US 3766062 A
Description (OCR text may contain errors)
United States Patent Ghee 3,766,062 LZ-ALKANEDIUL CONTAINING FABRIC SOF'IENING CUMPQSITIQNS Harold Eugene Wixon, New Brunswick, N.J., assignor to Colgate-Palmolive Company, New York, N.Y.
No Drawing. (Continuation of abandoned application Ser. No. 839,697, July 7, 1969. This application Aug. 3, 1971, Ser. No. 168,762
Int. Cl. D06m 13/32 US. Cl. 252-8.7 3 Claims ABSTRACT OF THE DISCLOSURE A fabric softening detergent composition comprising a higher 1,2-alkanediol and conventional detergent additives such as alkyl benzene sulfonates, hydrotropes, brighteners, builders, germicides, suspending agents, antioxidants, bleaches, coloring additives and perfumes. In addition the instant fabric softening composition may comprise the synergistic combination of a higher 1,2-alkanediol with a linear alkyl benzene sulfonate and a higher alkylol sulfate which combination unexpectedly results in superior fabric softening.
This application is a continuation of application Ser. No. 839,697, filed July 7, 1969, and now abandoned.
The present invention relates to the use of higher 1,2- alkanediols as fabric softening agents which may be used in conjunction with other conventional laundering additives.
Furthermore the instant invention is directed to a composition consisting essentially of a higher 1,2-alkanedio1, a linear alkyl benzene sulfonate, and a higher alkylol sulate which composition results in superior fabric softening.
The art of treating textile materials with such agents as brighteners, softeners, antistatic agents, germicidal agents and the like is at this point a fairly well developed and commercially important industry. In almost every instance the finishing of the textile material is accomplished upon the said material from the finishing mill prior to its formation into a garment or wearing apparel. Some of the finishes applied in the mill remain for a period of time with the fabric, but others are removed after or during the first or subsequent washes of the textile material. In the manner of finishing textile goods, fibers such as nylon, Dacron polyester, Orlon acrylic fiber and the like are equally in need of additional treatment to render the wearing properties of the garment acceptable to the trade. Among the desirable properties that may be provided by finishing are enhanced softness, antistatic activity, wrinkle resistance, stiffness or firmness, shape retention, rot resistance and the like. The particular end use of the fabric generally governs the nature of the property modifications provided by mill finishing. It is not generally feasible to effect all property modifications on a single fabric. Moreover, there are many fabrics that are not subjected to mill finishing at all. Therefore, there are many fabrics and garments made therefrom in the hands of consumers that would have enhanced value with certain property modifications.
It is also well known that many of the treatments applied in mill finishing are not durably fixed to fabric. Because of this, desirable properties initially present on the fabric are lost after initial or subsequent washing of the fabric or garments made therefrom. It is obvious, therefore, that the various fabrics or garments need subsequent treatment by the consumer to realize utmost utility and comfort.
The use of various and diverse chemical materials and particularly cationic quaternary ammonium compounds as softeners for textile products is very well known in the art. It is also well known to employ such materials for 3,766,062 Patented Oct. 16, 1973 their softening effect during the laundering operation and particularly in the rinse cycle of the laundering process. This technique has been necessitated by the fact that the softeners heretofore employed, being mainly cationic in nature, are not compatible with the major type of detergent used in the washing cycle. By far the predominating type of detergent used in home laundering processes is anionic in nature and more particularly is of the alkali metal higher-alkyl benzene sulfonate type. To employ a cationic substance, such as the aforementioned softenels, in conjunction with anionic detergent materials, results in a precipitate which is completely ineffective as a fabric softener. This manifestation of incompatibility is also undesirable because it removes detergent from the wash cycle and therefore requires more to accomplish the necessary and desired washing efliciency. As a consequence of these difficulties, it is absolutely necessary to add the presently available cationic softeners to the clothes in the absence of any anionic detergent and where this is done during washing it must be done during the rinsing cycle.
It is also well known that there is a tendency for laundered articles to yellow When treated with cationic agents. This yellowing of the textiles treated with cationics is believed to be caused by: (1) highly colored impurities or by-products in some commercial cationic finishing agents, or (2) the presence of high amounts of iron in the finishing agents that may cause staining typical of iron compounds, or (3) due to the presence of alkali when the materials treated with the cationics are ironed or pressed.
