5 to 10 microns in s i t e , they vi11 not penetrate beyond the extruaile cilia1 area and up t o the a l n o l l t tubes a d sacs where pulmonary abnormalities m y e x i s t . For example, Al-buterol, used in about half of a l l these products, requires deep penetration t o be effective.

To reduce thermally sensitive powdered drugs into the 2 - to LO-micron particle s i t e distribution, they MY be mixed v i a an appropriate non-solvent liquld o f high volatilfey into a slurry and then ground or milled.

ko

frictional heat is genarated. it fa instantly disstpated inco solvent vaming or ~ l a t i l i ~ a t i o n .Noam of the drug houaes hu explosion-proof equipment in their FDA-approved processing facllfties--nordo they have the Elamnabla gas detection &vices; blov-out walls; electroprotective systems; multi-stage, high-intensity ventilation: rad ocher system that would be needed ff the slurry liquld wore highly f l u r b l e [such u n-pentane (B.P. 98'F) or i s o Peneana (B.P.

-

-

86'F)I.

Co~equaatly. the slurrying agent must be non-

CFC Aerosol Applications Exempted in the U.S. 15

f l l r u b l e and available at a high level of p u r i t y .

fulfills et&

In

r.quir.uat.

-

s o n prellmlxury studles of

8

CFC-11 (B.P.

CFC-ll/hydxoe.rbon

-

74'F)

system, the hydro-

prop.llaaC v u found to a bad (stinging. ofly) t a s t e . especially if thm prodtact v u dorigmd f o r o r d entry, i n s t u d of nud inhalacion.

urbop

In 1977

.od 1978. tlm phumacmuticrl houses advised the

Divlsioa) of th. d a m facu. s t a t i n g that

110

FDA (Drug

alternatitn slurrying agent vas

d l a b l e f o r CFC-11, a d that noa-CFC propellants were inimical to product org.noleptics and perfornurce.

They also reported Chat, even i f nonflammable

and ochervise a c c e p u b l e altemrrtitns were available. they would require three

to f i a y e u r of davelopaeatd work. followed by a five-year study by the FDA

before nrrkatin$ approval could be obtained.

Crcs, th.se life-savlag

and ramodirl

Without a continuing supply of

drugs vould no longer be av8ilable.

These drugs wore marketed a f t e r extansim t e s t i n g by pharnnceutical firms and by the FDA (Drug Division).

Testing of an a l t e r n a t i v e formula would

have to proceed almost from the beginning and would take an estimated seven years t o coaplete.

The FDA favored the use of CFC-12/114 propellant blend

over the A-46 (lso-butane/proprn.) blend; the New Drug Amendment (NDA) granced

in the l a t e 1960s v u based o n l y on the CFC formula option.

Vqinrl f o u v are uet A Life-saving product. The exemption v u granted because. vhfle altemrrtivm p r o p e l l a n u vere available, they could not be used until 0 . n ~y e u s of r e t e s t i n g had been conducted.

Also, the market f o r the

products v u rather so111. and only about 6 . 6 g of CFCa were used p e r average 3 Av.02. dispenser.

Had the usage level been higher. the FDA night have noc

g r a t e d the exemption. feeling that other routes t o conrraception were

r~.iiabie.

16


Durlng 1988, houovmr. tha FDA granted an NDA t o the Upjohn Company f o r a hair r e s t o r e r product. Tho mukoter pr0vId.d information t o the agency on producta using both CFC md A 4 6 (iso-butano/propra. blend) p r o p e l l a n t opclous. Dospite the Moatred Protocol .ad heightened concerns about t h e s a a t o s p h a r i c 02hpt. th. F'DA sdected only tho CFC o p t i o n f o r marketing. 'Ibr product is

( 2 Av.02.).

A

.ad con-

q u i c k - b r e r l i n g f o u , is quite small i n s i r e

less than LO5 CFC blend.

Thus, it is extremely

slmllu t o the contracoptiva vaginrl f o u in p r o d u c t / p a c h g e c h a r a c t e r i s t i c s . Ultlmatoly. it could c a p w e

for

Airctaft

A

s u b s t a n t i d market.

( I h l n t m n n c e and Operation)

L i t t l e information is available on these a e r o s o l s .

Along v i t h the

Flying Insoct FUPIgaats d l s c l u s o d abova, those a o r o s o l s includo l u b r i c a n t s , Considarationr such as safecy. high f l d i l i t y p o t e n t i a l - - t h e l a r g e s t a i r c r a f t can hold a h s t a tank t r u c k - s i r e d load of a v l a t f o n fuel--h#e l e d the American P i l o t s Associacion

c l m n o r s , .ad o t h e r industrial item. value. and

( M A ) and r e l a t e d organizations t o r e c o m n d the r e s t r i c t i o n of s e r v i c e

a e r o s o l s to nonflamable options. TM nonflamable options f o r a l u b r i c a n t a e r o s o l a r e the f o l l o v i n g : CFC Type:

- Winterized

25

S M I 30 Uotor Oil

55

Modified Dimethylsiloxane ( S i l i c o n e Oil)

235

l,l,l-Trichloroethane

405

CFC-11

305

CFC-12

CFC Aerosol Applications Exempted in the U.S. 17

Alternative :

2x 5% 83X

SAE 30 Uotor Oil

-

Winterized

Uodified Dimethylsiloxane (Silicone Oil) l,l,l-Trlchloroeth~ne

5%

Odorlesa Uinerd. Spirits (Flash Point

5%

Cub00 Dioxide

129'F

( 5 4 . C ) Sat-A-Flash Closed Cup)

Following are tua options for spray paints for touch-up and corrosion control : CFC Type:

551

Aerosol Paint Concentrate (Gonerally Acrylic)

Hydrocarboa:

45x

CFC-12

5%

Aerosol Paint Concentrate

15%

(hamrally Accrylic) Acetone or Mechylene Chloride

30X

Hydrocarbon B l e d A-85

(namable)

52X Propme and *8X Iso-butane

Although APA would not approve of the hydrocarbon version. che Factory .Xu&

Research 6 Engineering Company has shown that the two formulations are

virtually indistinguishable in terms of intrinsic flammability. Hilitam Aerosols (For continuing military preparedness) The U.S. Armd Semicar purchases about 1,000,000 pounds of CFC-LZ/CFC-l1-propdl.d insecticides a year by contract.

Uost are Flying Insect Sprays for troops, but some are specialty items, such as Uasp and

Hornet Sprays with CFC-113, designed to protect maintenance personnel vorking on power stations and u t i l i t y lines. Significant numbers are exported to military h s e s overseas.


18

The Annd Forces also purchases various o t h e r a e r o s o l p r o d u c t s . and say at their o p t i o n select CFC f o r a r l a t i o n s , a p p a r e n t l y v i t h o u t s p e c i f i c j u s t i fication. Tha d a r o f CFC u r o s o l s is thought t o be r e l a t i v e l y lov. and

their us0 1s restricted t o niliurp aircraft ~ i n t e n m c e ,computer & - d u s t i n g ,

m m d fln finding, syputic u p a spray.. and specialty l u b r i c a t i o n .

Very l i t t l e information could be found. except that tho market is

ninucule. Wont. Allfad-Si@. LP

No

application.

‘sand blasting’

OIU

and Racon had no record of selling CFCs f o r such could k r @ m using such a product except f o r diamond

e x t r e a o l y l a u d mtallic surfacer t o micro-etch them.

Wont, vhich is the o a l y remaining doustic s u p p l i o r of CFC-11s f o r

this use. has not s o l d the product t o a whippod cream manufacturer o r food

company i n many y e u s . The original, whipped cream c o n s i s t e d of w a t e r d i s p e r s i o n s of e i t h e r

natural o r s y n t h e t i c whipped cream i n g r e d i e n t s , p r e s s u r i z e d vith CO, and 9,O ( o r t h e Whim’s i l h t u r e of there food grade p r o p e l l a n t s ) . For economic reasons, f o d a t i o n s vera then limited t o syntheeic vhipped creams v i t h

nitrous oxide (q0) p r o p e l l a n t .

The lfmiced s o l u b i l i t y of t h e N,O gas forced

marketers t o f i l l c a s t o o n l y about 55 t o 601 by -1pressures of NzO.

and t o use maximum

Otherulsa. th. product becaam ‘soupy” na8r the end of the

E m .

F r o o 1968 through 1971. when food a e r o s o l d i s p e r s i o n s increased dramatically in chr aerosol induatry. W o n t devoloped t h e i r Freon (Food P r o p e l l a n t )

C-318 (chemically. parfluorocyclobutana). which could be added t o the N,O a t the rate of 3 t o 6 g per 9 Av.02. can t o givo a nuch more uniform vhip throughout the life of tha dispenser. It also allwed 2 co 3 a d d i c i o n a l

CFC Aerosol Applications Exempted in the US.

Av.02.

19

t o be included i n the can, a t the p e m l t y of slight "soupiness" near

the end.

A mica1 use of 4.5 g The problom v u that the c-318 cost $7.50/1b. p.r w fncroud th. fatorg cost by $0.20 p e r can. and even more if e x t r a product -re .dd.d to th. can. S h e th. mu u a u loolud the s m i f r e as t h e original ouos. CoIUIIyrs bought th. 1-r-priced o r i g i n 8 1 formulas, and C-318

Want then obtained FDA approval f o r CFG-115, which vas vel1 knovn b u t

navar used for uroaols bae8ure it c o a t $l.SO/lb.

CFC-115 vas t r i e d i n savor81 products d u r i n g the 1977 t o 1978 p t i t i o n period. Marketers based their p e t i t i o n s on the argument thrt their sales vould s e r i o u s l y decrease

'bail-aut' a t t r i b u t e s of CFC-115, thrt the p r o p e l l a n t had only one c h l o r h .+om and should pose a reduced threat to t h m ozone l a y e r . and c h a t only about 5 gram8 vmre needed p e r can. A t the t h . roughly 38,000,000 units of whipped erewere s o l d a y e u , o r 190 metric t o m e s p e r y e a r o f CFC-115.

vithaut the

if 8-m-

muketmr used the p r o p e l l i n e .

The mrketer team also advised the FDA dirt practical.

M

o t h e r p r o p e l l a n t s Were

Freon C-318 w a s unavailable except i n p i l o t q u a n t i r i e s , t h e Food

G r a d a hydrocarboru gave the product an o i l y , s l i g h t l y b i t i n g o f f - c a s t e , and

n i t r o g e n v a s coo insoluble. After the p e t i t i o n w u levels, the p r i c e of CFC-115 anocher option. Th. A u r i c Vent Release (Em) mociunlso cans,

granted, v i t h limits on product tyee and usage i n c r e u e d moderately.

Marketers began t o look ac

Can Company had r e c e n t l y introduced t h e i r Rim on the top double seam of t h r e e - p i e c e a e r o s o l

which opened up a mmber of a p e r t u r e s if the can became dangerously

overpressurized.

The Deprrcment of T r a n s p o r t a t i o n (DOT) normally l i m i t s i f the cans v e r e ordered v i t h RVR

a e r o s o l p r e s s u r e s t o 180 p s i g a t 130'F

fixtures. m e product v u nonflirPrrble and not ocherwise hazardous i f i t d i d escape the c o n t a i n e r . U l t h c e l p , DOT granced an f n d u s t r y p e c i c i o n . which alloved marketers t o i n s e r t 17t more N,O

gas i n t o the product.

This reduced

20 Alternative Formulations and Packaging to Reduce Use of CFCs

the "soupineso" problem and slowly led to the complete eliminarion of CFC-Llj in these products. At least two firas are testing CFC-115 in anhydrous "edible whip"

products of tho general tpp. recently patented by the Ring Chemical Company in New Jersey.

It gives thu a tmtter taate than the 3% Propane mentioned in the

paten=. Cno firm is conridorlng uae o f CFC-115 until yFC-134r (CH,F-CF,) corns onto the market a d can perhaps be approved as a Food Grade propellant. Propane may also be used, as a l u x resort.

RATIONALE FOR EXCLUDED USES OF CFC AEROSOLS

Tbe aerosol drain opener vas developed by Glanorene, Inc. (Secaucus. SJ) about 1972. The actuator consisted of a 2 and 11/16 inch plastic hemisphere with the exit hole at the apex.

The u n i t was upended over the drain hole of a

clogged sink and pressed donnrrrd. opening a valve to allow CFC-12 gas inco the drain pipe. which normally acted to blow the clog out of the gooseneck. Problems were encountered when drain liquids were blown out of the other drain

in double sink installations. Many bathroom sinks had side orifices to prevent overflow, and these sometinas acted as pressure outlets as well.

Pipe

connectors sometimes separated. The product consisted of 100% CFC-12. It did not meet criceria such as life-safety. high value in use, no available alternative. and minimum consumption of CFC gas-liquids. Eventurlly the high cost, excessively large can size. infrequency of use, and the many problems caused consumers to discontinue purchasing it. The franchise was sold to another marketer. and sales eventually ceased.

21


A blend of &out 75b ultrapure CFC-113 and 25b CFC-12 is used to f l u s h across cb. microscopa lam while it is s t i l l in the microscope h o l d e r . Loose dry rp.cimens. v i m e n s udmr o i l . druta. .ad o t h e r o b j e c t s are conveniently

flushed off. afar which auy r

,

w

g CFC-113 quickly evaporates.

