19

Perfumes in Detergents
John Ramsbotham
International Flavors and Fragrances, Hilversum, The Netherlands

I.

INTRODUCTION

The word "perfume" is derived from the Latin roots "per" and " fumum," which together mean "through smoke." This is indicative of the practice of burning incenses and spices to produce odorous smokes in religious festivals. The term "fragrance" is used synonymously with " perfume" in the detergent industry and this convention is adopted here. The implication of the Latin root of fragrance is a " sweetness of smell," which is perhaps more descriptive of the functional use of perfumes in products than is the term "perfume. " The importance of fragrance to a detergent product's commercial success is virtually beyond question. If something does not " smell right " or laundered clothes do not smell fresh once washed, a consumer will very likely not repurchase a product no matter how clever the technology which it contains. Many chemists appreciate that something is necessary to cover product base (mal)odors but quite how this is achieved remains something of a mystery. In fact, a more technical product development often runs the risk that the aspects of (mal)odor are regarded as some sort of irritation which can be put off until a marketing department decides that a launch date is in sight. At this late stage in the day, a perfume house can find itself impossibly short of time to create a fragrance which is technically stable , does not destabilize the product, successfully masks all base malodors and is aesthetically acceptable. This review examines all the technical aspects behind perfume creation. Something of the nature of perfumes and the perfume industry is revealed in the fact that perfumes are complex blends of volati le organic chemicals. A detailed discussion of the individual perfume chemicals is outside the scope of this review, but excellent texts are available which itemize the ingredients in common use by perfumers [1] and their underlying individual chemistry [2]. At this early stage of the review, suffice it to say that a perfumer can access several hundred ingredients stretching across most classes of organic detergent chemicals. It goes without saying that these can potentially interact with each other and with the product base in a variety of chemical reactions. Interactions can be additionally complicated by a variety of solvent effects. In short, the more " technically complex " a base is in terms of physical structure and/or chemical composition, the more likely it is to be difficult to perfume. The comp lexity of this part of the creative process is all too frequently underestimated by outsiders to the industry. The perfume industry is almost as mysterious to outsiders as is a perfume itself. Many perfume houses are not public companies and, consequently, do not publish annual
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reports for shareholders. The top four companies operating on a transnational basis in supplying perfumes to the detergent industry are International Flavors & Fragrances, IFF (U.S. public company), Givaudan-Roure (part of Hoffman-LaRoche, Switzerland), Firmenich (private company, Switzerland), and Quest (lCI). Of these , only IFF issues an annual report for shareholders from its New York headquarters. P&G, Henkel , Colgate , and Kao are examples of firms with in-house perfumery groups catering exclusively or virtually exclusively for the company needs . There are many more national and smaller transnational companies. Readers interested in this aspect of the industry are best advised to contact the individual companies themselves; comparative publications are few and far between and the most recent are those by Unger [3]. However, in recent years, there are signs of more openness from the companies on their activities and the situation sketched here could change. Key players in the detergent industry are global operators, and once they have invested in a fragrance, they need to be able to obtain it reliably around the world in an identical form on each delivery and in sufficient quantities. This clearly implies that a major fragrance house also has to have an efficient global operation along with very high standards of quality control in manufacturing and raw materials. The raw materials of perfumery extend across natural and synthetic products and it will be appreciated that a fragrance house needs to obtain these to a constant high specification, which includes odor. To this extent , the perfume industry has an extra dimension beyond that of the finechemical industry. Against the background of these remarks, it can be appreciated that the major perfume companies also manufacture speciality raw materials used in their creations. Although many of these are manufactured by one company and sold to others, the perfumers of the company having immediate access to key specialities often have an inherent price advantage over their competitors. From a customer point of view, an important implication of this is that a competitor seeking to imitate a fragrance in a product will not be able to do this at a price advantage using the same key ingredients as the original and make a viable return. Invariably, alternatives or cheaper compositions will have inferior performance standards to the original perfume. A fragrance created for a customer is normally the exclusive property of that customer unless otherwise agreed and will not be sold to other customers. It is to the advantage of both the perfume house and client to have a clear modus operandi. The following discussions will hopefully make it abundantly clear that a situation in which the perfume supplier has full access to both the detergent formulation and details of the production process is ideal. Although major companies are coming to recognize this, there is still a widespread reluctance to reveal more than sketchy details and even sometimes release the base with which the perfume house is to work. Without belaboring the point, one major reason for this is a failure to realize that a fragrance has a technical dimension alongside the obvious artistic one. Simply bearing in mind that one is dealing with a blend of volatile organic chemicals focuses the thoughts in many cases. Some years ago, discussions in the industry gave rise to a series of articles dealing with the sort of information which should be exchanged in "perfume briefings"; it is still instructive to read through these as a guide to structuring one's own thoughts [4]. Having said all this, revealing information on products and processes involves professional trust which needs to be established. Patents (applications) when available invariably solve most queries of technical information. At least part of the reason for a perfume not being viewed as a technical component of a detergent formulation is that odor does not lend itself to being quantified by some sort of physical measurement. Moreover, although analytical techniques permit constantly better analyses of compositions to be obtained, one should never lose sight of the fact that

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a consumer is indeed purchasing performance in terms of smell and not a weight loss or gas-liquid chromatography trace. Thus, although some fragrance compositions may modify in technical terms during storage as a function of time, it is quite possible that this has been allowed for by the perfumer to achieve a particular organoleptic result. One wellknown perfumer in the detergent industry once remarked that a totally stable fragrance would never win a market test! Perhaps this is going too far, but his sentiment would be understood by many perfumers. This fact, coupled with the difficulties in describing odors once one gets beyond direct comparisons such as "it smells like oranges," only serves to reinforce the concept of a perfume as being somehow not really a component with "technical properties." The jargon in a fragrance house which enables perfumers and odor evaluators to talk to each other basically draws heavily on analogies with the senses of sight, touch, and hearing. Universally, volatile components of a fragrance are referred to as top or head notes, whereas increasingly less volatile fractions are typified as middle and base notes-analogies with music . Yet again, alongside more obvious verbal descriptors such as "sandalwood," "woody," or "musky," one will come up against expressions such as "very green." The description and classification of perfumes is a study in itself, as is the important relationship between odor and color. Most major fragrance houses have their own views on these important topics, but an excellent book which gives general insights into many of these creative aspects of perfumery remains that by Wells and Billot [5]; a recent volume from Calkin and Jellinek reveals much of modern perfumery [6]. Once you have found a perfume house and decided how to brief it, all that remains is to select the winning fragrance. Here again, we come up against all the subjective and artistic properties of smell, assuming that any technical problems have been resolved. Most perfume suppliers will be quick off the mark to convince you that their creative methods are the ones to go with via a convincing presentation and maybe even glossy literature. The fact remains that it is something of a gamble on which the perfume house does its best to shorten the odds! Perfume houses invariably work in competition with other houses on a "no cure, no pay" basis and a poor record is quickly punished. Any attempts to go in for these fabled massive profit margins which perfumes are popularly supposed to command will also reap a quick retribution either from competitors anxious to undercut the price or from the purchasing department of the customer armed with a report from his analytical department who will want to know what is going on. Sophisticated analytical equipment, an experienced analyst, and the actual sample of fragrance oil can reveal many detergent fragrance formulations to >90% accuracy nowadays. A perfumer creating for detergent and household products invariably has a maximum amount of money he can "spend" per ton of product. Whereas he needs to meet all the technical and aesthetic demands put upon him, he also needs to remember that manufacturing time and complexity cost money. This almost forces him to create as simple a composition as possible, naturally maximizing the content of his company's specialities. Having rather flippantly compared the process of actually selecting a winning perfume to a game of chance, this should not be interpreted as implying that the creative process itself leaves very much to chance . The actual creative team comprises perfumers, odor evaluators, and applications chemists. It is the job of the chemists together with the perfumers to ensure that a creation is technically sound; these aspects will be discussed in some detail in the following sections. Once a perfumer is clear as to which chemicals he is free to use, it is up to him to create the fragrance. Most major companies now have a department of odor evaluation experts who are highly trained in monitoring the (comparative) behavior of fragranced products in use. In the case of laundry detergents, for example, they are fully familiar with market trends and tastes in the product categories

