US 3654166 A
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3,654,166 DETERGENT COMPOSITIONS Hans-Werner Eckert, Dusseldorf, and Arnold Heins, Hilden, Rhineland, Germany, assignors to Henkel & Cie GmbH, Dusseldorf, Postfach, Germany No Drawing. Continuation-impart of application Ser. No. 656,136, July 26, 1967. This application Aug. 2, 1968, Ser. No. 749,596 Claims priority, application Germany, Aug. 14, 1967, H 63,601; May 8, 1968,P 17 67 413.4 The portion of the term of the patent subsequent to Jan. 25, 1989, has been disclaimed Int. Cl. 011d 3/30; D06m 13/38, 13/40 US. Cl. 252-117 9 Claims ABSTRACT OF THE DISCLOSURE Detergent compositions comprising (a) from 20 to 90 wt. percent of at least one surfactant selected from the group of anionic, zwitterionic and non-ionic surfactants, and (b) from 10 to 80 wt. percent of, as textile softener, an N-alkyl-N-acyl-N-polyhydroxyalkyl compound of the formula:
wherein R is alkyl having 10 to 22 carbon atoms, which can be interrupted by an ether oxygen in the vicinity of the nitrogen atom, R is alkyl having 7 to 21 carbon atoms, R, and R together containing from 23 to 39 carbon atoms and Z is a polyhydroxyalkyl having one of the following formulae:
( I) CHZOH 2- I J} 011-- HOH)m and I (011011) HzOH H2OH wherein in has a value of 3 or 4 and n has a value of 2 or 3.
RELATED APPLICATION AND TERMINAL DISCLAIMER This application is a continuation-in-part of Ser. No. 656,136, filed July 26, 1967, by the present inventors. The terminal portion of the life of any patent, based on the present application, extending beyond the life of any patent based on Ser. No. 656,136, is hereby disclaimed.
The compositions of the invention are detergents and represent novel combinations of wash active surfactants and textile softening agents.
The present invention relates to detergent compositions. More particularly, this invention relates to detergent compositions containing wash-active and textile softening agents.
Following the drying, mechanically or otherwise, of washed textiles, particularly those prepared from cotton and similar cellulose fibers, a perceptible hardening of the feel thereof can be detected. This is especially true where these textiles have been washed in drum-type washing machines. This phenomenon is particularly unpleasant in connection with articles of clothing which in their u'se come in contact with the human skin, as for example, in undergarments and in the case of bedding and handkerchieis. It is also true regarding other conventionally laundering items such as table linens, in connection with which a pleasant feel is considered highly desirable.
This undesirable hardening of the feel can be prevented in the laundering process by adding to the final rinse, cationic substances which contain at least two fatty "United States Patent 3,654,166 Patented Apr. 4, 1972 ice radicals of high molecular weight in their molecules. In practice, dialkyl dimethyl ammonium salts which can be suspended in water have been introduced in the form of so-called rinsing agents for this purpose. Since these cationic textile softeners form water-insoluble precipitates with the anionic wash-active substances, they cannot be added to the detergent itself. However, even when they are used in the final rinse, precipitates can be formed between the residues of anionic wash-active substances that remain in the rinse water or on the fibers of the washed textiles, and the cationic textile softeners.
Heretofore no detergent composition has been known which contained a textile softening agent that was compatible with the anionic wash-active agents.
In -accordance with the invention it has now been found that when an anionic and/or hybrid-ionic and/or non-ionic surfactant is mixed with a textile softening agent, the resulting mixture can be used as a textile detergent. The compositions of the invention are mixtures containing:
(a) from 20 to 90% by weight, preferably 30-70% by weight, of a surfactant of the above-named types, and
(b) from 10 to by weight and preferably 30 to 70% by Weight, of an N-al'kyl-vN-acyl-N-polyhydroxyalkyl compounds as textile softener, having the formula R IIIC 0-R,
R, is alkyl having 10 to 22, preferably 12 to 20, and most preferably 16 to 18 carbon atoms; wherein said alkyl can be interrupted by an ether oxygen atom in the vicinity of the nitrogen atom,
R is alkyl having 7 to 21, preferably 11 to 19, and most preferably 15 to 17 carbon atoms; R and R together having a total of 23 to 39, and preferably 27 to 35 carbon atoms, and
Z is polyhydroxyalkyl having one of the following formulae:
CH CH OH JHOEDm and H- H OH IHOH)n JHZOH wherein in has a value of 3 or 4 and n has a value of 2 or 3. (The polyhydroxyalkyl groups Z may be attached etherally to other polyhydroxyalkyl groups.)
Of particular practical importance are those compounds in which m is 4 and n is 3, i.e., derivatives of the glycamines. (These glycamines will be referred to hereinafter as glycamides.) Compounds wherein m is 3 and n is 2 are also suitable for use herein and can be substituted advantageously for the so-called glycamides.
The invention furthermore relates to dry, pasty or liquid detergent compositions and other washing aids containing the above surfactant-softener combinations and containing in addition the other conventional detergent components, the surfactant-softener combination amounting to from 5 to 80 and preferably 15 to 40% by weight, and the additional conventional detergent components amounting to from 20 to 95 and preferably from to 60% by weight of the resulting composition.
The conventional detergent components which can be present include, for example, neutral to alkaline reacting builder substances, complex formers, bleaching components, suds stabilizers, suds inhibitors and dirt carriers.
The invention additionally relates to Surfactant-textile softener combinations usable as textile deterents, as well as detergent compositions or washing adjuvants containing such surfactant-textile softener combinations which are characterized by a content of enzymes.
