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Chemistry of Soaps and Detergents: Various Types of Commercial Products and Their Ingredients
MARCEL FRIEDMAN, RONNI WOLF, MD PhD

Soapmaking from the Romans to the 20th Century


Soap is probably the oldest skin cleanser. For thousands of years, this product has been obtained from the saponification of oils and fats by alkali. As is true for most human discoveries, the first chemical saponification was found by chance. According to a Roman legend, soap was discovered accidentally near Mount Sapo, an ancient location for animal sacrifices not far from Rome. The animal fat, mixed with wood ashes (the ancient source of alkali) and rainwater, created an extraordinary soap mixture. Roman housewives noticed that the strange yellow mixture of the Tibers waters made their clothes cleaner and brighter than ordinary water. Soapmaking became an art in the time of the Phoenicians and saw significant advancement in the Mediterranean countries, where olive oil of a local origin was boiled with the alkali ashes. The famous Marseilles soap probably had its roots 1000 years ago in local soapmaking facilities. The real breakthrough in industrial soap production was made by a French chemist and doctor, Nicolas Leblanc, who invented the process of obtaining soda from common salt (L.eblanc process, 1780): 2NaCl+ H,SO, + Na,SO, + 2HCl Na,SO, + 2C --f Na,S + 2C0, Na,S + CaCO, + Na,CO, + CaS In this process, table salt was mixed with sulfuric acid, producing sodium sulfate, which was further heated at about 950C with coal and limestone to get a mixture from which the carbonate was extracted with water. Leblancs process increased the availability of alkali at reasonable cost, transforming soapmaking from a cottage industry into a commercial industrial manuFrom Neca Chemicals, Ltd., Petach Tikva, Israel, and the Sacklzr Faculty of Medicine, Tel Aviv University, Tel Aviv, Israel. Address correspondence to Dr. Marcel Friedman, Neca Chemicals, Ltd., P.O. Box 333, Petach Tikva, Israel.

facture. Soap, which had been a luxury item affordable only to royalty and the rich, became the main product for everyday personal hygiene. Nowadays, soap remains the essential base for cleansing solid bars. Even during the tough economic times of the 199Os, annual bar soap sales in the United States amounted to $1.5 billion. The total annual toilet soap market in Western Europe is more than 340,000 tons, giving an average of 0.82-kg consumption per person per year.

The Chemistry of Natural Soaps


It is surprising that in spite of technical achievements and scientific developments, classic soap is still based on the same chemistry as that of ancient soaps. Soap is chemically defined as the alkali salt of fatty acids. In general parlance, the term soap has taken on a more functional definition, by which any cleansing agent, regardless of its chemistry, is considered a soap. This sometimes misleading definition will be further considered as we deal with the chemistry of the synthetic detergents and the soapless soap revolution. Soap is manufactured by the saponification process, by which triglycerides (fats and oils) or fatty acids are transformed into the corresponding alkali salt mixtures of fatty acids. Today we can differentiate among three methods.
1. Direct neutral fut saponification, in which oils and fats

(sometimes after purification with various agents, such as active earth) are directly~saponified with alkali in a boiled or semiboiled kettle process. CH,OOCR CHOOCR CH,OOCR Triglyceride + 3NaOH + 3RCOONa Soap + CH,OH CHOH CH,OH Glycerol

The resulting mixture of soap and glycerin is treated with salt to precipitate the soap, which is then separated from the glycerin solution, washed, and dried. 2. Fatty acid suponificution, in which the fatty acid distillates (obtained from triglycerides by hydrolytic splitting) are neutralized. RCOOH + NaOH -+ RCOONa + H,O
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The soap bases obtained by the above two processes have a fatty acid content of 63 to 75%. They are then continuously dried to a final mass of 78 to 80% fatty acid content. These processes account for more than 95% of world soap production. In Japan, however, a third manufacturing process is used: 3. Fatty acid methy ester saponificatiorl. RCOOCH3 methyl ester + NaOH -+ 3RCOONa soap + CH30H methanol

Tddc 1. Toilet Soup lngredierits Ingredients


Cleansing surfactants
Soap

The methyl esters are obtained by catalytic transesterification of triglycerides with methanol or direct catalytic esterification of fatty acids with methanol. The end product of this process has a higher fatty acid content, at the expense of a more costly process. For economic as well as for toxicologic and ecologic reasons, the process must be carried out in sealed equipment with recycling of methanol.