This is a

great tim-saver f o r mq i n s t i t u t i d facilities vhere r e p e t i t i v e assays or r,uinrtioma are required.

F i r e t e n a d lumps of c h d n g gm a r e d i f f i c u l t t o remove from c a r p e t i n g

and o t h e r f l o o r coverings. but the task is g r e a t l y f a c i l i t a t e d by u s i n g a cheving gm f r e u a n t spray of CTC-12. which acts to drav down the gum t a m p e r r w e to about -6O'P (-51'C) surface.

Ib. -p&'

or lover by s u c c e s s i v e evaporations o f f rhe

chon becomes very b r i t t l e . able to be f r a c t u r e d o r The p i e c e s can then be removed vhile still

broken up w l t h a shrp blow. frozen.

This a e r o s o l product v u launched a f t e r the 1978 r e s t r i c t i o n s o r bans. I t is used mostly i n i n s t i t u t i o n s and accounts f o r about 350,000 l b s . of CFC-

12 p e r year. As of J u l y 1989, a t least fa0 major CFC s u p p l i e r s r e f u s e d sell any more CTC-12 f o r c h i s a p p l i c a t i o n .

The d i s p e n s e r s and a s s o c i a t e d horn devices

a r e made

to

by s p e c i a l c y f i r m s .

Arguments f o r continuing the use of lOOI CFC-12 in such packages a r e 1) che sense of v e i @ t i n e s s (15 A v . 0 2 . p e r can) c h a t connotes a good product: 2 ) the nonfl-bilicy

of t h e product

( S O M C ~ S

l a r g e amounts a r e r e l e a s e d a t one

time); and 3 ) marketers u s u a l l y manufacture their own products i n f a c i l i t i e s that a r e not explosion proof and vhere they could not s a f e l y produce the less

c o s t l y hydrocarbon p r o p e l l a n t a l c e r n r t i v e products.


Most of these m a r k r t e r / f i l l e r s produce a considerable v a r i e t y of a e r o s o l produces, all of thom p r e s s u r i z e d with CFC p r o p e l l a n t s o r c o n t a i n i n g 100% CFCb.

By Septombor 1989, several manufacturers had switched t o using HCFC-22

i n heavy w d l o d ( n o n u t o s o l ) c y l i n d a r s .

The p o r t a b l e dispenser area of this markot is divi&d i n t o

CJO

segments:

eh u r o a o l cppe and eh cylinbr - 0 . The a e r o s o l is l i m i t e d t o wo s i z e s : the w i n - p a c k of w 4 Av.02. CIPI i n a b e l t - c a r r i e r c a n i s t e r . with a common a c t u a t o r , ad the 12 t o 15 Av.02. pack, i n a red e-led, Kylnr-labeled aluminum contafnor, codod dad approved f o r use by Factory Mucual R&E Laborat o r i e s , U n d r m i t e r s Laboratories, o r 0x10 of the three o t h e r product t e s t i n g Laboratories recognized u reliable. The a e r o s o l s n e a r l y always use a blend of 20 t o 258 Halon 1301 (CSrF,) ad 80 eo 75# Halon 1211 (CBrClF,).

The

a pressure that w i l l allow the a e r o s o l t o pass s p e c i f i c y e t t h ~ w t i l l not exceed the 'DOT S p e c i f i c a t i o n 24" s p e c i f i c a t i o n f i r e testd. a t 130'F ( 5 6 * C ) , a d that is considered "self p r o p e l l of 180 psfg (euinm) o b f e c t i v a is to ob-

ing'

(not r e q u i r i n g

a' pressure gauge).

The c y l i n d o r o r tank porcion of this markot is s e v e r a l times l a r g e r . Several firma sell six o r more product s i z e s , o f f e r i n g the a e r o s o l s i z e f o r c a r o r boat and the l a r g e r s i r e s f o r home use.

The Halon is considorad " t h e product" s i n c e i t provides the f i r e extinguishing a c t i o n .

It is considered a l i f e - s a f e c y product.

Unfortunately,

bromine is a l s o 3 to 10 cimos more able t o d e s t r o y ozono than c h l o r i n e ( C l ) . dopending on che Halon molecule it is in. -der

Devices (For c a r s , trucks, and homos) Thhrse products a r e h i g h - i n t e n s i t y (100 t o 110 decibel) horns t r i g g e r e d

e l e c t r i c a l l y by varioua sensfng &vices.

h r g e amounts of gas a r e discharged

i n each alarm c y c l e t o achieve a p e r s i s t e n t s o n i c e f f e c t .

Because of c h i s ,

nonflammable g u is p r e f e r r e d , e s p e c i a l l y f o r indoor l o c a t i o n s .

The c o s t


23

premium f o r the CFCs (over the hydrocarbon a l t e r n a t i v e ) represents a small

incrennt of the Ov.ral1 M c e . (For pudicd purposes)

Those u r o s o l s a r e typically p d u g e d in dumfnum CUU. f i l l e d to 8 co 10 Av.02. vfth CPC-I2 o r blend of CFC-12 .ad CX-114. They a r e w e d by p w d i c a l persaoni.1 to parform nfnor t o p i c a l operations. such as the removal o f skin cancer. and i o f o r t h , by deadening I t mi&tha use of i n j e c t e d Novocaine and s b i l a r anesChillers have a l s o been used to shrink f i n g e r s and f a c i l i e a c e the

a splinter, thm

w a r t , a mn-wl.noOic

a f f l i c t e d area.

thetics.

r:.oovd of rings that have become too t i g h t . U s l u g f l i n v b l a gas r i t e r r u t i v e s i n a h o s p i t a l o r c l i n i c a l s e t t i n g would not be approved by the medical profession.

Roducts knovn to have such

propellants would aot be used, &spite t h e i r lower cost.

Dimethylecher is che

most e f f e c t i v e propellant f o r this application, buc i t is somewhat flammable.

A c y p i c r l formula f o r chis cype of aerosol p r o d u c t is as follows:

45*

Toluene d i - isocyanate

20r

Po.lyethylene Glycol (PEG) Derivatives

32r 3%

-

CFC 12 Dimthylether (DME)

The dimechylether is present only to bind up r e s i d u a l moisture t h a t can otherwise a c t t o c a u l y z e the reaction between the pro-polymer and che PEG

derivatives.

The f a c t that f t is a propellant is i n c i d e n t a l .

The CFC-12 is

used t o emure production of an e s s e n t i a l l y nonflammable, stable foam.

In cursory studies with foams containing hydrocarbon propellant blowing a g e n t s , i g n i t i o n was i n s t a n t and vas folloved by very rapid burning--with the product i o n of modest amounts of cyanides. cyanogen, and r e l a t e d toxic substances.

24


A p p r m i u t e l y 7Sr o f the u s u d t i r e i n f l a t o r c o n s i s t s of a v a t e r

disporrion of rerln and echyleno g l y c o l , ud a t r a c e of amphoteric s u r f a c t a n t ; 2% ia a hydrocrrban b l d A 4 6 ( b o - b u u r u md propano).

.

Uhon a t i r e is r e i d l a t a d vlth there p r o d u c u , the g u space v l l l then

caa+rin about 35 to 655 by v o l u m of f l d l e hydrocarbon gor. the Upper Explortva U

t

(UEL) of

This is w e l l

about 8.6 VZ f o r propme/butanes and

air, but in subsequant sctivitier ( r o w d i r e c t e d on the l a b e l ) this volume may bo d i l u t e d w i t h air i n t o the f l d l o range o f 1 . 9 eo 8.6 Vr. T i t e r in t h i s s t a t . have beon subjected t o removal. t o adjacent rim welding r e p a i r s , and t o o t h e r facldonZs &at r e d t e d in i n t e n d combustion, fragmentation of t h e t i r e , and s o v e r a , o f t e n f a t a l . injuries t o the o p e r a t o r . In 1906 Co-r

OIU

ruch marketer mot vith r e p r e r o n t a t i v e r of EPA and t h e C d r s i o n (CPSC) in Washington, DC. proposing t h a t

ROQICu Safety

tho ageneier pormlt tho rubrtitutton of the hydrocarbon p r o p e l l a n t by 559 CFC-

12/114 (40:60).

Tho agencies confirmed that they had the right t o do t h i s

because the CFCs would c o n a t i t u t e a p a r t of the product and because they had i n f l a t i n g action.

Within m o oontha the r e v i s e d product v u on t h e market.

I a w a u i t s i n c r e u e d . and during late 1988 another n n r k e t e r developed a

CFC-based t i r e i n f l a t o r formula. buc before going t o market, t h e marketers estimated that f o r every m i l l i o n pounds they purchased 18 s k i n cancers and 0 . 3 doatha would occur u n n u l l y .

The firm d i d n o t market the product.

The CFC p r o d u c t is cectmically i n f e r i o r and more c o a t l y than t h e s t a n d a r d hydrocarbon tlrpes; thorefore. i t has oaly boon marketed by one f i r m .

From 1981 t o 1986 a feu -11 theaa mor.

s p e c i a l t y firms produced CFC products of

For examplo. a firm formulated and packed an a b l a t i v e , very

h a r y foam using CFC-12/114 (u):60).

F i n g e r - r l n g r c o n t a i n i n g gemstones could


be p-ly

embeddad

25

Fn this foam while the back-side v

re-sizing operacioru by jawelerr.

u being welded during The s t o m a remained cool and did not become

serainad or crackad. Th. s~lf-fillerhad M explosion-proof facilities ( i n h i s b u u m t ) and v u comcerned about: the f l d i l f q of foam that carried

hydrocarbon praprllutta.

No o&

& d w m

v u f

of this m e .

non-dnag aorosol producu

Tvo firms purchum

d of Cpcs currmcly being used in the U.S. in

a

concentrate from the Dov Corning Corporation chat

contrins a silicone-bued adhesiw dispersed in CFC-113. Contract fillers pour the concentrate i n t o cans, seal them. and pressurize the contents vich cprbon dioxid.

(~0%).

Dov-Coming scienelstr say that alterrueives to CFC-113 are uniformly uaaccepuble for &e product.

For e u n p l e . the 7 to 8% of free-radical

reaction inhibitors in L,1.1-crichloroe~nehave unknown effects when broughc into conuct w i t h open wounds. The adhesive remover is required s i n c e the breathable silicone f i l m may bond the innermost layer of cotton gauze bandage t o the skin surface, preventing removal. Acetone, ethanol. and many other solvents are eicher ineffective or present toxicological problem. is required.

Thus, a self-pressurized adhesive remover

This consists of about 9 5 . 4 % CFC-113 and 4.6% CO,, in a fill

w e i g h t of 6.0 Av.02. per can.

Approximately 28 individual product types and groups have been or are being produced in aerosol formulas that conuin CFCs. C)%

This does n o t include

refrigeratfon/air conditioning refill products or ethylene oxide/CFC-12

g u sterilants, since these are not coruidared in aerosol exemptions or exclusioru.


Background data on each product or product group is provided. including

hou the CFC corporupr functions. ingredient(s) is ewlninod.

Industry's interest in preserving rhe CFC

In the excluded categories, petitions were noc

required, but metings wore often held, nonetholess, to firmly establish chat companies could go to p u k e + v i t h CFC-based products falling into these

utegorlor.

The p t i m u y reasons for requesting exempted s t a t u were the

uriavdlabilfty of substitutes. thr long tima dolays vhile obtaining an amended MIA from tho FDA. rolvoncy a d purity profiles (espocidly for CFC-113 u s e s ) . life-saving potential of tho product. and regulations in hospitals, aircraft organiutionr. e t c . against tho use of f l m b l e propellants in aerosols.

During tho 1977 to 1978 transition period. no nonflammable liquid propellant altexnatives to CFCs were toxicologically approved and commerciallv Today the sieuatlon has changed, with the clearance of available for US.. HCFC-22 and certain b l e d of HCFC-22/142b. and the forthcoming availability of HFC-1340. HCFC-123. HCFC-lklb. and HCFC-124.

As may tu anticipated, so-

exempted or excluded aerosol products are no

longer in use or have been replaced vith ones that contain alternative propellants. Houever. inhalant and solvent type products are steadily growing in s a l e s wLumo. See Section 3 for current U.S. consumption of CFCs and Section 4 for current and future alternative f o d a t i o n s for CFC aerosols. Section 5 presents a discussion of the costs of making these substitutions to alternative formulations.

3. Current U.S. Consumption of CFCs The mafn sources of Laformation f o r this r r c t i o n

a r e GFC manufacturers.

Product f o d u . m a r a g e product n e t weights, and the d i f f e r e n c e s i n t h e

sales v~luuasof similar produces azo estimated.

The production volume o f the

a e r o s o l industry ln units p e r year f o r 1988 is &terminad from v a l v e s a l e s and from c o a p u i s o n r w i t h the s w e y dau published $n 1987 by che Chemical S p e c i a l t i e s ~ W a c t u r e r ' sAssociation ( C S U ) and the C a n Maker's I n s t i t u t e (CXI).