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involved. This extends to laundering habits, machines used, the location of the machines, and so forth. It is the job of the odor evaluators to evaluate products under as near actual in-use conditions as possible and provide information to the perfumer on where his creation could be improved. Very often, perfumers will, in effect, be competing with each other as well as against leading products from the target market(s). Fragrance performance at all the so-called "magic moments" of product usage starting when the product is put into a washing machine right through until laundry is stored in the closet are critically evaluated. As if this is not enough, confirmatory market testing will also be conducted in some cases. While the perfume selection and creation is going on, chemists will be subjecting candidate submissions to all kinds of (accelerated) stability testing in an effort to ensure that neither product nor fragrance are unacceptable or incompatible with each other. (Designing and translating information into realistic data is something on which a book could be written.) In the light of all this test work, it is clear why fragrance houses can make demands for large amounts of product base and packaging and will need to know marketing plans and product positionings when working optimally. Fragrances have a long history of safe use and the industry has had the foresight to set voluntary stringent standards for itself in this respect via the Research Institute for Fragrance Materials (RIFM) and the International Fragrance Association (IFRA). All the major fragrance houses are members of these organizations and conform to their standards. Deeper insights into the workings of these international bodies and how they interface with national organizations are given in review articles by Schrankel [7], Jackson [8], and Stofberg [9]. The success of these bodies in regulating the registration of new fragrance chemicals and acting upon any findings which set existing compounds in an adverse light is evidenced by the relative lack of controversy around perfumes. In addition to safety and toxicity issues, IFRA also helps to set professional norms within the industry by defining guidelines on issues where national legislation is rather vague; a typical case in point is a "Statement on Natural Perfumes," Information Letter 325. This effectively prevented a potentially unedifying situation whereby all sorts of "nature-identical" and perfumes containing "significant quantities of essential oils" were all offered as "natural perfumes" within the widely differing norms of different national legislations. Of the reviews cited in the previous paragraph, that of Schrankel broaches the topic of the environmental fate of perfumes. This very topic was the subject of IFRA Information Letter 337 issued in 1990. This letter itemizes reasons why perfumes are not likely to accumulate in the environment or disrupt environmental equilibria under likely conditions of use. However, in recent years, the qualitative assurances set out in this letter have run into the quantitative requirements of environmental labeling schemes. Invariably, these assign some sort of "score" to the ingredients in a product which relate to the speed and extent of the biodegradability of the components in the environment. Although perfume ingredients are fairly simple organic chemicals with molecular weights invariably below about 300, there are literally thousands of them. Quantitative data on all their individual biodegradation characteristic, impact on aquatic organisms, and so forth are simply not available and one unfortunate consequence of this is that perfumes are generally given the most pessimistic score possible. This clearly poses a major problem for the industry and a professional unified approach from IFRA is now needed. In 1994, Information Letter 444 entitled" Environmental Impact of Perfumes-Cradle to Grave Assessment" probably signaled some early moves on this issue. It goes without saying that if some satisfactory agreements/data are not forthcoming to resolve this issue, particularly if eco-labels become of significant commercial importance to detergent products, then it could provide the impetus for the perfume industry to develop in some novel directions. For example, de-

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veloping fragrances and/or ingredients which deliver acceptable organoleptic performance at much lower concentration in products than is currently the case would be one way to minimize the volumes of fragrance used and thereby obtain more favorable "scores" under the latest European community eco-label legislation [10]. Environmental questions are as much a topic for debate in modern perfumery as for other branches of the detergent industry. This simply underlines the fact that fragrances, although frequently falling into the category of formulation "minors," can have quite major impacts on products. The following sections now explore the technological implications of some of these impacts. II. CHEMICAL AND PHYSICAL PROPERTIES

As was intimated earlier, a perfume is a blend of volatile organic chemicals which range up to molecular weights of about 300. In principle, these chemicals can contain one or more of the functional groups, which are dealt with in any basic text on organic chemistry, ranging from aliphatic hydrocarbons, alcohols, and aldehydes to terpenes. They also cover natural extracts or "essential oils" which are invariably themselves mixtures. The detergent perfumer will generally create a composition using between about 20 and 100 ingredients , which is invariably much less complex than the "fine fragrances" in cosmetic uses, which can extend to several hundred components. It will come as no surprise to learn that significant interactions between these components can occur, which can, in turn, have consequences for the odor of a fragrance and the way in which it interacts with product and package . A. Chemical Reactions in Perfume Oils

Anyone who has purchased a fine fragrance or cologne will be aware that as the partly used bottle stands on the dressing table, the contents darken in color with time. Blakeway and his co-workers have written one of the most comprehensive published studies of this phenomenon in recent years [11]. This publication quantifies more general comments made by Conover [12], which contains useful references to earlier work. Most of the data are of general relevance to perfume oils and emphasize the need for protecting some raw materials such as terpenes against (auto)oxidation reactions. However, reactions are not limited to oxidation and the following schematic equations summarize the kinds of interactions which proceed to an equilibrium:
OR'

RCH2.CHO + R'.OH

/
RCH2CH "" OH

hemIacetal

ester exchange
-CHO + NH2
~

-CH = N- + H20

Schiff's Base

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Any Schiff's base formation in a perfume itself is brought about by the deliberate inclusion of methyl anthranilate in the mixture. Work published almost 50 years ago by Wells [13] reviews some interesting Schiff's compounds of use to the perfumer. For the chemist, it is important to note that the formation of a Schiff's base can be quite slow and the compounds can be highly colored. Perfume oils delivered to a detergent manufacturer will be stable and matured, such that the consequences of the reactions reviewed in this section should be somewhat academic. However, autooxidation reactions such as

[0]
>

d-Limonene

carvone

carveol

can become significant if the protective effect of antioxidant is removed by effective dilution following inclusion in a product. Proctor and Gamble (P&G) has even taken out a patent in this area for adding extra antioxidant to dishwash liquid to stabilize terpenerich fragrances which otherwise can autooxidize and result in the "necking " or " paneling" of flexible plastic containers [15].

B.

Che mic al Reactions Between Perfumes and Bases

The chemical reactions described in the preceding section can all take place when one of the reactive groups is present in the perfume and the other in the product base. Generally speaking, the perfumer will do his best to avoid such interactions and it is, therefore , helpful for him to have a detailed knowledge of the product being perfumed. Problems most often arise due to the presence of small amounts of impurities inadvertently introduced when compounding the base; this is where a knowledge of product raw material component specifications and production processes is helpful. For example, discolorations which slowly intensify when a perfumed product is stored alongside an unchanging, unperfumed reference can often be traced back to Schiff's base formation between perfume aldehydes and some -NH 2 gro up present in a base component. Perfume chemists seem to develop a sort of sixth sense for this type of phenomenon and increasingly sophisticated analytical techniques prove an invaluable aid to troubleshooting. Some idea of the chemistry involved can be obtained from a study of perfumes and color reactions in soap published some years ago by Pickthall [16] which introduces other reactants such as heavy metals . Iron is particularly associated with forming colored complexes with some fragrances. Detergent bases themselves naturally have a pH when in aqueous solution. For the purposes of a perfumer, even powders must be considered as entities which are highly concentrated aqueous solutions in their packaging. During storage and in use by the customer, small amounts of moisture in a powder behave effectively as concentrated solutions as far as the fragrance is concerned. Having said this, it will be appreciated that product pH is a key property when deciding which perfume ingredients can be used; pH-related reactions such as ester hydrolysis, aldehyde condensations, and so forth all come into play. Pragmatically, a product base falling in the pH range 4.5-8.0 will permit a perfumer to utilize practically all the chemicals at his disposal. The choice falls off sharply on going from pH 8.0 to 10.0 and from pH 4.5 to 2.5. This fall accelerates even more sharply from

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pH 10 to 12 and from 2.5 to 1.5 to leave a situation in caustic soda or mineral acid-based cleaners where only about 25-30 perfume chemicals are left for the perfumer. Consideration of these ranges reveals the importance of the pH of the detergent formulation to the creative flexibility of the perfumer. Modern heavy-duty laundry powders in the pH range of about 9.5-11.0 vary quite markedly in their reaction to perfumes but can never offer the perfumer the creative flexibility possible in fine fabric or some "color care" products of pH 9 or lower. Similarly, the switch from fabric rinse conditioners of pH 5-6.0 to socalled ester quat formulations of <pH 3 presents perfumers with complex creative problems. Alongside the acidity or alkalinity of a base come the problems associated with reactive chemicals such as hypochlorite bleach, peroxygen salts with various activators or catalysts, and even the residual esterase activity of some enzymes. Here again, a knowledge of the product composition and perfume chemistry help to avoid problems associated with perfume deactivation of the detergent formulation. However, it is fair to say that the pH is the major determinant of which fragrance materials can be used. Although it is a fact that the perfumer can use computerized databases and theoretical considerations to rule out numbers of chemicals which will definitely not be stable in a particular formulation, restricting a perfume to only components which are individually stable in the formulation is widely agreed to run the risk of winning a test with the chemists but not with the consumers! For this reason, an important aspect of creating a perfume for a new detergent formulation involves discovering "synergisms" which permit a perfumer to utilize chemicals which, although not totally stable when tested alone, are acceptably stable once combined in a perfume composition. Fragrance raw material interactions of the type discussed in Sec. ILA offer some explanation for this phenomenon. This particular aspect of fine-tuning a perfume obviously needs great care and even changes in tetraacetyl ethylene diamine (TAED)-perborate bleach ratios can influence this. In the same context, the advantage to a perfume house which has a good range of speciality chemicals which are stable in aggressive bases and give odors otherwise unattainable is clear. Chemists and technologists always do well to remember that consumers are purchasing smell and product performance, not technical features such as perfect "weightloss-as-a-function-of-time" properties. There is an obvious desire on the part of the chemists to achieve a degree of technical perfection which a perfumer may find less necessary provided he can deliver a certain "smell experience" within the commercial lifetime of a product. It goes without saying that the technical performance of the product itself should not suffer by this. In short, a perfumer may decide that a certain quantity of a fragrance component can be lost by decomposition due to instability, but that a sufficient amount of the component will remain to deliver the nuance which is key to the performance. Another variant on this practice involves the deliberate creation of in situ chemicals in a base. As an example, in the days of hypochlorite bleach liquors with 8 - 10% available chlorine, some perfumers were known to take the view that a small amount of hypochlorite could be used to deliberately produce chloroform with primary or secondary alcohols added as perfume components. This gives a pleasant, characteristic sweetness to the fragrance note. It goes without saying that such a practice is no longer commercially feasible, not to say environmentally responsible in the light of absorbable organic halides [17]. In conclusion, the point being made is that an analytical chemist's view of chemical stability may not always coincide exactly with the actual properties of a commercially successful fragrance.