Instances of suitable enzymes include the proteases, amyla-ses, which can be incorporated into the compositions according to the invention either singly or in any combination. If the products are detergent compositions or washing adjuvants, the protease content can correspond to activities of 50 to 5000, and preferably 100 to 2500 LVE/ g., their amylase content can correspond to activities of 20 to 5000, preferably 50 to 2000 SKBE/g, and their lipase content to activities of 2 to 1000, preferably from 5 to 500 IE per gram of detergent or Washing adjuvant.
If the compositions according to the invention are surfactant-textile softener combinations as are often used in industrial laundries in combination with conventional builder materials, the enzyme content of such compositions should be regulated so that the preparation composed of the surfactant-textile softener combination toether with the other components of the detergent or washing aid are of the enzyme content stated above. As the surfactanttextile softener combination can amount to from 5 to 80%, and preferably from to 40% of the total detergent composition or of the washing aid, the enzyme activities for the surfactant-textile softener combinations are calculated at 62.5 to 100,000 LVIE for proteases, 25 to 100,000 SKBE for amylases, and 2.5 to 20,000 IE for lipases, per gram of surfactant-textile softener combination. Surfactant-textile softener combinations having activities close to the upper limits can be produced only if very active enzyme preparations are available. This is why the maximum activities are usually around 50,000 LVE, 50,000 SKBE and 10,000 IE per gram of surfactant combination. The enzyme activities preferably range from 250 to 15,000 LVE, 125 to 15,000 SKBE and 12.5 to 3,500 IE per gram of surfactant combination.
The above data on the enzyme contents and activities of the preparations according to the invention are based on the activities of those enzyme preparations which, on the date of filing, appeared to be usuable in the detergent field from the economic viewpoint. From the chemical standpoint, the enzyme activities of the preparations according to the invention can be increased as needed, so that the activities in the case of proteases and amylases can be increased up to 5 times, and in the case of lipases up to 10 times, the maximums stated above. If, therefore, enzyme preparations having higher contents of active enzyme should be made available in the future, which appear to be suitable for use in the detergent field from the economic viewpoint, the option of keeping the enzyme activity of the preparation at the above-stated level using smaller quantities of enzyme, or of increasing the enzyme activity using the same quantity of enzyme is presented.
Reference is made of the following literature in regard to determining enzyme activities:
Determination of activity of proteases by the method of Lohlein-Volhard: A. Kunzel: Gerbereichemisches T aschenbuch, 6th ed., Dresden and Leipzig, 1955 Determination of activity of amylases: I. Wohlgemuth: Biochernische Zeitschrift, vol. 9 (1908), pp. 1-9, and
'R. M. Sandstedt, E. Kneen and M. J. Blish: Cereal Chemistry, vol. 16 (1939), pp. 712-723 Determination of activity of lipases: R. Willstatter, 'Waldschmidt-Leitz and Fr. Memmen: Hoppe-Seylers Zeitschrift fur Physioloische Chemie, vol. 125 (1923), pp. 110117, and R. Boissonas: Helvetia Chimica Acta, vol. 31 (1948), pp. 1571-1576.
The glycamides suitable for use in formulating the mixtures in accordance with the invention can be produced by amidation in the known manner from the corresponding glycamines which are obtained by the hydrogenation of hexoses or oligomers thereof using Raney nickel and in the presence of higher alkylamines.
The hexoses employed in the hydrogenation are preferably monosacchardies such as glucose, mannose, galactose, fructose, sorbose or mixtures thereof, such as invert sugar. However, the oligomers thereof can also be used, such as, for example, maltose. Pentoses or pentose mixtures can be process in the same manner, in which case, compounds in which in is 3 and n is 2 are obtained, the same also being suitable for use as the textile softening agent. Mixtures of pentoses and hexoses can also be advantageously used.
The alkyl radicals of the amines which are used in the preparation of the textile softeners according to the invention can be similar to the radicals of the amidally bonded fatty acids, saturated or unsaturated, straight-chained or branched, and of synthetic or natural origin. Accordingly, the radicals R can be derived from decylamine, lauryl amine, myristylamine, cetylamine, stearylamine, oleylamine, arachylamine or behenylamine. The carbon chains of these alkyl radicals may also be interrupted by ether oxygen atoms in the vicinity of the nitrogen atom and preferably between carbon atoms 2 and 3 or 3 and 4, respectively (counting from the nitrogen atom).
The fatty acid radicals R -CO- can be derived from capric, lauric, myristic, palmitic, stearic, oleic, arachinic or behenic acid. Since the amines used for the preparation of the textile softeners are obtainable from the corresponding fatty acids through the amides or nitriles, both the alkyl amines and the fatty acid radicals may be 'in the form of homologous mixtures, as they are found, for example, in fats of natural origin. Accordingly, the radicals R and R CO- can be prepared from fats derived from plant, marine or land animal sources. They can be obtained, for example, from coconut oil, palm oil linseed oil, cottonseed oil, peanut oil, rape oil etc. hog lard, tallow, fish oil, whale oil or from fractions of the fatty acids contained in these fats and oils. The aforesaid radicals are preferably to be of a substantially saturated nature.
The invention is of particular practical importance in connection with the so-called complete detergents, i.e., the detergents that are used in the main washing process. These may be machine detergents characterized by low sudsing action, or even all-purpose detergents exhibiting good sudsing at temperatures up to 60 C. with the production of suds diminishing as the temperature rises above 60 C. In addition to surfactant components, such detergents may simultaneously contain foam stabilizers and foam inhibitors having an activity that depends directly on the prevailing temperature. The surfactant components usually comprise synthetic anionic, zwitterionic and/or non-ionic surfactants and soaps having, for example, 12 to 18 carbon atoms in their fatty acid radicals or in the free fatty acids corresponding to the soaps. The surface active sulfonates are of particular practical importance as synthetic anionic surfactants, as are the corresponding sulfates. The anionic surfactant component usually amounts to 50% of the entire surfactant content as has been set out above.