C a c e g o r i c d volumes a r e then dorived by extending and augmenting che

& t a i l e d C S U data vith s p e c i f f c data from industry c o n t a c t s . DISCUSSION O F

TWE DATA

Table 3 shovs published data ( 5 ) i l l u s t r a t i n g an a n a l y s i s of t h e major catmgories o f the domestic CFC market.

Tabla 4 shows a number of product

c a t e g o r i e s of a e r o s o l s i n vhich C F C s a r e still being used, o r have been used

since 1978.

The U.S. CFC a e r o s o l market i n 1986 vas 24,000,000pounds.

grew by 3 . 9 % in 1987 t o 25,000.000 pounds.

It

The CFC a e r o s o l market in 1988 was

p r o j e c t e d t o be about 25,500,000 pounds (as of October 1 9 8 8 ) .

The f o l l o v i n g paragraphs e x p l a i n t h e information p r e s e n t e d in Table 4 .

The source of the daca obtained on CFC q u a n t i t i e s and u n i t s f i l l e d is a e r o s o l s in the same vay a s t h e U . S . Daprrment of T r a n s p o r t x i o n : p r e s s u r e - r a s i s t a n c c o n t a i n e r s with a c a p a c i t y of 50 cubic inches--819.35 mi. o r 27.71 f l u i d ounces. Larger c o n c a i n e r s , the a e r o s o l i n d u s t r y . vhich & f i n e s

designaced as c y l i n d e r s or tanks, do not have che a e r o s o l exempcion. and (in g e n e r a l ) are f i l l e d and marketed by firnu ocher than those in t h e a e r o s o l

27

28


3.

TiiE mLLY HALOGFJATED U.S. CFC "T OF 1986 (CFC-11. -12. -113, -114,AND -115) ( 5 )

nn

PRODUCr TYPE

PERCENT

p.friger.nu

60

290

n i m hanu

28

200

Cleaning AgeQtS

20

145

OTnEaS

12

85

Liquid Freon Freerant Aorosols Etchntr Scarilanu

POUNDS

100

720

a.

Liquid Freon Freeranc (LFF) is 100% CFC-12.

b.

Etchrncr a r e perfluoro- o r highly f l u o r i n a t e d CFCs, mainly CFC-llL, but including CFC-113, CFC-Ll5, and FC-116. They a r e d e l i b e r a c s l y dagradod by plasnr ares co produce HF for tfm e t c h i n g of e l c c c r o n i c

P-. E.

Tha sterilants c o n s i s t of the U.S. Pacenced. marginally nonf l e l e blend of L22 echyLene oxide (EO) and 882 CFC-LZ. 3 o s c is s o l d t o medical f a c i l i c i e s i n large c y l i n d e r s . buc soma is marketsd In L2 A v . 0 2 . a e r o s o l concainerr.

d.

The 'Cleaning Agents' a r e LOO2 CFC-113.

a.

m

-

million

. . ~ ...

"' !j ~ ~ Qo ~ z z ... < ~ 0 ~ . ~ r.. ~ r.. o z o ...

s ti z ... ~ "" ...

i ~ 0 "' 0 ~ ...
:5 =o a'"' ~ 00

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0

~

..U..U .~ C U U

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c

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'0 =

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29

30

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.

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~

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.., .., Q

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.a .~ -= ~IC ~ ~ ..ou Q C .-o a ~B.. 0 -.~ Q 0.. ..0 ~ o~.. " ..a",Col< o ~ , , ..~ ' .,

0 .. %Q

0 -=

Q

0 ."

Q

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~ Q

... '4

>. .

4 ~

a .. ~o

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...

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-G 0

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.

Formulations

~ Ao

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!j..:~ ~..:% Q.

\.0 ~c "'

z o

t uc u .0 .u c

.Q 000 C'"" ... >-\.0 ...0 rOo...

~ "' rn ~ Q

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~ ~ " ~ c ... ... c o ~

-:; 0 ~ = ... .. = 0 ~

. ro1 ~ ~ < ~

r..(:) O(oJ ~< zu (oJ

>~ o

~

r..

>

"'

0 ~ ~

u~ ~u (oJ~ ~Q

~~ O~ >(oJ

~ u~ ~~

~: ~o

toJ"' z5 ~... ~"' o~ >~ ~

toJ .. ...

gu Qr.. OU ~r.. ~o

toJ"' (:)~

~

z

"'

~

o ...

z

u

z o

~(oJ (oJZ >... «

u~ r..z u~

o u

.a tn Eo U ~ Q O ~ Qo

on

Q GO .

00

I;

Current u.s. Consumption

o

0

...

~ 0

...o on

'0 G

C'O

C

0.. ~ Qo. C >00

~o

N 0

-U

'0 G

.'0..: U

-U..

.0 O

Q

N

0

0...

'

"'

V

I C..

G..

...'0 tnG ..~ G.

a OG U~

0 tn

...CUG

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OC.. U...~

0 ~

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O...N~... OOONOO

~

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0 ~

~ U

o 0 ...

-..U'O

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~

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~0000000 0000000

...V

N O

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V

0...N~...

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e

e G

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000000

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of CFCs

31

32

Alternative

~U ..~

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Ufo~ ~U.. ..0.,. m.QO

i m. ~

and

~~ 5..~.,.. O~... > >C to

U~ O~Z

Q

r-

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c..

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0

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r.g.,. O..U tor. foCU

Formulations

"0 . ~ c ... .. c o ~

~ ~ ID < Eo

MN. ..,Q .. "'... ~~I ~ ~ ~ > CC... to... ~... U:

~ 0ut,Q r.J:... UO "'! ~0 U ~

to

0 ..OQQ.

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fo m. ...,.

U .,. r.1 Q

..."'a 001" ..=...

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C..-

~ '" U 0 Q

= to 0

m.

0 ~ m.

Current U.S. Consumption of CFCs

fndustry.

33

The aorosol sunmys by the Chemical Specialties Nanufacturtr's

bsociacion. Inc. ( C S U ) , the Can nPlur's Institute

(a) Precision Valve I

Corporrcion (POC). a t 4.conridor o n l y those aerosols of capacitias equal to or less t b a 50 cubic inchas. Butaxm lighter Rui& a r e not coruidared eo be

aarosolr: hourat. CFC refill r m F ~ vithin the s i z e limitation

are.

Alchoqh s o 1 aulpeious hrrr been granted for producu marketad both as cyltnd.rr md as aerosols, aa dofind rbaa, for tha purposes of this tepori, the cut-off fa the 50-cubic inch laml; Larger s i z e s a r e not considered in any detpil.

of PJunbQts bv h

t Produr+ TWQ

man dwmlopfag numbers for che column titlad "Product V o l w for A11 Vorsio~t (NU U n i t s ) , " only unfu of the a x a c t product type vera considered.

For axample. the "old Release Agenu' line refers eo releas. w e d in che production of p l u t i c md alaatouric matorialr. relawe agants used for coy -tal

agants for molds Figures for mold

(tin-bismuth) soldiers; cookie forming, ice-

cubo-m8kars. s o w c.ndlel.king, and other applications are not included, even though a small quaaticy of CFC is w a d in thesa a r a u .

Similarly, "Flying Insect Sprays for Afrcraft Fumigation" vere noc compared with the 106,lr00,000-unitoverall flying insect aerosol oarkec.

The use of flying insect sprays based on CFC formulations in commercial food preparation araas has dwindlad to a h s t nothing. Previous formulas have been rtplacad by water-based. hydrocarbon-propellad formulas, supplemented b y

anhydrous, hydrocarbon-propelled types w i n g cine-metering canisters actached to walls or posts. A major concern v u rastricting thesa sprays t o food handling areas. Employees were apc to spray bathrooms, dressing a r a w , and other unauthorized loeacions. The higher cost

was

a further concarn.


Althougt! meter-sprayed aerosols are noe exeqted. the new formulas have

been slov to replace &e meter-spray CFC-12 w a s because the mater valve supplier could not r e d l y produce r complex valve modification that vould spray 40-45 mg s h o u of che 1ov-d.nsity hydrocarbon formulas in place o f the u a u d 100-110 mg burru of th. suadrrd CFC compositionr (7).

T b *Xiliur]r Aoroaols' category inc1ud.r NO sub-groups: t h e flying insect spray (CFC-eype) axid elecaic/eleceronLc maintenance and tasting products (also C F C - q p a ) . Th. U.S. gournnunt ordars 1,500,000 10-Av.02.

2% Toxicants and 98% CFC-l2/11 once a year. Depending on insece populrcions during any y e u , from about 1,250,000 to the f u l l c m i U formulacod v i t h

L.500.000 units a r e releaad for shipment from the sole supplier. %as. formulas account for up to 1,020.000 lbr of CTCs. In Table 4. the remining 380,000 Lbr of CFCs a r e for eleceric/el~ctronic maineenmce activi-

ties around s o w , r r d u . radio. servomotor. computer, airplane controls. and ocher sensitive. costly, or sparking types of equipment.

The three classes of meter-spray inhalant aerosols used for medical purposes can bo defined as follows:

Metered-dose steroid human drugs for oral inhalation; Metered-dore steroid huaur drugs for nasal inhalacion; and

Metered-dose adrenergic bronchodilator human drugs for oral inhalation. Information from the H u k e l l Idoratories Division of DuPont shows che equivalence of nasally and orally inhaled drugs of the steroid types; chey are generally identical except for che plaseic nose or mouthpiece.


35

Table 4 of the present report only gives a total figure for all merereddose iubalrnt drugs.

usmi

The breakdown of these drugs is as follows:

Steroid drugs--oral

20 ( % units)

Steroid drugs--nasal Ergorrrine Tartrate vasoconstrictor drugs Bronchodilator drugs--oral

10

3

"

67

Tha Ergotmine Tartrate types represent less than one percent of CFCs in this category. This inhalant is a cranial vasoconstrictor. used for

nigraine and prodrome control. Two new metered-dose ethical drug products. a hair restorer (quick-breaking foam) and a curative pulmonary spray for bronchial pneunonia--so far only FDA-approved for AIDS patients--are reporred to contain CFC propellants.

The volumes for these products are unavailable.

since each is made by only one firm and the market results would be too revealing.

The hair restorer was released Ln 1988 ad the other vas condi-

tionally approved in early 1989. Additional details on metered-dose CFC-containing drug aerosol products appear in Appendix A.

Conversion of Ppynds of CFCs Uhen calculating aerosol units offered for sale from pounds of CFCs consumed (and vice-versa) it is seen t h a t : Aerosols are regulated as "delivering systems" for net weight purposes, and m s t therefore be filled to an average of 0.10 t o

0.25 Av.02. over labeled veight, according to size.

-

An

average of about 8%

ad filling process.

total

propellant is lost during the handling

This includes leakages, machine discharges,

and the 1.5 to 2 . 5 % of all aerosol units lost through process leakage. bad quality, testing. samples, pilferage, etc.


Noc all CFC aerosols are 1008 CFC.

Examples o f CFC percentage

1ovml.a fn othor producu are:

CFC Usage - (lbs) k t u d f i l l ( l b s ) x CFC Loss Factor x CFC Fraction

U.S.

-

Units

Mm FILIE&s OF CFC PRODUCTS

A substantial &r

of

marketers and

contract

fillers currenrly produce

hestimated 58 of all aerosols thrt s t i l l conuin C X - t y p e propellants.

Some of eluse ffrma are lirtad in Table 5 .


TABLE 5.

37

URKREUS AND F X W CUBRMTLY PRODUCING C F C - m -sou IN M E U.S..

Ir Il.nufrctur*

cow.

Qltsooicr. Inc. nillmr-lefphmren Chemical C-Q-Y

Acme

nS1 Four. Fault FLnbr

AudioTex 6 C d e c t t o Cbugmtte Cold Spray Hollfster JC Coneax 6 Crime-Solv Dalfen Fopr (vA&ld) U t (Chawing C \ n Ru.) Drain P o r n r (ObroleCe?) XmleuaGen (four items) H i r n u 62 (Fraezaae) LmccTo- Safe K0rop.x Foam (Vaginal) Lubrf Bond .%ce (Several types) Hate (Ocher types) Xold-Eue C S0Lir-Cl.m Quick Freezm Fraez-It. Lubrite, ecc. I n d u s t r i a l Fr882ant Freer'n Check C 70 PSI St e e 1-One Seal Afd 6 Spra-Drf Zapper (Personal R o t e e t i o n ) (Concrict Ffllmr) (Contract F i l l e r )

-

Dri-Slid.

