Comparative value of fatty acids and resin acids of tall oil in soaps

Summary A study has been made of the detergency and foaming power of soaps made from a typical acid-refined American tall oil. Sodium soap of tall oil, straight tall oil fatty-acid soap, and straight tall oil resin-acid soap were evaluated. The effect of fatty acid-resin acid ratio was determined by using mixtures of those soaps. Sodium rosinate, sodium oleate, and mixtures of these soaps were used as comparison standards. Curves plotted show wash-test data and foaming values as functions of the ratio of fatty soap to resin soap. The data indicate in terms of detergency: a) tall oil soap has a higher value than sodium rosinate; b) sodium oleate is better than tall oil fatty-acid soap, but the latter is approximately equivalent to soaps from various unsaturated vegetable oils; c) both tall oil resin-acid soap and rosin soap have low detergency on cotton; d) the detergency of most mixtures of tall oil fatty-acid and resin-acid soaps at lower concentrations is greater than would be predicted from the individual soaps, indicating a synergistic effect. As a rough approximation, tall oil soap without unsaponifiables is equivalent to a corresponding mixture of sodium oleate and sodium rosinate. The presence of unsaponifiables lowers both detergency and foaming. Tall oil soap is somewhat less sensitive to hard water than sodium oleate. Significant differences between detergencies of soaps, and especially between soap mixtures, are obscured when launderometer tests are run at moderate soap concentrations. These differences are readily detected at lower concentrations. Presented at 113th meeting of the American Chemical Society, Chicago, Ill., April 14–23, 1948.     

肥（香）皂市场及趋势

概述了肥皂市场的发展状况及肥皂的创新与创意。随着消费者对更天然、更安全个人清洁用品的追崇，各种质地、香型、色泽、形态和包装的个人清洁用品充斥着市场，消费者面临着更多的选择。肥皂这一曾经最畅销的洗涤产品正面临巨大的冲击。肥皂行业只有对产品不断地进行升级，在配方上有所创新，在配方中添加一些有附加值的配料，保持肥（香）皂企业在清洗行业市场中的占有率，保持市场竞争力和企业活力，才能实现肥皂行业的长期可持续发展。     

The effect of some inorganic salts in dilute solution on the formation of calcium and magnesium soaps

1. The reactions in mixtures of dilute solutions of builders, pure soaps and hard water have been examined under conditions for optimum foam stability for the soap solution.
2. An attempt has been made to interpret these reactions on the basis of solubility products.
3. For dilute solutions of soaps of pure fatty acids a minimum mole ratio of builder to calcium or magnesium salts is required to prevent the formation of alkaline earth soaps. These mole ratios are different for each soap studied and vary with the particular calcium or magnesium salt and builder combinations.
4. The procedure used by previous investigators of this subject is discussed.

The authors wish to express their appreciation to C. W. Jakob for performing many of the determinations upon which this paper is based.     

国外肥皂和洗涤剂的发展沿革

综述了国外肥皂和洗涤品牌的发展历程。主要介绍了普通容皂,去臭护肤皂,等的发展和趋势。     

Trends in the soap and detergent industry in Asia/Japan

In Asia, except in a few countries where the soap and detergent industry is well developed, the production and consumption of soaps and detergents are low as compared with those in Western Europe and North America, and the ratio of detergent to soap is also low. But there are opportunities for future development and expansion of the industry. The course of future development, however, may differ from country to country depending on the national situation and the standard of living. The development of soaps and detergents in Asia should be made by closely relating their forms and formulas to the way of washing, the lifestyle, and customs in each country. As for the trend and situation in Japan, the problems confronted by soap and detergent makers are essentially the same as those faced by makers in Europe and America.     

The safety of household products

When detergents were essentially soap, it was easy to assume that they were perfectly innocuous in use. Even later, when synthetic actives and phosphate builders appeared, it wasn’t necessary to carry out extensive testing to confirm their safety. However, nowadays one has to say with certainty that a detergent product is not only safe to use but also to manufacture and release into the environ-ment. This is a big, often long and expensive, job. A battery of tests have had to be developed and every likelihood covered as far as pos-sible. The kinds of tests used will be briefly discussed and examples given of the lengths to which manufacturers go to ensure the safety of our products.     