A further disadvantage of the cationic fabric softeners is that many of them are waxy or gummy in nature, making them ditficult to weigh or measure, to mix or disperse With other textile-treating agents, and to place them in a form which may be readily applied to textiles.
It is therefore an object of the instant invention to provide a fabric-softening composition which may be used in conjunction with conventional detergent compositions.
Another object of the instant invention is to provide a detergent composition containing therein a fabric softening agent. It is a further object of the instant invention to provide a fabric-softening composition which may be introduced simultaneously with conventional laundering detergents directly into the wash cycle in a process for the laundering of textiles.
It is yet a further object to provide a fabric-softening composition which may be employed in conjunction with detergents and other cleaning, brightening and laundering additives in a single-step laundering operation.
Another object of the instant invention is to provide a fabric-softening composition comprising a higher 1,2- alkanediol.
A still further object of the instant invention is to provide a fabric-softening composition comprising a higher 1,2-alkanediol in combination with a detergent.
Yet a further object of the instant invention is to provide a fabric-softening composition comprising a higher 1,2-alkanediol, a linear alkyl benzene sulfonate, and a higher alkylol sulfate.
Still further objects and advantages of the instant invention will become apparent from the following more detailed description which appears hereinafter.
The fabric softening detergent compositions of the instant invention comprise a higher 1,2-alkanediol in combination with but not limited to detergent compositions including alkyl benzene sulfonates, hydrotropes, brighteners, builders, germicides, soil suspending agents, antioxidants, bleaches, coloring materials and perfumes.
The useful higher 1,2-alkanediol which may be employed in the instant invention include those 1,2-alkanediol which contain long chain alkyl groups. In the past 1,2-alkanediol with from ten to fourteen carbon atoms have been employed in various detergent compositions such as shampoos as foaming agents and these alcohol esters Were not employed for and did not provide a fabric softening action therein. In the instant invention, however, the useful 1,2-alkanediol are those which contain between fifteen and twenty-two carbon atoms in their alkyl chain. These include hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, eicosanol, stearyl alcohol, heneicosanol, docesanol, cetyl alcohol, and their salts, including the alkali metal and alkaline earth metal salts.
The useful detergents which may be used in conjunction with the instant fabric softening composition include anionic detergents such as alkylbenzene-sulfonic acid and its salts, and compounds of the formula 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 dodccylbenzene sulfonate, potassium dodecylbenzenesulfonate, sodium laurylbenzenesulfonate, sodium cetylbenzenesulfonate. Others are the alkali metal salts of the higher alkylsulfonic acids and the alkali metal dialkyl sulfosuccinates, e.g., sodium dioctylsulfosuccinate, and sodium dihexylsulfosuccinate, sodium sulfoethylphthalate, sodium loeyl-p-anisidinesulfonate; sodium tetradecanesulfonate; sodium diisopropylnaphthalenesulfonate; 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 included 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%) 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 Wollf-Keshner reaction. The 2-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:
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 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 of C10 t0 C22.
The linear parafiin 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 rou g In addition to the paraffin sulfonates illustrated above, others with the general range of C to C alkyls may be used, with the most preferable range being from C to C T11 2 linear alkyl sulfates which are contemplatedin this invention comprise the range of C to C Specific examples include sodium n-decyl sulfate; sodium n-dodecyl sulfate; sodium n-hexadecyl sulfate; sodium n-heptadecyl sulfate; sodium n-octadecyl sulfate; and the ethoxylated (1 to moles ethylene oxide) derivatives; and, of course, the other water-soluble salt-forming catlons mentioned above.
Also useful in conjunction with the instant inventlon are nonionic detergents such as alkaryl polyglycol detergents such as alkyl-phenol-ethylene oxide condensates (2- 200 moles ethylene oxide), e.g., p-isooctyl phenol-polyethylene oxide (10 ethylene oxide units), long chain alcohol-ethylene oxide condensation products (2-200 moles ethylene oxide), e.g. dodecyl alcohol-polyethylene oxides having 4 to 16 ethylene oxide units per molecule, polyglycerol monolaurate, glycol dioleate, sorbitan monolaurate, sorbitan monosterate, sorbitan monopalmitate, sorbitan monooleate, sorbitan sesquioleate, the condensation products of ethylene oxide with sorbitan esters of long chain fatty acids (Tweens), alkylolamides, amine oxides, phosphine oxides, etc.