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C.

Physical Chemistry of Perfumes

Reflection on the potential properties of a blend of volatile organic chemicals will quickly lead to the conclusion that one could expect some sort of solvent effect of perfumes in detergent bases. This is indeed the case and one should be on the lookout for viscosity changes and their consequences in liquid formulations . These consequences can be quite serious in liquids where a degree of structuring is present to hold insoluble components in suspension, such as is the case in a cream scouring formulation or a zeolite-built laundry liquid. If a fragrance is simply postdosed to such products, one can encounter phase separation, which renders the product unusable without a plaintive " shake well before use" warning. Cooperation between product formulator and perfume chemist is called for to adjust the structurants in liquids to allow for the effects of fragrance. The expression " perfume oil" also implies a measure of insolubility in water. Whereas some compounds such as phenyl ethyl alcohol (rose odor) and some more polar aldehydes are significantly water soluble, perfume oils are generally hydrophobic in nature. This can become important when fragrancing products with a significant oleophilic phase, such as concentrated dishwash liquids or fabric rinse conditioners with a significant liposorne-like micelle structure [18]. Fragrance tends to migrate out of the aqueous phase and concentrate in the oil phase. In the case of a simple micellar-type solution such as a dishwash liquid , a result of this is that the fragrance note from the bottle seems to weaken as a function of time as the migration process takes place. Components which go to make up a classic citrus note will exhibit this property to an extreme, being particularly hydrophobic. If the freedom is present to opt for other odors built up of less hydrophobic moieties, this phenomenon is less pronounced. It goes without saying that when these concentrated formulations are diluted into water, the fragrance does "burst " out. In a sense, this is a sor t of inherent microencapsulation process. In the case of the rinse conditioner or liquids having liposorne-like structures with alternate oil and aqueous phases, the migration of fragrance can simply break up the structures to such an extent that phase separation occurs. The solution to such a situation is often to add the fragrance at the same time as the structure is being formed, so that an equilibrium situation establishes. In short, fragrance oil is not always best stirred into a product as the final manufacturing step when everything has cooled. The ability of a perfume to partition itself within a structured liquid can be used to increase product viscosities. The technique here invariably involves incorporating compounds which can form hydrogen bonds with each other such as alcohols. Detergent formulators will probably be most familiar with this technique in the form of adding glycols to low-active DTDMAC rinse conditioners. Although similar solvents can be used with perfumes, a more elegant illustration of viscosity boosting by fragrance is given by the use of perfume tertiary alcohols in hypochlorite bleach formulations which are thickened by an amine oxide-based surfactant system. Presumably, the alcohol groups enhance hydrogen-bonding between the amine oxide micelles and mention of this is made in the patent literature [19]. The way in which a perfume partitions itself can also have important effects on its in-use performance, and although this topic will receive attention in Sec. VI, some general guidelines are relevant here. If a perfume is required to perform an air-freshening function in something like a toilet bowl cleaner, care needs to be exercised that fragrance is not so efficiently solubilized by the formulation that the great majority simply washes down the drain . Analagous rules apply to laundry care products, where affini ty for cloth is paramount to ensuring a good "freshness " after clothes are cleaned. As in many areas of perfumery,

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although a lot of theoretical predictions can be made to approach a desired goal , fragrance optimization invariably depends on pragmatic in-use evaluations using the formulator's actual base . Having dealt with fragrance solvent and partitioning effects, it is salient to examine aspects of fragrance volatility. The evaporation rate of an organic chemical in a mixture is proportional to its partial vapor pressure, which is expressed by the following equation derived from Raoult 's law:
P,

= P ?f,n

where Pi is the partial pressure in the mixture, p? is the vapor pressure of pure product, I', is the activity coefficient of the component, and n, the mole fraction in the mixture. Values of p?are fairly readily available and a knowledge of the composition of the perfume leads to values for 1I i' Activity coefficients present the first hurdle because they can be envisaged as correction factors relating to the departure of the behavior of a substance in a blend from its " ideal" behavior when pure. For example, alcohols exhibit a fair degree of structure forming by virtue of hydrogen-bonding. The extreme example is water, which can be envisaged as the first alcohol in a homolous series-s-H: OH , CH 30H, CH 3 CH 2 ' OH, and so forth. Without hydrogen-bonding, one would expect it to be a gas at ambient temperatures. When alcohols are blended with other organic chemicals such as hydrocarbons and esters, the hydrogen-bonded structures are partially broken down, and this is reflected by values of activity coefficients which are higher than 1.0. Some of the most nonideal blends comprise hydrocarbons and alcohols, and values of r can be as high as 5 or more . In practical terms, the implication of this is that the actual volatility of an alcohol in a blend with hydrocarbons can be considerably higher than one would expect on the basis of its vapor pressure as a pure substance. It will be appreciated that the complex nature of fragrance blends renders any calculations of their actual vapor composition at any time extremely complex, although the basic ideas are confirmed by analysis. In addition, there is no simple correlation betw een vapor pressure and perceived odor intensity. In short, the design of commercially successful perfumes by computer is a very long time away. Having said this, attempts have long been made to rationalize physical chemistry and perfume performance and one of the most comprehensive published reviews remains that of Louis Appell [20]. Most recently, P&G has incorporated som e of the preceding ideas into patent applications relating to fragrance design. They propo se, quite logically, that for a fragrance to perform from cloth after a laundry treatment, substantivity of the ingredients on the cloth is necessary. Accordingly, they suggest that octanol-water partition coefficients be used as a measure of hydrophobicity and boiling points as indications of volatility, and that these are key arbiters for substantivity in numerous products involving washing and rinsing, as is the case in detergent applications [21]. So-called "enduring perfume ingredients" are defined as having boiling points in excess of about 250C and a water insolubility expressed in terms of the logarithm to the base 10 of an octanol-water coefficient exceeding 3. The patents contain extensive illustrative data but, unfortunately, do not extend their discussions to encompass a consideration of odor thresholds alongside these physicalchemical criteria. In cases where the fragrance is required to " burst" or "bloom " from an aqueous medium, such as in toilet bowl cleaner detergent compositions, the waterinsolubility criterion is combined with a boiling-point requirement of less than about 260C [22] . Before leaving a consideration of physical properties of perfumes, it is noteworthy that some perfume compounds such as heliotropine or benzophenone are highly viscous

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liquids or even solids in their pure state . Handling is often facilitated by using them in solution and, to this end, odorless solvents such as diethyl phthalate (DEP) or dipropylene glycol (DPG) are used. Yet again, some compounds such as skatole are only used at very low concentrations and need dilution with solvents to enable accurate handling and weighing. In short , solvents in modern perfumery have a very functional purpose and are not simply present as cheap diluents.

D.

Microencapsulation and Absorption

In the light of the comments in Sees, II.B and II.C, the attraction of techniques for protecting perfumes in chemically hostile bases and delivering them where and when they are needed is overwhelming. The fact that there are so few detergent products which employ microencapsulated perfumes indicates that achieving these goals by perfume encapsulation is not as successful practically as we would like. The allure of the encapsulation technique is evident from the massive open and patent literature on the topic and the object of this section is to summarize where perfume microencapsulation in detergent products could be applicable. Fragrance absorbed or contained in a matrix in the form of a microparticle can be prepared in numerous ways, such as spray-drying, spray-chilling, drum-chilling, cryogrinding, coacervation, and so forth. These processes naturally put a price premium on the fragrance which has to be justified by some sort of perceivable performance benefit. Fragrance slowly diffuses out of most microencapsulates during the storage of a product. The "leaked" fragrance is then exposed to any potentially aggressive chemicals in the base, which often negates any major stabilizing effect of the microencapsulate. If a fragranceimpervious encapsulate is used, one then has to consider the question of to what extent the product needs additional conventional perfuming for "out-of-the-pack aesthetic purposes." The slow diffusion of fragrance from microparticles is sometimes claimed to promote perfume longevity or substantivity on a substrate. Practical evaluations of products often reveal that the levels of perfume emitted are, unfortunately, too low to be readily perceivable even though prolonged emission is indeed achieved . Finally, a point which is often overlooked, is the fact that a skilled perfumer can achieve quite surprising performance standards using his "conventional" technology. Observations such as those in the preceding paragraph lead to the conclusion that microencapsulated fragrance in detergent products will probably be employed to address situations where the use of a liquid perfume oil is a problem either to the product or the process or where some sort of "trigger" releases fragrance at an appropriate stage in product usage, thus avoiding premature perfume loss. An example of where a liquid fragrance could be a problem is to be found in the compact laundry detergents. Bulk densities are ever-increasing and this is reflected in considerably less porous products. Moreover, the replacement of compounds such as sodium perborate monohydrate by sodium percarbonate represents the removal of a relatively efficient absorbent by a nonporous entity. Fragrance conventionally sprayed onto such mixtures will take increasingly longer to soak in and one solution to this manufacturing problem would clearly be to supply the fragrance in a solid form . The problem of handling fluid components (i.e., fragrance and nonionic surfactants) in this context has recently been reviewed [23]. The basis of the technique is that fragrance can be readily absorbed on a wide range of inorganic solids, particularly aerosol silicas and zeolites, as has been described by several authors [24-28]. It goes without saying that one would be looking for the minimum retention of fragrance in the absorbate or encapsulate once the product was used. In this context, the destruction or