The sudsing ability of anionic and/or non-ionic surfactants can be controlled by the selection of appropriate fatty acid components. The suds inhibition, especially at elevated temperatures of from 60 to C., increases with the carbon number and with the degree of saturation of the fatty acid radical. A powerful suds inhibition is realized with synthetic anionic, zwitterionic or non-ionic surfactants by saponification from fatty acid mixtures consisting of at least 50% of fatty acids having 16 to 30 carbon atoms and at least 3%, and preferably of more than 5%, of fatty acids having 20 and more carbon atoms, wherein the saturated fatty acids containing at least 16 carbon atoms amount to at least 50% of the total soap content. The content of soap can be eliminated, or alternatively, can be replaced by synthetic wash-active substances, providing that the detergent composition contains other suds inhibiting substances, such as hereinafter set out.
Where the complete detergent in accordance with the invention contains, in addition to the surfactant combination, neutral to alkaline reacting builder materials, the quantity thereof usually ranges between 0.5 and 7 times, and preferably between 1 and 5 times the surfactant combination. Preferably, enough alkali is present in the latter builder materials so that a 1% solution of the finished detergent has a pH ranging from 8 to 12, and preferably from in the range of 9 to 11.
The composition of the complete detergents which are of particular practical importance are set out by the following ranges of components:
8-50, and preferably 12 to 30 wt. percent of a surfactant combination, containing:
-90, and preferably 25-70 wt.-percent of a surfactant of the sulfonate or sulfate type.
0-90, and preferably 540 wt.-percent of a non-ionic surfactant.
0 90, and preferably 10-50 wt.-percent soap.
10-80, and preferably 30-70 wt.-percent of a textile softener.
0-6, and preferably 0.5-3 Wt.-percent of a foam stabilizer.
08, and preferably 0.5-5 wt.-percent of a foam inhibitor, preferably a non-surface active foam inhibitor,
20-89, and preferably 40-85 Wt.-percent of builder substances, at least a portion of this component reacting alkalinely; the quantity of the alkaline and neutral reacting builder substances amounting preferably to from 0.5 to 7 times, and most preferably to from 1 to 5 times, the total wash-active substance.
3-30 wt.-percent of other detergent components, such as bleaching components and water.
The anionic, zwitterionic or non-ionic surfactants present in the surfactant combinations or detergents according to the invention contain in their molecules at least one hydrophobic radical having 8 to 30 carbon atoms and one anionic or non-ionic water-solubilizig group. The hydrophobic radical may be of an aliphatic or alicyclic, saturated or unsaturated nature, and may be directly bonded to the water-solubilizing group or through an intermediate. The intermediate can be, for example, a benzene ring, carboxylic acid ester group, carbonamide group, ethylene glycol radical or propylene glycol radical.
The hydrophobic radical is preferably an aliphatic hydrocarbon radical having about 10 to 18 carbon atoms, variations from this preferred number being possible, depending on the nature of the surfactant involved.
Those soaps which are suitable for use as anionic washactive substances are derived from natural or synthetic fatty acids, or, if desired, from resinic or naphthenic acids.
Of the synthetic anionic surfactants, the sulfonates and sulfates are of particular practical importance.
The sulfonates include, for example, the alkylaryl sulfonates, particularly the alkylbenzenesulfonates. Aliphatic sulfonates are also of interest, such as those which can be obtained, for example, from preferably saturated hydrocarbons containing 8 to 18 and preferably 10 to 16 carbon atoms in their molecules by 'sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen, followed by conversion of the products thus obtained to the corresponding sulfonates. Furthermore, mixtures of alkenesulfonates, hydroxyalkenesulfonates and hydroxyalkanesulfonates, such as those obtained, for example, from terminal or non-terminal C to C olefins by sulfonation with sulfur dioxide followed by acid or alkaline hydrolysis of the sulfonation products, can serve as aliphatic sulfonates. In the aliphatic sulfonates thus obtained, the 'sulfonate group is often positioned on a secondary carbon atom. However, by utilizing the reaction of terminal olefins with bisulfite, it is possible to prepare sulfonates having a primary, i.e., terminal sulfonate group.
The sulfonates which may be used according to the invention include esters formed by reacting ot-sulfofatty acids with monovalent or polyvalent alcohols containing 1 to 4 and preferably 1 to 2 carbon atoms.
Illustrative of the surfactants of the sulfate type are the fatty alcohol sulfates, particularly those derived from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Sulfonation products of the sulfate type which can be used according to the invention can also be prepared from terminal or non-terminal C to C olefins. This group of surfactants also includes sulfatized fatty acid alkylolamides, sulfatized monoglycerides and sulfatization products of ethoxylated and/or propoxylated fatty alcohols, alkyl phenols having 8 to 15 carbon atoms in their alkyl radicals, fatty acid amides, fatty acid alkylolamides, etc., 0.5 to 20 moles, preferably 1 to 8 moles and preferably 2 to 4 moles of ethylene and/or propylene oxide can be added to one mole of the afore-mentioned ethoxylated and/or propoxylated compounds.
Instances of other usable sulfonates, include, the fatty acid esters of oxyethanesulfonic acid and of dioxypropanesulfonic acid, as well as'the fatty acid amides of aminoethanesulfonic acid.