In addition to the anionic and nonionic detergents which may be employed in conjunction with the instant invention, cationic, ampholytic, and zwitterionic compounds have also been found to be useful. Representative of these compounds which may be employed in conjunction with the instant fabric softening compounds include quaternary ammonium compounds, e.g., distearyl dimethyl ammonium chloride, cetyl trimethyl ammonium bromide, sodium 3-dodecylamino propionate, fatty carbamides, etc.
The useful higher alcohol sulfates which may be employed in connection with the instant invention include those alcohol sulfates which contain long chain alkyl groups. In the past alcohol sulfates with from 10 to 14 carbon atoms have been employed in various detergents compositions such as shampoos as foaming agents and these alcohol esters were not employed for and did not provide a fabric softener action therein. In the instant invention however it has been found that if one employs an alcohol sulfate in combination with a linear alkyl benzene sulfonate and a higher 1,2-alkanediol, one obtains a surprising fabric softening action as compared to the action to the individual ingredients alone. The useful alcohol sulfates are those which contain between 16 and 22 carbon atoms in their alkyl chain. These include for example hexadecyl alcohol sulfate, heptadecyl alcohol sulfate, octadecyl alcohol sulfate, nonadecyl alcohol sulfate, eicosanol alcohol sulfate, stearyl alcohol sulfate, heneicosanol sulfate, docosanol sulfate, cetyl alcohol sulfate, tallol alcohol sulfate and their salts including for example the alkyline metal and alkaline earth salts and the like.
The useful sulfate esters of long chain alkyl alcohols may of course be prepared by conventional esterification reactions in which sulfuric acid is reacted with the alcohol to form the corresponding ester thereof.
The composition of the instant invention may also include, in addition to the fabric softening compounds and conventional anionic, cationic, and nonionic detergent compositions, builders, brighteners, hydrotropes, germicides, soil suspending agents, anti-redeposition agents, antioxidants, bleaches, coloring materials (dyes and pigments), perfumes, wager-soluble alcohols, foam boosters, non-detergent alkali metal benzene sulfonates, 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 II), 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 metals, alkaline earth metals, amine, alkanolamine, and ammonium. Other builders which are salts of oragnic 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 that when one employs a higher 1,2-alkanediol as disclosed above in combination with the above detergents and other conventional detergent additives one obtains an unexpected increase in the fabric softening characteristics of the resulting composition. It has further been found that when one combines specifically a 1,2-higher alkanediol with a linear alkyl benzene sulfonate and a higher alkylol sulfate one obtains still further improvements in the fabric softening characteristics of the resulting compositions.
In the composition of the instant invention we employ from about 0.5 to about of the higher 1,2-alkanediols and preferably from about 2 to about 10% thereof. If a higher alkylol sulfate is employed in the combination one may employ from about 1 to about thereof in a composition comprising said alkylol sulfate and preferably 2 to 15%. The alkylol sulfate is employed in a ratio of from about 0.2-2 to a. 1 part of linear alkylol benzene sulfonate.
The composition of the instant invention may be employed in either particulate, liquid, tablet, or any other conventional form. Furthermore, the compositions of the instant invention may be employed by absorbing the higher 1,2-alkanediol and a variety of water soluble or water dispersable materials such as phosphates, silicates, sulfates, chlorides, ureas, starch, clays, borax and the like. The instant invention will now be illustrated by the following more detailed examples thereof. It is noted, however, that the instant invention is not deemed as being limited thereto.
The distribution of a carbon chain lengths was as follows: C 30%; C 32.4%; C 23.2%; C 12.2%; and the diol composition had an average molecular weight of 260.5 and a melting point of 64 C. The composition was prepared by mechanically blending the ingredients thereof. The composition was then used to wash a terry cloth towel in hot water. The towel was rinsed and dried and subsequently tested for its degree of softness. The towel received a rating of ten on a scale of ten with a rating of ten being considered excellent in so far as softness and fluffiness are concerned and a rating of one indicating no noticeable change. A rating of five cannot generally be dis tinguished by the layman from the rating of one.