Soap and lime soap dispersants

In recent decades, soap has largely been replaced by petrochemicals and polyphosphates as the major components of laundry detergents in the U.S. Currently, the use of soap is primarily confined to the toilet soap bar field, and technological advances here have been mainly in processing. In view of the rising costs and increasing scarcity of petrochemicals and polyphosphates, tallow, a replenishable, inexpensive agricultural by-product, was examined as an alternate raw material. Tallow soap has a long history of efficacy and safety but suffers from poor performance in hard water and insolubility in cold water. It has now been shown that the performance of soaps can be drastically improved in cold water solubility and in hard water detergency by the addition to the soap of lime soap dispersing agents (LSD A). These are anionic or amphoteric surfactants possessing one or more bulky polar groups. These soap-LSDA combinations form mixed micelles in water and essentially take on the surface active characteristics of a single anionic surfactant. Soap-LSDA combinations wash well in hard water without curd formation; they can be “built” with various materials such as phosphates and trisodium nitrilotriacetate (NTA) to enhance detergency. Soap-LSDA combinations equal the conventional detergents in every performance respect and undergo biodegradation more readily and completely.     

Detergent action of rosin soaps and fatty acid — Rosin soaps

Summary A method for evaluating the detergent action of soaps has been described and applied to a series of soap solutions. The detergent action of rosin soaps, the effect of compounds present in soap or used with soap on the detergent action of a rosin soap, and the effect of rosin soap on the detergent action of tallow soap have been tested. The effect of temperature on the detergent action of some of the detergent solutions has also been determined. The results of these detergent tests on rosin, fatty acid and fatty acid-rosin soaps indicated the following: (1) Rosin soaps made from different gum rosins, produced from longleaf and slash pine gums, have equal detergent action; (2) The presence of soaps of oxidized rosin acids has no effect on detergent action of the rosin soap; (3) The detergent action of soaps made from pyroabietic acid, abietic acid and hydrogenated rosin parallels their ability to lower the surface tension of water and the amount of hydrogen present in the rosin acids; (4) The addition of builders that increase the alkalinity of the rosin soap solution improves the detergent action of the solution; (5) The blending of rosin soap with tallow soap improves the detergent action of the tallow soap in solutions having a soap concentration of 0.25 percent or more; (6) Temperature affects the detergent action of rosin and coconut oil soaps more than tallow soap.     

皂基在洗涤剂中的应用

皂基是一种最常用的表面活性剂,常在洗涤行业中被用作洗涤剂的活性组分,同时也是一种常用的控泡剂。通过在洗涤剂中添加几种不同的皂来研究皂的加入是否对体系的使用性能产生影响。结果表明,不同皂的抑制泡沫的性能大不相同,并且在洗涤剂中加入皂能显著减少洗衣后的漂洗次数,极大地节省了水资源。     

Market evolution of the soap and detergent industry within the past five years in western europe

Members of the Association Internationale de la Savonnerie et de la De’tergence (AIS) have furnished statistical information on various products showing growth in volume in total and in each of the countries. On the whole, the situation is favorable. In general, the global growth of the market of synthetic detergents is about 6% in volume per year, but it may vary greatly from one country to another. There is some doubt, however, that this growth rate will continue at a similar pace in the future. Although soaps have continued to decline in favor of detergents, we observe a certain stability of this type of product as a whole. As for detergents, they are increasing with respect to synthetic liquid products and washing powders. Such is not the case for cleaning products and auxiliary products. It is true, however, that the greater part of the market is presently taken by fabric washing and dishwashing products. In several countries, an important market for fabric softeners is developing recently; however, we do not yet have detailed statistical data concerning this market. While the greater part of synthetic detergent consumption has to do with household uses, there are at present many other applications. Products designed for indus trial uses are not in the AIS statistics and therefore are not covered in this study. Because the soap and detergent industry sells its products to the public, it pays close attention to the demands of the consumers, and we may expect it will continue to innovate and create new products. Within the framework of the AIS, we try to study market trends by presenting each year the statistical data of the preceding financial year (available from the AIS, 49 Square Marie Louise, Brussels). A retrospective study covering five years seemed to us interesting, and we venture to hope that the conclusions provided will serve to foresee the future.     

The antiseptic properties of surface active agents

Summary Soap has always been and still is a valuable antiseptic agent. Among the new synthetic detergents products are available which can be used in neutral or acid solutions to give a much stronger antiseptic action than is possible with soap solutions. These new detergents are valuable because a really worthwhile antiseptic action is obtained from products which are not toxic. The new detergents are non-volatile so that they are stable under storage conditions, and they dissolve rapidly to start their sterilizing action. Further study of these products is worthwhile and necessary because no antiseptic is of any value unless it is properly used. This paper was presented at the Chicago meeting of the American Oil Chemists’ Society, October 25–27, 1944.     

Marketing and economics of fatty alcohols

Alcohols represent 35% of the world’s major surfactant intermediates, with natural alcohols accounting for one-third of that percentage. Present trends suggest, however, that alcohols will become increasingly important in the detergent industry (the primary market for surfactants) during the next 10 years. Moreover, natural alcohols will frequently have an economic advantage over synthetics. Factors contributing to the growth of alcohols as surfactant intermediates include: better derivative biodegradability (especially compared to alkylbenzenes), better solubility (for use in low-temperature washing and in liquid detergents), better hard-water tolerance (for use in unbuilt liquid detergents), and a reputation for better detergency on synthetic fabrics. Factors favoring the natural alcohols (as opposed to the synthetics) include: frequently favorable raw material economics (especially as supplies of lauric oils increase), and integration of major manufacturers.     