Moisturizers Superfattening agent Bar-hardening agent Fillers Antioxidnnts (preservatives) Chelating agents Whitening agents Deodorants Fragrance Dyes and pigments Water ~ _-.- --._-----___

Synthetic detergent Glycerin, lanolin Fatty acid


Salt PJaCl)

Starch BHT (butyiated hydroxytoluene) EDTA Titanium dioxide (TiO,) Triclosan, trichlorocarban

Formulation

of Natural

Soaps

The formulation of soap bars involves a skillful combination of scientific thought and artistic creativity in the selection of appropriate ingredients of the formula. The typical components of a soap bar needed to achieve the expected performance are shown in Table 1. The challenge to a soap formuIator goes far beyond the production of an effective cleansing agent. To fulfill consumers expectations and needs, a broad range of qualities are demanded of a soap. In addition to cleansing properties, color, and odor, which are always thought of as the main attributes of soap, other qualities have to be taken into consideration: 1. Lathering (foam performance&--amount, quality, density, and stability. 2. Skin compatibility. 3. Soap bar texture. 4. Soap bar mushing (to overcome the tendency of the soap to form a gelatinous material on its surfacesoap mush, in contact with water). r Soap bar erosion rate (bar wear rate). 6: Chemical stability (odor, color, rancidity, and effluorescence) . 7. Physical stability (cracking). 8. Rinsability (from skin and bathtub). The desired benefits of the finished soap product are governed by a professional selection of appropriate surfactant cleansing raw materials (in this case soap) and of manufacturing process and by the marriage between the two. The type of the alkali used determines the hardness and solubility of the finished product. Sodium soaps are known as hard, being the workhorses of normal bars, cakes, and powders. Potassium soaps have a greater

solubility in water and are used in liquid and soft soaps. Triethanolamine soaps are known for their lower pM (because of the less alkaline nature of the cation), which allows the formulation of a milder transparent soap with a lower pH. The nature of triglycerides and fatty acids plays A key role not only in the performance and features of the end product but also in its cost. The commercial triglycerides used for soap manufacture are of animal origin (fats of tallow, lard, etc) and of plant or vegetable sourcle (oils of coconut, palm kernel, olive, etc). Most toilet soap bars are made of a mixture of feedstocks derived~ from tallow fat (75 to 85%) and coconut oil (15 to 25%?. The modern back to nature consumer trend created rt demand for vegetable soaps, mostly based on mixtures of palm oil (75 to 85%) and coconut oil (35 to 25%:), The toilet soaps contain about 80% of that mixture and about 12 to 14% water. For geographic considerations, local feedstocks, mostly vegetable-such as olive oil, rice bran oil, and sunflower seed oil-are successfullv used. The final performance is determined by length ot the hydrophobic fatty chain moiety, saturation extent of the fatty acid chain (number of double bonds), and fatty acid distribution and composition of the triglycerides. The most commonly used tallow fat is predominantly composed of 40 to 50% Cl8 fatty acids and 25 to 30% Cl6 fatty acids, about 5% of which are unsaturated. In many countries, soaps in solid form are strictly defined according to their purpose, toilet and laundry bars being the majority. Toilet soaps contain more than 80% fatty acids and about 12 to 14% water. Clearly, the formulation of soap is still a challenge. Todays formulators are still waiting for some exciting development to happen, even by chance, as in the wellknown story of Ivory soap. In 1878, after four years ct development, the Gamble brothers finalized the formula for a white soap. During the mixing of a large batch of this soap, the soapmaker went to lunch, leaving the mixer running. When he returned, he noticed that

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air had been incorporated into the mass of the molten soap. As he thought that his error would not be noticed, he did not discard the batch but proceeded to mold, cut, package, and ship the soap. A few weeks later, letters from pleased customers began to arrive at Procter & Gamble, asking for more of the soap that floated on water.