EXAMPLE II The ingredients in the above composition were blended In a beaker and heated until a clear, 1 phase liquid was produced. The composition was then used to wash a terry cloth towel in hot water. The towel was rinsed and dried and subsequently tested for its degree of softness as in Example I. The towel had a softness rating of eight.
EXAMPLE III The following detergent composition was prepared:
Percent Linear dodecyl benzene sulfonate, sodium salt 3.3 A1 1,2 octadecanediol 1.0
Sodium tripolyphosphate 6.7
The above ingredients were blended and subsequently used to wash a terry cloth towel in hot water. The towel was rinsed and dned and subsequently tested for its degree of softness as in Example I. The towel was given a rating of eight.
EXAMPLE IV The following detergent composition was prepared:
I Percent L1near dodecyl benzene sulfonate, sodium salt 3.3 A1. 1,2 hexadecanediol 1.0
Sodium tripolyphosphate 6.7
The above ingredients were blended and subsequently used to wash a terry cloth towel in hot water. The towel was rinsed and dried and subsequently tested for its degree of softness as in Example I. The towel was given a rating of eight.
EXAMPLE V The following detergent composition was prepared:
Percent Linear dodecyl benzene sulfonate, sodium salt 20.0 A.I.
Hexadecanediol, 1,2 4.0 Sodium xylene sulfonate 20.0 Potassium pyrophosphate 25.0 Water and impurities Qs.
The above ingredients were blended in a beaker and heated until a clear, 1 phase solution resulted. The composition was then used to wash a terry cloth towel and the towel was rinsed and dried and subsequently tested for its degree of softness. The towel tested was given a rating of eight.
EXAMPLE VI The following detergent composition was prepared:
Percent Linear tridecyl benzene sulfonate, sodium salt 12.0 A.I. Sodium tallow alcohol sulfate 11.00
The above ingredients were blended and the composition was employed to wash a terry cloth towel in hot water as in Example I. The towel was rinsed and dried and subsequently tested for its degree of softness. The towel was given a rating of seven.
EXAMPLE VII The following detergent composition was prepared:
Percent Linear tridecyl benzene sulfonate 12.00 Tallow alcohol sulfate 11.00 1,2-hexadecanediol 5.0
The above ingredients were blended and the composition was employed to wash a terry cloth towel. The towel was rinsed and dried and subsequently tested for its degree of softness. The towel was given a rating of ten.
EXAMPLE VIII The following detergent composition was prepared:
Grams A.I. Sodium dodecyl toluene sulfonate 10 1,2-hexadecanediol 10 Sodium tripolyphosphate 40 The above ingredients were blended and the composition was employed to wash a terry cloth towel. The towel was rinsed and dried and subsequently tested for its degree of softness. The towel was given a rating of eight.
EXAMPLE IX The following detergent composition was prepared:
Grams A.I. Sodium dodecyl toluene sulfonate 10 Sodium tripolyphosphate 40 The above ingredients were blended and the composition was employed to wash a terry cloth towel. The towel was rinsed and dried and subsequently tested for its degree of softness. The towel was given a rating of one.
As will readily be noted by a close scrutiny of the above examples, the addition of a 1,2-alkanedio1 having from 15-22 carbon atoms greatly improves the fabric softening characteristics of a detergent composition. Furthermore, the composition comprising a 1,2-higher alkanediol, a linear alkyl benzene sulfonate, and a tallow alcohol sulfate unexpectedly provided even better fabric softening characteristics.
1. A fabric softening detergent composition consisting essentially of (A) 0.5 to about 10% of a 1,2-C to C alkanediol,
(B) from about 1 to about 20% of a C to C alkylol sulfate, and
(C) a linear C to C alkyl benzene sulfonate, the
ratio of B and C ranging from 0.2 to 2 parts of B per part of C.
2. The composition of claim 1 where the diol is 1,2- hexadecanediol.
3. The composition of claim 2 wherein the alkylol sulfate is sodium tallow alcohol sulfate.
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2,679,482 5/1954 Ross.
2,941,951 6/1960 Jelinek et al.
3,296,145 1/1967 Findlan et al.
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3,392,122 7/1968 Obayashi et al.
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3,686,025 8/1972 Morton 2528.7 X
HERBERT B. GUYNN, Primary Examiner H. A. PITLICK, Assistant Examiner US. Cl. X.R. 252534, 553