US3714074A - Foam profile regulating composition and anionic detergent composition containing same and having inverse foam to temperature relationship - Google Patents

Foam profile regulating composition and anionic detergent composition containing same and having inverse foam to temperature relationship Download PDF

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US3714074A
US3714074A US00041359A US3714074DA US3714074A US 3714074 A US3714074 A US 3714074A US 00041359 A US00041359 A US 00041359A US 3714074D A US3714074D A US 3714074DA US 3714074 A US3714074 A US 3714074A
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J Inamorato
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Colgate Palmolive Co
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0026Low foaming or foam regulating compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds

Abstract

An anionic detergent composition having an inverse foam to temperature relationship is disclosed, as well as a composition for accomplishing this relationship when added to a detergent system. The inverse foam to temperature relationship is provided by a synergistic mixture of a fatty acid containing between about eight and 30 carbon atoms in the alkyl chain and a polyethoxylated mono fatty alkyl quaternary ammonium methosulfate, chloride, bromide, nitrate or sulfate salt having about 10 to 50 moles of ethylene oxide.

Description

Elite lnamorato 1 Jan. 30, 1973 i541 FOAM PROFILE REGULATING [56] References Cited COMPOSITION AND ANIONIC DETERGENT COMPOSITION UNTED STATES PATENTS CONTAINING SAME AND HAVING 2,954,347 9/1960 St. John et al. ..252 35s x 3,325,414 6/l967 lnamorato ..252/l37 RELATIONSHIP FOREIGN PATENTS OR APPLICATIONS [75] Inventor: Jack Thomas Inamorato, Westfield, 1066025 9 7 qreatgl-itain Primar Examiner-Richard D. Loverin 73 y g l 1 Asslgnee sg fi i s Company New Attorney-Herbert S. Sylvester, Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, Robert A. Bur- [22] Filed: May 28,1970 roughs, Thomas J. Corum, Richard N. Miller and 211 App]. No.: 41,359 Robe" Sum [57] ABSTRACT [52} U.S.Cl. ..252/528,.252/97,252/98, An anionic (ktergent compositicm having an inverse 252/99 252/102 252/110 252/117 foam to temperature relationship is disclosed, as well 252/121 252/321, 252/358 252/527 as a composition for accomplishing this relationship 252/546, 252/547, 252/DIG- when added to a detergent system. The inverse foam 252/DIG- to temperature relationship is provided by a syner- 1 'l Cl 1/12, Cl 1d 13/303301! l9/04 gistic mixture of a fatty acid containing between about Field of Search 523, eight and 30 carbon atoms in the alkyl chain and a polyethoxylated mono fatty alkyl quaternary ammonium methosulfate, chloride, bromide, nitrate or sulfate salt having about 10 to 50 moles of ethylene oxide.
25 Claims, 4 Drawing Figures A 3% E I 350 4% a: 9 Lu 3:
E 3 LL 250 5% I I I 1 0 I 2 3 4 5 TIME (MINUTES) PATENTEDJANSO I973 3,714,074
SHEET 10F 2 r /5% LAS-EFFECT 0F PALM/TIC 46/0 A 6% E 350 I .2 LL] I E E 250 TIME (MINUTES) /5% LAS-EFFECT 0F STEM/6 ACID I50 I I I W ENTOR TIME (MmuT s) JACK THOMA INAMORATO 2 up i14. SH.
ATTORNEYS PATENTEUJAH 30 I975 SHEET 2 OF 2 FOAM HElGHT(ml.)
FOAM HEIGHT (mL) I50 1 1 I I o 2 3 4 5 TIME (MINUTES) /5% L46 -3% 57/100040 49/25 EFFECT OF 11mm 45/ f 0% We 500 I50 I l I r INVENTOR TIME (MINUTES) JACK THOMAS INAMORATO ATTORN ms BY %ZW/% FOAM PROFILE REGULATING COMPOSITION AND ANIONIC DETERGENT COMPOSITION CONTAINING SAME AND HAVING INVERSE FOAM T TEMPERATURE RELATIONSHIP This invention relates to detergent compositions. More particularly, this invention relates to detergent compositions which have an inverse foam-to-temperature relationship and to means for accomplishing this relationship.
The use of synthetic detergents for washing clothes has assumed worldwide importance, due to the efficiency and cheapness of such products. These detergents are compounded with various additives to provide compositions having improved and desirable characteristics. Among these characteristics is that of maintaining a proper level of foam for suds.
Foaming, or sudsing, of detergents is an extremely important factor to consider when formulating a detergent composition. It is known, for example, that a detergent which over-foams does not do an efficient job of cleaning in a washing machine. On the other hand, in hand washing there is a desire on the part of most consumers for a substantial amount of foam produced by a detergent. It is therefore necessary to provide a detergent composition which produces enough foam to reassure the consumer but yet not so much foam as to inhibit the detergent action of the composition. This need has been satisfactorily achieved in many ways.
There is, however, another situation which requires a totally different approach to foam control in a detergent system. There are geographical areas where hot water is not readily available for one reason or another. In such areas as well as others, washing machines are designed with internal water heating systems which begin their cycle with cold water and gradually heat the same to the desired operating temperature which is usually the boil." Such washing machines are used extensively, for instance, in many European countries. It is well known, however, that a detergent system which provides an adequate level of foam when used with hot water will not foam at all in cold water. Conversely, a detergent system which is compounded so that a sufficient level of foam is produced in cold water will overfoam to the extent of overflowing the washing machine when used with hot water. Of course, a detergent system which over-foams can have a foam suppressor included therein. The problem then, naturally, is that such a system will produce no foam when used with cold water. In other words, most detergent systems have essentially a direct relationship between temperature and foam, wherein as the temperature increases the amount of foam increases.
Accordingly, it is a primary object of the present invention to provide a detergent system free of the aforementioned and other such disadvantages.
It is another object of the present invention to provide a detergent system having an inverse foam-to-temperature relationship.
It is still another object of the present invention to provide a detergent system which can be used in an environment wherein it will be subject to cold water as well as hot water and still provide a satisfactory foam level.
It is yet another object of the present invention to provide a composition which will impart an inverse foam-to-temperature relationship system.