(Contract F f l l e r ) Electro-Fraez. Falcon, e t c . F h v Flnder Benvenue Clobm Spray (For endoscopic wrk) h k i k i . Voltex C Term-Ouc

Tuckat, CA Iiauppauge, ANY D m b u r y , (3

A a r a w - P a c i f L e capany Crarm Industrial Prodaictr

san b m d r o . C h Hebron. IL

C0lp-Y C.C. Electronics Division

Bockford. I L

colpurl,

ut0801 b e lbdiC8l

Productr co. Hollfrrmr l b d i c a l R o d u c t r -son Laboratorier, f n c . S C . V r n - ~ lC l h d u l corp. Johnson rad J o b o n . Inc. Avmor, Limited nfrvick I ~ + r i e s Inc. , B.1murC.n Manufacturing Co. T.ch Spray, Inc. h b i S ChOdCAlS, h C . Holland-Rancor Co.. Inc. Electrofilm. Inc. smith 6 wesson co. Clnmral Ordinance Equip. Co. Ch.p-PJr. L n c . Sentry Chemical Company W o r k Electronic P r o d u c t s Rolau: The Supply corp. Chemlronfcs. Inc. Madison Bionics, Inc. O r b I n d u s t r i e s , fnc. s a h q d Security colpany b r o s o l Systems, Inc. Chu. Products, Inc. Drl-Slid., Inc. Armstrong k b o r a t o r i e s . Inc. Falcon Engineering Co. h r i c a n Cas C Chemical Co. Bmnvenue h b o r a t o r l e s . Cnc. Globe Hedf u l Instruments ,

Neodmssr,

KS

I m i n e , CA Chicago. IL Erie. PA M t . Vernon, NY Raritan. NJ Montroal (Canada) Carlsudt, NJ Dellno. HN Amarillo, TX Cincinnati, OH Trenton, NJ Vanmncia, CA Springfield. M S p r i n g f i e l d , .XA Winchester, 5N Stone Mountain. CA Sarasota. FL Lake Geneva, UI Hauppauge, NY Franklin Park, IL Upland, PA Hnrleysville, PA Macedonia. OH Mayvood. I L Freemont, SI Uest Roxbuzy. MA Mountainside, YJ Northvala, NJ Bcdford, OH C l a a m o t c r . FL

I=. Wki Electronics Company

aInhalant drug producers are not l i s t e d .

Hauula. Hawaii

4. Suggested Alternative Formulations for Exempted and Excluded CFC Aerosols

The CFC p r o p e l l m u in e x q c e d and excluded a e r o s o l s a r e c u r r e n t l y p r e f e r r e d f o r a variety of reasons.

Such reasons include their nonflan-

mability, high p u r i t y . d q u e s o l v e n t c h a r a c t e r i s t i c s (CFC-113 i n p a r t i c u l a r ) , o r the fact chat they ha-

bean made an e s s e n t i a l p u t of New Drug Amendments

(NDAs) f o r p h r m r c e u t i c a l meter-spray a e r o s o l products. O t h e r propdlants or b l e d

MY e x h i b i t

Since

s o w o f these p r o p e r t i e s .

1983, a set of f o u r alternatives t o CFCs has bean c o m e r c i a l i z e d , and another set

of f o u r is expected t o coma onco the market i n 1992 o r 1993 i f t h e r e s u l t s

of t o x i c o l o g i c r l t e s t i n g programs continue t o b e favorable.

The p h y s i c a l

p r o p e r t i e s o f the aighc a l t e r n a t i v e s a r e summarized in Table 6 .

All the

p r e s e n t l y a v a i l a b l e a l t e r n a c i v e p r o p e l l a n t s a r e gases a t room temperature.

-

o r l o v e r ; t h e r e f o r e , none can be considered a direcr-

Boiling p o i n t s a r e 14'F

replacement f o r CFC-11 (B.P.

73.3.F)

o r CFC-113 (B.P.

-

about LZO'F),

which

a r e liquids a t room temperaeures. Although HCFC-22 is nonflaimaable and is commercially a v a i l a b l e , t e r a t o genic u n c e r t a i n t y has discouraged marketers of metered-dose pharmaceutical Lnhalanc a e r o s o l sprays.

The extreme solvene a c t i v i r y of dimethyl e t h e r is zn

additional concern f o r those firms marketing drug products in s o l i d suspension

forms because of Oscvald Ripening e f f e c t s that change p a r t i c l e sirs d i s t r i b u tions. In t h i s section.

No

o r more formulation options will be presented for a

number of produccs that c u r r e n t l y use r e g u l a t e d CFCs.

Some have a r e l a t i v e l y

g r e a t e r p o t e n t i a l f o r s t r a t o s p h e r i c ozone d e p l e t i o n than o t h e r s .

38

Although the

~ ~ j ~ ~ a. O ~ a.

~ O cn ~ ~ < ~ ... ~ < ~ ~ ~ ~ < ~ ~ ~ ~ r.. ~ ~ ~ ... cn cn O a.

Q ~ ~ z toI ~ ~ u

'0 toI ~ ~ < ~

U

N ...= IU-o U U r.. =

r.. U I r.. U ... ... U

.N

o

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U

~ U =

r

I U,V

;9 U o I V... ..-0 = U

.., N ...=

...u I U r.. U =

.. =

~ .. .., = ...U... I I -0 U ..N r.. r.. = U

.U

~ N

... = U r.. = U

..-0

O =

U -..,

... r.. U = U N ...N

,

-0

...I... I ...~ U r.. N r.. ...I U U = U

~ N ." ...I..' UI... r.. = I ...~ >0 ~.c a..

.c

...r.I Q N N I U r.. U =

. ."

..

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. ...~

. N-o

~

...I

...I..'

...,

~

-a. Q.o -..,

0'

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0'

~ >~

Q.. -Q

r.. ~ e W

r

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~ Q o

r..

.c Z

.c Z

... ...

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.c Z

.c Z

r.. Z

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r..

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2

Suggested Alternative

N ...Z

... ..,

~

0

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...

, .

...

>0

r..

.. C

...>0..

.Z I

0

OC "'...

~ ~= ...

... .~...o I O'~ ~Cr.I

~ r.I

...~~ r..~-

i

~ r..

0' C

0. ~-

'0 .~ .. ~ e ...Z .. ..I .

I .Z

Formulations

~ 0 ... .. =' ~

~

.. ~ ..

r.. Z

Z

E . >

O

... ~

::: 4 0

ing about 5% non-ionic surfactant, 20% xylenes, 72% deodorized kerosene, and 3% carbon dioxide are used for cleaning the exterior of car engines. After use. the cleaner can be flushed away with tap water.

It is generally ad-

visable to perform the cleaning operation outside on a cool engine that is not running.

Hydrocarbon propellants, such as propane (A-lOe), have been used for

these products, but they are not recommended because of their flammability. A

second anhydrous version, in this case not containing any surfactant

materials, is carburetor and choke cleaner.

It typically contains 60% toluene

or (better) xylenes, 30% diacetone alcohol or acetone, and 10% propane.

It is

obviously extremely flammable, and should be used in small amounts and with care in an open and well-ventilated area.

The engine should be cool and

246


TABLE 26.

HARD SURFACE CLEANER FORMTIATIONS

INGREDIENTS

FORMULA A

FORMULA B

(%)

(X)

0.50

Atlas C-3821 Detergent Tergitol 15-S-9 .(Non-ionic surfactant)

0.50

Tetrasodium EDTA (38%

5.00

Triethanolamine

-

in water)'

8%

1.00

Propylene Glycol klonobutyl Ether

5.00

Sodium Meta-Silicate 5-Hydrate

0.10

Sodium Sesqui-Carbonate Morpho1ine

4.00

6.00

0.10 0.20

Ammonium Hydroxide (29% NH, in Water)

0.15 1.00

Sodium Hydroxide ( 5 0 % ) or Citric Acid (50%)b

9.S.S

9.5.c

Fragrance

0.10

0.15

82.10

79.90

7.00

7.20

Deionized Water Isobutane (A-31)

'Although a specific surfactant was mentioned, any one or more of che following may be used:

-

Linear primary alcohol polyglycol ether (9 to 12 mol ethylene glycol (ETO); average) ; Linear secondary alcohol polyglycol ether (9 to 12 mol ETO: average); or Nonylphenol polyoxyethylene (9 to 13 mol ETO; average).

These reagents are used to adjust pH value to 10.5 2 0.2 at 2 5 ° C

. . (a sufficient quantity). Quantum sufficrf

247

Example Non-CFC Alternative Formulations

turned o f f .

Any excess should be removed before t h e car i's r e s t a r t e d .

use of a no&-ble

The

p r o p e l l a n t , such as HCFC-22 o r carbon dioxide, would a c t

t o make the o v e r a l l product only s l i g h t l y less fl-ble.

The f i n a l v e r s i o n of a hard-surface cleaner is oven c l e a n e r . both c a u s t i c formulas and 'pre-caustic"

formulas.

There a r e

The c a u s t i c ones use from 4

t o 8Z sodium hydroxide a c t i v a t e d by t r i e c h a n o l m i n e t o c u t through the v a r n i s h - l i k e d e p o s i t s of grease and food s p a t t e r s on oven s u r f a c e s .

The o t h e r

form containa alkali metal acetates and sometimes o t h e r organic salts i n a

water and s u r f a c t a n t s l u r r y .

The product is sprayed on the oven s u r f a c e s ,

a f t e r vhich the oven is closed and heated.

This causes t h e organic s a l t s t o

pyrolyse v i a a d i s t i n c t l y N o - s t a g e process, producing the oxide, carbon dioxide, and water.

The oxide then hydrates t o the hydroxide form, which

begins d i s s o l v i n g t h e baked-on greases and ocher residues.

' the

Table 27 presents

formulations of oven c l e a n e r s .

I

The c a u s t i c nature of Formula A in Table 27 allows it t o r a p i d l y corrode aluminum s u r f a c e s , and t h i s is o f t e n mentioned on l a b e l s .

Under U.S. regula-

t i o n s , i f an oven cleaner contains more than 2% of a c a u s t i c such a s sodium hydroxide, the dispenser m u s t be f i t t e d v i t h a c h i l d - r e s i s t a n t c l o s u r e .

The

same r e g u l a t i o n s permit one exempt package s i z e designed f o r homes without

c h i l d r e n and f o r a d u l t s v i t h physical problems l i k e a r t h r i t i s vho would o t h e r v i s e have g r e a t d i f f i c u l t y using the product.

In p r a c t i c e , t h e market-

place has shown a s t r o n g preference f o r the products wichout the s p e c i a l c l o s u r e s , so that dispensers t h a t have t h i s f e a t u r e a r e nov only a token p a r t of the o v e r a l l s a l e s p i c t u r e .

S e l f - c l e a n i n g ovens i n the U.S., Europe, and

o t h e r a r e a s w i l l reduce s a l e s of aerosol oven c l e a n e r s .

The o t h e r type of heavy-duty cleaner is designed f o r the s p e c i a l t y cleaning of t e x t i l e s .

The b e s t known is the pre-laundry cleaner s t a i n

remover, which is sprayed d i r e c t l y onto a s t a i n and onto the inner neck band of s h i r t s , s h i r t c u f f s , and o t h e r a r e a s where d i r t and grime seem t o concentrate.

After spraying, the garment may then be laundered.

Some formulations

contain enzymes f o r the more e f f e c t i v e removal of proteinaceous s t a i n s ; e . g . ? grass s t a i n s o r bloodstains.

Others use a mild detergent system and claim

248

Alternative

Formulations

TABLE

and Packaging to Reduce Use of CFCs

27.

OVE.'I

CLEANER

FORMULATlO~S

FORMULA A

INGREDIENTS

FORMULA B

Potassiwa Formate

6.0

Potassium

6.0

Sodiwa

Acetate Hydroxide

Calcium

Dodecylbenzene

Compatible Sodium

Sulfonate

0.5

Thickener

0.2

Nitrite

Triethanolamine Tetrasodium

-99% EDTA

Deionized

\later

Isobutane

(A-31)

.38%

0.2

1.0 1.0 87.8

78.3

5.0

6.0


249

that the treated garments may be stored for several days before washing, if

50

desired. The two major formula types are anhydrous and water-based. generally contains 25 to 40% water.

The latter

Originally, soil removal was accomplished

by u s h g 20 to 25% perchloroethylene, in addition to the usual anionic/nonionic detergent system and hydroxylic solvents. The perchloroethylene (Cl2C-CC1,)

w a s a major benefit t o the cleaning activity, doing such a good

job, in fact, that many users complained that their clothes were cleaner and whiter where the product was applied than in the other areas. Some wondered if the product contained a bleaching agent.

The marketers maintained a

service for taking care of shirts and other garments submitted to them by consumers for correction or replacement, and what they normally did was to immerse the entire item in the concentrate for a few minutes, rinse it off. dry the garment and return it.

The super-cleaning ability of the aerosol

product had removed soils that resisted ordinary cleaning methods and that had built up on the garment over months of use. turning the cloth slightly grey or slightly tan.

Eventually, the perchloroethylene vas deleted, after the Bruce

Ames “mutated Salmonella“ test suggested that it might be a carcinogen and after a number of more odor-conscious consumers complained that traces of the chlorocarbon odor could be detected in clothes even after they were automatically washed, dried, and ironed.

The two main formula types of textile

cleaners are illustrated in Table 28. The isopropanol functions as a mild cleaner, but (just as importantly) as a foam destabilizer and suppressant. Ethanol may also be used for this purpose.

In either case, percentages may vary according to the foaming

tendencies of the overall formula. CarDet and Rue Cle anel: This unique product was introduced around 1964 by S. C. Johnson & Son, Inc.

It is presented in a very large can, such as the 75x192 mm (USA:

300x709) or the new, necked-in 72x261 mm (USA:

211-213/214~1005).which have


TABLE 28.

