CA1231807A - Detergent softener composition - Google Patents
Detergent softener compositionInfo
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- CA1231807A CA1231807A CA000527364A CA527364A CA1231807A CA 1231807 A CA1231807 A CA 1231807A CA 000527364 A CA000527364 A CA 000527364A CA 527364 A CA527364 A CA 527364A CA 1231807 A CA1231807 A CA 1231807A
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Abstract
Abstract The present invention provides a spray cooled softener composition comprising an intimate blend of a cationic amine softener and from 2 to 20% based on the weight of said mixture of a water-soluble non-ionic ethoxylate surface active compound. The composition is useful as an additive in detergent compositions and acts to reduce spot staining caused by the interaction of anionic surfactants and cationic softeners used in conventional detergents.
In addition, the softness of fabrics laundered in detergents which include the composition of the present invention is enhanced.
In addition, the softness of fabrics laundered in detergents which include the composition of the present invention is enhanced.
Description
2 3 1 8 ~7 The presen-t applica-tion is divided out of Canadian Patent Application Serial No. 440,506 filed November 4, 1983.
That invention relates to detergent compositions and in particular to detergent softener compositions capable of impart-ing improved softness, detersive effects, soil an-ti-redeposition and antistatic properties to fabrics treated therewith, particular-ly in a machine laundering process. The detergent compositions are also outstanding in that they result in less greasy staining (due to the cationic softener) of the laundered and dried clothes.
Compositions for simultaneously achieving detergency and an appreciable level of softness in the machine laundering of fabrics, and thus suitable for use in the wash cycle, are well-known and widely available commercially. The fugitive interaction between anionic surfactant, perhaps the most commonly used of the available types of surfactants, and cationic softeners particularly those of the di-lower-di-higher alkyl quaternary ammonium type, is likewise well recognized in the patent literature. Such interaction often results in the formation of unsightly precipit-ates which become entrapped within or otherwise deposited upon the fabric being washed. Discoloration or other aesthetically dis-pleasing effects are for the most part inevitable. the net result is often a depletion in the effective amount of anionic surfactant available for useful purposes since the loss of anionic surfactant is -the primary consequence.
Remedial techniques heretofore proposed to abate the aforedescribed cationic-anionic problem through divergent as to USSN 439,652 I.R. 3975 DIV I
approach seem convergent as to result namely, less than satisfac-tory. Thus, although the most effective types of cationic quaternary ammonium softeners, as exemplified by the aforementioned di-higher alkyl type quats, such as distearyl dimethyl ammonium chloride, can function in the wash cycle in the presence of anionic surfactant, builder, etc., the quantity needed to achieve effective softening is usually coterminous with amounts of pro-motive of undesired cationic-anionic interaction. As a yeneral rule, at least about twice as much cationic softener is required for softening as for antistat~
In United States 3,325,414, dealing primarily with detergents of controlled foam or sudsing capability, the cationic-anionic problem and attendant detrimental effects are discussed in detail. The patent additionally points out that certain quater-nary ammonium compounds, among the class of cationic agents, are generally unstable when heated and when in contact with alkaline builders, the instability being manifested by the development of strong amine odors and undesirable color. The compositions of the patent are limited to the use of quaternary ammonium halides having but one higher alkyl group, the given structural formula for the cationic softener being correspondingly limited. Cationic soften-ers of this type are markedly inferior to the di-higher alkyl types at least insofar as fabric softening activity is concerned.
Other prior art teachings at least tactically avoid the use of cationic softeners altogether proposing the use of, for exaMple, anionic materials as softening agents. United States
That invention relates to detergent compositions and in particular to detergent softener compositions capable of impart-ing improved softness, detersive effects, soil an-ti-redeposition and antistatic properties to fabrics treated therewith, particular-ly in a machine laundering process. The detergent compositions are also outstanding in that they result in less greasy staining (due to the cationic softener) of the laundered and dried clothes.