Cleansing Soapless Bars-A

Breakthrough

The alkali pH of natural soap is produced by the hydrolysis of soap in aqueous solution, by which a quantity of alkali is released, raising the pH of the water to about 10 or 11. The pH is further increased by residual amounts of alkali retained in the soap during manufacture. The high pH of natural soap is probably the main cause of the well-known negative soap effect. Another major disadvantage of natural soap is its behavior in hard water or saltwater. Historically, this was the major reason for the first replacement of alkali soap by the new generation of alkali-free neutral soapless soaps. During the Second World War, sailors who spent months at sea under severe freshwater restrictions had to use seawater for washing. Under these conditions, they realized, normal soap did not foam. This was actually the main motivating factor in the search for a new type of foaming cleansing agent. The answer was provided by the synthetic detergents (syndets) that became commercially available in the late 1940s and early 1950s. The difference in the behavior of the syndets in hard water or saltwater is correlated to the solubility of the soap. Natural soap forms insoluble and inactive salts in the presence of magnesium and calcium, contained in hard water: 2 RCOONa + Mg + (RCOO),Mg + 2Na 2 RCOONa + Ca++ -+ (RCOO),Ca + 2Na When water is very hard or contains a high level of electrolytes (as in seawater), the foaming performance of soap is seriously inhibited, if not eliminated. In addition, the insoluble salts precipitate on the surfaces of sinks and bathtubs as a gray fatty mass, unsightly and difficult to remove. Unfortunately, the same happens in the cleansing of the skin, on which calcium and magnesium salts precipitate. The dermatologic drawback of this is obvious. The synthetic surface-active agents (surfactants) do not have these important disadvantages, and it is for this essential reason that they have been used in the manufacture of dermatologically recommended syndet bars.

of any two-phase system, such as gas-liquid, liquidliquid, or liquid-solid. To achieve this, the surfactants must dissolve in each of the two phases. This is accomplished by the presence of two distinct groups in their molecular structure. In a water-oil system, one group will be easily soluble in water (hydrophilic); the other will be insoluble in water (hydrophobic) but soluble in oil (lipophilic) (Fig. 1). The balance between hydrophobic and hydrophilic features governs the application of the surfactant as a detergent, wetter, or emulsifier. A known scale, characterizing the surfactant according to its hydrophilic-lipophilic balance (HLB), was presented by Griffin. According to this system, highly hydrophobic surfactants have low HLB values, starting at 1, whereas highly hydrophilic molecules are given high HLB values, up to 40. Detergents, for instance, have values in the range of 13 to 15, compared to only 4 to 6 for water in oil emulsifiers. There are four main types of surfactants, classified by the nature of their hydrophilic head: anionic, cationic, amphoteric, and nonionic. The first three are charged molecules. Anionic surfactants possess a negative charge that has to be neutralized with an alkaline or basic material before the full detergency is developed. Cationic surfactants are positively charged and therefore have to be neutralized by a strong acid before they can develop surface properties. Amphoterics include both acidic (negative) and basic (positive) groups in their molecules and are positively or negatively charged, according to the pH of the solution. The nonionic surfactants contain no ionic constituents, having no electric charge (Fig. 1). Soap is the simplest anionic surfactant. Since the saponification reaction is a simple hydrolysis of natural materials, soap is often considered a natural surfacFigure 2.
Lipophilic My chain Hydrophilic /-----\/m-l//-\. ( -. _ j end

Anionic surfactant

\-e-v.>
Cationic surfactant

mu -

Chemistry of Synthetic Surfactants


A surface-active agent is defined as a chemical substance that, even at low concentration, absorbs at the surface, reducing the free surface energy at the interface

-z;