PRE-LAUNDRY CLEANER FORMllATIONS

INGREDIENTS

FORMULA A

FORMULA B

Linear primary or secondary alcohol polyglycol ether [2 to 4 mol ethylene glycol (ETO)]

12.0

Linear primary or secondary alcohol polyglycol ether (7 to 10 mol !ZTO)*

12.0

10.0

Diethylene Glycol Monomethyl Ether

12.0

5.0

Sodium Laurate/Kyristate

0.4

-

4.0

5.0

20.0

786.7

Isopropanol

99%

Lov-odor n.Paraffinic or iso.Paraffinic C,, Hydrocarbons) Solvent (Clo

-

Ammonium Hydroxide (28% NH, in Water)

0.5

Fragrance (Typically lemon/lime)

0.5

Enzyme Concentrate (Optional)

1.0

Deionized Water Propane A-108 or Propellants A-85 Carbon Dioxide

0.5

30.1

7.5 2.8

'Hay be replaced with octyl or nonyl phenol polyoxyethylene (9 to 13 mol €TO) or other non-ionics of similar HLB value.


251

capacities of about 820 and 980 mL, respectively. This allows one can to clean a carpet of maximum area. The products

use

sodium lauryl sulfate, which acts to pull the dirt and

grime out of the carpet fibers and then dries so that vacuum-cleaning can effectively remove it.

An

emulsified polymer is included to prevent rapid re-

soiling of the absorbent fibers. Table 29 gives a typical carpet cleaning formula. Intensive wetting of the warp and voof of the carpet is not desired, as would occur if sodium stearate/palmitate soaps were to be used.

Excessive

wetting lengthens drying time, and might also cause mold formations at the base o f the carpet or rug. The sodium/magnesium lauryl sulfate combination vets only the surface of the fibers, where most of the dirt is collected. In particular, the magnesium lauryl sulfate helps surround the dislodged dirt into a more friable, dried mass on the surface of the fibers, for easy removal with a vacuum cleaner. The sodium lauryl sarcosinate functions as a corrosion inhibitor, more

or less specific to lauryl sulfate ion and ethoxylated or propoxylated Lauryl sulfate moieties. However, for it to function well, there must be a virtual absence of chloride ion, bromide ion, and copper ion. The highly purified "toothpaste" grade of sodium lauryl sulfate (SLS) is acetone extracted or otherwise treated to remove any chloride ion that may be present, depending on the method of synthesis used.

Sodium nitrite has often been added to these

formulas as an additional corrosion inhibitor. The upholstery shampoo is a related aerosol product that uses such detergents as sodium lauryl sulfate or morpholinium stearate, plus ingredients such as lauryl-monoethanolamideas a corrosion inhibitor and foam stabilizer. The foam is worked into the upholstery covering with a rough cloth or softbristle brush, then allowed to dry before removal. A water-wipe is often used to remove the last bits of product, so that a slightly soapy feeling will n o t be noticed.


TABLE 29.

RUG AND CARPET CLEANER PRODUCT FORMUIATION

INGREDIENTS

FORMULA

Sodium Lauryl Sulfate (very l o w in Chloride Ion)‘

1.60

Magnesium Lauryl Sulfate (very l o w in Chloride Ion)b

1.20

Sodium Lauryl Sarkosinate

-

(30% in Water)‘

Styrene Kaleic Anhydride Copolymer

-

(15% in Water)

3.00 20,00

Optical Brightener; as Calcofluor SD (Optional)

0.02

Ammonium Hydroxide (28% NH, in Water)d

0.16

Fragrance

0.08

Deionized Water

66.44

Isobutane A-31

7.50

‘As Maprofix 563, by the Onyx Division of Witco Chemical Co. b A s Maprofix Mg. ‘As Maprosil 30.

*Used to adjust the pH value to 9.8 2 0.2 at 25’C, although up to about 1.5% may be used if the clean odor of ammonia (NH,) is desired.


253

d Absorbent Fabric Cleaaerp A relatively unique aerosol product uses the extreme absorbency o f very

finely divided silica povder to literally soak up stains by capillary action. Silica, which has been made by the pyrolysis of silicon tetrachloride, is able to absorb hundreda of times its own veight of various liquids, even greases and gels, and this principle is used here.

The silica, in the form of an

slurry in 1,l.l-trichloroethane, is sprayed onto the The solvent quickly evaporates, causing the silica

essentially nonfl-ble fabric to be treated.

powder to absorb any available liquid materials.

After complete drying, the

loaded silica is brushed off the cleaned fabric, using light strokes, so as not to embed it in the fiber matrix.

The aerosol dispenser often comes with a

special plastic cap whose top is molded to have 100 to 200 thin, comb-like tines or bristles. 'The cap is used to brush off the silica.

A typical formulation follovs: ABSORBENT SILICA CLEANER FO-TIONS

Fumed Silica Povder 1,1,1-Trichloroethane Isopropanol

-

99%

6.00

68.00 10.00

Fragrance. Propane A- 108

0.05 15.95

The selection of silica powder and a valve with optimum design features are keys to success, since with an incorrect combination, valve plugging may occur.

The user can correct this problem only 40 to 60% of the time.

There

are also considerable problems with evaporation, concentrate l o s s e s , t o x i c o l o gical response to l.l,l-trichloroethane vapors (unless used in a vellventilated room) and weight control in the manufacture of these products, so that one should not undertake their manufacture lightly.

254


These cans, when actuated under totally non-conductive conditions, will build up a static charge in the 67,000 to 285.000 V range, based on the results of one fairly large study.

This does not adversely affect the

consumer in any way, but if a filled can is j m e d , defective. or otherwise quickly discharges the contents in a gas house vhile momentarily not grounded, the spark to a nearby grounded surface may cause ignition of the discharge plume, perhaps with serious consequences. No viable corrective methods for this phenomenon have yet been devised.

The air freshener was the second aerosol product to be developed commercially, after insecticides.

It was marketed in the U.S. as early as 1948,

mainly by oil companies, and then by chemical specialties marketers such as the Colgate-Palmolive Company.

The formulas were initially combinations of 1%

fragrance, 15% low-odor petroleum distillate, and 84% CFC-12/11 ( 5 5 : 4 5 ) , until about 1961, when the S. C. Johnson & Son, Inc. firm began to market their line

of "Glade" Air Fresheners in a water-based form. These formulations now make up the largest segment of this category.

The remaining segments are the

"super-dry" sprays, typically containing 99% propellants, and the alcoholic types that average about 50% ethanol.

Typical examples of the three versions

are presented in Table 30. The use of dimethyl ether propellant in Formula B is justified by the increased solvency of perfume resins that might otherwise precipitate. As mentioned earlier, Formulas 0 and C have a Volatile Organic Compound

(VOC) level of essentially 100 percent. After February 28, 1990. the State of New Jersey (U.S.) has forbidden the marketing of these formulas unless the VOC content is somehow reduced to 50% or less.

The use of 1.1.1-trichloroethane

(not a VOC. though it has a potential for stratospheric ozone depletion) is not permitted.

Ultimately, it may be necessary to use a combination of

something like 6 parts water and

** parts HFC-152a (replacing 50 parrs

Propellant Blend A-60) to be in compliance with the regulations. will have a major effect on the retail cost of these products.

of

This change


255

AIR FRESHENER FORMULATIONS

TABLE 30.

INGREDIENTS

FOXHUIA A

FORMULA B

FORMULA C

(X)

(Z)

(X)

Fragrance

1.00

1.50

2.00

Odorless Petroleum Distillates

6.28

Lanpolamide 5 Liquid (Croda, Inc.) PEG LPnolinamide and PEG Lanolate ester 50% in Deodorized Kerosene (HLB 3.65)

0.72

-

6.00

-

38.00

S.D. Alcohol 40-2 (Anhydrous). Sodium Benzoate

0.15

Deionized Water

59.85

Propellant Blend A-60b

32.00

Dimethyl Ether

4.00

90.00

50.00

8.50

.Specially Denatured ethanol, where 400 g of tertiary butanol [(CH,),COH] and 42 g of brucine sulfate are added to every 3,600 liters of anhydrous e thano1. bContains typically 62 weight percent isobutane. 2 weight percent of n.butane and 40 weight percent of propane.

256


. . This category has often been compared with air fresheners, but there are more differences than similarities. First, the "D/D" products are regulated by the U.S. &PA. so that planning and formula development should be carried

out at least three years before the marketing phase begins.

Secondly, most of

the label is given to a description of the formula, disinfectant claims, and directions for disinfecting hard surfaces. The ability of the product to function as a space spray is limited by the low levels of propellant used, since the main use is as a surface spray, and labeled uses limit space spraying to storage rooms, closets, and other enclosed spaces for deodorizing purposes only.

(Fragrance benefits are not mentioned on the label, although a

pleasant fragrance is always included, even in "Hospital Strength" D/D products.)

Two formulation types and two propellant types are currently in

use.

The

base product contains either an o.pheny1-phenol system or a quaternary ammonium disinfectant system in a hydro-alcoholic solution.

Either 5% carbon

dioxide or about 20% hydrocarbon propellant blend is used as the pressurizing medium.

In terms of units sold, the o.pheny1-phenol and carbon dioxide syscem

is probably the most popular. The EPA requires that the labels of these products list the active ingredients, plus certain other data.

An example from the label of one such

product is shown below: Active Ingredienrs: n-Alkyl (60% C,,, 30% C,,, 5% C,,, 5% C18) dimethyl benzyl ammonium chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . n-Alkyl (68% C,,, 32% C,,) dimethyl ethylbenzyl ammonium chlorides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Ethanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . n-Alkyl (92% C,,, 8% C16) n-ethyl morpholinium ethyl sulfate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Inert Ingredients: 46.7282 Contains sodium nitrite

0.072% 0.0722 53.088% 0.040%


257

The first two ingredients are available as BTC 21234, which is sold as a 50% active ingredients solution (and in other strengths) by the Onyx Division of the Witco Chemical Company.

Similarly, the last n-Alkyl compound is sold as

Atlas 6-272, generally as a 352 active ingredient solution, by IC1 America,

Inc. Two examples of these formulas are provided in Table 31. The quaternary smmonium chloride products came along well after the market for D/D aerosols vas well established and approaching 100,000.000 units sold a year in the U.S.

The strengths and weaknesses of their antimicrobial

spectrum of efficacy is different from that of o.pheny1-phenol and its close derivatives, as would be expected.

Also, since the quaternaries are much less

volatile than the substituted phenols, the protective effects may last longer. This may be important when considering regrovth potential for molds in leather, wood, books, and other relatively porous substrates.

No one has

attempted to market a product containing both microbial types, perhaps because of the degree of toxicological and microbiological testing that would be required, Since they have chloride ion (a strong corrosion promoter) double-lined cans and heavy amounts of strong corrosion inhibitors have been required to achieve an adequate shelf life for the quaternary ammonium formulations.

For

some time, combinations of sodium nitrite and morpholine were preferred for

the inhibitor system, but after it vas found that up to about 10 parcs per million of morpholinium-N-nitrosamine (a carcinogen) could be formed in s i t u over one year of room-temperature storage, marketers acted to change the sodium nitrite to sodium benzoate and eliminate the reaction.

. srnfectant . Cleaners This type of product vas partially covered under "Hard Surface Cleaners" (see Table 26). but the disinfectant version adds a new dimension of cleaning that is generally appreciated by the consumer.

Most of the larger marketers

of heavy-duty cleaners are able to cope vith EPA's requirements for premarketing registration, plus federal and state fees, and have preferred this type of presentation.

The disinfectant cleaner is really nothing more than


TABLE 31.

DISINFECTANT/DEODORANT FORMULATIONS

INGREDIENTS o.Pheny1-phenol (98% purity) BTC-212%

FOBMTIA A

FORMULA B

(X)

f%)

0.110

(502 in water)'

0.288

Atlas G-271 ( 3 5 X in water)'

S.D. Alcohol 40-2 (Anhydrous)b

0.114 73.380

52,068

Fragrance

0.110

0.110

Sodium Benzoafe

0.200

0.220

Morpholine

0.200

0.200

21.000

25.000

Deionized Water

22.000

Propellant Blend A-40' Carbon Dioxide 'For chemical compositions, see preceding page. bFor chemical composition, see note 'a' of Table 30. '10 w t X propane and 90 wt X isobutane.

5.000

Example Non-CFC Alternative Formulations 259

the standard type, except for the inclusion of 0.20% or so of biocidal

material in the fomula.

When a quaternary microbicide is used, the formula

has to be adjusted to eliminate incompatible anionic surfactants that might precipitate the active cationic moiety.

Some remain acceptable, as will be

seen in the formulation presented in Table 32. Normally, two cypes of valves are used for both these and the regular hard surface (basin. bath, and tile) cleaners. The can may be used in different positions, including some where the dip tube may protrude into the gas space.

The simplest and least costly approach is to use a valve with a

very large diameter, a .jumbo" dip tube, with an inside diameter of about 6 . 4 mm.

For the relatively long cans in general use. such tubes will contain 7 to

8 grams of product.

If the container is turned upside down--for instance, to

more comfortably spray the base of a toilet bowl--the special dip tube will hold sufficient product for about 6 seconds of spray time.

After this, gas

will be emitted, signalling the consumer to reverse the can for a second or In the second approach one might use the Sequist Valve Company Model NS-

wo.

36 (Ball-check) valve. A &-am diameter stainless steel ball travels in a short plastic slot. just below the valve.