Other objects and advantages of the present invention will become apparent from the following detailed description thereof:
According to the present invention, a composition is provided for regulating the foam profile of a detergent system, comprising a synergistic mixture, of a fatty acid and a polyethoxylated quaternary ammonium salt. In another aspect of the present invention, a detergent composition is provided having an inverse foam-totemperature relationship which comprises an anionic detergent, inorganic builders, and a synergistic mixture of a fatty acid and a polyethoxylated quaternary ammonium salt. The detergent composition could have other additives such as brighteners, germicides, soil suspending agents, antioxidants, bleaches, coloring materials, and perfume. It is quite unexpected to find that the mixture of fatty acids and polyethoxylated quaternary ammonium salts provide the inverse foamto-temperature relationship, since each of the ingredients, when used alone, does not exhibit any such properties. I
The useful fatty acids which may be employed in the present invention include those saturated linear acids containing between about 8 and 30 carbon atoms in their alkyl chain. These include:
capric acid lauric acid myristic acid palmitic acid stearic acid arachidic acid behenic acid lignoceric acid cerotic acid melissic acid oleic acid linoleic acid as well as various natural and synthetic mixtures thereof.
The preferred fatty acids, however, are those having alkyl chains of from about 14 to 22 carbon atoms. One such preferred fatty acid is stearic acid. Another preferred acid composition is available commercially under the name Hyfac 431. l-Iyfac 431 is a hydrogenated fish fatty acid having the following approximate composition:
8 percent myristic acid 29 percent palmitic acid 18 percent stearic acid 26 percent arachidic acid 17 percent behenic acid 2 percent oleic acid Other commercially available mixtures of fatty acids are those which are available under the name Hystrene." For instance, Hystrene' 7022 comprises about C to C fatty acids. Hystrene 9022 comprises about C to C fatty acids, and I-Iystrene 9018 has about 90 percent stearic acid. Another such commercial product is Neofat 18-58, which is a hydrogenated tallow acid. The fatty acid, used in combination with the polyethoxylated quaternary ammonium salt, should be present in the final detergent composition in an amount from about 1 to about 6 percent by weight of the total detergent composition.
to a detergent The polyethoxylated quaternary ammonium salt component of the synergistic mixture can be any such salt, although a polyethoxylated mono fatty alkyl methyl ammonium salt is preferred. For instance, a polyethoxylated (40 moles of ethylene oxide) dicoco methyl ammonium methyl sulfate has been used. Still more preferred, however, are the polyethoxylated (15 moles of EO) mono fatty alkyl methyl ammonium chlorides, which are commercially available under the name Ethoquad. Specifically, the most preferred such salt is Ethoquad 18/25, which is polyethoxylated (15 moles) stearyl methyl ammonium chloride. Other suitable quaternary salts having about to 50 moles ethylene oxide may be used. Any suitable anion can be used including other halides (e.g. bromide), nitrates and sulfates.
The useful detergents which may be used in conjunction with the foam profile regulating composition of the present invention include anionic detergents such as alkylbenzene-sulfonic acid and its salts, and compounds of the formula alky1-phenyl-SO -M, wherein alkyl is an alkyl radical of a fatty acid and M is hydrogen or an alkali metal, which compounds comprise a well known class of anionic detergents and include sodium dodecyl-benzene sulfonate, potassium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate. Others are the alkali metal dialkyl sulfosuccinates, e. g., sodium dioctylsulfosuccinate, and sodium dihexylsulfosuccinate, sodium sulfoethylphthalate, sodium lauryl-p-anisidinesulfonate; sodium tetradecanesulfonate; sodium diisopr0pylnaphthalenesulfonate; sodium octylphenoxyethoxyethylsulfonate, etc.; and the alkali metal alkyl sulfates, e. g., sodium lauryl sulfate.
Among the above noted alkylbenzene-sulfonic acid and salts thereof, the preferred compounds include those which are biodegradable and which are particularly characterized by a linear alkyl substituent of from C to C and preferably from C to C It is, of course, understood that the carbon chain length represents, in general, an average chain length since the method for producing such products usually employs alkylating reagents of mixed chain length. It is clear, however, that substantially pure olefins as well as alkylating compounds used in other techniques can and do give alkylated benzene sulfonates wherein the alkyl moiety is substantially (i. e., at least 99 percent) of one chain length, i. e., C C C or C The linear alkyl benzene sulfonates are further characterized by the position of the benzene ring in the linear alkyl chain, with any of the position isomers (i. e., alpha to omega) being operable and contemplated.
The linear alkyl benzene sulfonates are generally and conveniently prepared by sulfonating the corresponding alkyl benzene hydrocarbons which in turn may be prepared by alkylating benzene with a linear alkyl halide, a l-alkene or a linear primary or secondary alcohol. Pure isomers (of the l-phenyl isomer) are prepared by reduction of the acylated benzene (alkyl phenyl ketone) using a modification of the Wolff- Keshner reaction. The Z-phenyl isomer is obtained from n-undecyl phenyl ketone and methyl magnesium bromide to form the tertiary alcohol which is dehydrated to the alkene and then hydrogenated. The S-phenyl isomer is obtained similarly from a n-heptyl phenyl ketone and n-butyl magnesium bromide. The
other isomers are obtained in a similar manner from the appropriate n-alkyl phenyl ketone and n-alkyl magnesium bromide.
In addition to the benzene sulfonates one may also employ the lower alkyl (C to C analogs of benzene such as toluene, xylene, the trimethyl benzenes, ethyl benzene, isopropyl benzene and the like. The sulfonates are generally employed in the water soluble salt form which include as the cation, the alkali metals, ammonium, and lower amine and alkanolamine.
Examples of suitable linear alkyl benzene sulfonates are:
