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Formulating Detergents and Personal Care Products A Guide to Product Development Louis Ho Tan Tai Lambersart, France ;ri; Lacs PRESS Champaign, Illinois AOCS Mission Statement To be a global forum to promote the exchange of ideas, information, and experience, to enhance personal excellence, and to provide high standards of quality among those with a professional interest in the science and technology of fats, oils, surfactants, and related materials. AOCS Books and Special Publications Committee G. Nelson, chairperson P. Bollheimer, Memphis, Tennessee N.A.M. Eskin, University of Manitoba, Winnipeg, Manitoba J. Endres, Fort Wayne, Indiana T. Foglia, USDA, ERRC, Wyndmoor, Pennsylvania M. Gupta, Richardson, Texas C. Hammond, CONDEA Vista, Austin, Texas L. Johnson, Iowa State University, Arnes, Iowa H. Knapp, Deaconess Billings Clinic, Billings, Montana K. Liu, Hartz Seed Co., Stuttgart, Arkansas M. Mathias, USDA. CSREES, Washington, D.C. M. Mossoba, Food and Drug Administration, Washington, D.C. F. Orthoefer, AC Humko, Cordova, Tennessee R. Patzer, Agri Utilization Research Institute, Marshall, Minnesota J. Rattray, University of Guelph, Guelph, Ontario A. Sinclair, Royal Melbourne Institute of Technology, Melbourne. Australia G. Szajer, Akzo Chemicals, Dobbs Ferry, New York B. Szuhaj, Central Soya Co., Inc., Fort Wayne, Indiana L. Witting, State College, Pennsylvania S. Yorston, Shur-Gain, Mississauga, Ontario Copyright 0 2000 by AOCS Press. All rights reserved. No part of this book may be reproduced or transmitted in any form or by any means without written permission of the publisher. Previously published in French as DBtergents et Produits de Soins Corporels. Copyright @ Dunod, Paris 1999. The paper used in this book is acid-free and falls within the guidelines established to ensure permanence and durability Any reference in this publication to any drawing, specification, chemical process, or other data should not be regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented or registered compound or formulation or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indi- cation thereof, are not to be considered unprotected by law. Library of Congress Cataloging-in-PublicationD ata Ho, Louis Tan Tai. [Detergents et produits de soins corporels. English] Formulating detergents and personal care products : a complete guide to product development / Louis Ho Tan Tai. p. cm. Includes bibliographical references and index. ISBN 1-893997-10-3 (alk.paper) 1. Detergents. 2. Cosmetics. I. Title. TP990.H613 2000 668 '1Mc21 00-057592 CIP Printed in the United States of America with vegetable oil-based inks. Foreword to the English Edition When I first saw a translated version of this book, it immediately became clear to me that: This was a truly unique volume, and after an acceptable English text was devel- oped, It would be an excellent addition to the publications by AOCS Press. The book is unique in many ways: It is the most complete guide to detergent and personal care product develop- ment I have seen in 50 years of experience in the detergent area. It is written from the perspective of the formulator-and one with superior competence at that-who is central to the development of a product and sees it through all of the stages of conception, development, manufacture, consumer testing, and quality control. Beyond these, it covers relevant peripheral topics such as analysis, perfumery, packaging and laundering equipment, subjects not usually found in texts on detergents. It discusses as much theory as is needed to explain the “why” behind the many choices a formulator must make in the course of his activities. At the same time, it offers helpful and practical advice, which reflects the expe- rience the author acquired in the course of his career. It represents a distillation of a lifetime of experience by a creative and respect- ed practitioner in the field. It is written in an informal style, more like a series of instructive lectures rather than a dry review. The U.S. reader should note that the book is written from a French perspective, with examples taken from the French market and French legislation. It is stronger on detergents than on personal care products-hence the sequence of these subjects in the title. These limitations are minor compared to the scope and breadth which the book provides. The latter have inspired me to spend many hours on editing the original translation to make this book accessible to English-speaking readers. Arno Cahn Arno Cahn Consulting Services, Inc. Pearl Rive&N ew York May 2000 V Foreword to the Original Edition This book is about the essential contribution of detergent products to the develop- ment of cleanliness and hygiene in the world. The anguish caused by the last great epidemics at the beginning of the century (when Spanish flu is estimated to have killed 3 million people) is little more than a distant memory. Cleanliness and hygiene are now part of our civilization, providing both an effective barrier against the spread of disease and a large degree of comfort and even pleasure in our day-to-day lives. This book explains the role and structure of detergents in the highly pragmatic manner that typifies its author. He provides a wealth of details on the components and how they can be put together to produce an optimum result. No matter how important the subject may be, in the same way that it is no longer necessary to know how a car works to be able to drive it, there is no obligation to read this book to be able to benefit from the cleanliness offered by detergents. Having said that, there are many people other than the researchers, engineers, and technicians working in the detergents industry who would do well to read this work, including the following: Suppliers of raw materials, basic chemicals, petrochemicals, biological material, fragrances, and packaging Technicians in the textile, pottery, and porcelain industries Washing machine manufacturers Health authorities (dermatologists, poison-control