With the can upright. an orifice ac

the bottom of the slot is closed off, forcing the product to travel up the dip tube and through the valve.

With the can inverted, the ball closes off an

orifice at the opposite end of the slot. This acts to plug the opening from dip tube to valve and at the same time opens a "vapor-tap" type orifice directly into the valve chamber. The valve has only two minor deficiencies: it always leaks slightly becween the plastic and the ball, to give a vapor-tap effect, and secondly, it works poorly when the can is in an essentially flat position.

The price is significantly higher than that of the standard valve

or jumbo dip tube valve. A good delivery rate for the hard-surface cleaners is about 1.23 g/sec at 21.C.

ture.

at the 460-mm vacuum crimp pressure of about 2 . 5 4 bar at that tempera-

A valve with a 0.46-mm stem and 0.41-mm W-ST button will provide che desired rate.

260 Alternative Formulations and Packaging to Reduce Use o f CFCs

TABLE 32.

DISINFECTANT CLEANER FORMULATIONS

INGREDIENTS

FORMULA (X)

Sodium Meta-Silicate 5-Hydrate

0.10

Tetrasodium EDTA (38% A.I. in Water)'

4.12

BTC 2125H (50% A.I. in

0.40

Sodium Benzoatc

0.10

Sodium Tetraborate 10-Hydrate

0.10

Morpho1ine

0.20

Ammonium Hydroxide (As 29% NH, in Uater)

1.10

Atlas C-3821 Non-ionic Surfactant'

0.50

Butyl Cellosolve (or similar)d

6.00

Potassium Hydroxide (45% A.I. in Water)

0.05

Fragrance

0.15

Deionized Uater

80.18

Isobutane A-31

7.00

'Tetrasodium Ethylenediamine-tetraacetate, such as Cheelox BF-13, or Versene 30 (Dow). bSee previous pages f o r complex formula of ingredients.

'By IC1 America. Inc.

dBy Union Carbide Corporation. be used.

Propylene Glycol Monomethyl Ether may also


261

Products In 1988, the U.S. paints and coatings industry marketed approximately 325,000,000units, ranging from very small touch-up paints to large-size units for domastic or industrial furniture finishing. A substantial number of filling plants specialize in self-fill or contract filling operations. It is a complex area, vith five main categories: enamels, lacquers, varnishes, stains, and primers, vith subgroups of each. Large numbers of colors have also to be Considered. The largest sales are for the alkyd- and acrylic-base paints. Both are available in anhydrous and water-based formulations, although the water-based techniques are better developed in some countries than others, as is the use of dimethyl ether as a paint propellant. The formulas to follow illustrate a bronze metallic specialty lacquer (anhydrous). tvo

alkyd types and an acrylic type.

The last three are based on some

excellent work by W o n t that has been widely distributed. The term lacouer refers to a coating that dries by the simple evaporation of the solvent system. Originally, it related to the cellulosic varieties, but these have been almost completely displaced by the thermoplastic acrylics. The acrylics have better resistance to mild chemicals, weather. and sunshine. They are a preferred base for various metallic finishes (aluminum. bronze, and gold powder finishes) because of their low acid number and water-white color. Four different paint formulations are illustrated in Table 3 3 . A

prototype valve that might be evaluated is the Newman-Green Model R-10-

123 (0.33-rn vapor-tap), but with a butyl rubber seal gasket. The actuator is

a No. 120-20-18. This valve delivers the four products shown in Table 3 3 at about 0.95 g/sec at 21.1.C. During the development of various paint aerosols, alterations in the formula or valve may be required if the applied product exhibits low gloss, blushing, sagging, bubbling, peeling, deleafing of metallics, valve plugging, poor adhesion, low durability, or other problems. For example, adding more xylenes to Formula A would slow down the final drying of the film, resulting in better smoothness and higher durability. The disadvantage must be weighed against the two advantages, keeping in mind that the consumer will note the

262

N

1

oom

m

c

d

I

.

)

d

m

~

o

o

o

oooCI-?m 1

??".??-!

O o O m N u o

???????

o

~ d m 0 3 0 0 0 0 *

??-!

0

?

Bm o m

8

I

0

1I I

u

?

?

o

N

U

l N l m

o

?

m

?

4

OD

m

"'2'3

I


s

bl

al s o u u w

h

2

0

C

U

rl

0

v

rl W

0

-1

m

c

Example Non-CFC Alternative Formulations 263

2

CI

0

U


disadvantage rather soon

after the product is used, but may not detect the

other differences until later, if at all. Paints and coatings are generally packed with a small glass marble that helps agitate settled material back into a uniform dispersion. Also, to prevent premature use by children or others, a tamper-resistant and tamperevident valve cover or protective cap is used.

The outer cap is often colored

the same as the product within the can, or it may carry a self-adhesive top label to help the customer make selections. ture P

o

w

The original aerosol furniture polishes were introduced around 1950. They contained self-polishing floor waxes in a simple oil-in-water emulsion form.

In 1955. silicone emulsions were included, since they added lubricity

and made the rubbing out process much easier.

They also improved the sheen

and conferred water resistance to the polish.

At first, formulators added an

intermediate viscosity silicone, such as Dow-Corning DC-200 dimethylsilicone fluid (1,000 cstks), at a low-volatiles level about the same as that of wax: 0.7 to 1.5% of the total.

But as they found that silicones soaked into the

polishing cloth more readily than wax, they began to increase silicone levels. In addition, it was found that combinations of lower- and higher-viscosity silicones functioned better than the single intermediate viscosity type.

The

higher-viscosity silicone added shine or brilliance, but too much caused the polished surface to be subject to marking.

Two illustrative examples are

shown in Table 3 4 . The preparation of furniture polish concentrates can present fire and explosion hazards, especially if the more volatile aliphatic hydrocarbons are used, such as Isopar C. which has a flashpoint of 5'C. Isopar C to 80'C

Heating batches of

or so to facilitate the dissolution of waxes has caused four

major explosions and subsequent fires.

This is because very heavy vapors o f

the hydrocarbon seep over the tank rim. fall to the floor, and spread outward until a spark or fire source is contacted.

Less than 1 volume percent of


TABLE 3h. ~~

FURNITURE POLISH FOWUIATIONS

~~

INGREDIENTS

FORMlLA 'A

FORMULA Bb

(%)

(X)

Wax S and Wax N (1:l ratio) Hoechot

1.25

1.25

Silicone Emulsion LE-461 (50% A.I.) UCC

1.40

1 40.

Silicone Emulsion LE-462 (50% A.I.) UCC

0.35

0 35

Arlacel C (Non-ionic surfactant) IC1 Am.

0.15

1.25

Isopar C or E (C, or C, iso.paraffinics) Exxon Oil Company

2.00

Lemon Oil. Technical Grade

0.75

0 60

Glutaraldehyde ( 5 0 % A.I.) UCC

0.05

0 03

Sodium Nitrite

0.05

0 05

Deionized Water Isobutane A-31

86.00

7.00

33

ooc

44 67

17 50

'Oil-in-water version. %ater-in-oil version.

265

(Better product; more costly.)

'Any n-paraffinic, iso.paraffinic, or multi-brancheate low-odor hydrocarbon may be used, at 12 to 36%. About 20% is an average.


flammable vapor in air is required for ignition.

Air-tight compounding tanks

and good ventilation is required. A related product is the wood paneling cleaner, conditioner, and polish. Pre-finished plywood wall panels, natural wood kitchen cabinets, and similar surfaces have relatively thin varnished or lacquared surfaces compared vith furniture, so that the use of water-based polishes like those just described vould result in some water penetration of the wood, and the finish vould be gradually lifted or peeled.

As a result, these products are anhydrous and de-

emphasize the use of wax-type ingredients.

The formulation in Table 35

provides good gloss, sealing, and detergent resistance. W

w

l

d De-Ice=

The windshield de-icer spray is a product representat re of automotive aerosols.

zens of

The most effective de-icer is methanol (CH,OH), and it

is used to some extent. despite its vell-known toxicity and the corresponding need for special labeling under various U.S. government regulations. such as the CPSC regulations. Isopropanol [(CH,),CHOH]

and n.propano1 (CH,-CH,-CH,OH)

are less hazardous but are less effective and more costly.

Since a simple

alcohol or alcohol/water de-icer would allow refreezing of the liquid to occur as soon as the alcohol was sufficiently diluted or evaporated, it is customary to add a certain amount of glycol to formulas.

Here again, ethylene glycol

(HO-CH,-CH,-OH) is the most effective, but it also is quite poisonous, so propylene glycol [HO-C(CH,)H-CH,-OH]

is used instead.

If very thin ice films are dissolved by an anhydrous alcohol/glycol product. after vhich the alcohol largely evaporates, vision will be obscured by the heavy glycol layer that remains.

To resolve this final problem,

certain amounts of water are included in the formulas.

The higher-quality

products vi11 have about 20%. while the economy types may have as much as 50 percent.

Table 36 presents a typical formulation.


TABLE 35.

WOOD PANEL POLISH FORMULATIONS

FORMUTA (%l

INGREDIENTS D.C. 536 Fluid ( A n adnofunctional polydimethylsiloxane Dov Corning Corporation) copolymer

2.00

-

D.C. 200 Fluid (12,500 cstko) (Dimethylsiloxane polymer Dov Corning Corporation) Uitcamide 511

-

Witco Chemical Company

Isopar L and/or Isopar U Isopar K

-

-

-

Exxon Company

2.00 1.00

26.50 65.20

Exxon Company

Fragrance

0.05

Isopropanol (anhydrous)

0.25

Carbon Dioxide

3.00

Pressure (460-tmVacuum Crimp) bar at 21.1.C

7.40

TABLE 36.

WINDSHIELD DE-ICER FORMULATIONS

INGREDIENTS

FOWLA (%l

Methanol

-

Technical Grade

Propylene Glycol

-

Technical Grade

Deionized Water

54.00

18.00 25.00

Morpholine

0.10

Span 80 or Igepal CO-410 Non-ionics

0.05

Sodium Benzoate

0.05

Carbon Dioxide

2.80

267


The Igepal CO-410 ( R o b & Haas Co.) surface active agent is present in the formula in Table 36 because it improves the wetting activity of the formula, allowing it to penetrate more effectively into fissures and cracks in the ice, and then betveen the ice and the glass, for faster removal. PESTICIDE AEROSOL PRODUCTS Pesticides consist of insecticides, insect repellents, disinfectants, rodenticides, nematocides, herbicides, and a host of other products designed to reduce or elbinate pests in s i z e ranges extending from viruses to rats. All these products fall under the punriew of the EPA FIFRA if they are made or marketed in the U.S.

Other nations have similar regulations.

When pesticide

products are designed for use on the skin in the form of "outdoor lotions" that protect against solar radiation. poisonous plants, infections from scratches, and also contain insect repellant, the EPA still has control but may consult with other agencies, such as the FDA in this case, before giving pre-market clearance.

Information has been presented earlier on the dis-

infectant cleaner and disinfectant/deodorant spray, which are regulated by the EPA in the U.S.

. ides . Jnsect ic The insecticide was the first commercial aerosol product, used as early as 1944 for both military and domestic applications.

These early sprays were

true "aerosols" (unlike any of. today's products, except one type) and used 85 to 90% of CFC-12 to disperse the pyrethrin-containing concentrates.

The first

major segmentation of this product form came in 1953. with the introduction of the bug killer:

a coarse spray consisting of at least 75% kerosene-based

concentrate, used for surface wetting, instead of the usual space spray format.

By 1961. water-based space sprays came onto the market, and many

years later this technology was applied to the surface spray as well.

A l s o in

the early 1960s. a "whole-house insecticide." or "toral release indoor fogger" spray vas developed, typically using 85% CFC propellants. insect sprays were developed later in the 1960s.

Other specialty

They included the wasp and

hornet spray, pressurized with nitrogen or carbon dioxide, and which could


269

throw a stream or streaming spray up to 6 meters. A number of pet-stock sprays were also introduced. Later. hormonal flea-control sprays, biocidal sprays, and other types were introduced. The space sprays are now essentially all water-based,since the other formulations were too costly and could not compete with the obvious economies offered by combinations of approximately 6 5 % water and 30% hydrocarbon propellant. The only exceptions are the total release indoor fogger (TRIF) and toxicant/propellant (T/P) sprays. The water-based space sprays can be closely compared with the air

freshener shown in Table 30. Formula A. By removing the perfume ingredient and replacing it vith a toxicant blend, the transition is complete. The water-based space sprays include the flying insect spray, house and garden spray, patio fogger. and a portion of the TRIF products. As a unit, they make up approximately 5 5 % of the insecticide aerosol volume. The TRIF spray made a difficult transition during 1978, when CFC

propellants were banned in the U.S.

Since it is designed to be latched open

and to discharge the entire contents of the can within two or three minutes, there is a greater inhalation and flammability hazard than is the case with most aerosols, which release only a few grams at a time. The flammability aspect related to

two

factors: the size of the container (and the number used

at one time), and the degree of product flammability. When problems have occurred, they have been caused by gross consumer misuse; for example, when two or more large cans have been set off in a relatively small area containing an ignition source such as the pilot light of a stove (range and oven), gasfired refrigerator or gas-fired hot water heater. Table 37 presents three forms of commercial formulations for these products. The relative flammability of the TRIF sprays can be assessed by using a

slight modification of the Department of Transportation (DOT) Closed Drum Test in.the U . S . The ZOO-liter drum is laid on its side, with the open end closed off vith a film of plastic. A candle is lit at the bottom and the spray is immediately introduced, using the test formula but

a

different valve more

270


TABLE 37.