Compositions for simultaneously achieving detergency and an appreciable level of softness in the machine laundering of fabrics, and thus suitable for use in the wash cycle, are well-known and widely available commercially. The fugitive interaction between anionic surfactant, perhaps the most commonly used of the available types of surfactants, and cationic softeners particularly those of the di-lower-di-higher alkyl quaternary ammonium type, is likewise well recognized in the patent literature. Such interaction often results in the formation of unsightly precipit-ates which become entrapped within or otherwise deposited upon the fabric being washed. Discoloration or other aesthetically dis-pleasing effects are for the most part inevitable. the net result is often a depletion in the effective amount of anionic surfactant available for useful purposes since the loss of anionic surfactant is -the primary consequence.
Remedial techniques heretofore proposed to abate the aforedescribed cationic-anionic problem through divergent as to USSN 439,652 I.R. 3975 DIV I
approach seem convergent as to result namely, less than satisfac-tory. Thus, although the most effective types of cationic quaternary ammonium softeners, as exemplified by the aforementioned di-higher alkyl type quats, such as distearyl dimethyl ammonium chloride, can function in the wash cycle in the presence of anionic surfactant, builder, etc., the quantity needed to achieve effective softening is usually coterminous with amounts of pro-motive of undesired cationic-anionic interaction. As a yeneral rule, at least about twice as much cationic softener is required for softening as for antistat~
In United States 3,325,414, dealing primarily with detergents of controlled foam or sudsing capability, the cationic-anionic problem and attendant detrimental effects are discussed in detail. The patent additionally points out that certain quater-nary ammonium compounds, among the class of cationic agents, are generally unstable when heated and when in contact with alkaline builders, the instability being manifested by the development of strong amine odors and undesirable color. The compositions of the patent are limited to the use of quaternary ammonium halides having but one higher alkyl group, the given structural formula for the cationic softener being correspondingly limited. Cationic soften-ers of this type are markedly inferior to the di-higher alkyl types at least insofar as fabric softening activity is concerned.
Other prior art teachings at least tactically avoid the use of cationic softeners altogether proposing the use of, for exaMple, anionic materials as softening agents. United States
3,676,338 is representative, this paten-t teaching the use of an-ionic softener referred to a.s "branched-chain carboxylic acids,"
as fabric softener. Presumably, anionic detergent would be stable in the presence of -the anionic softener.
As the foregoing demonstrates, the remedies proposed necessitate the discarding of softeners and principally those of the di-higher~di-lower alkyl quaternary ammonium salt and cyclic imide types, these having been determined by experience to be among the most effective softeners thus far developed in the art.
I'he problem of cationic incompatibility in anionic deter gents is also acknowledged in United States Patents 3,936,537 and
as fabric softener. Presumably, anionic detergent would be stable in the presence of -the anionic softener.
As the foregoing demonstrates, the remedies proposed necessitate the discarding of softeners and principally those of the di-higher~di-lower alkyl quaternary ammonium salt and cyclic imide types, these having been determined by experience to be among the most effective softeners thus far developed in the art.
I'he problem of cationic incompatibility in anionic deter gents is also acknowledged in United States Patents 3,936,537 and
4,141,841 and it is therein proposed to employ as an essential ingredient in combination with the cationic substance an organic dispersion inhibitor. An important characteristic of such in-hibitors is a maximum water solubility at 25C of 50ppM. Similar disclosures may also be found in United States Patents 4,113,630;
4,196,104 and 4,272,386. In United States Patent No. 4,230,590 to Wixon heavy duty detergents comprising conventional builder, principally anionic surfactant components, cationic softener and a mixture of fatty acid soap and cellulose ether are disclosed. The soap-cellulose ether mixture is in the form of a spaghetti, flake or other shape and is present in the composition as substantially homogeneously dispersed, discrete particles.
In United States Patent No. 4,298,480 to Wixon heavy duty detergents having compositions similar to that described in the preceding paragraph with the exception that cellulose ether is ex-2~ J 807 cluded therefrom ore disclosed.
In United States Patent 4,329,237 to Wixon heavy duty detergents also similar to those in the preceding two paragraphs are described except that the particles of soap are in admixture with nonionic surfactant.
Although the above mentioned soap and cationic softener containing detergent compositions possess desirable softening and detersive proper-ties, it has been found that optimum softening without spot staining may not be attained.