The detergent compositions according to the invention may also contain surface active synthetic carboxylate's, such as for example, the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the fatty acid amides of aminocarboxylic acids such as glycocol or sarcosine.
The non-ionic surfactants which are hereinafter referred to as non-ionics include products, the solubility of which in water is attributable to the presence of polyether chains, a-minoxide, sulfoxide or phosphinoxide groups, alkylolamide groupings, and generally, to an accumulation of hydroxyl groups.
Of particular practical interest are the products which are obtained by the addition of ethylene oxide and/or glycide onto fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid amides and sulfonic acid amides. The'se non-ionics contain from 4 to 100, preferably 6 to 40, and most preferably 8 to 20 ether radicals, and in particular ethylene glycol ether radicals, per molecule. Further, propylene or butylene glycol ether radicals may also be present in these polyglycol ether radicals or terminally located thereon.
The non-ionics still further include the Water-insoluble polypropylene glycols which have been made Water-soluble by the addition thereto of ethylene oxide and are well known by the tradenames Pluronics and Tetronics" and also the products of the addition of propylene oxide onto alkylene diamines or lower aliphatic alcohols containing l to 8 and preferably 3 to 6 carbon atoms, known by the commercial name Uncon Fluid.
Suitable as non-ionics are also the fatty acid or sulfonic acid alkylolamides, which are derived, for example, from monoor dialkylolamine, from dioxypropylamine or from other polyoxyalkylamines, such as the glycamines. They can be replaced by amides prepared from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.
As aminoxides, the non-ionics derive from higher tertiary amines having one hydrophobic alkyl radical and two shorter alkyl and/0r alkylol radicals containing up to 4 carbon atoms each have proved to be of particular interest.
The sudsing ability of the detergents according to the invention can be increased or diminished by appropriate combinations of the different surfactants. Thus for example, the addition products of propylene oxide and the above-described polyethylene glycol others are characterized by a low sudsing capacity. By varying the number of ethylene glycol and propylene glycol radicals present in the molecule, products can be obtained having very varied turbidity points. These non-ionics act as suds inhibitors on other non-ionics at temperatures above their respective turbidity points. As a result, they can be used in the surfactant combinations according to the invention together with other non-ionics and they can also be used in combination with other surfactants, as non-ionic component, for example, in the previously mentioned combinations of sulfates and/or sulfonates, soaps and nonionics.
The detergents, however, may also contain suds inhibitors which are not surfactants. These include, for example, hydrocarbons of high molecular weight, such as paraffin, fatty acid esters, for instance, fatty acid triglycerides, or fatty acid esters of monovalent alcohols, etc. These foam inhibitors have a good effect, particularly in combinations of soap and surfactants of the sulfonate type.
Products of the reaction of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, have proven to be of particular practical importance. The tri to hexa-alkylmelamines or dito tetraalkyldiaminechlortriazines thusly obtained have a remarkably broad spectrum of activity which is independent of the type of surfactant involved, so that they are very well suited, either alone or in combination with one another or in combination with the I previously mentioned foam inhibitors, for suppressing the sudsing activity of surface active sulfates or sulfonates, soaps, zwitterionic or non-ionic wash-active substances, independently of whether the surfactant or surfactant combination involved has of itself a low or high sudsing capacity.
The action of these suds inhibitors is temperature-dependent, and usually starts at a point within the melting range of the suds inhibitor. This provides an additional way of adapting the temperature-dependence of the dctergent to the requirements of practice.
The surfactant combinations of the invention can be marketed as such, for use in conjunction with wash alkalies, complex formers and other conventional components used in the washing medium by commercial laundries. However, the surfactant combinations can also be combined with these conventional detergent additives to make a ready to use laundry detergent or laundry aid.
Of the conventional detergent additives, the watersoluble condensed phosphates, particularly the pyro-, trior tetrapolyphosphates are of special practical importance.
They can be replaced by the known organic complex formers or alternatively can be combined with them.
The latter include, for example, nitrilotriacetic acid, ethylenediaminetetracetic acid, N-oxycthylethylene-diaminetriacetic acid, polyalkylene-polyamine-N-polyacetic acids and other known organic complex forming agents, it also being possible to use combinations of different complex formers. As illustrative of the other known complex formers, there may be mentioned the diand polyphosphonic acids having the following formulae:
no on HO OH and x on l it ou wherein R represents alkyl and R alkylene having 1 to '8, preferably 1 to 4, carbon atoms, and X and Y represent hydrogen or alkyl having 1 to 4 carbon atoms. Carboxymethylcnephosphonic acid (HOOCCH PO(OH) can also be used according to the invention as a complex former. The aforesaid complex formers can all be present as free acids, but preferably are employed as their alkali salts.
In place of the condensed phosphates, or instead of the complex formers, or in combination with the latter, alkali reacting builder materials can be present in the detergents according to the invention. These include such materials as the carbonates, bicarbonates or silicates of the alkalis. Neutrally reacting inorganic or organic salts can also be incorporated into the detergent compositions as, for example, the alkali salts of sulfuric acid, benzene, toluene-, naphthaline-sulfonic, or sulfobenzoic or sulfoacetic acid or the salts of sulfodicarboxylic acids.
The detergents according to the invention are used preferably as white laundry detergents at boiling temperatures erably as white laundry detergents at boining temperature or close to boiling temperature. Therefore they advantageously are formulated to contain a bleaching component based on active oxygen or active chlorine.