TOTAL RELEASE INSECT FOGGER FORMULAfIONS

INGREDIENTS Pyrethrum Extract

-

20%

Piperonyl Butoxide: Technical

FORMULA A

FORMULA B

FORMULA C

(%)

(%)

(%)

2.00

2.00

1.00

1.00

Emulsifiable Concentrate Petroleum Distillates

8.00

12.00

Methylene Chloride l.l,l-Trichloroethane

12.00 15.00

55.00

40.00

Deionized Water Propane A-108

7.00

50.00

30.00

Isobutane A-31

15.00

HCFC-22

15.00

35.00

271


compatible vith the test procedure than the "latch open" type. The n&ber

of

grams of product sprayed into the drum until the Lower Explosive Limit (LEL) "poof" is reached and recorded.

From that figure, the number of cubic meters

that the dispenser can bring to the

LEL composition is readily calculated.

The usual insect repellent is used to keep users from being bitten or s t u n g by various flying insects.

The most c o m o n ingredient is N,N-Diethyl-m-

toluamide in concentrations of If to 30X of the total formula.

Sometimes

other repellents are added for protection against insects only partially repelled by the DEET active ingredient.

They include MGK Repellent 11 and ?fGK

Repellent 2 6 4 and are offered by the Mclaughlin. Gornley & King Company, of Minneapolis, PIN (U.S.). A typical formula is shown in Table 3 8 . Variations on Formula Type 26 include replacing the hydrocarbon propellant vith 4 . 5 % carbon dioxide, replacing the ethanol vith isopropanol, and removing the three MGK products, while increasing the level of DEET repellent to about 30 percent. The transfer efficiency from dispenser to skin or clothing is only about

55 to 65%. making other forms more attractive by comparison.

Lotions and

sticks are available, as vell as roll-on forms. PHARMACEUTICAL PRODUCTS These products are generally perceived as those that are inhaled, injected, or otherwise inserted into the body to mitigate or control medical problems such as migraine headaches, asthma, hemorrhoids, etc., or to provide a contraceptive function, such as vaginal contraceptive foam.

A few of these

products have already been covered in the foams area of this chapter.

The

primary one that remains is the metered dose inhalant drug (PIDID), which represents a U.S. market conservatively estimated at vell over 100,000,000 units per year and served by at least 28 brand-named products. As is common vith the rest of the aerosol industry, products are self-filled and also

272


I N S E m REPELLENT FORMULATIONS

TABLE 38.

FORMULA

INGREDIENTS

(%)

N,N-Diethyl-m-toluamida (95% A.I. min.)

20.0

HGK Repellent 11

2.0

MGK Repellent 326

1.5

MGK 264

1.5

S.D. Alcohol 40-2 (Anhydrous)

54.9

Fragrance

0.1 20.0

Propellant A 4 6 16 w t X propane and 84 wt X isobutane

TABLE 39. ~~

BETA-ADRENERGIC BRONCHODILATOR FORENLA ~

Ingredients

~

~~

~~

d10.5 g Can

~

Percentage (w/w)

Terbutaline Sulfate (Drug)

0.075

0 714

Sorbitan Trioleate (Excipient)

0.105

1.000

CFC-11

2.580

24.571

CFC-114

2.580

24.571

CFC-12

5.160

49.144

273


contract filled. One or more self-fillers also contract fill for their competitors. At this time, all of these products use one or more of the

following propellants: CFC-11, CFC-12, and CFC-114. The volume of propellants used is approximately 1,900 kilotonnes (4,200,000pounds) in the U . S . alone. Table 39 shows a typical published formulation. Others are suggested in U.S. Patent literature and other documents.

Use of hydrocarbon propellants for some of these products is not satisfactory because of production problems related to flammability, the oily, stinging taste they have when inhaled nasally or orally, and their very low density (considered from the standpoint of drug precipitation rates during use). CFC-11 is slurried with the drug and one or more excipient materials, and this mixture is added to aluminum aerosol cans or bottles. They are then fitted with a ferrule-type meter-spray valve which is hermetically sealed to the container by a clinching or under-tucking operation. The CFC-12, sometimes mixed with CFC-114, is then introduced backwards through the valve. CFC-11, with a boiling point of about 23'C, is unmatched by any other nonflammable solvent of acceptable toxicology. Its replacement will necessarily depend on the availability of one or more of the "future alternative" HCFC and HFC propellants due to come on the market in 1992 or 1993. For the 90% of

PU)ID

products that use very finely divided microcrystal-

line drug particles (averaging from 3 to 5 microns), it is important to have a system of l o w solvency. Othewise. the larger particles will get still larger and the smaller ones (because of their higher surface energy) will get smaller until they vanish. This disturbance will severely limic the product effectiveness.

Even with the optimum particle size distribution, the body's

defenses are such that only 7 to 12% of the drug reaches the target areas. With the formation of larger particles in the container, this could drop below one percent.

io

274


The time frame needed for additional toxicological testing of the HFC and HCFC propellants, such as that being &ne

in the Program for Alternative

Fluorocarbon Toxicity Testing (PAFl'T)I. PAiTT 11, and PAFl'T I11 consortium tests sponsored by the chemical producers, is on. development. tions writing.

element of the new product

Another is actual formula and package development and specificaA third is the opening of each company's "New Drug Applica-

tion" to the FDA, reqwscing an "Amended New Drug Application" (ANDA). The entire documentation is reviewed in such procedurer. which typically take from

3 to 5 years to complete if there are

M problems.

One industry concern is

that the FDA MY not have sufficient staff to process approximately 27 concurrent ANDAS with anything like their usual timing.

These considerations

suggest that it would be to the advantage of chemical producers to cooperate in their efforts to have new products cleared by the FDA within the generally

planned transition period ending abouc 2000. The viability of new formulas depends on their solvency and toxicology. Preliminary results from PAFTT vi11 be released in September 1989.

Because of

the tincertainty about HCFC-123. three possible formulas are suggested here for consideration (see Table 40). The use of HCFC-124 is optional. since it merely serves co reduce the pressure slightly. The CFC-113 is used as an additive to the slightly flammable HCFC-1Glb to create a nonflammable blend for slurrying purposes.

If

the pharmaceutical firms and their fillers can handle a slightly flammable slurrying agent (pure HCFC-14lb). there will be no need to use the CFC-113 (or CFC-11). INDUSTRIAL AEROSOL PRODUCTS There are numerous aerosols used only in industrial or institutional applications. Two will be considered here:

a lubricant spray for phar-

maceutical pill- and tablet-making rotary molding machines, and an induscrial

275


TABLE 40. --DOSE

INGREDIENTS

Z " T

DRUG FORHUIATIONS

FORHUTA A I%)

FORMTIA B

FORMULA C

(%)

(X)

Drug (as a microcrystalline suspension)

0.5

0.5

0.5

Excipient(o)

1.0

1.0

1.0

-

HCFC 123

13.5

CFC-113 (or CFC-11)

4.5

HCFC - 141b

9.0

HFC-134a HCFC-124

10.0 75.0

13.5

85.0

75.0

-

85.0

75.0 - 85.0

none

10.0

-

none

10.0

-

none

276


adhesive.

For the first application, the products must be nonflammable, and

leave only a Food Grade [Generally Recognized as Safe (GUS)-Listed] residue on surfaces to be contacted by the pharmaceutical pill or tablet. A current formulation is shown below:

Innredients

txy

Lecithin (Soy Bean source)

2.0

Sorbitan Trioleate

0.5

Ethanol (Anhydrous)

2.5

CFC-113 (Especially purified)

70.0

CFC - 12

25.0

An intermediate step could replace the CFC-12 vith a mixture of

LO parts HCFC-

142b and 20 parts HCFC-22, reducing the CFC-113 to 65 parts in the process. This vould reduce the CFC content by 32 percent. When the future alternative propellants become available, the formulations shown in Table 61 could be considered, Substantial testing of these prototype formulas in Table 41 vould be required as a prerequisite to commercial use. Adhesive SDray A typical industrial product is the adhesive used to coat automotive gaskets before setting them in place on engine blocks or other equipment. Aerosol products have a substantial niche in this market area. A typical formulation is illustrated in Table 42. The product is sprayed onto the gasket while it lies on a waxed paper or ocher suitable substrate. After a minute or so, much of the methylene

chloride will have evaporated, bringing out the stickiness of the resins. After another five minutes. the gasket is ready to be applied to the engine block or other item.


TABLE 41.

ROTARY TABLET W C H I N E DIE LUBRICANT FORMULATIONS

FORMULA A

INGREDIENTS

FORMlLA 8 '

Lecithin (Soy h a n source)

2.0

2.0

Sorbitan Trioleate

0.5

0.5

Ethanol (Anhydrous)

2.5

2.5

77.0

HCFC-123 HCFC-14lb

55.0

HCFC - 22

HCFC 124

30.0

18.0

10.0

'Formula B could replace Formula A if HCFC-123 does not become commercially available. TABLE 42. GASKET ADHESIVE !?ORHUIATION

INGREDIENTS

FORHULA

~

Isopropanol

LO

Resin 80-1211.

5

Stabilite Ester Number 3b

5

Methylene Chloride

50

Xylenes

10

Propellant Blend A - 7 0

20

Hade by the National Starch and Chemical Company.

%de

by Hercules, Inc.

277

Section II

Alternative Aerosol Dispensing Systems

I1 of

as

are But

1. Introduction imposing number of packaging alternatives to the standard aerosol dispenser are available.

Several use aerosol containers, but segregate the

propellant gas, and employ a finger-pump, trigger-pump, hand-operated piston action, a metal spring, screw device, or other mechanism to dispense the product or form tlie propellant gas within the container as required.

Others

take the form of rather specialized, non-aerosol containers designed to enable the usar to create air pressure or product pressure, or to operate screw-on finger-pump or trigger-pump metering valves.

The pump-sprays, in all their

diverse forms, represent the most widely used alternative.

Such packaging

options as stick applicators, pads, etc. offer alternatives to the aerosol system but do not provide sprays; these will only be briefly described. A substantial number of aerosol alternatives will be described in Part I1 of this report, beginning with those that are most similar to conventional

aerosols--and that may even be considered aerosols by various persons and authorities--and continuing with alternate packaging forms that bear no resemblance to aerosol products.

The term "aerosol" vas used by the scientific community at least as far back as 1838 to describe dispersions of liquids in a gaseous medium, such as fog, mists, and clouds, where the particles were true colloids, having diameters of approximately 0.005 to 0.200 microns ( p ) .

Particles of this

magnitude were able to remain air-borne indefinitely. The smallest particles are the same size as many larger molecules, such as starches, proteins, and rubbers, and this part of the definition has not changed over the years.

279

But


the high end of the size range o r i g i n a l l y defined a s the l i m i t of microscopic v i s i b i l i t y , has changed g r e a t l y .

The s o - c a l l e d "coarse aerosol" ( t o the

p h y s i c i s t ) now includes dispersions of p a r t i c l e s ranging from 0 . 2 t o about 20 microna ( p ) .

Since the p a r t i c l e s i z e d i s t r i b u t i o n of comnercial aerosol

sprays is generally in t h e 1 t o 100 micron ( p ) range, a t l e a s t some of the sprays meet the expanded classical dofinition.

Some e a r l y d e f i n i t i o n s of anroaol products were based on p a r t i c l e s i z e . For example. around 1969, the U.S. Department of Agriculture (USDA) designated t h a t the 'true aeroaol" i n a e c t i c i d e waa one in which a t least 808 of the p a r t i c l e s had a mean diameter of 30 microns ( p ) o r l a s s , and i n which no p a r t i c l e could have a mean diameter g r e a t e r than 50 microns ( p ) .

To meet

these requiremants, chemists had t o design formulas with 80 t o 85% o r more of propellant.

The r a t i o n a l e w a s that t h e spray p a r t i c l e s had t o be very s m a l l

t o remain airborne f o r tvo minutes t o tvo hours t o c o n t r o l f l y i n g i n s e c t s . The products soon became known as space sprays. A t about t h e same time, t h e USDA introduced the "pressurized spray"

concept f o r insecticides chat were'slightly more coarse.

The mass median

diameter of a11 p a r t i c l e s had t o be about 25p. and some could be above SOU Because t h e l a r g e r p a r t i c l e s f e l l t o the f l o o r in less than one minute, marketers had t o use l a b e l d i r e c t i o n s t h a t advised the user t o spray an a d d i t i o n a l 2 5 - 5 0 8 more product i n t o the a i r space of rooms. F i n a l l y , about 1951, the " r e s i d u a l spray" i n s e c t i c i d e w a s defined. E s s e n t i a l l y a l l p a r t i c l e s had t o be l a r g e r than 50p, so t h a t such t o x i c a n t s as Chlordane, Strobane and DDVP (dichlorphos) vould not be inhaled t o any significant extent.