sodium n-decyl benzene sulfonate sodium n-dodecyl benzene sulfonate sodium n-tetradecyl benzene sulfonate sodium n-pentadecyl benzene sulfonate sodium n-hexadecyl benzene sulfonate and the lower corresponding lower alkyl substituted homologues of benzene as well as the salts of the cations previously referred to. Mixtures of these sulfonates may, of course, also be used with mixtures which may include compounds wherein the linear alkyl chain is smaller or larger than indicated herein provided that the average chain length in the mixture conforms to the specific requirements ofC to C Other anionic detergents are the olefin sulfonates,including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkane-sulfonates. These olefin sulfonate detergents may be prepared, in known manner, by the reaction of with long chain olefins (of 8 25, preferably 12 21, carbon atoms) of the formula RCH=CHR where R is alkyl and R, is alkyl or hydrogen, to produce a mixture of sultones and alkenesulfonic acids, which mixture is then treated to convert the sultones to sulfonates.
The linear paraffin sulfonates are also a well known group of compounds and include water soluble salts (alkali metal, amine, alkanolamine, and ammonium) of:
l-decane sulfonic acid l-dodecane sulfonic acid l-tridecane sulfonic acid l-tetradecane sulfonic acid l-pentadecane sulfonic acid l-hexadecane sulfonic acid as well as the other position isomers of the sulfonic acid group.
In addition to the paraffin sulfonates illustrated above, others with the general range ofC to C alkyls may be used, with the most preferable range being from C to C The linear alkyl sulfates which are contemplated in this invention comprise the range ofC to C Specific examples include sodium n-decyl sulfate; sodium ndodecyl sulfate; sodium n-octadecyl sulfate; and the ethoxylated (l to moles ethylene oxide) derivatives; and of course, the other water soluble salt-forming cations mentioned above.
The composition of the present invention may also include in addition to the foam profile regulating com pounds and conventional anionic detergent compositions builders, brighteners, hydrotropes, germicides, soil suspending agents, anti-redeposition agents, antioxidants, bleaches, coloring materials (dyes and pigments), perfumes, water soluble alcohols, non-detergent alkali metal benzene sulfonates, fabric softening compounds, enzymes, etc.
The builder is, generally, a water soluble, inorganic salt which may be a neutral salt, e. g., sodium sulfate or an alkaline builder salt such as phosphates, silicates, bicarbonates, carbonates, and borates. The preferred builders are those characterized as condensed phosphates such as polyphosphates and pyrophosphates. Specific examples of alkaline salts are: tetrasodium pyrophosphates, pentasodium tripolyphosphate (either Phase I or Phase 11), sodium hexametaphosphate, and the corresponding potassium salts of these compounds, sodium and potassium silicates, e. g., sodium metasilicate and alkaline silicates (Na O; 2Si0 and Na O; 3SiO sodium carbonate, potassium carbonate and sodium and potassium bicarbonate. Other salts may also be used where the compounds are water soluble. These include the general class of alkali metal, alkaline earth metal, amine, alkanolamine, and ammonium salts. Other builders which are salts of organic acids may also be used, and in particular the water soluble (alkali metal, ammonium, substituted ammonium and amine) salts of aminopolycarboxylic acids such as:
ethylene diamine tetra-acetic acid nitrilo triacetic acid diethylene triamine penta-acetic acid N-(Z-hydroxyethyl) ethylene diamine triacetic acid 2-hydroxyethyl-iminodiacetic acid 1,2-diaminocyclohexane diacetic acid, and the like.
In addition to the above ingredients, one may as previously delineated employ hydrotropes in connection with the compositions of the instant invention. The useful hydrotropes include such compounds as sodium xylene sulfonate, potassium xylene sulfonate, sodium and potassium toluene sulfonates, in the position isomers thereof, and ethyl benzene sulfonate.
It has now been found, quite unexpectedly, that when the synergistic mixture of a fatty acid and a polyethoxylated quaternary ammonium salt as disclosed above is added to a conventional detergent system, or is used in combination with the above detergents and other conventional detergent additives, an inverse foam-to-temperature relationship is exhibited by the resulting system.
In the composition for regulating the foam profile of a detergent according to the present invention, there is employed from about to 75 percent fatty acid and from about 85 to 25 percent polyethoxylated quaternary ammonium salt. Preferably, there is employed from about 25 to 60 percent fatty acid and from about 75 to 40 percent polyethoxylated quaternary ammonium salt. In terms of the total detergent system, there is employed from about 1 to 6 percent fatty acid and from about 1 to 6 percent polyethoxylated quaternary ammonium salt, and preferably from about 3 to 5 percent fatty acid and from about 2 to 3 percent polyethoxylated quaternary ammonium salt. All of said percentages are by weight, based on the total amount of the composition being used. In the case of the detergent systems, the percentages are based on an anionic detergent concentration of about 8 to 18 percent by weight. When less anionic detergent is present in the system, a
correspondingly lesser amount of each of the fatty acid and the polyethoxylated quaternary ammonium salt can be used. Builders when used may range from 10-85 wt percent.
The present invention will now be illustrated by the following, more detailed examples thereof. It is noted, however, that the present invention is not deemed as being limited thereto.
EXAMPLE 1 In this example, several detergent systems were tested to determine their foam profile by means of a graduated cylinder shake test. The shake test is performed by adding 200 mililiters of the detergent solution to be tested to a 500 mililiter graduated cylinder. The cylinder is then shaken an established number of times, and the foam height and rate of suds collapse is noted. In each case, the detergent composition was 0.5 percent in tap water at 160 F. and the detergent formulations were as follows:
Formulation Ingredients l 2 3 Sodium tridecyl benzene sulfonate l0 l5 5 *Non-ionic detergent 2 5 Soap 2 2 Sodium tripolyphosphate 35 35 24 Trisodiurn nitriloacetate 5 Sodium carboxymethylcellulose 0.5 0.5 0.5 Polyvinyl alcohol 0.2 0.2 0.2 Sodium silicate 7.5 7.5 7.5 "Sodium sulfate Q5. 0.5. 0.8.
*Neodol 45-1] polyethoxylated (11 moles) linear alcohol primarily H l5' "Sodium soap of 80% tallow 20% coconut fatty acids.
*Balance with minor amounts of water and optical brighteners.
The following results were obtained:
TABLE 1 Time (mins) Formulation EXAMPLE 2 Detergent formulation number 2 was again tested by the shake test, with the addition of of Hyfac 431, Ethoquad 2C/50 DMS percent actives) (polyethoxylated [40 mole] dicocomethyl ammonium methyl sulfate). The results are shown in Table 2:
