Reduction of phosphate builder in tallow-based detergent formulations

Laboratory washing tests using two different kinds of standard soiled cotton were made to compare built solutions of hydrogenated tallow alcohol sulfate (HTAS), sodium methylα-sulfotallowate (NaMeαST) and linear alkylbenzenesulfonate (LAS) in hard water of 300 ppm at 60 C. Most of the experiments were at 0.25% total concentration (0.05% active ingredient plus 0.20% builder). Phosphate reduction, without loss in detergency, can be accomplished in some cases but not in others, depending both upon the detergent and the test cloth. Both cloths have shown with HTAS as the active ingredient, that reduction in phosphate builder is possible without loss in detergency. The effect of other changes in formulation has been determined. Presented at the AOCS Meeting, Minneapolis, October 1969. Deceased. ARS, USDA.     

Tallow based detergent formulations: Mixtures of alcohol sulfates,salts ofa-sulfo acids and esters,and soap

Saturated (I, ROSO₃Na) and unsaturated (II, R’OSO₃Na) tallow alcohol sulfates, the disodium salt ofa-sulfonated saturated tallow fatty acids (III, RCH(SO₃Na)CO₂Na), the sodium salt of the methyl ester ofa-sulfonated saturated tallow fatty acids (IV, RCH(SO₃Na) CO₂CH₃), and commercial tallow soap flakes (V) were compared, singly and in combinations, as built and unbuilt solutions in soft and hard water, with respect to foam height and detergency, using four different types of standard soiled cotton. Built solutions of combinations of the two most soluble detergents, II and IV, at concentration 0.05% total active ingredient plus 0.20% builder in hard water of 300 ppm, remained perfectly clear on standing for several months. Built solutions containing I or II had the best foaming properties. The presence of soap decreased foam height. Cloths A and B showed the detergency of built solutions to be in the order I=II>IV>III>V, and all combinations containing I or II were superior detergents. With cloth C, detergents ranked in the order I=II=IV>III>V, and many combinations containing I or II with IV were synergistic. Cloth D did not distinguish sharply between detergents in built solutions in hard water. In general, detergent systems containing tallow alcohol sulfates witha-sulfo esters had the most desirable solubility, wetting, foaming, and detergent properties. Presented at the AOCS Meeting, Philadelphia, October 1966. E. Utiliz. Res. Dev. Div., ARS, USDA.     

Nonbuilt heavy duty liquids: Detergency and formulating parameters

The detergency of nonbuilt heavy duty liquids containing linear alkylate sulfonate and/or linear alcohol ethoxylate nonionic active is discussed. Single cycle detergency on a broad range of linear alkylate sulfonate-nonionic compositions was evaluated on cloths soiled in the laboratory with a mixture of synthetic sebum and dust and a commercially available soiled cloth, ACH #120A. The effects of multiple cycle wash testing also were covered. Formulating parameters to produce usable nonbuilt heavy duty liquids are discussed. The nonionic of choice for maximum detergency in nonbuilt heavy duty liquids should be derived from ca. a 14 carbon chain length alcohol with ca. 70% ethylene oxide. For optimum solubility, linear alkylate sulfonate should be the sodium salt derived from a linear alkylbenzene of ca. 235–240 mol wt, a product like that currently used in light duty liquids. The presence of linear alkylate sulfonate in nonbuilt heavy duty liquids helped reduce product clear point. Nonionics were found to give the best performance on cotton cloth. Linear alkylate sulfonates were most effective on synthetics. Multiple cycle testing with Spangler soil on nonbuilt heavy duty liquids was shown to be unnecessary. Mixed active systems gave the best overall product on the basis of performance and physical properties.     