:/^---(I 3Amphoteric sutfactant

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FRIEDMAN

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tant. All other surfactants, obtained by many simple or highly sophisticated reactions, are considered synthetic surfactants. Like soap, most surfactants used in personal cleansing bars are anionic. A list of the anionic surfactants (including soap) that are used as active ingredients in cleansing bars is given in Table 2. Examples of some other surfactants used in personal cleansers, for different synergistic roles other than cleansing (such as plasticizing, moisturizing, binding, and filling) and for improving the overall performance of the finished bar, are presented in Table 3. The cationic surfactants have only minor use in personal cleansers, primarily because of their incompatibility with anionic surfactants, as the anion and cation precipitate each other.

Table 3. hurediewts lngredienf7

of Soav

---

Surfactants Plasticizer and binders Lather enhancers Fillers and binders Water Fragranct Opacifying agents

Mass-Market

Syndets of Combars

Soapless cleansing bars have come a long way since they were first developed more than 40 years ago. It was then that a West German doctor formulated a mild cleansing bar for his patients who, because of sensitive skin, were unable to use ordinary, natural soap. The bar of those times, however, was made from surfactants similar to those popular and still widely used in shampoos. In fact, some soapless soap manufacturers defined their bars as solid shampoo, promoting a successful marketing approach. A similar approach was adopted by the Israeli market, the only one in which the syndet cleansing bar covers more than 50% of the total soap bar market. This market share is greater than in any other market, although the European and American markets of syndet bars have been growing immensely during the past three years. According to 1991
Table 2. Aniorlic Cleansina Bars
Surfactads Used 61s Actioe Ingredients

~1

SurfacfantName
Sodium carboxylate (soap) Sodium alkyl sulfate Disodium alkyl sulfosuccinate Disodium amido sulfosuccinate Sodium acyl taurate Sodium acyl isethionate Sodium alkyl sulfoacetate Sodium alkyl sarcosinate Disodium acyl glutamate Sodium monoglyceride sulfate n-Sulfo fatty acid esters Sodium dodecyl benzene sulfonate Sodium alkyl ether sulfate ol-Olefin sulfonate RCOONa ROSO,Na

Chemical Formula

ROCOCH6O,NaKH,COONa RNHCOCHKXI,NaKH,COONa RCON(CH,)CH,CH,SO,Na RCOOCH,CH,SO,Na ROCOCH,SO,Na RCON(CH,)CH2COONa RCONHCH(COONa)CH,CH,COONa RCOOCH,CHOHCH,OSO,Na RCHfSO,NaKOOCH., RC,HsSO,Na ROfCH,CH,O),SO,Na RCHRCH-CHCHCH,SO&a

reports, Germany appeared to be the major European soaplesscleansing bar manufacturer, with consumption of about 30 million bars per year. Although this accounts for only 5 to 6% of the total volume of the German soap market, it may account for up to 20% of the total value market, since syndet bars are substantially higher priced. The high price of the syndet bars is due not only to the more expensive formulation than that of the natural soaps but also to the marketing positioning and strategy. Most of the successful brand names in Germany are positioned on a dermatologic platform as premiumpriced, upscale products, focusing on their benefits to the skin. These premium-priced products are sold primarily through pharmacies and drugstores, whose high margins results in a final consumer price of $2 to $3.0~per 100-gm bar. In France, where the soapless soaps are categorized as pair1 dermatologique, leading brands account for about 2% of the total soap market and are priced similarly to their German counterparts. Thirty years ago, Neca, an Israeli manufacturer, took an entirely different approach. Neca was the first to recognize the mass-market potential of a bar with the benefits of a synthetic soap but sold at a popular price. In 1964 the company introduced Neca 7, a soapless cleansing bar with a dermatologic value similar to the European synthetics but priced at 50 to 70 cents per 100-gm bar and marketed as an all-purpose cleansing bar through all distribution channels. Neca 7 quickly became the leading brand in Israel and now commands 35% of the total soap market, with consumption of 2 million bars per month by a population of 5 million. Neca 7 can probably be considered the worlds bestselling soap per capita. The same marketing approach has been successfully applied in the United States by Lever Brothers, which followed the same strategy of mass-market distribution, pricing, and promotion for its soaplessand combination cleansing bars, especially Dove and, more recently, I,+ ver 2000. In 1955, Dove was introduced as different from other toilet bars because it looks like a soap, it3 used like a soap, but it is not a soap. Later, Lever began emphasizing that Dove contains one quarter moisturizing cream and wont dry your skin like soap,