TABLE 2 Time 2 2 4% 2 4% 2 4% 2Cl50 DMS (mins) Alone Hyfac 431 ZC/SO & 4% Hyfac 431 DMS 500- 500- 500 450 l 500- 450 500- 325 2 500- 350 500- 215 3 500- 240 500- 4 500- 220 500- 5 500- 500 It can be seen from the results of this comparative test that formulation number 2 alone rapidly foamed and then maintained the same foam level. Formulation number 2 with 4 percent l-lyfac 431 added produced a heavy foam which broke in about 4 minutes. Formulation number 2 with 4 percent Ethoquad 2C/50 DMS showed no improvement in the foam profile over formulation number 2 alone. Formulation number 2 with both 4 percent Hyfac 431 and 4 percent Ethoquad 2C/50 DMS produced a foam which broke in about two minutes. Thus, it is shown that the detergent system with both Hyfac 431 and the polyethoxylated quaternary ammonium salt showed the desired foam profile.
EXAMPLE 3 Formulation number 2 was again tested, using the shake test, under the same conditions as in the previous examples, and with other additives. Ethoquad 18/25 was substituted for Ethoquad 2C/50 DMS. Ethoquad 18/25 is polyethoxylated moles) stearyl methyl ammonium chloride. Other fatty acids which were tested were palmitic acid and triple pressed stearic acid.
Ethoquad 18/25 was used in concentrations up to 6 percent by weight. There was no change in the foam profile when only the polyethoxylated quaternary ammonium salt was used.
Palmitic acid, triple pressed stearic acid, and Hyfac 431 were evaluated in concentrations varying between 1.0 and 6 percent by weight.
Three percent Ethoquad 18/25 was added to formulation number 2, along with Hyfac 431 in concentrations ranging between 0 and 5 percent in increments of 1 percent. The foam profile for each system was determined by the cylinder shake test under the same conditions as previously described.
The graph of FIG. 1 indicates the foam profile of the system with various concentrations of palmitic acid. FIG. 2 illustrates the results obtained with stearic acid, and FIG. 3 indicates the results obtained with Hyfac 431. FIG. 4 illustrates the results obtained by adding Ethoquad 18/25 alone to the detergent composition, and compares that result with the addition of variable amounts of Hyfac 43 1, together with Ethoquad l8/25.
It is clear from FIGS. 1 through 4 that palmitic acid is the least effective fatty acid for suppressing foam, and Hyfac 431 is the best. Both stearic acid and Hyfac 431 show good suppressing properties when at least 3 percent of the fatty acid is present in the formulation. Better suppressing occurs when the level of fatty acid is increased above 3 percent. This improvement is more pronounced with Hyfac than with the stearic acid system. The Ethoquad 18/25 produces no foam suppressing action. Ethoquad 18/25 combined with l-Iyfac 431 at or above the 2 percent level suppresses the foam better than the Hyfac 431 alone. This is a clear indication that there is a synergistic system present.
EXAMPLE 4 It should be noted that the previous examples used a detergent system comprising 15 percent linear alkyl benzene sulfonate* detergent. In this example, a system comprising 10 percent linear alkyl benzene sulfonate* detergent was evaluated. Three systems were formulated containing Ethoquad 18/25 and stearic acid, Ethoquad 18/25 and Hyfac 431, and Hyfac 431 alone, these formulations being denoted 4, 5 and 6 respectively. Their composition is as follows:
TABLE 3 Ingredients Water LAS Ethoquad l8/25 Hyfac 431 Stearic Acid Sodium Silicate Sodium Carboxymethylcellulose Polyvinyl Alcohol Sodium Tripolyphosphate NaOH NaSO sodium tridecyl benzene sulfonate These systems were evaluated in a Westinghouse front loading washing machine. The detergent systems were used at a concentration of 0.5 percent using an 8 lb. clean load of laundry. The systems were testing at both 160 and F, using tap water. The wash cycle was 10 minutes.
At the two products containing fatty acid and Ethoquad 18/25 did not cause any over-foaming problems during the 10 minute wash cycle. The system containing Ethoquad 18/25 and Hyfac 431 generated a little less suds than the system with stearic acid. The system with Hyfac 431 alone generated a full door of foam after 5 minutes. The test then had to be stopped to prevent overflowing.
At 80 F, all three products gave a full door of suds in less than thirty seconds.
EXAMPLE 5 Detergent formulations were prepared having the following compositions:
TABLE 4 Ingredients Water- LAS Hyfac 431 Neofat l8-58 Ethoquad l8l25 Sodium Tripolyphosphate Sodium Silicate Sodium Carboxymethylcellulose Polyvinyl Alcohol NaOH Sodium Sulfate sodium tridecyl benzene sulfonate Both of these products were tested in the Westinghouse washing machine at 160 F, as in Example 4. Formulation number 7, containing Hyfac 431 and Ethoquad 18/25, gave the same results as formulation number 5. The detergent system of formulation number 8, however, gave a full door of foam after five minutes of washing. Formulation number 8 was tested repeatedly with soiled laundry, all other conditions being the same, and produced a foam which never exceeded a height above one-third of the washing machine door.
EXAMPLE 6 The products of Example were re-evaluated with the addition of sodium perborate equivalent to 30 percent. The use of the sodium perborate did not effect the results. Additionally, formulations containing 30 percent sodium perborate and 1 percent magnesium sulfate and 0.25 percent EDTA to preserve and stabilize the sodium perborate were tested. Again, there was no change in the results.
The following examples demonstrate the foam profiles of various detergent systems under the conditions of use to be encountered in Europe. The detergent compositions were tested in a Miele automatic washing machine, which is of German manufacture. The machine is a front loading, tumbler type washing machine equipped with a heater that raises the water temperature from room temperature to the boil. The machine operates on 220 volts, 50 cycle alternating current. In each instance, the machine was set on the white clothes setting, and a 5 pound load of clean clothing was used. The water capacity is 1 1 liters. A detergent concentration of 0.5 percent was used in each cycle. This detergent concentration was provided by using 56 grams of detergent.
The machine operates on two cycles, a pre-wash cycle and a wash cycle. In the pre-wash cycle, the temperature of the water climbs from 70 to 120 F, and the total cycle is 12 to 14 minutes. The drum rotates for about seconds, rests for 4 seconds, reverses direction, and the operation is repeated. At the end of the cycle, the machine stops, drains, and remains motionless until the wash cycle starts.