Beef tallow in shortening preparations

Summary Experimental shortenings were prepared from various mixtures of tallow and cottonseed oil. Three series of shortenings were produced by somewhat different procedures: a) mixtures of tallow and cottonseed oil were hydrogenated and then catalytically rearranged; b) mixtures of hydrogenated tallow and cottonseed oil were rearranged; and c) mixtures of hydrogenated tallow and cottonseed oil were rearranged in the presence of 0.43% glycerine. Certain combinations and treatments of tallow and cottonseed oil produced shortenings which compared reasonably well with standard vegetable shortenings. Presented at the 29th Fall Meeting of The American Oil Chemists’ Society, Philadelphia, Pa., Oct. 10–12, 1955. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Soap-based detergent formulations I. Comparison of soap-lime soap dispersing agent formulations with phosphate built detergents

Blends of soap with small amounts of lime soap dispersing agents are efficient detergents in hard water and require little or no tripolyphosphate builder. Lime soap dispersing agents examined include sulfated ethoxylated fatty alcohols, sulfated N-(2-hydroxyethyl) fatty amides, methyl esters of α-sulfo fatty acids, 2-sulfoethyl fatty acid esters and N-methyl-N-(2-sulfoethyl) fatty amides as well as nonionics derived from tallow alcohols. Detergency evaluations were carried out with three commercial soiled cotton cloths as well as by a laboratory multi-wash technique. Formulations containing 80% soap, 10% lime soap dispersing agent and 10% builder gave optimum detergency values. Builder effectiveness was rated tripolyphosphate>silicate (1:1.6)> metasilicate = citrate = oxydiacetate = nitrilotriacetate>carbonate≫sulfate. The detergency of soap-lime soap dispersed combinations compared favorably with a standard brand household heavy duty granular detergent in 50, 150 and 300 ppm hardness water on three soiled cloths. Presented at the AOCS Meeting, Atlantic City, October 1971. East. Market. Nutr. Res. Div., ARS, USDA.     

Soap-based detergent formulations: XIII. Formulations with alpha-olefin sulfonates as lime soap dispersants

Heavy duty household type detergents were formulated from tallow soap-AOS(α-olefin sulfonate)-builder combinations. Various commercial AOS samples were evaluated. These were derived either from closely fractionated α-olefins such as C₁₄, C₁₆, and C₁₈ or from samples representing broader mol wt ranges such as C₁₄−C₁₆ and C₁₆−C₁₈. The builders incorporated into these combinations were a sodium silicate (Na₂O∶SiO₂=1∶1.6), sodium tripolyphosphate, sodium citrate, sodium carbonate, and trisodium nitrilotriacetate. Detergency evaluations of 0.2% solutions in 300 ppm hard water (as CaCO₃) were determined with three commercial soiled cloths and by a multiwash test in which clean cloth was repeatedly soiled and washed. The relative proportions of soap, AOS, and builder were varied to obtain maximum detergency, and comparisons were made to other soap-LSDA (lime soap dispersing agents)-builder combinations as well as to a commercial high phosphate detergent used as a control. Detergency performance of soap-AOS combinations ranked just below that of the commercial high phosphate detergent control and below that of soap formulations containing sodium methyl α-sulfotallowate. Presented at the AOCS meeting, Philadelphia, September 1974.     

抗再沉积剂在洗衣液中的应用研究

分别选用了聚丙烯酸钠、改性聚乙二醇、苯乙烯-丙烯酸共聚物和改性聚乙烯亚胺配入洗衣液中,考察其在洗衣液中的抗再沉积性能。通过去污实验和循环洗涤实验,测定了污布和白布在洗涤前后的光谱反射率。去污实验表明,抗再沉积剂的加入可明显提高洗衣液对皮脂污布的去污力。循环洗涤实验表明,加入抗再沉积剂均可以提高洗衣液对棉布的白度保持,而当采用2种抗再沉积剂复配使用时,抗再沉积效果较好,对棉布的白度保持比对照样品提高3%～12%。     

Studies on replacement of phosphate builders in laundry detergents using radiolabeled soils