centers) Government agencies (industry, hygiene, health) Professional and scientific organizations (chemicals, detergents, perfumery) and consumer and environmental associations Industrial and university libraries Teachers specialized in formulation, and their students . .. and all the rest of us who are not forbidden from taking an interest in these headed and tailed molecules that Coluche described as “smng small arms” (“des petits bras musclCs”) to hold back stains. When Louis Ho Tan Tai asked me to comment about his book, I accepted will- ingly, knowing his skills and teaching abilities from the countless conferences and presentations at which I had the pleasure of observing him. We were fortunate to work together in Lever France for several decades, myself as Chairman in the later years, and Louis Ho Tan Tai as the free-floating technical electron. To better under- stand the author, I would like to highlight three characteristics that typify him: 1. In the family of researchers, he is one of a rare breed of “inventors” who not only observe new phenomena but are also capable of imagining how their apparently independent properties can be combined to produce innovation. vii viii Foreword to the Original Edition 2. His acute listening skills, which allow him to understand a problem quickly and clearly and which give him the inspiration to find instantly at least half the solu- tion. As the proverb says the rest is just trials, experiments, objective evaluation, combined with concentrated work, rigor and determination. 3. Finally, for Louis Ho Tan Tai, lonely understanding is a source of great frustra- tion. His great skill has always been in sharing his knowledge, making complex concepts clear, and giving his listeners the comforting feeling that they have at last become intelligent. It is doubtless in this spirit that Louis Ho Tan Tai decided to write his book, leav- ing some trace of a lifetime of hard work and passing on his vision of the many facets of detergency, while at the same time being conscious, as Copernicus said, that “knowledge is a living structure, never perfect” and that in the fullness of time, somebody else will come along to build our knowledge further. J. Lier Former Chairman of Lever France President Prodimarques Preface During my career with Unilever, which lasted for about 30 years, of which 25 were spent in the Development Department of Lever France, I was fortunate enough to be personally involved in a wide variety of activities, such as basic studies, process development, product development, perfume studies, product performance evalua- tion, and physicochemical analyses. With such extensive professional experience, I feel a strong need to share my knowledge with others by writing this work. Why write yet another book on detergents and personal care products? Indeed there are already many publications covering these areas, but they are sometimes purely theoretical, or they cover only limited categories of products, or they are sim- ply out of date. The aim of this work is to cover both theory and practice, using the most recent knowledge, encompassing all of the relevant categories and products, and examining all aspects of the development of these products from concept stage to their launch onto the market. During my professional life, I had frequent opportunities to speak at university conferences and seminars on one aspect or another of the subjects covered by this book; in all cases, my audiences were very interested in what I had to say. I was also fortunate to be able to train young managers in a pragmatic and didactic approach, and wrote a “Bible” for them in which they could find both the theory and practice of new product development. I believe that this book, which is more complete and up to date (without divulging proprietary information) should interest the universi- ties, and students and engineers working in the industry. And why not also the less young who may wish to revise what they knew and may have forgotten with time? In writing this book, I have had in mind my country of birth, Vietnam, and also all countries on the road to development. In a number of ways, this book should be of great help to their engineers because they may not have all of the information readily available, and obtaining it could be costly. In addition, a lack of knowledge may lead to mistakes involving technology, the environment, and the safety of work- ers and consumers. If only because of the level of advertising (particularly on television), consumer products including detergents may have a poor brand image at least among certain seg- ments of the population. Through this book, I aim to show the extent of research and development, and the industrial equipment resources that lie behind the products con- cerned and support the efforts by the main manufacturers to put quality products that are safe for their users and that respect the environment onto the market. When I discussed my project to write this book with my friends, all of them encouraged me strongly, and I thank them for this and for their support. We will now offer an overview of the different parts of this book so that the reader can understand clearly which subjects are dealt with and go directly to the chapters that may be of particular interest. The introduction to the work outlines a number of generalities one must be familiar with in order to understand the world of detergents and its evolution. These include the history, the world markets, details of the stages in the development of a product, and consumer habit surveys. IX X Preface The first part deals comprehensively with the products. It seemed important to dedicate a complete chapter to surfactants, which are present in all products. The other main ingredients making up a detergent are also dealt with separately in the Chapter 2. The following chapters deal with the different categories of products, including types of problems (stains) encountered, formulation principles, and the products themselves, including examples of formulations. This is a vast area, cover- ing