Bleaches on the basis of active oxygen include the in organic per compounds, such as perpyrophosphates, perpolyphosphates, percarbonates and perborates. Commercial sodium perborate having the approximate composition NaBO -H O -3H O is of particular practical importance. In place of the latter, perborates can be used which are partially or completely dehydrated, i.e., dehydrated down to the approximate composition NaBO -H O Further, NaBO -H O borates containing active oxygen can be used, in which the ratio of Na O to B 0 is less than 0.5 l, and preferably ranges from 0.4 to 0.15:1, and in which the ratio of H 0 to Na ranges from 0.5 to 4:1. These products are described in German Pat. 901,287 and in US. Pat. No. 2,491,789.
As illustrative of the active chlorine compounds that can be used as bleaching agents in the detergent compositions of the invention, there are included compounds of both an inorganic and organic nature. The inorganic active chlorine compounds include alkali hypochlorites, which are preferably used in the form of their mixed salts or of compounds formed by addition onto orthophosphates or onto condensed phosphates, such as pyroand polyphosphates, or alkali silicates. If the detergent compositions and washing aids contain monpersulfates and chlorides, active chlorine forms in aqueous solution.
As organic active chlorine compounds there are preferably used the N-chlorine compounds in which one or two chlorine atoms are bonded to a nitrogen atom, the third valence of the nitrogen atom being preferably jointed to a negative group, as for instance, to a CO' or group. These compounds include dichloroand trichlorocyanuric acid, chlorinated alkylguanide or alkylbiguanides, chlorinated hydantoins and chlorinated melamines.
The detergent compositions can furthermore contain stabilizers for the bleaching component, and particularly for the per compounds if the same are present. Often the complex formers as set out above have a stabilizing action.
,However, other types of stabilizers may be present in their stead or together with them, as for example, those stabilizers acting as such by virtue of their large surface area. Such stabilizers include, for example, the silicates of magnesium or tin. Water-insoluble stannic acid can also be used as a stabilizer.
The action of the bleaching components and primarily of the per compounds can be promoted by activators as known in the prior art. These include small quantities of heavy metal ions, particularly copper ions, which are present, preferably in the form of mixed silicates of magnesium.
Dirt carriers may also be contained in the detergents of the invention. The latter act to keep the dirt which is removed from the fibers in the Washing suspended in the Wash water and thereby preventing graying. Water-soluble colloids, usually of an organic nature, are suitable for this purpose, such as for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether carboxylic acids, and ether sulfonic acids of starch or cellulose, and salts of acid sulfuric esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. Starch can also be used as can, starch products other than those named above, such as for example, decomposed starch, aldehyde starches, etc. Polyvinylpyrrolidone is also suitable for use as a dirt carrier.
The enzymes which are suitable for use in accordance with the invention can be derived from animals, microorganisms (such as bacteria or fungi) and plants, and particularly from digestive ferments, yeasts and bacteria strains. Generally they are composed of a mixture of different enzymatic agents of complex composition. Such compositions are called proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, des-molasses or nucleases, according to the nature of their action. The enzymatic agents obtained from bacterial strains or fungi, such as Bacillus subtilis and Streptomyces griseus have proved to be of particular advantage. Instances of other usable enzymes are pepsin, pancreatin, trypsin, papain and diastase. The enzyme preparations derived from Bacillus subtilis, however, have the advantage over the latter enzymes in that they are relatively resistant to alkali, per compounds and anionic Wash-active substances, and are not appreciably inactivated even at temperatures between 45 and 70 C. Their relativel great stability against oxidizing agents is based possibly on the low content of free sulfhydryl groups.
The enzymes are marketed by the manufacturers usually in preparations to which cutting agents have been added. Sodium sulfate, sodium chloride, alklai ortho-, pyroor polyphosphates, particularly tripolyphosphate, are suitable as cutting agents. Often the still moist enzyme preparations are combined with calcined salts, which then bind the water of crystallization that may be present in the enzymatic agent, while agglomerating the particles into larger particles if desired.
If the enzymatic agents are available as dry products, it is possible to use the non-ionic organic compounds in liquid or paste form, such as ethylene glycol, polyethylene glycols, butylene glycol or polybutylene glycols and the known surfactants in liquid to paste form which are obtained, for example, by addition of ethylene oxide and, if desired, propylene oxide onto the starting materials used for the production of such products, for the purpose of binding the enzymatic agent to the preparation that is to be made in each case. For this purpose, a mixture of the components of the surfactant combination or detergent composition and the enzymatic agent is sprayed together with the non-ionic or the enzymatic agent is dispersed in the said non-ionic substances and this dispersion is combined with the remaining components of the composition. If the balance of the components of the composition are solids, the dispersion of the enzymatic agents in the non-ionic components can be sprayed onto these solid components.
If textiles, particularly those on a basis of cotton, which have been soiled with proteinic, starchy and/ or oily stains,
are washed with the surfactant-softener-enzyme combinations according to the invention or with the detergent compositions according to the invention, the enzymes which they contain bring about a more rapid removal of the stains, even at relatively low temperatures, particularly when the stains consist of dried blood, pus, gravy, etc. The textile softeners contained in the products of the invention can then act on the textiles at a relatively early point in the washing process. In this manner a combined action of the enzymes and of the textile softeners is achieved.
If it is desired to market, not the final detergents, but surfactant-softener combinations having an enzyme content, this is quite possible. The formulas for such enzymecontaining surfactant-softener combinations can easily be obtained from the above examples by eliminating the builder materials (from CMC to perborate, as Well as such components as the dye and perfume). Nevertheless, it is possible to incorporate into the surfactant-softenerenzyme combinations builder materials in small amounts and also such substances as dirt carriers (CMC), complex formers (EDTA) and brightening agents.
The invention is illustrated but not limited to, by the following examples.