Our co-pending application Serial No. 440,5061 from which this application is divided, provides stable detergent softener compositions capable of providing improved softness without stain-ing, detergency, antistatic and soil anti-redeposition properties to fabrics treated therewith in a laundering process in cold or hot water.
There is also provided by Application Serial No. 440,506 a particulate detergent softener composition capable of imparting improved softness, detergency, antistatic and nonstain properties to fabrics treated therewith in a laundering process, the composi-tion comprising by weight from about 5 to 40% of water-soluble non-soap, organic surfactant, from about 10 to 60% of water-soluble, neutral to alkaline builder salt, from about 2 to 20% of cationic amine softener-nonionic mixture, and from about 0 to 20% of water-soluble or dispersible fatty acid soap which may be admixed with about 2 to about 50% by weight of nonionic organic surfactant, based on the weight of the soap-nonionic organic surfactant mixture, wherein the cationic-nonionic mixture is substantially homogeneous-ly dispersed in said composition as discrete par-ticles.
In another aspect, our co-pending application provides a process for preparing the composition hereinbefore defined which comprises spray drying the non-soap organic surfactant and builder salt and to the spray~dried material post-adding the balance of ingredients.
The present invention provides a spray cooled softener composition comprising an intimate mixture of a cationic amine softener and from 2 to 20~ based on the weight of said mixture of a water-soluble non-ionic ethoxylate surface active surfactant compound. This composition finds use in the detergent softener compositions of the parent application.
In the spray cooled softener composition the cationic amine softener is preferably selected from (a) aliphaticl di-(lower) Cl - C4 alkyl, di-(higher) C14 - C24 alkyl quaternary ammonium salts, (b) heterocyclic compounds, and mixtures of (a) and (b). Said cationic amine softener is in intimate admixture with a water-soluble nonionic surfactant (2 to 20~ by weight based on weight of cationic amine softener-nonionic surfactant mixture).
By adding the cationic amine softener in intimate admix-ture with the water-soluble nonionic ethoxylate surfactant of the present invention in flakes, granules and the like form, the spot staining of the clothes after drying is substantially mitigated In addition, the softness in the fabrics laundered is generally unexpectedly enhanced. The nonionic surfactant also contributes 3 1 ~7 to soil anti-redeposition, especially in non-phosphate formulas.
The inclusion of the nonionic ethoxylate surfactant in the cationic amine softener composition has the following addition-al advantages. Typically, nonionic surfactants are post-added to spray-dried detergent compositions. As a result, the post-added nonionic surfactant increases the -tackiness of the detergent product. In the present invention, the nonionic surfactant is included with the post-added cationic amine softener which leads to a significant improvement in the flowability of detergent compositions.
The nonionic surfactants useful in admixture with the cationic amine softener are known materials. Such nonionic sur-factants may be broadly defined as water-soluble compounds pro-duced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be ali-phatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between20 hydrophilic and hydrophobic elements.
For example, a well known class of nonionic organic surfactants is made available on the market under the trade mark of "Pluronic"O These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propy-lene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a 2 8 ~7 molecular weight of from about ~,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of -the product is retained up to the point where polyoxyethylene content i5 about 50 percent of the total weight of the condensation product.
Other suitable nonionic synthetic surfactants include:
1. The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about six to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to
4,196,104 and 4,272,386. In United States Patent No. 4,230,590 to Wixon heavy duty detergents comprising conventional builder, principally anionic surfactant components, cationic softener and a mixture of fatty acid soap and cellulose ether are disclosed. The soap-cellulose ether mixture is in the form of a spaghetti, flake or other shape and is present in the composition as substantially homogeneously dispersed, discrete particles.
In United States Patent No. 4,298,480 to Wixon heavy duty detergents having compositions similar to that described in the preceding paragraph with the exception that cellulose ether is ex-2~ J 807 cluded therefrom ore disclosed.
In United States Patent 4,329,237 to Wixon heavy duty detergents also similar to those in the preceding two paragraphs are described except that the particles of soap are in admixture with nonionic surfactant.
Although the above mentioned soap and cationic softener containing detergent compositions possess desirable softening and detersive proper-ties, it has been found that optimum softening without spot staining may not be attained.