Conductance behavior of lithium soaps in aqueous methanol

Conductance behavior of lithium soaps (abietate, oleate, and myristate) has been used to evaluate the true dissociation constant, limiting molar conductance, and thermodynamic parameters (viz., enthalpy, free energy, and entropy changes) for dissociation. The soaps behave as week electrolytes in mixtures, and the Debye-Huckel-Onsagar equation is not applicable for these soap solutions.     

Historical and marketing trends of natural/synthetic fatty acids

As long as a substantial portion of raw materials for natural fatty acids are relatively inexpensive by-products of other major industries, natural fatty acids should fulfill the world's projected needs at least through 1985. Production of synthetic fatty acids may also increase; however, at the present time the cost of their raw material and processing has made them largely noncompetitive, except in a few cases. Synthetic organic acid manufacturers currently supplying short chain products will continue their efforts to enter the detergent range fatty acid market area. We expect some breakthrough in synthetics during the life of our forecast. However, potential producers have yet to develop an economically competitive synthetic fatty acid as a replacement for natural fatty acids in the U.S. Petroleum-based products include odd, even, and branched chain acids whose performance must be proven. Finally, the petroleum base for synthetic fatty acids no longer has the price stability we have been accustomed to in the past. Recent changes in price of ethylene and forecasts are evidence of this trends for the future.     

The chemistry of detergent perfumery

Detergents constitute a low-price, bulk item, which consumes a large quantity of aromatic materials. Detergent perfumes must not only meet the normal requirements of odor and stability but also strict demands in low price and high availability. The perfumes used in detergents are normally a complex mixture consisting of synthetic materials produced from either petroleum or coal tar products, isolates of natural products or synthetics derived from isolates and natural products such as the essential oils. The synthetics and isolates which are commonly used in detergent perfumery are discussed with their methods of production. The essential oils that can meet the demands of price and availability are listed.     

C-21 dicarboxylic acids in soap and detergent applications

A unique polycarboxylic acid, 5(6)-carboxy-4-hexyl-2-cyclohexene-1-octanoic acid, has been available commercially for over 15 years. A new high-purity (>97%), light-color version of the C-21 dicarboxylic acid has been developed recently. Soaps of the C-21 dicarboxylic acid can be used as hydrotropes to increase the solubility of nonionic surfactants in aqueous solutions containing builders and/or anionic surfactants. Since these soaps are anionic fatty acid derivatives, they reduce the surface tensions of formulations, thus improving detergency. The nontoxic and biodegradable nature of this dicarboxylic acid makes it an attractive formulation component. This paper outlines application evaluations of the soaps prepared from the C-21 dicarboxylic acids. These evaluations demonstrate how the soaps interact with nonionic surfactants or pine oil to provide clear formulations, how they wet cotton skeins in neutral to highly alkaline solutions, and how they inhibit gel formation when preparing high-solids fatty acid soap solutions. Furthermore, the preparation and characterization of the soaps of the C-21 dicarboxylic acid products are discussed. Mass-balance equations describe the preparation of aqueous soap solutions at any given concentration. Characterization of the resulting soap solutions includes acid number, pH, color, color stability, foam stability, surface tension as a function of concentration, and hard-water compatibility.     

Foaming properties of soap solutions

Summary This paper reports results, obtained by the “liquid drainage” method and a modified “foam time” method, on the stability of foams from solutions of soaps and detergents. The two methods gave qualitatively equivalent results. Rates of drainage of liquid from soap and detergent foams were not proportional to the volumes of liquid in the foam. The stabilities of foams from 0.1 percent solutions of soaps of most of the natural fats and oils tested were much greater than those of foams from single soaps that were sufficiently soluble to form solutions of this concentration. The foam time of a mixture of equal volumes of two 0.1 percent solutions was not equal to the average of the foam times of the separate solutions. A number of electrolytes, organic liquids, pectic materials, and vegetable gums greatly increased foam stability. Data on 0.03 percent sodium tallow and palm oil soap solutions indicated a maximum foam time at a pH of about 10.6. Increasing the concentrations of ten soaps from 0.05 to 0.1 percent more than doubled the foam time.     

Laundry products in bar form

Synthetic detergents have all but replaced soap in the developed countries. Laundry products in bar form, however, are still the major detergent in much of the world where manual washing predominates. This article reviews the types of laundry bars in existence today, their consumption, typical compositions, and the processes by which they are manufactured.