The following glycamides have proven to be suitable for use as textile softening agents in the surfactant-softening agent combinations according to the invention and in the detergent compositions or washing aids containing them. In a number of the compounds the radicals R1\- and/or R CO' are derived from fatty acid mixtures of natural origin. The unsaturated fatty acids contained in these fatty acid mixtures were saturated to a substantial degree in the course of the process of their manufacture. The radicals R -CO however, are of the same degree of saturation as the fatty acid mixtures from which they are derived.
(a) Glucamide 1= 12 25 2= rl a5 Total 29 C atoms Glucamide r= 14 29 2 l5 31 Total 29 C atoms Glucamide r= 1e a3 2= 11 23 Total 27 C atoms Glucamide 1= 1a si R2:C'1H15 Total 25 C atoms Glucamide R1'=C36H6OC16H33 2= 15 a1 Total 34 C atoms Glucamide R =C to C mixture from coconut fatty acid, avg.
approx. C R =C to C mixture from tallow fatty acid, avg.
Total approx. 29 C atomn Glucamide R =C to C mixture from tallow fatty acid, avg.
approx. C R =C to C mixture from coconut fatty acid, avg.
Total approx. 30 C atoms Fructamide R =C to C mixture from coconut fatty acid, avg.
approx. C R :C to C mixture from tallow fatty acid, avg.
Total approx. 29 C atoms (i) Glucamide mixture from invert sugar R =C to C mixture from coconut fatty acid, avg.
Rg=C to C mixture from tallow fatty acid, avg.
Total approx. 29 C atoms (j) Glucamide mixture from invert sugar R =C to C mixture from tallow fatty acid, avg.
approx. C R =C to C mixture from coconut fatty acid, avg.
Total approx. 29 atoms In the following examples there are described the compositions of a number of surfactant-softener combinations according to the invention and of a number of detergents containing such surfactant-softener combinations. The following terms which are used in examples are defined as follows:
ABS-represents the salt of an alkylbenzenesulfonic acid obtained by condensing straight-chained olefins with benzene and sulfonating the alkylbenzene thus produced; the resulting alkylbenzen'e sulfonate having to 15 and preferably 11 to 13, carbon atoms in its alkyl chain.
Olefin sulfonate-designates a sulfonate (usually 12-16 carbon atoms) obtained by sulfonating a straightchained terminal or non-terminal olefin with 50;; and thereafter hydrolyzing the sulfonation product with lye. It is comprised essentially of alkenesulfonate and hydroxyalkanesulfonate, but also contains small amounts of disulfonates.
Oleyl alcohol-+10 EO--Coconut alcohol+ EO Nonylphenol+9.5 or +60 E0 as the case may beidentify products formed by the addition of the stated amount of ethylene oxide onto the hydroxyl compounds named (coconut alcohol=an alcohol made from coconut fatty acid).
Coconut alcohol+9 EO'+12 PO--represents a product formed by the reaction of 12 moles of propylene oxide with a product of the addition of 9 moles of ethylene oxide onto 1 mole of a coconut alcohol.
Fatty acid monoethanolamide+8 EOrepresents a product formed by the addition of 8 moles of ethylene oxide onto 1 mole of monoethanolamide prepared from coconut fatty acid.
The composition of the fatty acid mixtures from which the various soaps contained in the surfactant combinations or detergent compositions are derived can be seen in the following table:
TABLE I.-COMPOSITIONS OF THE FATTY ACID MIXTURES CO RRESPONDING TO THE SOAPS Unless otherwise stated, the anionic surfactants and other salts are present in the form of their sodium salts. All percentages are percentages by weight.
In the examples, the suds inhibitor is associated with the surfactant combination. This is incorrect, insofar as the special suds inhibitors mentioned in the description of the invention are not to be considered as surfactants. They are nevertheless listed together with the surfactant combination because they certainly affect the sudsing ability of the surfactants. In the preparation of the detergent compositions the suds inhibitor used in each case was dissolved in a suitable organic solvent or motten and sprayed by means of a nozzle onto the moving surfactant combination or detergent which was in powder form. Where surfactant combinations containing synthetic sulfates or sulfonates in admixture with soap are involved, parafiin or paraffin oil, for example, is suitable for suds inhibitor. In the case of the surfactant combinations described, an N-N'-N"-trialkylmelamine was used as the suds inhibitor. Equally good results were obtained when this suds inhibitor was replaced by a bis-(alkylamino)- monochlortriazine or with a mixture of 10 to of the melamine derivative and 90 to 10% of the chlortriazine derivative. In all of these triazine derviatives, the alkyl radicals were in the form of mixtures of homologs having from 8 to 18 carbon atoms. The suds inhibiting action set in at temperatures of about 50 C. and reached its full extent at temperatures above 65 C.
The following Examples 1 to 8, describe various surfactant combinations containing percentages of the textile softening agents according to the invention.
Example 1(a) Percent ABS 42 Oleyl alcohol+l0 EO 14 Soap E 6 Textile softeners (a-j) 38 Examples 1(b) and (c) In the surfactant combination according to Example 1(a), (b) 25% of the weight of the ABS was replaced by olefin sulfonate (c) all of the ABS was replaced by alkane sulfonate. Products that were similarly usable were obtained in each instance.