The wash cycle is divided into two stages, the heating stage and the washing stage. In the heating stage, cold water washes a second charge of detergent into the drum. During this 30 minute stage, the temperature climbs from about 90 F to over 190 F. The drum rotates for 4 to 5 seconds, rests for 10 seconds, reverses direction, and repeats the operation. At the end of the heating period, the machine changes its drum action and goes into the washing stage.
The washing stage lasts 18 minutes. During this time, the drum action is the same as that described for the pre-wash cycle. The temperature fluctuates between 190 and 200 F during the whole washing stage.
EXAMPLE 7 Detergent compositions were made having the following formulations:
TABLE 5 Ingredients 9 l0 1 l 12 Water 8.50 8.50 8.50 8.50 Sodium Tridecylbenzene Sulfonate 10.00 10.00 15.00 10.00 Sodium Hydroxide 0.45 0.45 0.45 0.45 Hyfac 431 3.00 4.00 Stearic Acid 3.00 5.00 Ethoquad 18/25 2.00 2.00 3.00 2.00 Sodium Tripolyphosphate 35.00 35.00 35.00 35.00 Sodium Silicate 7.00 7.00 7.00 7.00 Sodium Carboxymethyl Cellulose 0.50 0.50 0.50 Polyvinyl Alcohol 0.20 0.20 0.20
Sodium Sulfate 0.5. 0.8. Q8. 0.8.
These products were evaluated using both the shake test and the Meile washing machine. In each case, a high foam was produced at F and a low foam at 160 F.
Thus, it has been shown that a synergistic combination of a fatty acid and a polyethoxylated quaternary ammonium salt provides a means of controlling the foam profile of a detergent system in order to produce an inverse foam-totemperature relationship. It is to be clearly understood that the ratios of anionic detergent and various of the inorganic builder salts can be varied within suitable detergent limits.
in the description and claims, reference to fatty acids or the like includes the corresponding water-soluble soaps thereof, preferably the alkali metal soaps such as sodium and potassium. In general, the fatty acids per se and soaps thereof may be used interchangeably depending upon economics, method of manufacture of the composition with other ingredients and its use in washing. For example, fatty acids may exist in the product when post-added to a detergent powder; or partly or wholly in the form of soap when added to a slurry or solution during manufacture of detergent products in the presence of alkaline materials or in alkaline washing solutions.
Accordingly, it is clear that the objects of this invention, set for that the outset of the specification, have been successfully achieved. The invention has been disclosed and described with respect to certain preferred embodiments, and various modifications thereof will become obvious to one skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and scope of the invention, which is not limited to the exemplary embodiments, but is defined only by the claims.
I claim:
1. A composition for regulating the foam profile of a detergent system, said composition consisting essentially of (1) from about 15 to 75 percent of fatty acid containing between about eight and 30 carbon atoms in the alkyl chain, and (2) from about to 25 percent of polyethoxylated, mono fatty alkyl quaternary ammonium methosulfate, chloride, bromide, nitrate or sulfate salt having about 10 to 50 moles of ethylene oxide.
2. A composition according to claim 1, wherein said fatty acid contains from about 14 to 22 carbon atoms.
3. A composition according to claim 2, wherein said fatty acid is stearic acid.
4. A composition according to claim 2, wherein said fatty acid is hydrogenated fish fatty acid.
5. A composition according to claim 2, wherein said fatty acid is hydrogenated tallow acid.
6. A composition according to claim 2, wherein said fatty acid is a mixture of C to C fatty acids.
7. A composition according to claim 1, wherein said fattyacid is present in from about 25 to 60 percent by weight of said composition.
8. A composition according to claim 1, wherein said salt is a polyethoxylated (15 mole) mono fatty alkyl methyl ammonium chloride.
9. A composition according to claim 8, wherein said salt is polyethoxylated (15 mole) stearyl methyl ammonium chloride.
10. A composition according to claim 1, wherein said salt is polyethoxylated (40 mole) dicoco methyl ammonium sulfate.
1 1. A composition according to claim 1, wherein said salt is present in from about 75 to 40 percent by weight of said composition.
12. A detergent composition having an inverse foam to temperature relationship consisting essentially of (1) from about 1 to 6 percent by weight of fatty acid containing between about eight and 30 carbon atoms in the alkyl chain, (2) from about 1 to 6 percent by weight of polyethoxylated mono fatty alkyl quaternary ammonium methosulfate, chloride, bromide, nitrate or sulfate salt having about to 50 moles of ethylene oxide, and (3) from about 8 to 18 percent by weight of anionic detergent.
13. A composition according to claim 12, wherein said anionic detergent is a linear alkyl benzene sulfonate having about 10 to 22 carbon atoms in the alkyl group.
14. A composition according to claim 13, wherein said alkyl group has about 12 to 15 carbon atoms.
15. A composition according to claim 12, which includes about 10 to 15 percent linear alkyl benzene sulfonate, and builder salts selected from the group consisting of alkali metal and ammonium polyphosphates, silicates, borates, sulfates and combinations thereof.
16. A composition according to claim 12, wherein said fatty acid contains from about 14 to 22 carbon atoms.
17. A composition according to claim 16, wherein said fatty acid is stearic acid.
18. A composition according to claim 16, wherein said fatty acid is hydrogenated fish fatty acid.
19. A composition according to claim 16, wherein said fatty acid is hydrogenated tallow acid.
20. A composition according to claim 16, wherein said fatty acid is a mixture of C to C fatty acids.
21. A composition according to claim 12, wherein said fatty acid is present in from about 3 to 5 percent by weight of said composition.
22. A composition according to claim 12, wherein said salt is a polyethoxylated (15 mole) mono fatty alkyl methyl ammonium chloride.
23. A composition according to claim 22, wherein said salt is polyethoxylated (15 mole) stearyl methyl ammonium chloride.
24. A composition according to claim 12, wherein said salt is polyethoxylated (40 mole) dicoco methyl ammonium sulfate.
25. A composition according to claim 12, wherein said salt is present in from about 2 to 3 percent by weight of said composition.