Our co-pending application Serial No. 440,5061 from which this application is divided, provides stable detergent softener compositions capable of providing improved softness without stain-ing, detergency, antistatic and soil anti-redeposition properties to fabrics treated therewith in a laundering process in cold or hot water.
There is also provided by Application Serial No. 440,506 a particulate detergent softener composition capable of imparting improved softness, detergency, antistatic and nonstain properties to fabrics treated therewith in a laundering process, the composi-tion comprising by weight from about 5 to 40% of water-soluble non-soap, organic surfactant, from about 10 to 60% of water-soluble, neutral to alkaline builder salt, from about 2 to 20% of cationic amine softener-nonionic mixture, and from about 0 to 20% of water-soluble or dispersible fatty acid soap which may be admixed with about 2 to about 50% by weight of nonionic organic surfactant, based on the weight of the soap-nonionic organic surfactant mixture, wherein the cationic-nonionic mixture is substantially homogeneous-ly dispersed in said composition as discrete par-ticles.
In another aspect, our co-pending application provides a process for preparing the composition hereinbefore defined which comprises spray drying the non-soap organic surfactant and builder salt and to the spray~dried material post-adding the balance of ingredients.
The present invention provides a spray cooled softener composition comprising an intimate mixture of a cationic amine softener and from 2 to 20~ based on the weight of said mixture of a water-soluble non-ionic ethoxylate surface active surfactant compound. This composition finds use in the detergent softener compositions of the parent application.
In the spray cooled softener composition the cationic amine softener is preferably selected from (a) aliphaticl di-(lower) Cl - C4 alkyl, di-(higher) C14 - C24 alkyl quaternary ammonium salts, (b) heterocyclic compounds, and mixtures of (a) and (b). Said cationic amine softener is in intimate admixture with a water-soluble nonionic surfactant (2 to 20~ by weight based on weight of cationic amine softener-nonionic surfactant mixture).
By adding the cationic amine softener in intimate admix-ture with the water-soluble nonionic ethoxylate surfactant of the present invention in flakes, granules and the like form, the spot staining of the clothes after drying is substantially mitigated In addition, the softness in the fabrics laundered is generally unexpectedly enhanced. The nonionic surfactant also contributes 3 1 ~7 to soil anti-redeposition, especially in non-phosphate formulas.
The inclusion of the nonionic ethoxylate surfactant in the cationic amine softener composition has the following addition-al advantages. Typically, nonionic surfactants are post-added to spray-dried detergent compositions. As a result, the post-added nonionic surfactant increases the -tackiness of the detergent product. In the present invention, the nonionic surfactant is included with the post-added cationic amine softener which leads to a significant improvement in the flowability of detergent compositions.
The nonionic surfactants useful in admixture with the cationic amine softener are known materials. Such nonionic sur-factants may be broadly defined as water-soluble compounds pro-duced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be ali-phatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between20 hydrophilic and hydrophobic elements.
For example, a well known class of nonionic organic surfactants is made available on the market under the trade mark of "Pluronic"O These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propy-lene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a 2 8 ~7 molecular weight of from about ~,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of -the product is retained up to the point where polyoxyethylene content i5 about 50 percent of the total weight of the condensation product.
Other suitable nonionic synthetic surfactants include:
1. The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about six to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to
5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.
2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
3. The condensation product of aliphatic alcohols having from 8 to 30 carbon atoms, in eithex straight chain or branched chain configuration, with from 2 to 100 moles of ethylene oxide e.g., a coconut alcohol-ethylene oxicle condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
Nonionic surfactants include nonyl phenol condensed with either about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol with an average of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.
Othex examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol con densed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; bis-(N-2-hydroxyethyl) lauramide; nonyl phenol condens-ed with 20 moles of ethylene oxide per mole of nonyl phenol;
myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide; and di-iso-octylphenol condensed with 15 moles of ethylene oxide.