Example 2 Percent ABS 37 Oleyl alcohol+l0 EO l7 Textile softeners (aj) 46- Example 3 Percent ABS 44 Oleyl alcohol+ 10 E0 14 Soap D 4 Textile softeners (a-j) 38 Example 4 Percent ABS -1 34 Fatty acid ethanolamide+8 EO 13 Soap C 20 Textile softeners (a-j) 33 Example 5 Percent Coconut fatty alcohol+20 E0 48 Coconut fatty alcohol+9 EO+12 PO 25 Textile softeners (a-j) 27 Example 6 Percent ABS 49 Oleyl alcohol-H0 EO l6 Textile softeners (a-j) 33 Suds inhibitor 2 Example 7 Percent Olefin sulfonate 32 Oleyl alcohol+10 E0 i 16 Soap A 15 Textile softeners (a-j) 34 Suds inhibitor s-....---..--..-...--........... 3
13 Example 8 Percent Olefin sulfonate 32 Oleyl alcohol-l-IO EO 16 Soap B t 14 Textile softeners (a-j) 34 Suds inhibitor 4 The following examples describe a number of detergents which cont-ain combinations of basic materials in addition to the surfactant combinations according to Examples 1 to 8.
Example 9 Percent Surfactant combination per Examples 1-8 19 Na P O1 45 Na O-3.3SiO 4.5 MgSiO v i 1.0 CMC 1.5 N3BOZHZOZ'3HZO Rest: Brighteners, perfume, sodium sulfate and wate Example Percent Surfactant combination per Examples l-8 20.8 Nil-51 301 Y N3203.3Sl02 MgSiO 2.5 CMC 0.8 NaBO -H O -3H O 31.3
Rest: Brighteners, perfume, sodium sulfate and water.
Example 12 Percent Surfactant combination per Examples 1-8 19.5 Nitrilotriacetate 19.0 Hydroxyethanediphosphonate 14.0 Na P O NaBO -33SiO 4.5 MgSiO n 1.0 CMC 1.5 NaBO 'H O -3H O 16.0
Rest: Brighteners, perfume, sodium sulfate and water.
Rest: Brighteners, perfume, sodium sulfate and water.
14 Example 15 Percent Nonylphenol+60 E0 12.0 Soap D 4.0 Textile softener (f) 20.0 Sodium hexametaphosphate 40.0 Na O'-3.3SiO 4.0 MgSiO 2.4 CMC 1.6 NaBO2'H2O '3H2O Rest: Brighteners, perfume, sodium sulfate and water.
Same composition as in (a), but with only 10% textile softener (f).
Example 16 Percent Sodium salt of a methylesterified a-sulfofatty acid from hydrogenated tallow 12.0 Soap E 4.0 Textile softener (f) 20.0 Sodium hexametaphosphate 40.0 Na o-assio 4.0 MgSiO 2.4 CMC 1.6
'NaBO H202 Rest: Brighteners, perfume, sodium sulfate and water.
0 Same composition as (a), but with only 10% textile softener (f).
Example 17 Percent Olefin sulfonate from C -C olefin 12.0 Soap D 4.0 Textile softener (f) 20.0 Sodium hexametaphosphate 40.0 Na O-3.3SiO 4.0 MgSiO' 2.4 CMC 1.6
NaBO3'H202'3H2O Rest: Brighteners, perfume, sodium sulfate and water.
The detergents of Examples 9 to 12 and 14 to 17 contain sodium perborate tetrahydrate as the bleaching component. This can be replaced wholly or partially by other per compounds, such as those mentioned in the description of the invention. lActive chlorine compounds can be used instead of the per compounds. If no value is placed on the bleaching component it can be eliminated all together along with the magnesium silicate serving as its stabilizer. In such cases the percentages of the bleaching component and magnesium silicate are replaced by increasing the percentages of the other components proportionally, unless it is desired, for special reasons, to increase the percentage of a certain component, such as the surfactant, the textile softener or the builder material by that amount.
If terrycloth is washed in a drum-type Washing machine under the usual conditions, using the described detergents, the fabric is fluffy after drying and has a softer feel than when it is washed using a detergent of the same composition in which the textile softener has been replaced by the same amount of sodium sulfate. The difference in the compressibility and in the feel of the fabric becomes more apparent after several washings.
:Detergent compositions were prepared in the conventional manner, with a composition that differed from those of Examples 9 to 17 only in that they also contained enzymes. For this reason, only the quantities of the enzymes are now set out it being possible, depending on the desired effect, to add any enzyme or any enzyme combination in accordance with the invention to any of the detergent compositions described in the above examples. The enzymes which were employed were the commercially available products which had been adjusted to the following activities by the manufacturer by adding sodium sulfate in quantities of about 7 to 15%:
A protease having 125,000 LVE/g. An amylase having 75,000 SKBE/ g. A lipase having 10,000 IE/ g.
In addition to the quantity of enzyme utilized, the enzyme activity is set out in the examples, with reference to one gram of detergent.
The suds inhibitors were incorporated into the detergents compositions in the same manner as described above or alternatively they were mixed in the form of fine powders with the detergent. If they were sprayed on, the suds inhibitors were fixed to the solid particles of the preparation or to a solid component of the preparation; it is even possible that they wholly or partially envelop the said particles.
(A) A detergent composition according to Examples 9-17 containing 0.3-1.5 wt. percent protease (375-1875 LVE/g.).
(B) A detergent composition according to Examples 9-17 containing 1.2 wt. percent lipase (120 IE/g.).
(C) A detergent composition according to Examples 9-17 containing 0.4 wt. percent protease (500 LVE/g.) and 1.0 wt. percent amylase (750 SKBE/g.).
(D) A detergent composition according to Examples 9- 17 containing 2.0 wt. percent amylase (1500 SKBE/g.).
(E) A detergent composition according to Examples 9- 17 containing 0.2 wt. percent protease (250 LVE/ g.) and 0.5 wt. percent amylase (375 SKBE/g.) and 0.5 wt. percent lipase (50 IE/g.).