Claims (24)

1. A composition for regulating the foam profile of a detergent system, said composition consisting essentially of (1) from about 15 to 75 percent of fatty acid containing between about eight and 30 carbon atoms in the alkyl chain, and (2) from about 85 to 25 percent of polyethoxylated, mono fatty alkyl quaternary ammonium methosulfate, chloride, bromide, nitrate or sulfate salt having about 10 to 50 moles of ethylene oxide.
2. A composition according to claim 1, wherein said fatty acid contains from about 14 to 22 carbon atoms.
3. A composition according to claim 2, wherein said fatty acid is stearic acid.
4. A composition according to claim 2, wherein said fatty acid is hydrogenated fish fatty acid.
5. A composition according to claim 2, wherein said fatty acid is hydrogenated tallow acid.
6. A composition according to claim 2, wherein said fatty acid is a mixture of C20 to C22 fatty acids.
7. A composition according to claim 1, wherein said fatty acid is present in from about 25 to 60 percent by weight of said composition.
8. A composition according to claim 1, wherein said salt is a polyethoxylated (15 mole) mono fatty alkyl methyl ammonium chloride.
9. A composition according to claim 8, wherein said salt is polyethoxylated (15 mole) stearyl methyl ammonium chloride.
10. A composition according to claim 1, wherein said salt is polyethoxylated (40 mole) dicoco methyl ammonium sulfate.
11. A composition according to claim 1, wherein said salt is present in from about 75 to 40 percent by weight of said composition.
12. A detergent composition having an inverse foam to temperature relationship consisting essentially of (1) from about 1 to 6 percent by weight of fatty acid containing between about eight and 30 carbon atoms in the alkyl chain, (2) from about 1 to 6 percent by weight of polyethoxylated mono fatty alkyl quaternary ammonium methosulfate, chloride, bromide, nitrate or sulfate salt having about 10 to 50 moles of ethylene oxide, and (3) from about 8 to 18 percent by weight of anionic detergent.
13. A composition according to claim 12, wherein said anionic detergent is a linear alkyl benzene sulfonate having about 10 to 22 carbon atoms in the alkyl group.
14. A composition according to claim 13, wherein said alkyl group has about 12 to 15 carbon atoms.
15. A composition according to claim 12, which includes about 10 to 15 percent linear alkyl benzene sulfonate, and builder salts selected from the group consisting of alkali metal and ammonium polyphosphates, silicates, borates, sulfates and combinations thereof.
16. A composition according to claim 12, wherein said fatty acid contains from about 14 to 22 carbon atoms.
17. A composition according to claim 16, wherein said fatty acid is stearic acid.
18. A composition according to claim 16, wherein said Fatty acid is hydrogenated fish fatty acid.
19. A composition according to claim 16, wherein said fatty acid is hydrogenated tallow acid.
20. A composition according to claim 16, wherein said fatty acid is a mixture of C20 to C22 fatty acids.
21. A composition according to claim 12, wherein said fatty acid is present in from about 3 to 5 percent by weight of said composition.
22. A composition according to claim 12, wherein said salt is a polyethoxylated (15 mole) mono fatty alkyl methyl ammonium chloride.
23. A composition according to claim 22, wherein said salt is polyethoxylated (15 mole) stearyl methyl ammonium chloride.
24. A composition according to claim 12, wherein said salt is polyethoxylated (40 mole) dicoco methyl ammonium sulfate.
US00041359A 1970-05-28 1970-05-28 Foam profile regulating composition and anionic detergent composition containing same and having inverse foam to temperature relationship Expired - Lifetime US3714074A (en)