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"activation" of the perfume carrier by some sort of "trigger" clearly offers a solution to any problems of retention. There are basically two triggers for detergent products-moisture and heat. Moisture in the form of sweat has been successfully exploited in deodorant formulations, but the scope is much wider, as Miles has pointed out in an article on the topic of moisturetriggered encapsulation systems for fragrances in household and personal product [29]. The same trigger is commercially exploited in tumble drier sheets by P&G and a characteristically comprehensive patent series dealing with the use of 13-cyclodextrins as clathrates in this end use has appeared over recent years [30]. Significant quantities of perfume are clathrated or "trapped" in the cyclodextrin, which is, in turn, entrapped on cloth [31,32]. Subsequent exposure of a towel to moisture or clothing to sweat is claimed to be sufficient to release a burst of fragrance. The concept of using heat as a trigger in tumble driers where the heat of the drier accelerates perfume release from a wax has been mentioned by Unilever [33]. Numerous other claims for encapsulated fragrances are found in the literature in a range of detergent formulations. However, the conspicuous lack of products utilizing microencapsulated fragrance is evidence of the difficulty in achieving acceptable cost/ performance figures. The concentrated or compact detergent powders probably signal one possible point of breakthrough for encapsulation technology, particularly where consumers demand a high level of perfume on cloth. Modern compacts are increasingly less porous and some have reached a stage where conventional perfume dosage is limited to around 0.4 wt% if problems of manufacture or in-pack agglomeration are to be avoided. There is at least one major soaper who has addressed this dilemma by spray-drying a portion of the fragrance dose in a modified starch. This obviates problems of the type just referred to, as well as sidestepping the dilemma of overintense pack odors. The encapsulated fragrance is released into the wash liquor when water hits the powder and dissolves the starch.

E.

Preservative and Antimicrobial Properties of Perfumes

One of the functions of essential oils in plants and herbs is to protect the vegetation against attack by fungi and bacteria. This biocidal property of essential oils is well documented [34,35] and, not surprisingly, this activity is shared by a large number of synthetic fragrance ingredients [36]. Efforts to utilize this activity have attracted continued interest over the years, particularly in personal care products, to make products free of proprietary preservatives and utilizing the so-called "natural protection" of essential oils or perfumes. A recent paper has summarized the salient literature in this area and concludes after detailed tests that although it may be theoretically possible to use certain "cocktails" to obtain acceptable product protection, the limitations on perfumer creativity in terms of the choice and high concentration of ingredients needed render the concept fairly impractical [37]. Generally household detergent products have not attracted the same degree of attention, although Unilever does consider the possibility in a patent [38] which places rather more stringent constraints on perfume ingredient selection than prior art. The data indicate that adequate preservative action of aqueous detergents could be obtained although perfumer flexibility is clearly restricted. Perhaps the future lies in developing synergistic combinations of fragrance and proprietary preservative [39].

F.

Semlochemical Activity of Perfumes

Continuing on the theme of the previous section, essential oils produced by some plants repel predatory insects, whereas in other plants, oils attract insects to assist with pollina-

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tion. This behavior-modifying or semiochemical activity of essential oils has long been recognized and a comprehensive compilation of the essential oils with an anecdotal history for repelling all manner of crawling and flying insects as well as the treatment of any stings and bites with essential oils has been published by WOTWood [41]. The various types of mosquito represent one of the largest single categories of insect pest for which there is an interest in developing repellents. Citronella and lemongrass oils are widely reported repellents, with lavender, pennyroyal, tansy, and sassafras probably less recognized. Although there is no doubt that essential oils such as citronella work in the case of mosquitoes, proprietary repellents such as diethyltoluamide (DEET) are generally considerably more effect ive [42]. Having said all this, there are undoubted advantages to be had from semiochemical fragrances used either alone or as (synergistic) additives alongside chemicals such as DEET in a range of products. Reference has been made to individual essential oils and the patent literature extends this to combinations of oils which are perfumes in the sense of the technical definitionblends of volatile organic chemicals. Beldock and Beldock describe blends of at least 0.01 % terpineol and citronella plus either similar levels of geraniol and/or rhodinol extra [43]. These chemicals can be used as well as a fragrance in insect -repellent lotions or sprays and favorab le comparative data against DEET-based products are presented. Claims for repelling mosquitoes and blood-sucking insects are claimed for blends of pennyroyal, anise , and chrysanthemum oils [44]. Emphasis is given to the fact that the combinations have a pleasant smell in contrast to prior art. Implicit in this type of literature is the fact that some sort of synergy exists in blends . Further study of the literature in the general area also reveals that the synergy extends to activity in combination with DEET. Not surprisingly, activity can be very concentration dependent and can be influenced by the product base itself. Published data extending observations on the semiochemical nature of essential oils to synthetic perfume ingredients are relatively scarce and are the virtual monopoly of International Flavors & Fragrances. Reference 45 refers to earlier publications in describing the use of some chemicals in soaps, polymers, candles, and detergent bars. At the time of writing, the only significant detergent use of fragrance as a semiochemical is in hardsurface cleaners and is reviewed in a Lever patent application [46]. The reasoning is that insects such as cockroaches can be transporters of germs and, therefore, cleaners which tend to repel them are desirable. Under sterile conditions with no food present, the patent demonstrates that a level of more than 0.5 wt% limonene in a cleaner is sufficient to render a surface totally undesirable to cockroaches relative to a surface not limonene treated . The whole picture becomes less clear-cut when food sources are introduced, when flying as opposed to crawling insects are considered, and when proprietary repellents are introduced as target standards.

III.

PERFUME MODELS, STRUCTURES, AND JARGON

Consideration of the comments in Sec. II quickly leads to the realization that although technically helpful generalizations can be made to rationalize the behavior of a perfume in a detergent formulation , one needs to be very cautious when trying to make more specific predictions based on the known behavior of individual perfume components. Despite this somewhat pessimistic statement, there are some models used to portray perfumes which can be very helpful to the chemist when attempting to rationalize the behavior of a fragrance. The basic model is that shown in Fig. 1 of a triangle divided into at least

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r
general increase in raw material price increasing volatility

j
Figure 1

MIDDLE

BACK (substantivity)

Triangle model of perfume.

three parts to represent the major segm ents of a fragrance. The most volatile components used by the perfumer, such as low-mol ecula r-weight esters and aldehydes, are referred to as "top" or " head notes." These compounds tend to accumulate in the headspace of products and play a major role in determining the initial impact of perfumes when a product is freshly smell ed from its packaging. Generally speaking, these molecules have relatively little affinity for substrates such as textiles and do not contribute much to the long-lasting properties or " substantivity" of the perfume. This latter property is governed by the so-called " back" or " base notes " of the fragrance (represented at the bottom of the triangle). The compounds in this segment of the perfume are rather involatile. Their molecular weights can extend up to about 300 and, physically, some of them are almost solid in their pure state. Between the top and base note components comes the body of the fragrance in the form of the " middle notes " which determine the character of a perfume. It goes without saying that the perfumer deals with much more detailed subdivisions than this, but it is sufficient for technical purposes. The reference to " notes" illustrates the difficulty in talking about odors, as direct comparisons with fairly well-known smells such as those of lemon or lavender are no longer sufficient. One has to resort to comparisons involving the other senses. The use of the word " note" in the context of a perfume " composition" clearly draws analogies with music and the sense of hearing. The other common analogy is with colors and artistryone frequentl y hears that a perfume has very " green" top notes. There is a complex jargon which perfumers use to describe the smells they have created; this jargon is necessary for communication with their colleagues when deciding on how modifications need to be made . One needs a common vocabulary to point to the relevant bit of the perfume. Here again , we come up against an area of perfumery which lies outside the scope of a technical review. However, chemists interested in delving further into this aspect will find that all the major perfume suppliers have genealogies to describe cosmetic or fine fragrances, which include descriptors of odors. Some discussion is to be found in the various textbooks already cited , and Refs. 47 -50 deal with various aspects of this topic in more detail. Returning to a consideration of the model shown in Figure 1, the volatility of the ingredi ents increases as one goes from the base to the apex of the triangle, as one would expect. Coupled with this , the less volatile a component is, the more complex its molecular

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structure tends to be. In general terms, back note components cost a lot more energy to synthesize and move around a perfume compounding plant than do top note chemicals and this is mirrored in higher costs. The commercial consequence of this is that substantivity costs money and modifying perfumes to be more substantive in a very pricecompetitive product can present the perfumer with a lot of problems. Another aspect of this is that fragrances which do not need to be substantive, such as those used in dishwashing applications, are generally cheaper per kilo than those for a fabric rinse conditioner, for which "lasting freshness" is a key feature of the product. Another way in which the simple triangular model can be helpful in anticipating problems was illustrated some years ago when a major manufacturer decided that a fragrance being very successfully used in heavy-duty detergent powders should also be used to continue the brand image in a new liquid laundry product. The liquid had a more neutral pH than a concentrated solution of the powder and aggressive chemicals such as bleaches were absent. Quite correctly, it was reasoned that the perfume would be technically stable in the liquid and that a product launch should go ahead. It transpired that the level of perfume used in the liquid to give acceptable out-of-bottle smells was around three to four times the conventional dose for such a product. The reason for this can be illustrated using the triangular model again, as shown in Fig . 2. Traditional laundry detergent powders are packaged in cardboard boxes which certainly permit fragrance to be lost once opened by the consumer. Products can be used at high laundry temperatures. Product base malodors from solids are generally easy to cover and so the perfumer would tend to construct a fragrance akin to the rather squat triangle in Fig. 2, where the heavier components in the perfume ensure low perfume losses. Laundry liquids, by contrast, tend to be used at lower temperatures and are stored in sealed bottles such that perfume loss is not such an item of concern. However, masking base malodors over liquids in sealed bottles is often a key feature relative to a powder and this leads to the triangle rather richer in top notes in Fig. 2. Using the powder fragrance to achieve the headspace concentration needed in a liquid inevitably leads to high dosing and (unnecessary) high perfume cost. The solution to this is to let the perfumer rebalance his fragrance . The emphasis in the discussion so far has been on how a perfume is built up or structured to achieve performance characteristics. It goes without saying that these char-

LIQUID
Figure 2

SOLID

Perfumes for solids and liquids.