The fabric detergency performance of systems containing different types of surfactants and several builders of reduced phosphate content has been compared using a radiolabeled sebum-clay soil. Use of this soil allows quantitative measurement of both sebum and clay removal from soiled swatches, generally cotton and permanent press Dacron-cotton. One study compared alkylbenzene sulfonate (LAS), alcohol sulfate (AS), alcohol ethoxysulfate (AEOS) and alcohol ethoxylate (AEO) as surfactants in formulations containing from 0–45% sodium tripolyphosphate (STPP). Especially under hard water conditions, the AEO and AEOS considerably out-perform the LAS and AS at equal use concentrations and are less sensitive to phosphate reduction. Tests with cotton swatches soiled with five different carbon black-oil mixtures generally rank the surfactants in the same order, although individual responses of the cloths vary considerably. A further study compares the effect of replacing STPP with sodium nitrilotriacetate (NTA) in formulations containing varying amounts of AEO or LAS. Detergency improves significantly with increasing surfactant concentration, particularly with AEO, and declines as builder strength is reduced. AEO exceeds LAS considerably in performance under the test conditions even at relatively high concentrations of LAS. Another study compares the performance of AEO and LAS at equal concentrations in formulations containing a variety of builders. AEO is generally superior to LAS in removing both sebum and clay soils and is less sensitive to builders and water hardness. The builders generally rank in this order: STPP > NTA = citrate > carbonate > sulfate. Presented at the AOCS Short Course, “Update on Detergents and Raw Materials,” Lake Placid, N.Y., June 1971.     

Soap-based detergent formulations: XXVI. Hard water detergency of soap-lime soap dispersant combinations with builders and inorganic salts1

Blends of soap and 3 lime soap dispersants—the sulfated tallow alkanolamide (TAM), the coconut-oil-derived amido sulfobetaine (CAHSB) and the cocoamido betaine (CAB)—were formulated with 3 builders—sodium tripolyphosphate (STPP), trisodium nitrilotriacetate (NTA) and trisodium 2-oxa-1,1,3-propane tricarboxylate (OPT). Varying amounts of sodium sulfate were added to these formulations, and the effects of builders and sodium sulfate on detergency at 300 ppm water hardness were studied. At levels below 60%, STPP was not an effective builder for TAM formulations. Dilution of STPP-built TAM formulations with sodium sulfate substantially decreased detergency. Detergency of TAM formulations was improved by incorporation of NTA or OPT and such formulations could tolerate dilution with sodium sulfate without serious loss in detergency. NTA or STPP improved the detergency of CAB formulations but OPT did not. Addition of sodium sulfate caused some loss in detergency in all CAB formulations. Addition of STPP to CAHSB formulations caused a slight loss in detergency, but addition of NTA or OPT had no appreciable effect. Dilution of STPP-built CAHSB formulations with sodium sulfate affected detergency adversely, although not as severely as in STPP-built TAM formulations. Dilution of NTA-or OPT-built CAHSB formulations with sodium sulfate had little effect on detergency. CAB and particularly CAHSB are superior to TAM in dispersing lime soap curd. Therefore, addition of NTA, STPP, or OPT to the amphoteric formulations did not affect detergency to the same extent as in TAM formulations. Further evidence of the superiority of amphoteric lime soap dispersing agents (lsda) in dispersing lime soap curd was provided by the effectiveness of soap, CAHSB, silicate formulations in detergency studies at 1,000 ppm water hardness. Presented at the Annual AOCS Meeting, San Francisco, April 1979. Agricultural Research, Science and Education Administration, U.S. Department of Agriculture.     

Soap-based detergent formulations: X. Nature of detergent deposits

The cumulative deposition of detergent residue on unsoiled cotton and polyester-cotton permanent press finish cloth was determined for a variety of detergent formulations after washing 25 consecutive times in 300 ppm hard water in a laboratory Tergotometer. Included in this study were: a phosphate-built laundry detergent, two carbonate-built detergents, tallow soap and various tallow soap formulations with anionic and amphoteric lime soap dispersing agents, and a glassy sodium silicate. Sample swatches washed with each formulation were analyzed for calcium, magnesium, and organic acid content. Fabric washed with the carbonate detergents showed the highest calcium and magnesium content, while those washed with the phosphate detergent and the soap-lime soap dispersant-builder formulations had the lowest. Fabric washed with soap alone had a much higher fatty acid residue than those washed with the other detergent formulations. However, the amount of organic acids left on the fabric after washing with a soap-lime soap dispersing agent formulation was no greater than that produced by phosphate- and carbonate-built detergents. The presence or absence of deposits also was verified visually with a scanning electron microscope. Each formulation also was tested for detergency by measuring the soil buildup in a multiwash procedure. Generally, the buildup of soil paralleled the deposit of detergent residue on the unsoiled cloths.     