(F) A detergent composition according to Examples 9- 17 containing 1.0 wt. percent protease (1250 LVE/g.) and 0.3 wt. percent amylase (225 SKBE/g.) and 0.4 Wt. percent lipase (4O IE/g.).
What is claimed is:
1. A detergent composition consisting of to 90 wt. percent of at least one member selected from the group consisting of anionic, zwitterionic and non-ionic surfactants and 10 to 80 wt. percent of a textile softening N- alkyl-N-acyl-N-polyhydroxyalkyl compound having the formula:
R NC O-R;
wherein R is (1) alkyl or alkenyl of 10 to 22 carbon atoms, or (2) alkyl or alkenyl of 10 to 22 carbon atoms with an ether oxygen linkage between either the 2 and 3 or 3 and 4 carbon atoms from the nitrogen atom,
R is alkyl or alkenyl of 7 to 21 carbon atoms,
R +R have 23 to 39 carbon atoms, and
Z is (1) -CH (CHO'H) CH OH or (2) -CH (CH OH) (CHOHhCHgOH 2. The composition according to claim 1 wherein R has 12 to 20 carbon atoms, R has 11 to 19 carbon atoms,
16 R -l-R have a total of 27 to 35 carbon atoms, and wherein of 100 parts of the combination of said surfactants and said N-alkyl-N-acyl-N-polyhydroxyalkyl compound, 30 to parts thereof consist of the latter.
3. A composition according to claim 1, wherein said anionic surfactant group member is present in an amount of at least 50% of the total quantity of surfactants present.
4. A composition according to claim 1, additionally containing at least one detergent builder.
5. A composition according to claim 4, wherein the mixture of surfactants and the textile softening compound is present in an amount of from 5 to Wt. percent and said builder substances are present in an amount of from 20 to 95 wt. percent.
6. A composition according to claim 4, additionally containing an active amount of an enzyme selected from the group consisting of the proteases, carbohydrases, esterases, lipases, oxidoreductases, catalses, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases.
7. The composition of claim 6, wherein said enzyme is elected from the group conisting of:
protases 62.5 to 50,000 LVE/ g. of total composition,
amylases 25 to 50,000 SKBE/g. of total composition,
lipases 2.5 to 10,000 IE/g. of total composition.
8. A composition according to claim 4, wherein said mixture of surfactants and textile softening compound is present in an amount of from 8 to 50 wt. percent and comprises:
0 to wt. percent of a member selected from the group consisting of anionic sulfonates and sulfates,
0 to 90 wt. percent of non-ionics,
0 to 90 wt. percent of soap, and
10 to up to 80 wt. percent of said textile softening compound, and wherein said builder substances are present in an amount of from 20 to 89 wt. percent.
9. A method for washing and softening a textile-fabric article comprising laundering said article in water containing dissolved therein a detergent composition according to claim 1.
References Cited UNITED STATES PATENTS LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT, Assistant Examiner US. Cl. X.R. 252-88, 132, 137, 152; 260-404 0 UNl'JIrlI.) s'rlx'l xcs PA'JICN'L omen CERTIFICATE OF CORRECTION Patent No. 3,654, 166 Dated April 4, 1972 Inv nt Hans-Werner Eckert. e15 al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected. as shovm below:
line 5 "Postfach" iri the address should have been omitted line 68 "laundering" should be --laundered- Col. 2 line 25 "compounds" should be --compound-- I line 5 1' "etherally" should be --'ethereally-- line 72 I I "deterents" should be --deterg-ents- .1
Col. 3, line 5 after "amylases" insertend lipases-- Col. 3 line 40 "usuable" should be --usable-- line 66 "Physioloische" should. be --Physiologische'- Col. 4, line 2 "monosacchardies" should be --monosaccharides-- lirie 6 "process" should be --processed-- line 32 ihserta comma after "palm'oil" Col. 5, line 39 I "water-solubilizig" I should -be --water-solubilizing-- UNI'JEI) 5131'11-35 lfAfl'l'lN'l OFFICE. .(lE R llFlCj-l'lli OF CORRECTION P666116 116. 3,654,166 Dated April 4, 1972 I fl' Hans-Werner Eckert, et al It is certified that error appears in thcabovcidcntiied patent and that said Letters Patent are. hereby corrected as shoym below:
061. a, line 28 4 "temperatures" should be temperature-- line 29 cancel in its entiisety line 61 I "j ointed" should be -j oined- -c61.'10,- line 52 "C H 0C H should be C H 00 H line 60 6 "29 C atomn" should be --29 C atoms" line 67 1 f "(h) Fructamide" should be --(h) Glucamide-'- Col. ll -line 58 in the Table, under the heading "C"; 5th, item,
"3" should be --l3-- Col. 13 line 26 6 4 Na 0,3,3Si0 should be -'-MgSi0 3.3 8-1.0
- 2 .2 4 A 3 2 C01. 16 line 18 v f "'catal'ses" should-'be c'atalases v line 21 V "eleqtted'l should be --selected line 22' "protases" should be --p'roteases-- Pz ltcnt No. 3 654 166 Dntcd A ril 4-, 1972 -Invcntor( s) Hans-Werner Ecker-fi, et a1 If is certifiedthat error appears in the above-identifiedpatcnb and that said Letters Patent are hereby corrected as shown below:
Col. 16, line 53 4 1 the reference to British patent '7 l l,423; 5/ l 957 shuld be 771,423 4/1957" 7 Signed and sealed this 10th day of October 1972.
(SEAL) Attest; I
EDWARD M.FLETGHER,JR; ROBERT GOTTSCHALK.
-Attesting Officer 7 Commissioner of Patents