the cleaning and care of textiles, dishes, and other hard surfaces (floors, kitchens) and the care of a specific surface, our bodies, with bath and shower products, sham- poos, and toothpastes. Because the range is very large, we restrict ourselves to the main products and leave aside, intentionally, the smaller products or associated product categories such as pretreatment products for clothes or cosmetic products. The second part covers in detail subjects that are common to the whole indus- try of detergents and personal care products, including performance testing, manu- facturing processes, perfumes, packaging, analytical methods, and consumer tests. Quality assurance and environmental safety issues are also covered. The book would not be complete if it did not look into the future. The world of detergents evolves continuously as new molecules and new product concepts appear every day. The trends of today that give clues to the products of the third millenni- um are examined in the final chapter. That summarizes in a few stages the main contents of this book. We think the book contains enough material so that all of its readers can easily find the parts that fit their needs without losing time reading what is not of interest to them or search- ing in numerous works that may not at times even be available. Enjoy the reading! Louis Ho Tan Tai Lambersart, France Contents Foreword to the English Edition ........................ v Foreword to the Original Edition ....................... vii Preface ........................................... ix Introduction ....................................... 1 Chapter 1 The Main Surfactants Used in Detergents and Personal Care Products and Theories of Detergency ................ 15 Chapter 2 The Main Ingredients Used in Detergents and the Mechanisms by Which They Act ....................... 49 Chapter 3 Detergent Powders. Bars. Pastes. and Tablets .............. 138 Chapter 4 Liquid Detergents .................................. 156 Chapter 5 Fabric Softeners ................................... 174 Chapter 6 Hand and Machine Dishwashing Products ................ 186 Chapter 7 Other Hard Surfaces: All Purpose Cleaners. Scourers. Bathroom Cleaners. and Window Cleaners ............... 209 Chapter 8 Skin Care Products ................................. 227 Chapter 9 Hair Care Products ................................. 242 Chapter 10 Oral Care Products: Toothpastes ....................... 262 Chapter 11 Product Performance Evaluation ....................... 279 Chapter 12 Manufacturing Process .............................. 296 Chapter 13 Perfume in Detergent and Personal Care Products .......... 314 Chapter14 Packaging ........................................ 335 Chapter 15 Storage Tests ...................................... 354 xi xii Contents Chapter 16 Analytical Methods .................................. 359 Chapter 17 Consumer Testing .................................. 373 Chapter 18 Quality Assurance ................................... 385 Chapter 19 Toxicology and Ekotoxicology ......................... 397 Chapter 20 Latest Trends ...................................... 418 Index ............................................ 433 Introduction A Little History. . . It is not our intention to spend much time looking at the history or to trouble the reader with useless dates. However, it did seem of interest to us to summarize briefly how detergents have evolved from their ancestor (soap) to the products we know today. Soap is the first detergent known to our civilization. Earlier research had attributed soap to the Gauls, until the discovery of a “hypocaust,” or underground chamber in which water was heated; this earliest ancestor of today’s bathroom was discovered in the Indus Valley (urbanized by 2500 B.c.). From the same period, Sumerian clay tablets gave the following recipe for soap making: wood ashes heat- ed with oil. Our famous Gallic ancestors had therefore discovered nothing new in this area, which did not prevent a number of their descendants from leaving their names associated with significant discoveries. Honor has been saved! A number of Egyptian papyruses also mention how to make soap, i.e., natural soda known as Trona (which formed a crust around the edge of certain lakes) that was mixed with fats. Even though its manufacture was simple, soap has remained for centuries a luxury product used for washing, a cosmetic, and even a medicine! It took the efforts of two French scientists to turn soap into an everyday prod- uct. At the end of the 18th century, Leblanc discovered that soda could be pro- duced from sodium chloride; some years later, Chevreul explained the chemical reaction between alkalis and triglycerides. From then on, as industrial manufactur- ing became easier and better understood, the use of soap became general. Soap lost its image as a luxury product reserved for the privileged, becoming an everyday product to the point that with the increase in population and living standards, one of the raw materials necessary for soap making became scarce, leading in turn to the replacement of animal fat by vegetable oils. During this period, many factories started operations around the Mediterranean area, giving birth to the famous “Savon de Marseille.” Although soap has wide application, it has definite limitations when used on its own. The principal drawback is the formation of very disagreeable calcium (lime) soaps. An early improvement came with the addition of sodium silicate, which both softened the water and eliminated iron ions that caused textiles to yellow. A second stage was completed with the observation that when clothes were dried in direct contact with grass in the fields they were whiter (thanks to the combined action of light and the oxygen ofthe air), giving rise to the idea of creating an ingredi- ent capable of reproducing the phenomenon. The arrival of sodium perborate in deter- gent formulations was in itself a mini-revolution. It was Henkel in Germany who first 1

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