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which remain the slogans of the present advertising campaign. In 1993, Dove was the best seller, accounting for 16.4% of the U.S. bar soap market. The success of soapless and combo bars in United States was so dramatic and sustained that in 1991 Lever Brothers was able to oust Procter & Gamble from the leadership position in the toilet soap market. A comparison between the two giants shows a market share increase from 24.1% in 1983 to 31.5% in 1991 for Lever Brothers (based on dollar volume), as compared to a decrease from 37.1% to 30.5% at the same time for Procter & Gamble. The Wall Street Journal dramatically reported buoyant sales of Lever 2000 soap bring sinking sensation to Procter & Gamble. Two years later, in 1993, Procter and Gamble gave a prompt answer in this soap war, regaining the leadership with the success of its Whitewater Zest and, especially, Oil of Olay cleansing bath bars. The marketing strategy of the Oil of Olay bar-a beauty bar at a competitive price-helped Procter and Gamble to take over the top position by May 1993 with a 32.5% share, compared to 31.5% for Lever Brother. The key to Procter and Gamble success was mostly due to over 10 years of research and development, which enabled the creation of a unique formula, which contains a specially engineered synthetic cleansing system. This emphasizes again the importance of a properly chosen formulation for a targeted cost-effective product.

Surfactan ts
The choice of surfactants and their proportions not only determines the cleaning and lathering characteristics but also influences mushing, plasticity, and, of course, skin compatibility. European and Israeli formulations are based mostly on a blend of alkyl sulfates and alkyl sulfosuccinates, reaching about 40 to 50% surfactant content. The pH of the bar is normally adjusted between 5.5 and 7.0. It has been found that the potassium salts give much better mushing and plasticity properties than the sodium salts, and there is an optimum K:Na ratio for minimum mushing. The U.S. mass-marketed brands are based on other surfactants. The leader, Dove, is based on fatty acid isethionates, specifically sodium cocoyl isethionate. As this is an expensive ingredient, the formulation includes about 30% of fatty acid (specifically stearic acid and a minor proportion of coconut acid) and fatty acid soap, mostly neutralized to a final pH of 7 to 7.5. The product contains some dodecyl benzene sulfonate (1 to 2%) as a lather enhancer. This overall surfactant blend reduces the final cost of the formulation but, because of the price of cocoyl isethionate, still keeps it expensive. Compared to European bars, Dove has a rather soft and dull appearance and might seem somewhat slimy to the European consumer. Oil of Olay is also cocoyl isethionate based, but in a more sophisticated, well-performing formulation. Since the mildness concept has been strongly advertised by Lever Brothers as an intrinsic property of isethionate bars, a serious change has taken place in the formulation of bars in Western Europe in the past few years. Products have been reformulated, and more expensive isethionate bars, claiming even milder properties, have been introduced. The drawback of the cocoyl isethionate bar, easily consumer perceived, lies in its strong, characteristic odor. This odor, recalling the coconut source of the fatty acid, needs a higher dosage of fragrance to be covered, which creates a problem in the fragrance-free hypoallergenic formulations. The other major surfactants used in U.S. formulations are sodium cocomonoglyceride sulfate (in Colgates Vel) and sodium cocoglyceryl ether sulfonate (in Procter & Gambles Zest combo bar). In Japan, acyl glutamate, made by Ajinomoto, is the basic surfactant of Minon, a very expensive soapless cleansing bar, sold at about $6 per 75 gm. An interesting evaluation of the cleansing effect of various bars indicates that alkyl sulfate and sulfosuccinate blends have the highest cleansing power, followed by acyl glutamate and triethanolamine soaps.