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acteristics are influenced by the medium being perfumed. For example, changing the viscosity of a fluid modifies the rate at which perfume diffuses out of it and this can be reflected in changes of perceived intensity and even a modification in note. Some solid components such as zeolites and clays can preferentially absorb the smaller molecules used in top notes and this can modify the perceived balance of a fragrance . For reasons such as this, it is important to test even the most apparently conventional base to ensure optimal perfuming. It is apparent that fragrance substantivity in detergent products is very much an operational phenomenon and not something inherent only in the perfume itself [51,52]. The interactions between the fragrance components modified by the base effects referred to in the previous paragraph illustrate how skilled the perfumer needs to be to achieve a composition or blend which preserves a particular character of odor. Some attempt was made by Pickthall to discuss the matter scientifically over 40 years ago [14] and the opening words of his paper are as true today as when he wrote them. "It is remarkable that so little has been written on these two important phenomena in perfumery, namely, blending and fixation." Perhaps it is not so remarkable, as the phenomena are so complex to attempt anything more than generalizations. However the term "fixation" is one we have not yet reviewed and it is important in the context of substantivity. "Fixing" a perfume implies that one adds something to the composition to render it longer-lasting. It will be appreciated that this is very closely associated to the process of re-creating a perfume or reblending it to render it more substantive. Nowadays, the distinction between the two processes is very blurred. However, one still encounters the term "fixateur" in the context of a specific additive which when put into a perfume (usually the claim is "any" perfume) enhances its long-lastingness. Many claims involve compounds well known to the perfumer, such as the various "musks," and are really targeted at cosmetic perfumes. Nonetheless, simply adding these compounds to a perfume effectively reblends it and maybe even ruins its balance, not to say anything about its actual cost. This situation is invariably even more exacerbated in detergent formulations and attempts to enhance substantivity by fixateurs are invariably inferior and more costly than asking the perfumer to try and reblend his composition. Similar remarks apply to socalled "boosters" which are claimed to enhance the impact of a fragrance by enhancing its evaporation rate. In fact, I am inclined to share the view of a colleague who referred to these types of chemicals as "pixie dust" -at least this is kinder than "snake oil"! In the context of ingredients which actually prolong perfume perception without impairing the balance of a fragrance by reducing intensity, the reader is referred to Sec . VI.A. and the references to highly substantive but essentially odorless perfume alcohol esters which slowly hydrolyze to release fragrant alcohols.

IV.

PERFUME FUNCTIONALITY

A prime object of fragrancing a detergent formulation is to render it aesthetically pleasing to the user. However, many formulation components are inherently malodorous and simply putting a perfume in among them will just put a pleasant smell alongside the bad ones. Attempting to overpower malodors with high doses of fragrances is also doomed to failure, even if it is commercially feasible. The perfumer has to make his compositions such that they mask out any perception of malodors by the user and leave a totally aesthetically pleasing impression. Perfumes which are formulated with this malodor-masking property are referred to as "functional" fragrances. In recent years, the idea of extending this

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property of fragrances into detergent formula tions has been evidenced in package claims such as "removes dirt and odors" on laundry products. In this context, the perfume which is substantive on the cloth after the laundering process is called upon to mask any lingering domestic malodors and suppress the onset of their perception on the laundered garment. These domestic malodors can vary from stale tobacco smoke and cooking smells to sweatgenerated body malodors. It will be appreciated that this aspect of fragrance functionality is applicable and relevant to virtually all products used in the household and institutional environments.

A.

Malodors in Products

Malodors which are inherent in product formulations usually arise from low-molecularweight impurities which are usually of a polar nature. Examples of these are fatty alcohols in ethoxylated alcohol nonionic surfactants (fatty malodors) and traces of pyrrolidones in poly(vinyl pyrrolidone) dye transfer inhibitors (e.g ., 2-pyrrolidone = mouse-like odor). Inadequately preserved products can decay and develop malodors in storage; the most common malodor is the intense fatty odor caused by rancidity usually resulting from heavy-metal-catalyzed oxidation of unsaturated fatty acids typically found in soaps and some fabric conditioner actives. Product usage can also generate low-molecular-weight malodorants. Examples here include the vinegar-like odors arising from (per)acetic acid generated in TAED -persalt bleach systems and the butyric acid-like malodors (fat/vomit) associated with lipase enzyme activity on fatty stains on damp cloth. Malodors which are inherent in product usage often need to be identified using a combination of a good nose and analytical equipment-often a combination of a GLC and a mass spectrometer. Once the malodor has been identified, its source has to be traced and it helps to have a knowledge of how the ingredients in the formula are made, as well as what they are. For example, some manufacturers produce an innocent surfactant such as sodium dodecylbenzene sulfonate by in situ neut ralization of the acid. This can leave "pockets " of extremes of pH in some production processes for a period which is long enough to permit other detergent ingredients to come into contact with them and degrade. In one memorable mystery, persistent malodors were traced to the parts per million of mercaptans generated from an alkaline reaction of the optical brightener containing traces of DMF solvent. In short , it is not possible to give general rules for this sort of detective work, but a knowledge of the product and production process on the part of the application chemist and an open dialogue with the manufacturer are vital. It goes without saying that the best form of malodor control in prod uct formulation is to try and limit it where possible at the source by keeping product specifications tight and modifying production processes. Some commoner sources of product malodor will also be referred to in Sec. VI. It is often a good idea to let the perfume house evaluate individual formulation components as well as the final formulation to pinpoint the source of troublesome base malodors.

B.

Chemical Nature of Malodorants

The chemical identity of many common malodorants is fairly well recognized [53-55]. The low-molecular-weight aliphatic carboxylic acids are responsible for rancid malodors and vomit/sweat/toilet smells. Molecules containing a nitrogen or sulfur atom are also invariably malodorous. Sulfides are associated with bad egg and garlic-like odors. Mercaptans and thioacids account for bathroom-like sme lls and boiled cabbage and are delib-

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erately used as warning signals in domestic gas supplies. Fatty amines are responsible for fishy-urinic malodors. In the context of product bases, one is fortunately faced with identifying either a single substance or usually a very simple mixture. Clearly, any molecule falling into the chemical categories just summarized should be viewed with suspicion. Turning to the nature of malodors which account for environmental or domestic problems such as bathroom, body, or kitchen smells, we are invariably faced with quite complex mixtures. Moreover, although the general character of these smells is instantly recognizable, there can be considerable variations in their compositions due to different diets, cultures, and habits. (We will address the problems associated with this for the perfumer in the following subsections.) However, if we sidestep the problem of variations in malodor composition for the moment, it is instructive to look at some published malodor compositions to see how they indeed are made up of blends of the types of chemical reviewed in the last paragraph. The compositions in Table 1 were published by the U.S. General Services Administration Federal Supply Service as a suggestion for workers involved in creating standard malodors These standard malodors were recommended for use in aerosol formulations which could be used to create malodors in test rooms. In all cases except the tobacco malodor (#3), 0.1 pbw of malodor is mixed with 4.9 pbw of dipropylene glycol and put into an aerosol with 95 pbw propellant. The tobacco malodor was used at 0.2% pbw with 4.8

Table 1

Chemical Composition of Some Malodors Isovaleraldehyde Phenyl acetic acid Butyric acid Indole (0.5 % in DPG) p-Cresyl isovalerate p-Cresyl phenyl acetate Mecaptoic acid Dipropylene glycol WC#5 Dipropylene glycol Skatole I3-Thionaphtole (2-napthalenethial) Mercaptoacetic acid 1I-Caproic acid (hexanoic acid) p-Cresyl isovalerate 1I-Methyl morpholine Hospital #7 Beechwood creosote Tetrachloroethane Quinoline Guaiacol Eugenol Methyl salicylate Isopropanol Kitchen #2 Kitchen #1 Tobacco #3 30.0 3.0 0.25 1.5 1.5 2.75 5.0 26.00 62 .82 0.91 0.91 21.18 6.00 2.18 6.00
0042

Kitchen #1 Diacetyl (2,3 butanedione) Pyridine Diallyl sulfide (Thia allyl ether) Dimethyl sulfide Heptaldehyde Paraldehyde Propionic acid Acetic acid (glacial) Tobacco #3 Furfural Pyridine Methyl ethyl pyridine (5 ethyl 2 methyl pyridine) Mercaptoacetic acid Beechwood creosote Pyroligneous acid Dipropylene glycol Occupied Space Tobacco #3 Body odor #4 Bathroom- WC #6 Body odor #4 WC#5 Kitchen #1 DPG Body Odor #4 1I-Caproic acid (hexanoic acid)

3.85 3.85 9.23 40.00 3.85 1.90 36.92

0040

5.0 0.1 12.6 0.7 1.2 30.6 49.8 90 10 5.0 30 .0 7.5 57 .5 30.0

36.21 8.36 8.36 4.18 4.18 38.29 50 50

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pbw DPG. It goes without saying that many workers will have their own variants on the preceding formulas , but they are illustrative of how malodors are built up. The actual compositions of malodors are invariably even more complex than those just quoted and one which has received considerable attention is sweat-generated body malodor. Quite remarkably, it was only as recently as 1990 that Dr. George Preti of Monell reported at an American Chemical Society meeting that 3-methyl-2-hexenoic acid is the chief cause of underarm odor. It had previously been widely assumed that combinations of isovaleric acid and androstenol were the guilty parties [56]. A subsequent patent taken out by Monell [57] contains detailed compositions and comprehensive references.