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US4130870A 1970-05-28 1970-05-28
US4160170A 1970-05-28 1970-05-28
US4139270A 1970-05-28 1970-05-28
US4160270A 1970-05-28 1970-05-28
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US00041359A Expired - Lifetime US3714074A (en) 1970-05-28 1970-05-28 Foam profile regulating composition and anionic detergent composition containing same and having inverse foam to temperature relationship
US00041601A Expired - Lifetime US3716499A (en) 1970-05-28 1970-05-28 Ternary foam control composition and built anionic detergent composition containing same
US41308A Expired - Lifetime US3704267A (en) 1970-05-28 1970-05-28 Ternary foam control composition and built anionic detergent composition containing same
US41392A Expired - Lifetime US3696056A (en) 1970-05-28 1970-05-28 Ternary foam control systems with amines or amides and detergent compositions containing same
US00041358A Expired - Lifetime US3730912A (en) 1970-05-28 1970-05-28 Ternary foam control systems and detergent compositions containing same
US00041602A Expired - Lifetime US3709836A (en) 1970-05-28 1970-05-28 Built anionic detergent composition having inverse foam-to-temperature relationship and process for producing same

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US41308A Expired - Lifetime US3704267A (en) 1970-05-28 1970-05-28 Ternary foam control composition and built anionic detergent composition containing same
US41392A Expired - Lifetime US3696056A (en) 1970-05-28 1970-05-28 Ternary foam control systems with amines or amides and detergent compositions containing same
US00041358A Expired - Lifetime US3730912A (en) 1970-05-28 1970-05-28 Ternary foam control systems and detergent compositions containing same
US00041602A Expired - Lifetime US3709836A (en) 1970-05-28 1970-05-28 Built anionic detergent composition having inverse foam-to-temperature relationship and process for producing same

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CA (6) CA945037A (en)
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DE (1) DE2126061A1 (en)
DK (1) DK138662B (en)
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US3920563A (en) * 1972-10-31 1975-11-18 Colgate Palmolive Co Soap-cationic combinations as rinse cycle softeners
US3959165A (en) * 1972-09-15 1976-05-25 Colgate-Palmolive Company Biodegradable, non-polluting, heavy duty synthetic organic detergent composition
US4028262A (en) * 1972-10-16 1977-06-07 Colgate-Palmolive Company Citrate-carbonate built detergent
US4153570A (en) * 1977-02-01 1979-05-08 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Low-foaming liquid washing agent concentrates
US4167561A (en) * 1973-12-28 1979-09-11 Lever Brothers Company Hypochlorite disinfecting compositions and use thereof
US4284435A (en) * 1979-11-28 1981-08-18 S. C. Johnson & Son, Inc. Method for spray cleaning painted surfaces
US4308024A (en) * 1978-11-03 1981-12-29 Lever Brothers Company Fabric softening composition
US4492646A (en) * 1980-02-05 1985-01-08 The Procter & Gamble Company Liquid dishwashing detergent containing anionic surfactant, suds stabilizer and highly ethoxylated nonionic drainage promotor
US4561998A (en) * 1982-05-24 1985-12-31 The Procter & Gamble Company Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid
US4637890A (en) * 1986-01-23 1987-01-20 The Procter & Gamble Company Detergent composition providing rinse cycle suds and turbidity control containing a soap, quaternary ammonium salt and a silicone