Among the above-listed nonionic surfactants, the con-densation product of aliphatic alcohols having from 8 to 22 carbon atoms with ethylene oxide is preferred. Typical examples of such nonionic surfactants are Neodol* 25-7, a product of Shell Chemical CoO, which comprises the condensation product of C~2 15 alcohol with 7 moles of ethylene oxide, and Neodol* 23-6.5 which is the *Trade marks ~23~8n7 product of a C12 13 alcohol with 6.5 moles of ethylene oxide.
Cationic amine softeners useful herein are known materials and are of the hiyh-softening type. Included are the N,N-di-(higher) C14 - C24, N,N-di~(lower) Cl - C4 alkyl quaternary ammonium salts with water solubilizing anions such as halide, e.g~, chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.
For convenience, the aliphatic quaternary am~onium salts may be structurally defined as fo]lows:
R N R X
wherein R and Rl represent alkyl of 14 to 24 and preferably 14 to 22 carbon atoms; R2 and R3 represent lower alkyl of 1 to 4 and preferably 1 to 3 carbon atoms, X represents an anion capable of imparting water solubility or dispersibility including the afore-mentioned chloride, bromide, iodide, sulfate and methosulfate.
Particularly preferred species of aliphatic quats include:
di-hydrogenated tallow dimethyl ammonium chloride di-tallow dimethyl ammonium chloride distearyl dimethyl ammonium methyl sulfate di-hydrogenated tallow dimethyl ammonium methyl sulfate ~eterocyclic imide softeners of the imidazolinium type may also, for convenience, be structurally defined as follows:
_ 9 t 7 R -CY
wherein R4 is lower alkyl of 1 to 4 and preferably 1 to 3 carbons;
R5 and R6 are each substantially linear higher alkyl groups of about 13 to 23 and preferably 13 to 19 carbons and x has the afore-defined significance. Particularly preferred species of imidazo-liniums include:
methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trade mark 10Varisoft 475 as a liquid, 75% active ingredient in isopropanol solvent, methyl-l-oleyl amido ethyl-2 oleyl imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trade mark Varisoft 3690, 75% active ingredient in isopropanol solvent.
The cationic-nonionic mixture may be first mixed in the desired amounts to form a substantially homogeneous mass which can be worked, according to well known technique, until it is suffi-20ciently "doughy" or plastic to be in suitable form for, preferably, extrusion or other process, e.g., pelleting, granulation, stamping and pressing. Working may be effected, for example, by roll mill-ing, although this is not essential, followed by extrusion in a conventional soap plodder with the desired type of extrusion head.
The latter is selected in accordance with the shape, to geo-metric form, desired in the extrudate. Extrusion in the form oE
spaghetti or noodles is particularly preferred. Other shaped forms such as flakes, tablets, pellets, ribbons, threads and the like are suitable alternatives. Special extruders for the fore-going purposes are well known in the art and include or example Elanco* models EXD-60; EXCD-100; EX-130 and EXD-180, a suhler*
extruder and the like. Generally, the spaghetti extrudate is a form-retaining mass, i.e., semi-solid and essentially non-tacky at room temperature requiring in most cases no further treatment such as water removal. If necessary, the latter can be effected by simple drying techniques. The spaghetti should have an average length of from about 2 to 20 mm. with about 95% thereof within a tolerance of 0.5 to 20 mm. and an average diameter or width of from about 0.2 to 2.0 mm. with a range of 0.4 to 0.8 mm. being prefer-red. The bulk density of the spaghetti will usually, having reference to the type of cationic amine softener and nonionic surfactant used, be from about 0.9 to 1.3 g/cm3. Flakes will measure about 4 mm. in length and breadth and 0.2 mm. in thickness, pellets have a cross section of 2.5 mm. while tablets have a cross section of 2.5 mm. and thickness of 2.5 mm.
It is preferred however to use the mixture in prilled form. The pr7 lls are produced by spray cooling a liquefied mixture *Trade marks I 3 ~7 of the cationic amine softener and the nonionic surfactant. In the most preferred embodiment a liquid nonionic surfactant is used (e.g., Neodol* 23-6.5) and this is added to melted cationic amine softener. A typical cationic amine softener is Arosurf* TA-100 (dimethyl dis-tearyl ammonium chloride) and as supplied this mater-ial forms a very fluid liquid when melted and heated to 90C.