C.

Malodo r Counteraction

Malodors, like perfumes, are composed of volatile chemicals. In cases where the source of the malodor is limited to principally one or two chemicals, it may be feasible to tackle it chemically. For example, many malodors arise because of organic acids. If these can be induced to form esters or salts , their malodorous properties will be diminished and even eliminated. The alkaline action of baking soda to neutralize many acidic malodors is a well-known remedy to keep refrigerators fresh and illustrates this. In the context of malodors arising as a result of biological processes such as body odors, there may be ways to interfere with the process so that malodor does not develop [56-58]. For example, armpit malodor develops when bacteria degrade sweat. Therefore, chemicals to kill the bugs or render their life less hospitable by lowering the humidity (antiperspirant) or modifying skin pH will inhibit the malodor development. The existence and feasibility of such methods to control malodors should naturally always be considered alongside the use of perfumes. However, a general point to bear in mind is that many chemical neutralization processes obviously rely on a molecular contact between malodorant and neutralizer. If this cannot be achieved, then, obviously, chemical malodor control will be impaired. Before considering how and when perfumes can assist in malodor control, it is important to have a brief understanding of how we perceive malodors. There are two basic mechanisms. Odor quality and identification proceed via the olfactory nerve, and stimuli or " sensations" are a function of the activation of the trigeminal nerve [59] . Many perfumes offer a relatively low activation of the trigeminal system, whereas some of the classic malodors are strong trigeminal stimulants. Without having a deep knowledge of these two perception mechanisms, it can be appreciated that trying to mask trigeminal stimulation using olfactory nerve stimulation presents the perfumer with a problem. It is therefore necessary to be aware of which malodorants offer significant trigeminal activation; some examples from Ref. 59 are Sweet: bromoform, chloroform, ethylchloride, iodoform, nitrobenzene Sour: acetic, butyric, propionic, and valerianic acids Painful/prickly: acetone, acetic acid, ammonia, formic acid, thiophene, bromine Fortunately, some odorants available to the perfumer also have a significant degree of trigeminal activity: Cool sensations: camphor, eucalyptol, menthol, peppermint, and safrole In addition to the above, other common perfume ingredients are also known to be good trigeminal stimulants and examples are isoamyl, butyl, ethyl, and fenchyl acetate esters , fenchol, menthone, and pulegone. Fina lly, one should not fall into the trap of

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thinking that all malodors are trigeminal in character; skatole and indole, for example, are primarily olfactory nerve stimulants. Trigeminal stimulants such as hypochlorite bleach liquors, ammonia, or vinegar in a cleaner or excessive butyric acid evolved by lipase action are virtually impossible to mask using classic perfumes. In Sec. II.B, reference was made to the in situ formation of chloroform in a hypochlorite bleach liquor. The sweet sensation of this trigeminal stimulant alongside the choking-prickly sensation of the bleach is perhaps one rationalization for this old technique. In general terms, putting a perfume into a rather strong trigeminal stimulant leaves one with the impression of an odor alongside a sensation. A good example of this is the use of perfume in the so-called "apple-vinegar" cleaners in Germany. The best one can hope for is to render an (un)pleasant sensation somewhat more bearable or create a situation in which the perfume lingers longer in the air than the trigeminal stimulation . The psychology of powerful cleaners not smelling particularly pleasant at the time of use but leaving reassuringly pleasant aftereffects is clearly operative in such cases . Perfumes have a long anecdotal history of removing the perception of malodors. Exactly how they achieve this is still not fully understood, although our knowledge is increasing rapidly and a chapter on the "Perception of Odor Mixtures" by Laing in Ref. 59 is a good review in this area. From the point of view of the perfumer, recourse to the triangular model introduced in Sec. III (Fig . 1) provides one qualitative mean of visualizing malodor masking. The middle and back note components of a fragrance potentially comprise many odor chemicals which individually can have quite malodorous smells. A popular example in this respect is the chemical civetone which is key in giving classic fragrances such as "Chanel No.5" important aspects of their performance and character. Civetone itself has an intense fecal note when smelled alone. This sort of fact had led to one way of visualizing malodor masking by perfumes, as is illustrated in Figure 3. In short, a perfumer confronted with a malodor(s) attempts to construct a fragrance with something of a "hole" in it into which the elements of the smell being masked somehow fit. This method of attempting to visualize the masking technique is clearly highly qualitative, but it does help to emphasize that a masking fragrance blends with but does not necessarily chemically destroy malodorants. Moreover, implicit in the concept is that the "hole" is invariably complex and that an appropriate concentration of perfume is required to function. Published literature on masking malodors by perfumes (as opposed to academic studies) falls into two classes. The Lever group of companies have a long series of patents and applications which describe techniques used to construct fragrances which fall into the general "perfume with a hole category. " Recent applications [60,61] describe how fragrance materials, including some having inherently low odor intensities, such as diethyl phthalate (DEP) solvent, can be combined to have a deodorant effect in use. Fragrance materials are divided into six classes in a defined manner (viz. phenolic substances, aldehydes and ketones, esters, alcohols and ethers, nitrogen-containing substances, and essential oils). The deodorant fragrance has to contain at least five different components from preferably three predefined groups and components from at least four of the six classes. The candidates also have defined malodor-reducing values against isovaleric acid solutions. Although the thrust of the claims is to cover sweat-generated body malodors (underarm patch assessment) in the widest range of products, earlier publications [62] have claimed that control of many other malodors can also be achieved against models such as those proposed by the U.S. Federal Supply Services and given in Sec. IV.B. This latter feature illustrates the fact that malodor coverage is not necessarily totally specific for one malodor. Whereas "universal malodor" coverage is rather ambitious, the skilled perfumer

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+
MALODOR

PERFUME

TOTAL PERCEPTION
Figure 3

Malodor masking by blending.

can indeed create fragrances using proprietary techniques such as those described by the Lever companies to encompass a wide range of malodors. Having said this, it will be appreciated that some variations in malodor type can often be tolerated and this caters for variations within a malodor type mentioned in Sec. IV.A. The second group of published data concerns various malodor-neutralizing chemicals . By implication, such chemicals can be used by the perfumer as magic bullets to confer some sort of deodorizing property to his fragrance. These chemicals have the advantage that they come complete with documentation as to their claimed efficiency, but this should always be reconfirmed in the actual fragrance which is being used. An excellent earlier review of this area which is still relevant today was prepared by Johnsen [63], who discusses many chemicals and their deodorizing mechanisms. Many perfume companies have access to a proprietary deodorizing cocktail which undoubtedly has some malodorneutralizing capacity when used appropriately. However, suffice it to say that such chemicals should really be evaluated once formulated into fragrances in a commercially relevant manner. Because their neutralizing power is dependent on a molecular contact with the malodor, this may not always be effective in every formulation and very often it limits the perfumer in formulating a fragrance which can also potentially react with the neutral izer. Whatever technique is used to create the fragrance, the advantage of having a composition which blends with a malodor is that this process takes place in the nose . The implication of this is that the source of the malodor and the location of the perfume need not coincide. The operational advantage of this in domestic and laundry products in situations where a malodor unavoidably develops or is present is a clear bonus.

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V.

PERFUME, MOODS, AND SYNESTHESIA

Although the importance of having a technically stable perfume along with an aesthetically pleasing odor is obvious, other features of perfume choice such as associations of smell with product color and emotional feelings (i.e., product positioning) have not yet been mentioned. The phenomenon of stimulation of one of the senses to influence the others is known as synesthesia and this can be very important in the selection of fragrances. Many of the comments made in the following account would have been limited to personal cosmetic fragrances up until a few years ago but are applied increasingly to the full range of consumer products. Jellinek has recently published a comprehensive review of work dealing with the influence of perfumes on moods and emotion [64]. Although this area has only relatively recently been the focus of intense interest in the perfume industry, aromatherapists will be quick to point out that the ability of essential oils to modify mood states has been known for hundreds of years [65]. In the context of consumer products, aromatherapytype claims are the ones invariably encountered in the marketplace. The 5000 years of accumulated largely anecdotal evidence on the way in which the 30 or so aromatherapy (eessential) oils influence mood states is sufficient to satisfy advertising authorities when a manufacturer makes a soft marketing claim for a product. For example, references to a sensual foam bath formulation along with references to jasmine and sandalwood or claims for refreshing or relaxing feelings are taken as being relatively harmless marketing and not misleading. However, there is a much more serious side even to this example and a lot of research is going on to understand topics such as human pheromones [66]. The aromatherapy oils are IFRA-approved fragrance ingredients and a perfumer will generally construct a fragrance around ones having the appropriate anecdotal mood associations so that the appropriate marketing claim can be made for products. More general perspectives on fragrance as a "silent persuader" have been reviewed in a recent book by Dorland [67]. In the context of soft marketing claims, simply taking essential oils as part of a fragrance and ignoring any interactions both with other fragrance ingredients and the product base odor is scientifically suspect. Moreover, limiting the choice of fragrance ingredients to 30 or so essential oils while obviously restricting perfumer creatively may also not be feasible in some bases for technical/stability reasons . Considerations such as these render it imperative to understand how fragrances, in general, influence people's feelings and this has given rise to studies under the general umbrella terms of aromachology or aroma science [64]. Generally speaking, it seems that psychological responses to smell can be classified into eight mood states which are in general line with emotional responses following stimulation of the other senses. These moods are qualitatively summarized in Fig. 4 [68]. The mood states fall into four positive states on the right-hand side of the figure and four negative ones on the left. Those at the top of the diagram are high-arousal states, whereas those at the bottom are low-arousal states. Emotional response to an odor invariably involves modifications in several mood states and this applies both to fragrance ingredients as well as perfumes [68]. Although Fig. 4 is a clear oversimplification of matters and the mood states, in reality, overlap each other, certain general statements can be made. The most important of these is that selecting a fragrance on aesthetic grounds really only reliably correlates with a feeling of happiness or euphoria. Correlations with states of sensuality, relaxation, and stimulation are not reliably present, although it goes without saying that experienced perfumers and odor selectors will have a fair idea of the suitability of a fragrance for use in