These were used only f o r spraying baseboards, doorway

sills, wasp-nests, and o t h e r inanimate surfaces. The piston-pump i n s e c t i c i d e sprayer could dispense d i s p e r s i o n s of p a r t i c l e s about 2Sp i n s i z e with deodorized kerosene formulacions and those 20p i n s i z e with the more flammable athanol and isopropanol compositions.

finger-spray and ( l a t e r ) t r i g g e r - s p r a y insecticides generally provided d i s t r i b u t i o n s of p a r t i c l e s in the 30 t o 8Op range.

Consequently, much more

The

Introduction 281

had to be used for the control of flying insects, and the range of action was also much Less than that of aerosol dispensers.

The confuaion between "aerosol" (the colloid sol) and "aerosol" (the dispenser) has existed since the aerosol industry w a s born in 1943.

In an

intern81 report, the Acdomic Press Inc. publishing house M n t i O M d that more copies of one of their M V textbooks 1 -(

S

w

, C.N. Davies

-

Editor,

1966) had gone to recipients in the aerosol packaging industry than to the intended audience of physicists. physical chemists, and meteorologists, mainly because of the lack of contents identification in

SOP.

advertising and

The industry made an attempt to rename itself as the

proPotiona1 materials.

"Self-pressurized Dispenser Division" of the Chemical Specialties Manufacturers Association. Inc. (CSHA) but the proposal vas defeated.

Today,

the vords "aerosol" and 'self-pressurized" product are used interchangeably. For the purposes of interstate transportation, the U.S. Interstate Cotmerce Comission (XCC), n w a branch of the Department of Transportation

(DOT). defined the aerosol package in 1948 as follows: "A sealed package containing base product ingredienu, fn which one

or more propellants is dissolved or dispersed. and fitted with a dispensing valve." Despite the fact that many self-pressurized products thought of as aerosols do not strictly meet this definition, nearly a11 are currently shipped under Section ORPI-D of the tariff.

(The definition has been modified

slightly over the years.) Other definitions are listed below without special comwent: CSPIA Definition:

'A pressurized sealed container with liquified or

compressed gases so that the product is self-dispensing," FDA Definition:

"A package consisting of a container and valve, into

which is added a base product and propellant, causing the dispenser to be


under pressure. and able to discharge the product as a spray, foam, liquid, gel, or other form."

H.R. Shepherd (Book) Definition, 1960:

A '

container whose contents are

expelled through an opened valve by means of tha internal pressure of the materials contained therein.' P.A. Sanders (Book) Definition, 1979:

(Also used by CSMA)

"A self-

contained sprayable product in vhich the expelling force is supplied by a liquified gas." National Paints and Coatings Association (NPCA) Definition:

A '

self-

contained package which contains the product and the propellant necessary for the expulsion of the former." British Aerosol hnufacturers Association, Ltd. ( W ) .1971:

'As

integral ready-to-use package incorporating a valve and product which is dispensed by prestored pressure in a controlled manner when the valve is operated.' Most of these definitions were created by one person, then approved by a committee or by a brief committee action.

Some are ill-conceived or outdated

and either do not cover all aerosols, or cover products not commonly denoted as aerosols.

In a recent inquiry to the DOT, a product consisting of a

mixture of Halon-1301/1211 ( 2 0 : 8 0 ) was finally judged to be a non-aerosol and denied the standard aerosol O M - D exemptions because it contained no base product ingredients.

Two materials other than propellant had to be present to

be designated an aerosol.

The prospective marketer finally added a drop of

kerosene (a mixture of ingredients) to 13 Av.02. (369 g) of the Halon blend, and is now selling the product. At a recent industry meeting, representatives from the Metal Box Division

(CMB) in England stated that they had persuaded British Aerosol Manufacturers Association (BAMA) and the F U (Federation of European Aerosol Associations) in Western Europe that self-pressurized products placed in their "Bi-Can," a

Introduction

283

compartmented can containing an inner plastic bag for the base product, should This would give them preferred treatment by the

not be considered aerosols.

folloving transportation authorities:

0

ADR

European Agreement for the International Carriage of Dangerous

Good. by Road.

RID International Convention Concerning the Carriage of Goods by Rail (Borne 1961; Annex 1).

0

U T A International Air Transport Aasociation (Restricted Articles

Board).

0

INCO International Plaritime Consultative Organization (United Nations).

They asked for industry support in the U.S.

No action was taken.

Another definition of an aerosol product that has often been published is as follows: *A hermetically sealed metal. glass or plastic container, fitted or able to be fitted with a valve, and containing a base product and/or a liquified and/or high-pressure propellant, able to dispense the contents in a controlled manner as either a spray, foam, stream, gel. paste, lotion, gas. powder or combination.” In the U.S., for the purpose of interstate transportation, aerosols are limited to 50 cubic inches (819.35 mL) in metal cans, or to 4 fluid ounces (118.28 mL) in non-metallic containers.

The United Nations recommendation is

1000 mL for all products, and this is generally followed in Europe.

In Japan

and other countries, the capacity limit is 1400 nL. although other restrictions apply.

A few countries permit “aerosols” up to 20 liters in

capacity if made of steel.

In the U.S., steel cylinders up to 40 liters in

capacity are used for insecticide sprays, egg treating mineral oils, and other

284


specialized applications. They are not considered aerosols.

In some beauty

shops, hairspray concentrates are dispensed from pressure tanks maintained at about 100 psig (7.04 bar) compressed air pressure at ambient temperature. The operator uses a thin hose urd breakup nozzle for product applications. These

products are also not considered to be aerosols.

2. Description of Aerosol Packaging Alternatives BAG-IN-CAN TYPES

The Seuro C a

I n 1954, Croce p a t e n t e d a perfume s p r a y i n which t h e perfume c o n c e n t r a t e and t h e p r o p e l l a n t w e r e c o n t a i n e d i n s e p a r a t e r e s e r v o i r s ( U . S . P a t e n t

2,689,150). And i n 1955. t h e Metal Box Company, Ltd. v a s g r a n t e d a B r i t i s h p a t e n t f o r a d e v i c e t h a t would permit the d i s p e n s i n g o f flowable p r o d u c t s where t h e product and p r o p e l l a n t were k e p t s e p a r a t e from one a n o t h e r ( B r i t . P a t e n t 740,635).

I n 1958, t h e C o n t i n e n t a l Can Company, I n c . f o r m a l l y i n t r o -

duced t h e i r Sepro Can. which c o n t a i n e d a n accordion-shaped polyethylene p l a s t i c a l l o y bag i n s i d e a s p e c i a l l y designed a e r o s o l can measuring 1 1/8" by

6 1/8" (53 x 156 mm).

The u n i t v a s f i l l e d by f i r s t adding as much c o n c e n t r a t e

as p o s s i b l e t o t h e bag, t h e n s e a l i n g the top with a one-inch a e r o s o l valve.

A f t e r t h a t , p r o p e l l a n t gas vas i n j e c t e d through a small h o l e i n t h e base s e c t i o n o f t h e can and t h e h o l e v a s plugged with a s h o r t l e n g t h o f rubber cording.

Only a f e u grams o f p r o p e l l a n t were needed t o d i s c h a r g e from 1 7 5 t o

250 grams of product ( a c c o r d i n g t o i t s d e n s i t y ) , si'nce t h e two were k e p t s e p a r a t e by t h e bag.

Also. t h e p r o p e l l a n t would never be d i s c h a r g e d d u r i n g

t h e l i f e t i m e of t h e can. b u t would remain i n s i d e u n t i l t h e empty u n i t w a s crushed, shredded, i n c i n e r a t e d o r r u s t e d through i n a dump s i t e , e x c e p t f o r an i n f i n i t e s i m a l amount t h a t might seep through t h e plugged and double seam can s e a l s and escape i n t o t h e atmosphere. C r o s s - s e c t i o n a l views of t h e Sepro Can. a mechanized o r pneumatic squeeze cube. a r e s h o w i n Figure 2 .

285

286


I

l

/ SEPRO BAG

\

e PROPELLANT CHAMBER Figure 2 .

CHARGl NG VALVE The Sepro C a n

CAN

BODY

Description of Aerosol Packaging Alternatives

The Sepro Can. from the term "Separate =duct

and Propellant," was

designed to permit gas-free dispensing and the dispensing of viscous produ that had a positive yield point.

287

S

It was hoped that this package would

facilitate the growth of the aerosol business by allowing a new range of products to be packaged under pressure. The standard aerosol cannot dispense products with viscosities much

beyond 350.000 cps.. since such chemicals and formulas usually have a positive vield point, or, in other words, exhibit shape retention. For example, if a toothpaste is filled into an ordinary aerosol can and placed under 100 psig (7.04bar) of nitrogen pressure, an appropriate valve and spout will dispense the produce very nicely, although some slight expansion of the extruded paste may occur as dissolved nitrogen gas slowly forms almost invisible foam bubbles in the product.

(This is too insignificant a feature to be observed by the

casual user.) Within the aerosol can, however, each actuation causes a further cavitation of the initially flat toothpaste surface. At a certain stage the crossThe cavitation area will deepen with each

section looks as shown in Figure 3 .

additional actuation, until it reaches the bottom of the dip tube. At that point the nitrogen gas will exit in a fraction of a second, and the remaining product cannot be dispensed. Toothpastes have been prepared without positive yield points. so that the cavity left after each actuation will slowly heal--or flatten out. However, they tend to drip off the toothbrush to some extent and will also leak out of the valve spout orifice onto the top of the container. Some of the nitrogen propelled (nitrosol) toothpastes of the early 1960s had spout plugs, connected to the spout by a fairly thin polyethylene filament. They were designed to be applied to the spout orifice after actuation, to prevent dripping. Sometimes the pressure created by releasing nitrogen gas caused them to pop out. One major marketer (Colgate) kept such a product on the market for about twelve years, selling 300,000 cans a year to persons who liked the dispensing system.

288


Figure 3 .

Ordinary Aerosol Dispenser with Toorhpaste. (About 15 percent Dispensed)

Description of Aerosol Packaging Alternatives

289

But a slowly diminishing business of this small magnitude was unappealing to Colgace and they finally dropped the item.

In the mid-l960s, the Continental Can Company developed and vigorously promoted to marketers the folloving four Sepro Can sizes:

202 X 214m 202 X 006mm

(3-fluid ounce capacity)

202 X 509mm 211 X 6041m

(7-fluid ounce capacity)

*

(5-fluid ounce capacity) (16-fluid ounce capacity)*

Never produced commercially.

A major detraction was the need for marketers to spend about twice as much for Sepro Cans as for ordinary aerosol cans, as well as to install specialized "gasser-plugger" and other equipment on their packaging lines. also had a few quality problems.

The package

Except for "Edge." a patented gel-type

shaving cream developed by S.C. Johnson C Son, Inc. in 1969, no major uses developed. The evolution of the plugging technology went through several stages. A: first, a gasser-plugger would inject a liquified or non-liquified gas into che filled can (1 to 7 g) and then ram the end of a 5/32" (0-mm)diameter lubricated neoprene cord or rod into the 1/8" (3.2-mm) diameter hole in the center of the can base.

After insertion, the machine would cut the rubber cord off

from the rest of the reel. These early machines, required to perform three fairly complex operations in a sealed area, were production nightmares and generally the rate-limiting factor in manufacturing operations.

Much later, engineering improvements were

made to increase the viability of this sealing approach. Then Continencal Can Company announced an improvement known as the Nicholson Model 2 plug valve.

It consisted of a solid rubber billet or plug,

partly splined on ehe side wall, which was designed to fit part-way into the


can hole during manufacture.

In the filling operation, propellant gas was

introduced through the splined channels, after which a small ram was used to force the plug fully into the hole, making an hermetic seal.

This plug, with

only slight residual modifications, is still in use today. The early plastic bag designs were highly pleated or accordion-walled, and this caused problems when filling viscous concentrates such as pastes and gels.

The Continental Can Company purchased a single-head and twin-head Elgin

spin-filler, useful for filling these products, which they loaned to certain marketers and larger contract fillers to help in product development work. Larger machines, such as six- and twelve-head Elgins, were available.

A

very

large Consolidated Equipment Company eighteen-head filler was modified for by S.C. Johnson 6 Son, Inc. as a spin filler.

use

Finally, the Pfaudler Mfg.

Company later introduced a six- and twelve-head spin filler. The Consolidated and Pfaudler machines have a pressurized bowl option, for containing any vapors from shaving gels that contained isopentane [(CH,),CH-CH,-CH,]

or other

flammable or excessively volatile concentrates. Every concentrate was found to have an optimum spin-filling rate, generally in the range of 400 to 1200 r p m .

Below 400 r p m , the centrifugal

force was often insufficient to effectively drive the concentrate into the pleated areas, causing unwanted air pockets to form and survive. Over 1200 r p m , concentrate vortexing would exceed gravity and product would be spun

upward and out of the container. During 1971. the products shown in Table 43 were being packaged in the Sepro Can dispenser. The labeled formulas for the "Edge," "Rise." and "Foamy" gel shave creams are presented in Table 44. In accordance with Food 6 Drug Adninistracion (FDA) regulations, these cosmetic products must list their ingredients in

order of decreasing percentages; those present in concentrations of less chan one percent may be placed in any order.

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