Formulation

of Soapless Cleansing Bars

The list of surfactants presented in Table 2 gives only a few of the thousands of synthetic detergents and innumerable plasticizers, binders, moisturizers, and fillers available for formulating syndets. It follows, therefore, that todays formulators are limited only by their own degree of imagination and chemical skills. Constructing the formula of a syndet or combination bar is a complex challenge, as the final qualities and requirements are numerous and sometimes contradictory. The properties required from the finished bar have been already mentioned here and will be further exposed in the following chapters of this issue. A major requirement for the formulation of syndets is workability (processibility). This is the ability of the base to be converted into bars by the use of the appropriate soap equipment. The formula ingredients should provide sufficient plasticity necessary for extrusion (plodding) and stamping of the bar. To achieve all these requirements and properties, a good syndet bar is essentially composed of a blend that includes the ingredients listed in Table 3.

Natural sodium soaps were ranked last in this evaluation. Most of the surfactants used, as well as plasticizers or binders, are of vegetable origin, which is a valuable marketing advantage, offering Kosher and natural formulations (Tables 2 and 4).

Lather Enhancers
The foaming properties of different surfactants and finished syndet formulations can be checked by several methods whose description is beyond the scope of this article. The most common and reliable of these is the mechanical inversion test. By this test a higher foam performance was found for alkyl sulfates and sulfosuccinates than for isethionate and natural soap. To enhance the lather performance of the primary surfactant in lather formation speed, lather stability, or cold water performance, some foam enhancers can be used. Dodecyl benzene sulfonate, sodium lauryl sulfate, alkanolamides, and even fatty acids perform this function well.

stearate, stearic acid, fatty acid ethoxylate, hydrogenated castor oil, paraffin wax, fatty alkyl ketones, and a combination of hydrogenated triglycerides with fat!v alcohols or acids. The plasticizers and binders have high melting points and high molecular weights. It seems that their binding activity is obtained when the melting point of the massis simply raised. Ingredients such as gums and gum resins provide additional cohesion by acting a> binders.

Fillers
The so-called fillers are, by definition, cheaper ingredients, used to reduce the bar cost. In the case of syndets, the fillers are not inert ingredients but participate in improving the internal structure and hardness of the finished product. The fillers can therefore be called additional binders. The best-known fillers are dextrin, starch, and modified starch (degraded, ethoxylatedb. Talcum powder has also been used as a filIer against mushing, while buffered borax is added to reduce specific gravity and lower wear. The drawbacks of the fillers are a rough surface trx ture, loss of slip, and loss of attractive overall appearance. For this reason, one should not exceed an optimal concentration of these substances.

Plasticizers

and Binders

To obtain good processibility and usage properties, the formulation is stabilized with plasticizers and binders. Plasticizers are included to facilitate better extrusion and stamping of the syndet bar. The plasticizers act by lowering the viscosity of the material at the manufacturing temperature, providing flow under pressure. Binders prevent separation of macroscopic aggregates, caused by local stress, providing cohesion and anticracking behavior of the solid product. Natural soap does not have plasticity problems, as the soap itself is a classic plasticizer, beyond its cleansing surfactant role. Plasticizers and binders strongly influence lathering, mushing, and wear characteristics. Generally, the plasticizers and binders are used together and one material can perform at least two roles. They are capable of absorbing some, or all, of the free water of the syndet, binding the various ingredients together, plasticizing the mass, and acting as emollient, all at the same time. The plasticizers most commonly used are long-chain fatty alcohols (higher than C16), polyol esters (glycerol monostearate, sorbitan stearate, and giycerol mono- and distearate), polyethylene glycol, sodium Table 4. Surfactants Used for lmaruuement of Soaa Perforuzance
Surfactant Name
Fatty acid alkanol amide Fatty acid ethoxylate Fatty alcohol Polyethylene glycol Fatty alcohol ethoxylate Glycerol monostearate Alkyl amido propyl betaine