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stress

sensuality

depression

~~IIII
apathy

III
relaxation

happiness

Figure 4

Olfactively influenced mood states.

these contexts. However, personal and cultural experiences will also influence these matters and cannot be ignored when trying to develop creative rules for widely different geographical locations. The techniques used by perfume companies to build these mood states predictively into perfumes are obviously proprietary secrets! Something of the hidden depths of these techniques can be appreciated when it is realized that unpleasant smells generally correlate with an enhancement of negative mood states at the expense of positive ones. In this context, the efficient masking of any base malodors is of relevance. Moreover, we have also seen that many important fragrance ingredients are individually rather malodorous and, therefore, individually also tend to have negative mood associations. These elements have to be incorporated into a fragrance with positive psychological associations by the perfumer; again, proprietary techniques exist to achieve this. The obvious applications of these sorts of studies is to create fragrances which are both aesthetically and psychologically appropriate for a chosen product positioning. Whereas this is almost self-evident in personal care type products such as the "relaxing" bath product referred to earlier, some household products have much more tenuous claims to an emotional positioning. A cleaner needs to leave something smelling "fresh," for example, and the actual meaning of this attribute needs to be defined in terms of mood states. Having said all this, one needs to emphasize that we are not talking about mindbending drugs but more about creating odors which are compatible with mood states; this aspect of creative perfumery is only just starting to be exploited, although its commercial potential has long been recognized [69]. One expects a lemon smell to come from something yellow and not a pronounced blackcurrent or strawberry note. Synesthesia tells us quite simply that lemons are yellow, blackcurrent is black, and strawberries are red. As soon as the odor begins to have less clear associations with well-known objects, color associations are less self-evident. Like perfumes, colors are also associated with emotions and, not surprisingly, with fragrances. In a study on color associations, Jellinek puts the matter quite succinctly as "certain colors go with a perfume, others do not" [70]. On this note, suffice it to say that it always pays

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to let the perfume supplier see the pack and product presentation package at an early stage in the creative process to ensure that the perfume does indeed "go with the product."

VI.

PERFUMES IN FORMULATIONS

It is clear that creating a winning fragrance for a detergent product is very much a mul-

tidisciplinary team effort which demands a clear technical insight, on the one hand, with the realization that the artistic element of the perfume is being purchased by the consumer, on the other. It is the object of this final section to review more specific technical features of categories of detergent products which give problems in perfumery. It will be immediately apparent that some problems such as malodors from free alcohol in alcohol ethoxylates will be common to several categories of products. To avoid tiresome repetition, such phenomena are not repeatedly referred to in the following account.

A.

Heavy-Duty Laundry Powders

Problems arising from surfactant systems are twofold. The more serious one involves base malodors which often can be traced to very low levels of (low-molecular-weight) fatty acids or alcohols. Intense fatty notes from free alcohol in ethoxylated fatty alcohols can be very troublesome. The second feature is that improvements to the fat-solubilizing power of the surfactant system will tend to result in higher levels of perfume solubilization with resulting lower cloth deposition. Base malodors are always best tackled at the source and a perfumer can readily advise which malodor he can more easily cope with when asked. Suppliers of surfactants can sometimes modify their process or product specification to accommodate matters; the narrow-cut ethoxylates and the processes of "topping and tailing" nonionic ethoxylates are examples of this. In situ neutralization of acids to form anionics such as sodium dodecylbenzene sulfonate and the consequent possibility of (localized products) extreme pH were referred to in Sec. IV.A. The presence of oxidizing agents or bleaches in powders presents an obvious limitation to the perfumer. One has to view powders as being subject to moisture during part of their life and the packaging obviously plays a role here; thus, appropriate stability testing is always advisable. Any change in the formulation which has a bearing on the bleaching power could influence the perfume stability. The limitation on fragrance raw material choice increases in the order sodium perborate, sodium percarbonate, perborate + TAED, percarbonate + TAED. In addition to this, changing the ratio of the persalt to activator needs to be monitored. Clearly, the utilization of other bleach systems demands similar precautions. Enzymes manufactured for use in modern detergent formulations often have an unpleasant odor when delivered in bulk, but covering any traces of this in fully formulated product rarely presents a problem for the experienced perfumer. However, it is theoretically possible that problems could arise from some of the carrier materials used. For example, PVP could conceivably introduce traces of pyrrolidone malodors, whereas clays such as Kaolin and bentonite can introduce heavy metals and/or selectively absorb some fragrance components. Some sulfur-containing chemicals used in production processes can be sources of malodor, although this is rare. Of all the enzymes currently used, only the lipase or fat-splitting enzymes are a regular source of problems, in that their activity is primarily on damp cloth rather than in the wash liquor itself. In cases of heavy staining, short-chain fatty acids such as butyric acid can be evolved , and because they have trigeminal activity,

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they are all but impossible to mask using perfume. Generally, one has to arrive at a compromise as to the maximum level of lipase which can be used without incurring excessive malodor. One ingenious exploitation of this damp cloth activity is revealed by Firmenich [71] whose proposal was to use fatty esters of fragrant alcohols in either detergent s or fabric softeners. The ester is decomposed by esterase activity to release the alcohol. P&G have a similar but more specific application involving geranyl succinate [72], which is used in some of their fabric softeners, but which makes no direct reference to lipase but rather to slow decomposition by hydrolysis and thereby improved fragrance substantivity. A similar idea using sulfonates of specified perfume alcohols is also claimed by P&G [73]. Builders and sequestrants generally pose no unexpected problems for the perfume in terms of chemical stabilities. However, it is possible that changes in the porosity of a builder can influence the distribution of fragrance onto a powder base such that the top notes tend to be more absorbed into the pores. This can influence out-of-the-pack performance and dictate a certain rebalancing of the fragrance. Reformulating from sodium tripolyphosphate to a zeolite builder would clearly be a common situation where this would be expected. Analogous phenomena could occur with components such as layer and disi1icates and some clays which have an absorptive capacity. A less immediately obvious feature of changes in builder component could involve the moisture content of the base . For example, switching from phosphate to zeolite builders invariably raises the hygroscopic character of a base which can clearly induce a higher" activity " of the bleach in the pack. This will, in turn, provide a more aggressive environment for "minors" such as the perfume and enzymes. In a similar vein, an inadequately powerful sequestrant system will tend to permit heavy-metal-catalyzed decomposition of the bleach, which can be responsible for unexpected instabilities in fragrance. The increasing use of polymeric additives in detergent formulations generally poses no problems. Increasingly rarely, one does detect an accumulation of "plastic-related" odors in the headspace of newly opened containers and one source can be due to traces of monomers from the polymer. One of the more notoriously difficult odors is that reminiscent of a mouse cage ; this is related to pyrrolidone in PVP. The general pH of the powder can influence the freedom of material choice of the perfumer. In-pack pH generally lies anywhere from 9 to 11 and a shift of even half a unit in this critical area can tip the balance between stability and instability. Finally, the porosity of the base and the application of perfume has been referred to in Sec. II.D.

B.

Fabric Conditioner

The prime feature of liquid rinse additives playing a role in perfumery is their pH. In general terms, actives containing ester linkages in their structures need to be formulated at quite acidic pH and this does limit a free ingredient choice. Product base malodors are often related to decomposition of the side chains by in-pack hydrolysis (too high product pH) and/or rancidity reactions when unsaturation is present. This latter reaction is particularly troublesome because it cannot be predictably reproduced and is autocatalytic. Perfumery can do little to mask it and all the standard techniques familiar to the soap producer are worth trying (viz. addition of sequestrants, antioxidants, or even borohydride treatment) . Equally troublesome and irreproducible is the bacterial attack of some bases. The " dirty" smell characteristic of this evil can be prevented by adequately preserving the product.