The effect of sodium carboxymethyl cellulose on synthetic detergent systems

Summary Certain forms of sodium carboxymethyl cellulose have been shown to be highly effective as synthetic detergent promoters. Formulations containing a sodium alkyl aryl sulfonate type of synthetic detergent, alkaline salts and a type of sodium carboxymethyl cellulose developed for high detergency promoting properties surpass high quality fatty acid soaps in both carbon soil removal and whiteness retention on cottons. Methods having a relatively high order of precision for the evaluation of detergency have been presented in detail. By these methods two fundamental characteristics of detergency—as applied to the laundering of cotton fabrics may be independently measured.     

Use of experimental design in detergency tests with a natural soil

A balanced incomplete block design is used to obtain detergency data in a test where cloth swatches are soiled by rubbing against the skin. The design provides increased precision in the data by adjusting for differences among soilers. The wash treatments are part of a second order rotatable design in three variables: the ratio of sodium nitrilotriacetate to sodium tripolyphosphate builder, pH of the wash solution, and temperature. The effect of builder ratio was not highly significant. Soil removal increased with higher pH and went through a maximum with increase in wash temperature. Redeposition was also measured by reflectance values obtained for unsoiled areas of the swatches. Redeposition increased with increase in wash temperature. One of five papers presented at the Symposium, “Basic Aspects of Detergency,” AOCS-ISF World Congress, Chicago, September 1970.     

Soap based detergent formulations. V. Amphoteric lime soap dispersing agents

A series of amphoteric surfactants was prepared by the reaction of 1,3-propanesultone with fat derived primary amines, N-methylalkylamines, N,N-dimethylalkylamines, and N-acyl-N′,N′-dimethyl-1,3-propanediamines. Both mono- and disulfopropylated derivatives of the primary amines were synthesized. All compounds were found to be excellent lime soap dispersing agents. The quaternary sulfobetaines were found to possess the best detergency properties both by themselves and when formulated with tallow soap with or without sodium silicate builder. The detergency performance of such formulations is ca. the same as that of a commercial phosphate-built detergent. Presented at the AOCS Meeting, New Orleands, May 1973. ARS, USDA.     

Fractionation of animal fat glycerides by crystallization from acetone. Am improved lard oil

Summary Various edible and inedible grades of animal fats, such as lard, grease, tallow, and selectively hydrogenated lard, grease and tallow were separated into “oils” and “stearins” by crystallization from acetone. The chemical and physical properties as well as the yields of oils and stearins obtained by this method are described. Antioxidants and metal deactivators are much more effective in stabilizing lard and grease oils produced from partially hydrogenated fats than in stabilizing corresponding products from unhydrogenated fats. Report of a study certain phases of which were made under the Research and Marketing Act of 1946. One of the laboratories of the Bureau of Agricultural and Industrial Chemistry, Agricultural Research Administration, United States Department of Agriculture.     

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.     

Dishwashing performance of mixed palm stearin sulfonated methyl esters—Nonylphenol ethoxylate alcohol

The dishwashing performance of sodium salts of α-sulfonated methyl esters derived from palm stearin (α-SMEPS) and nonylphenol ethoxylate alcohol (NPEO) in mixed micelle systems was evaluated as a function of weight ratio at different water hardness values (5.12, 51.2, and 512.0 ppm CaCO₃) and temperatures (20, 30, and 45°C). Manipulating several parameters, such as weight ratios in α-SMEPS and NPEO mixtures, washing temperature, and water hardness, can enhance detergency performance. In comparison, detergency efficiency of the mixtures increased as follows: α-SMEPS/NPEO 400<α-SMEPS/NPEO 120<α-SMEPS/NPEO 95.     