Performance-

and Appearance-lmprooing

Additives

Chemical Formula
RCONH, RCOO(CH,CH,O),,CH,CH~OH ROH HO(CH,CH,O),H RO(CH,CH,O),H RCOOCH2CHOHCH,0H RCONHCH2CH,Nf(CH&IHzCOOH

One perceptible drawback of the syndets is their solubility and mushing in water, due to the high solubility of the surfactants. A syndet bar behaves much like paste, not like structured gel. Under certain formulations, this pastelike mush is unable to return to a solid state by losing water from the mush layer. One major solution used for alkyl sulfate syndets is to use their potassium salts, which give a low mush and an economical base. Other low-solubility improvers are inorganic salts, such as sodium sulfate and sodium chloride, together with dimmer linoleic acid. Aluminum triformate is also effective in sulfosuccinate formulations. A desirable property like slipping has been obtained by the addition of zinc stearate and ethoxylated sorbitan ester. Sodium isethionate is added in an acyl isethionate formulation to reduce the wear rate. Antibacterial additives, such as trichlorocarbanilide and triclosan, are further examples of successful additives for deodorant bars. The humectants and moisturizers are very important for skin afterfeel and for dermatologic marketing claims. A variety of such additives have been researched, including glycerin, methyl glucose ethers, lanolin derivatives, mineral oil, isopropylmyristate, glutamates, and lactates.

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Conclusions
The soap industry is an ancient one whose origins go back to the days of the Phoenicians. At the end of the 1940s and beginning of the 195Os,the industry took a giant step forward when it introduced the soapless soaps, and since then it continues to advance and to improve. The demands made on a good soap are many and varied and sometimes even contradictory. Preparation of soap formulas is extremely complicated and requires, together with knowledge of chemistry and engineering, both imagination and inspiration. In the limited amount of space available to us, we have tried to give the reader an idea of the different ingredients of soaps, their functions, and their effects. The formulation of soaps today is the result of research and development, as well as trial and error, done over many years by large research teams. It is not surprising, therefore, that in a review of the present kind it should be possible to reveal only a small fraction of the secrets of this huge industry-all the more so, since the article is intended for physicians who are not familiar with the sophisticated chemistry and equipment used in this industry. The formulation of a soap is as closely related to its marketing strategy (the consumer needs, the targeted consumer segment, the purposes for which it is intended, and the chosen distribution) as it is to the production process chosen and its intended technical characteristics. Indeed, a soaps marketing strategy and

technical requirements are closely linked, influencing each other in a circular fashion. Thus, while the marketing strategy will dictate a soaps target, price, and characteristics, these must be executed by way of a formulation that in turn affects the final products actual price and characteristics. There is thus a close and reciprocal relationship between formulation and manufacturing, on the one hand, and marketing and the commercial aspect, on the other. Soap formulation and production are totally commercial, not theoretical processes, forming the backbone of a worldwide, multibillion-dollar industry. We thus considered it necessary to deal with this aspect as well, without which no discussion of the subject could be satisfactory or thorough.

General References
1. Spitz L. Soap technology for the 1990s.Champaign, IL: American Oil ChemistsSociety, 1990. 2. Osteroth D. Production of toilet soap. Darmstadt: GIT Verlag, 1986. 3. Davidsohn AS, Milwidsky B. Synthetic detergents.7th Ed. Essex,England: Longman Scientific & Technical, 1987. 4. Hollstein M, Spitz L. Manufacture and properties of synthetic toilet soap.7 Am Oil Chem Sot 1982;59:442-8. 5. Milwidsky B. Syndet bars. HAPPI 1985;22:58-70. 6. Colwell SM. Soap wars. SoapsCosmeticsChemical Specialties 1993;69:22-8. 7. SchoenbergT. Formulating of mild skin cleansers. Soaps CosmeticsChemical Specialties1983;59:33-38.

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