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Liquid rinse conditioners which contain above about 8 wt% active matter can exhibit all sorts of viscosity behavior once fragrance is added. In cases where there is a welldefined micellar structure such as in distearyl dimethyl ammonium moieties [18], the art of adding perfume is to ensure that it is distributed in an equilibrium manner within the structure by adding it as the liquid structure is formed. By implication, this means that it can be added at elevated temperatures and not necessarily as the final production step. In cases where the liquid structure is not well defined and/or the base comprises a mixture of active substances, each formulation requires an individual treatment. Pragmatically, one needs to establish if particular classes of compound are going to have extreme effects on viscosity. Finally, a commonsense rule but one which is very valid is simply, "If an additive/perfume gives a physico-chemical problem, use as small a quantity of it as possible." Admittedly, this might be easier said than done, but it does illustrate one of the advantages of concentrating a fragrance. Solid rinse additives are invariably encountered in the form of tumble drier sheets. The major problem here is one of avoiding premature fragrance loss and this is maybe one instance where some form of heat-triggered fragrance encapsulation is warranted; this has been extensively patented by Procter and Gamble (Sec. 11.0). Solid or powder rinse conditioners, although they are frequently a topic for the patent literature, have never been a real commercial success because of rather poor cold-water dispersability characteristics. Perfume problems would probably be primarily associated with fatty base odor coverage.

C.

Light-Duty Laundry Liquids and Powders/Booster Products

Most of the features in the preceding two sections come back in the other areas of laundry care. Light-duty laundry products tend to have milder pH's than heavy duties and are invariably free of an oxidizing bleach and permit a higher degree of perfumer flexibility. Laundry liquids, in general, have a fatty acid or soap component and this can be a source of inherent base malodor. Booster products often involve a bleach component and this provides obvious limitations.

D.

Hard-Surface Cleaners

The presence of trigeminal stimulants such as acetic acid (vinegar) and ammonia is a feature of some products, but this is not a problem because the odor is very much a perceived signal of "activity." Other product (mal)odors which are peculiar to cleaners but are not perceived positively can often be traced back to the various solvents. In this context, glycol ethers can be troublesome, although they are generally excellent solvents for fragrances in formulations [74]. Although alternative chemicals without the odor have been proposed [75], toxicological considerations are producing a move to using propylene glycol ether analogs. Whereas these latter do not present technical difficulties as such [76], their solubilizing power for perfumes is significantly inferior to that of traditional glycol ethers and this is sometimes a problem in formulations such as window cleaners, which often contain insufficient solubilizing surfactants. Many of the lemon- and pine-type fragrances used in cleaners depend on terpene chemicals. These chemicals have characteristic odors and are generally good grease-cutting solvents. However, they are highly water insoluble. In the early eighties, Procter and Gamble started to issue a series of patents [77] which basically claim cleaners which are clear and comprise 1-20 wt% surfactant, 0.5-10 wt% mono- or sesquiterpenes, and

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0.2-to wt% of a polar solvent (benzyl alcohol or glycol ether). Whereas a discussion of cleaner technology is outside the scope of this review, suffice it to say that the perfumer needs to be aware that he could quite easily cause a formulation to infringe these patents by using a very terpene-rich fragrance. Products of the P&G technology are invariably microemulsions and Colgate has recently claimed that the grease-cutting power of cleaners, in general, is significantly higher than would be expected when the perfume oil is present as the oil phase of a microemulsion [78]. Finally, the formulator and perfumer both need to be aware of the fact that when a fragrance is being used in a cleaner, its oil-like character can contribute to streaking in some formulations. This may need checking in some compositions; generally, the problem is related to the water insolubility of the perfume.

E.

Manual Dishwash Liquids

Generally, perfuming these products is fairly straightforward. The major barrier in terms of base-related malodors can often be traced to low levels of free-acid impurities. Besides experimenting with fragrance, it is sometimes feasible to raise the pH of the formulation slightly and observe a significant alleviation of the problem. Having said this, citrus-like or terpene-rich fragrances are very commonly used and the phenomenon of autooxidation and the possible resulting paneling of bottles needs to be adequately protected against [15]. A more unexpected phenomenon can occur when concentrated formulations are prepared. Highly water-insoluble perfume moieties such as the terpenes tend to diffuse into the oil phase of the surfactant micelles. The more significant this becomes, the more one can be confronted with a phenomenon that the smell of perfume from the product becomes less intense in spite of a proportionately higher perfume dose . If this is accompanied by an explosive release of the perfume in water when using the product, micelle diffusion is indeed a likely cause. Short of changing either the perfume or the surfactants, there is no viable remedy for this. In Sec. IV, product base odors and their control were discussed at some length and the difficulty of masking trigeminal malodorants using conventional perfumes was explained. Lamberti [79] provides an ingenious method for masking the odor of ammonia derived from urea hydrotrope hydrolysis in manual dishwash liquids. His solution is to include esters such as methyl or ethyl lactates which hydrolyze at comparable rates to that of the urea to liberate lactic acid, which subsequently forms ammonium salts. An alternative mechanism of ammonolysis involves direct interaction between the ammonia and the esters. The removal of acidic or basic malodors by reacting them with either bases or acids is sometimes useful as a quick diagnostic tool. In the case of a dishwash liquid, for example, if a malodor is diminished by raising the pH and then returns or is intensified by lowering the pH, there is a high chance that acids are responsible for the malodor. This sort of knowledge plus insights into formulation and ingredients can sometimes help in transforming a problem into one of manageable proportions. Finally, one still comes across fragrance discoloration on storage. The culprit here is invariably a Schiff's base (see Sec. II.B) formed between a perfume aldehyde and a trace of the -NH 2 group coming from alkanolamide foam booster or even urea hydrotope. More subtle is the discoloration of water-white dishwash liquids, where care has to be given to formulating fragrances with minimal or no inherent color.

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F.

Hypochlorite-Containing Products

These products range from sodium hypochlorite bleach liquors themselves to substances such as the chlorinated isocyanurates which generate hypochlorite in contact with water and are used in machine dishwash powders. As we have seen earlier, these products are among the most restricting to the perfumer because of the combination of an extremely high pH and the oxidizing power of the hypochlorite ion. There is, in practice, a little more creative freedom with the dishwash powders just referred to and multisurface cleaners containing a maximum of 1% available chlorine. However, this clearly needs to be determined from base to base . There is one class of dry bleach which should never be fragranced and that is calcium hypochlorite, which can ignite in the heat of exothermic oxidation of fragrance addition. Hypochlorite bleach liquors fall into two classes; the thickened cleaner-sanitizers and preparations with minimal additives for laundry usage. Starting with the latter formulations, one needs to remembe r that even when technically stable perfume chemicals are used [80], they will need solubilizing. Whenever an organic chemical is added to a hypochlorite bleach liquor, the rate of the inherent breakdown of sodium hypochlorite to oxygen and sodium chloride (the " gassing reaction ") is increased . This can be limited by ensuring that the solubilizer requirement of the fragrance is minimized. Moreover, any addition to a bleach liquor effectively consumes alkaline buffer and it is expedient to ensure that free alkali equivalent to about 1 wt % sodium hydroxide is present once the perfuming process is complete. In spite of all precautions, additions to the bleach liquor will accelerate its loss of available chlorine and an agreement needs to be reached between the perfumer and bleach manufacturer as to what can be tolerated. Generally speaking, one must be prepared for an increase of between 5% and 10% in the rate of loss of available chlorine on going from unfragranced to fragranced bleach liquor. Some ideas about stability tolerances can be obtained from the patent literature [81]. The thickened hypochlorite bleaches share all the characteristics detailed above, but the solubilizing power of the detergent thickeners invariably renders the solubility of fragrance as only a relatively minor problem. However, as we have seen in Sec. II.C, fragrance can enhance the viscosity of some thickening systems. A general caution applicable to both the manufacture and bottling of bleach which contains solubilized fragrance is that one must be prepared for more failures arising from stress-cracking. Although this seems most serious for PVC piping, it is not limited to this plastic, and the only totally certain cure in a plant is to use titanium piping. The problem seems related to the presence of the detergent (solubilizer/thickener), which enhances the wetting of the plastic by the bleach liquor. This same phenomenon presumably facilitates any penetration of the plastic by fragrance and this is most likely in the case of PVc. Fortunately, the problems with packaging are relatively rare but have attracted the attention of major bleach producers [82]. G. Soap and Syndet Bars

The largest categories by far are for personal cleansing and for laundry usage. The traditional fatty acid based soap bars have a pH of around 9-9.5 and contain between 1.0 and 1.5 wt% perfume. Once unwrapped in a bathroom, they can function almost as air fresheners in some cases. The traditional " pan process" for soap preparation presents the very real possibility that sometimes quite considerable quantities of heavy metals, principally iron, are introduced into the soap and these can present the perfumer with a variety of

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color reactions we related in Sec. II.B [16]. Besides metal contents, the quality of tallow, palm , or coconut oils clearly influences the base odor of the soap-poor odor and poor color invariably go hand-in-hand. The prime cause of actual base malodor is rancidity and the autocatalytic nature of this dictates that sequestrants and antioxidants are actually present in the feedstock used by the soap manufacturer if this is not used totally fresh [83]. The results of rancidity are readily apparent and the trigeminal stimulation of the fatty acids renders malodors all but impossible to mask completely. In recent years, the use of soaps prepared from distilled fatty acids (DFA soaps) has improved base quality, although the pH problem remains for the perfumer. Laundry bars introduce the use of fillers and builders which are not present in bars used for personal cleansing. On the one hand, these can introduce heavy metals; on the other, they can " absorb" certain fragrance top notes as we discussed in Sec. IV.A and the extent to which they do this and the degree of perfume rebalancing which is needed is dictated by testing. Syndet bars for personal cleansing are predominantly of approximately neutral pH and present no special problems to the perfumer as a rule.

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