Solid nonionic surface-active agents

Summary Methods have been described for converting liquid nonionic surface-active agents of the polyoxyethylene type to solid compositions by complexing with urea. It is shown how these solid products may be made in the form of free-flowing powders, flakes, bars, pellets, or tablets. The surface-active properties of two commercial detergents based on this discovery are reported. Besides showing the excellent detergency of these products in washing artificially soiled cotton, it has been shown that they enhance the detergency of alkalibuilt sodium alkylaryl sulfonates in hard water.     

Long chain alkanesulfonates and 1-hydroxy-2-alkanesulfonates: Structure and property relations

Even chain sodium alkanesulfonates from the Strecker reaction, odd chain sodium alkanesulfonates from the alkaline decarboxylation of α-sulfo acids, and sodium 1-hydroxy-2-alkanesulfonates from the reduction of esters of α-sulfo acids were compared with respect to Krafft point, critical micelle concentration, detergency and foam height. Sodium alkanesulfonates and crude fusion products from the α-sulfo acids (mixtures of alkanesulfonates of one less carbon atom with a lesser amount of a soap of two less carbon atoms) are more soluble and have better detergent and foaming properties. Sodium 1-hydroxy-2-alkanesulfonates resemble monosodium salts of α-sulfo acids. Alkanesulfonic acids and 1-hydroxy-2-alkane-sulfonic acids obtained from the sodium salts by ion exchange have lower Krafft points and are more readily soluble. The critical micelle concentrations of 1-hydroxy-2-alkanesulfonic acids and α-sulfo acids are nearly the same and about equal to those of alkanesulfonic acids of one less carbon atom. Presented at the AOCS meeting in Toronto, Canada, 1962. A laboratory of the E. Utiliz. Res. & Dev. Div., ARS, U.S.D.A.     

Computerization in fabric detergency testing

An automated method is described which greatly speeds the calculation of fabric detergency test results. Laboratory determination of fabric detergency commonly involves replicated, bench scale washing of small pieces of cotton artificially soiled with various oil-carbon black mixtures. Reflectance measurements before and after washing give a measure of the amount of soil removed. Often, in a program involving several variables, thousands of reflectance measurements may be involved. By converting the electrical signal from the reflectometer to digital form, and feeding this value to a card punch, the reflectance values are systematically recorded on punched cards. Using an appropriate computer program, the reflectance changes for each test are calculated and tabulated, the saving in operator time is large and statistical examination of the data can be incorporated with the program. An example of the type of data output is given. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., March 1968.     

Lipid distribution on cotton textiles in relation to washing with cellulase

Enzymes are used widely as effective additives to laundry detergents for improved detergency on soiled fabric. They have potential for cleaning of “dingy” soils in addition to the stain removal benefits. Cellulases contribute to the overall whiteness of cotton-containing textiles when worn and washed several times, meaning that their cleaning is not associated solely with the regions characterized by high amounts of fatty material, e.g., collars/cuffs. The focus of this research was to study further the performance of cellulases for whiteness maintenance of cotton textiles. Cotton garments soiled by multiple wearings and washed using a cellulase treatment were evaluated using scanning electron microscopy and X-ray microanalysis. Washing with cellulase significantly reduced residual soil concentrations at all morphological locations on the cotton fibers for each set of matched garments. The relative concentrations of residual soil on the fabrics agreed well with the color differences measured at 440 nm. Cellulase affected removal of oily soil from within the cotton fiber secondary wall, resulting in residual oil concentrations similar to those at morphological locations that were more accessible for detergency such as the fiber surface and crenulations. Since cellulase hydrolyzes cellulose, it was expected that the effect would be within the structure of the fiber, i.e., secondary wall. The cellulase effect on redeposition garments was similar to garments worn and washed. As with lipase, the enhanced removal of soil from the interior bulk structure of the cotton fiber with use of cellulase is unique, since most other detergent components have higher functionality at fabric, yarn, and fiber surfaces. We think that cellulase is functioning by hydrolyzing cellulose from the internal surfaces of fibrils within the secondary wall, opening up the pore structure for enhanced detergency and forming a new surface with each washing.