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DE2213557A1 (en) * 1972-03-12 1973-09-27 Henkel & Cie Gmbh METHODS AND MEANS FOR WASHING AND SOFTENING TEXTILES
AU5503373A (en) * 1972-06-06 1974-11-07 Colgate Palmolive Co Low-foaming detergent composition
DE2243306A1 (en) * 1972-09-02 1974-03-21 Henkel & Cie Gmbh FOAM REGULATED DETERGENTS, ESPECIALLY FOR DRUM WASHING MACHINES
US3920564A (en) * 1972-09-20 1975-11-18 Colgate Palmolive Co Softener-detergent composition
US3879309A (en) * 1973-01-17 1975-04-22 Louis Gatti Detergent bar made from mixed fatty acid derivatives
US4029607A (en) * 1974-03-29 1977-06-14 The Drackett Company Drain cleaning compositions
FR2439230A1 (en) * 1978-10-17 1980-05-16 Seppic Sa USE OF FATTY AMINES FOR IMPROVING THE PROPERTIES OF FOAMS, AND IMPROVED FOAMING AGENTS CONTAINING SUCH AMINES
AU531818B2 (en) * 1978-11-20 1983-09-08 Procter & Gamble Company, The Detergent compositions having textile softening properties
ATE10646T1 (en) * 1979-09-29 1984-12-15 The Procter & Gamble Company DETERGENT COMPOSITIONS.
US4460485A (en) * 1983-07-15 1984-07-17 Lever Brothers Company Polyester fabric conditioning and whitening composition
AU570738B2 (en) 1983-10-26 1988-03-24 Unilever Plc Detergent powder
GB8519363D0 (en) * 1985-08-01 1985-09-04 Procter & Gamble Dispersible fabric softeners
US4686060A (en) * 1986-01-23 1987-08-11 The Procter & Gamble Company Detergent composition providing rinse cycle suds control containing a soap, a quaternary ammonium salt and a silicone
US4847089A (en) * 1986-07-16 1989-07-11 David N. Kramer Cleansing and distinfecting compositions, including bleaching agents, and sponges and other applicators incorporating the same
US5019280A (en) * 1986-11-14 1991-05-28 The Procter & Gamble Company Ion-pair complex conditioning agent with benzene sulfonate/alkyl benzene sulfonate anionic component and compositions containing same
US4915854A (en) * 1986-11-14 1990-04-10 The Procter & Gamble Company Ion-pair complex conditioning agent and compositions containing same
US4824582A (en) * 1986-11-14 1989-04-25 The Procter & Gamble Company Articles and methods for treating fabrics
US4913828A (en) * 1987-06-10 1990-04-03 The Procter & Gamble Company Conditioning agents and compositions containing same
US4756850A (en) * 1987-06-10 1988-07-12 The Procter & Gamble Company Articles and methods for treating fabrics
US4861502A (en) * 1988-02-08 1989-08-29 The Procter & Gamble Company Conditioning agent containing amine ion-pair complexes and composiitons thereof
US4857213A (en) * 1988-02-08 1989-08-15 The Procter & Gamble Company Liquid detergent containing conditioning agent and high levels of alkyl sulfate/alkyl ethoxylated sulfate
US5073274A (en) * 1988-02-08 1991-12-17 The Procter & Gamble Co. Liquid detergent containing conditioning agent and high levels of alkyl sulfate/alkyl ethoxylated sulfate
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US6210732B1 (en) 2000-02-03 2001-04-03 James A. Papanton Cooking oil additive and method of using
US7244453B1 (en) 2006-01-24 2007-07-17 Lucia Mihalchick Litman Anti-chlorine shampoo composition
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Cited By (12)

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Publication number Priority date Publication date Assignee Title
US3910855A (en) * 1972-05-16 1975-10-07 Richard M Abeles Liquid cleaning compositions
US3959165A (en) * 1972-09-15 1976-05-25 Colgate-Palmolive Company Biodegradable, non-polluting, heavy duty synthetic organic detergent composition
US4028262A (en) * 1972-10-16 1977-06-07 Colgate-Palmolive Company Citrate-carbonate built detergent
US3920563A (en) * 1972-10-31 1975-11-18 Colgate Palmolive Co Soap-cationic combinations as rinse cycle softeners
US4167561A (en) * 1973-12-28 1979-09-11 Lever Brothers Company Hypochlorite disinfecting compositions and use thereof
US4153570A (en) * 1977-02-01 1979-05-08 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Low-foaming liquid washing agent concentrates
US4308024A (en) * 1978-11-03 1981-12-29 Lever Brothers Company Fabric softening composition
USRE34062E (en) * 1978-11-03 1992-09-15 Lever Brothers Company Fabric softening composition contains water-insoluble surfactant and aliphatic mono-carboxylic acid
US4284435A (en) * 1979-11-28 1981-08-18 S. C. Johnson & Son, Inc. Method for spray cleaning painted surfaces
US4492646A (en) * 1980-02-05 1985-01-08 The Procter & Gamble Company Liquid dishwashing detergent containing anionic surfactant, suds stabilizer and highly ethoxylated nonionic drainage promotor
US4561998A (en) * 1982-05-24 1985-12-31 The Procter & Gamble Company Near-neutral pH detergents containing anionic surfactant, cosurfactant and fatty acid
US4637890A (en) * 1986-01-23 1987-01-20 The Procter & Gamble Company Detergent composition providing rinse cycle suds and turbidity control containing a soap, quaternary ammonium salt and a silicone

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NL7107442A (en) 1971-11-30
US3696056A (en) 1972-10-03
US3716499A (en) 1973-02-13
FR2093742A5 (en) 1972-01-28
CA949417A (en) 1974-06-18
AT325182B (en) 1975-10-10
GB1286054A (en) 1972-08-16
CA944652A (en) 1974-04-02
CA945037A (en) 1974-04-09
US3730912A (en) 1973-05-01
BE767873A (en) 1971-10-18
US3709836A (en) 1973-01-09
SE382464B (en) 1976-02-02
US3704267A (en) 1972-11-28
DK138662B (en) 1978-10-09
CA945034A (en) 1974-04-09
CA954004A (en) 1974-09-03
CH552053A (en) 1974-07-31
DK138662C (en) 1979-03-19
DE2126061A1 (en) 1971-12-09
CA945036A (en) 1974-04-09

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