The liquid mixture of cationic and nonionic may in another prefer-red embodiment may be allowed to cool to room temperature or as necessary to solidify. The solid may then be yround to desired particle size and post added to other detergent ingredients.
Generally, from 2 to 20~ by weight of nonionic surfact~
ant based on the weight of the cationic amine softener-nonionic surfactant mixture is contemplated. Preferably the nonionic should be used in amounts of from 5 to 15% with about 10% being particular-ly preferred in the case of Neodol 23-6.5.
In the detergent softener compositions of toe parent application utilizing soap particles with or without cellulose ether or nonionic surfactant as taught in the above-described Wixon patents the useful fatty acids include generally those derived from natural or synthetic fatty acids having from 10 to 30 carbons in the alkyl chain. Preferred are the alkali metals, e.g., sodium and/or potassium soaps of C10 - C24 saturated fatty acids, a particularly preferred class being the sodium and/or potassium salts of fatty acid mixtures derived from coconut oil and tallow, e.g., the combination of sodium coconut soap and potassium tallow soap in the mutual proportions respectively of 15/85. As is known *Trade marks as the molecular weight of the fatty acid is increased, the more pronounced becomes its foam inhibiting capacity. Thus, fatty acid selection herein can be made having reference to the foam level desired with the product composition. In general, effective results obtain wherein at least about 50% of the fatty acid soap is of the C10 - C18 variety. Other fatty acid soaps useful herein include those derived from oils of palm grounclnut, hardened fish, e.g., cod liver and shark, seal, perilla, linseed, candlenut, hempseed, walnut, poppyseed, sunflower, maize, rapeseed, mustard-seed, apricot kernel, almond, castor and olive, etc. Other fatty acid soaps include those derived from the following acids: oleic, linoleic, palmitoleic, palmitic, linoleic, ricinoleic, capric, myristic and the like, other useful combinations thereof including, without necessary limitation, 80/20 capric-lauric, 80/20 capric-myristic, 50/50 oleic-capric, 90/10 capric-palmitic and the like.
The nonionic surfactants useful in admixture with the cationic amine softener are also useful in the soap particles.
Where the soap and nonionic surfactant are used in combination, the soap is used with at most equal and preferably minor quantity of nonionic surfactant, e.g., from about 2% to about 50% of the mixture preferably from about 5% to about 40%, more preferably from about 8 to about 30%, and most preferably from about 8 to about 20%, based on the total soap-nonionic surfactant admixture for incorporation into the final detergent composition, usually by post blending of both soap and the cationic-nonionic mixture with dried detergent.
1 23 ~07 Although surfactants of conventional type can be used in the detergent softener compositions of the parent application, it is preferred that at least about 9G% and preferably at least about 95~ of the total surfactant or detergent be of the anionic type, these materials being particularly beneficial in heavy duty detergent for fabric washing. Suitable anionic surfactants gener-ally include the water soluble salts of organic reaction products having in their molecular structure an anionic solubilizing group such as SO4H, SO3H, COOH and PO4H and an alkyl or alkyl group hav-ing about 8 to 22 carbon in the alkyl group or moiety. Suitable detergents are anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as: water soluble sulfated and sul-fonated anionic alkali metal and alkaline earth metal and detergent salts containing a hydrophobic higher alkyl moiety, such as salts of higher alkyl mono- or poly-nuclear aryl sulfonates having from about 8 to 18 carbon atoms in the alkyl group which may have a straight preferred or branched chain structure, preferred species including, without necessary limitation: sodium linear tridecyl-benzene sulfonate, sodium linear dodecyl benzene sulfonate, sodium linear decyl benzene sulfonate, lithium or potassium pentapropylene benzene sulfonate; alkali metal salts of sulfated condensation products of ethylene oxide, e.g., containing 3 to 20 and prefer-ably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 18 carbon atoms or with alkyl phenols having alkyl groups containing 6 to 18 carbon atoms, e.g., sodium nonyl phenol pentaethoxamer sulfate and sodium lauryl alcohol triethoxamer sulfate; alkali metal salts of saturated alcohols containing from about to 18 carbon atoms, e.g./ sodium lauryl sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acid, e.g., fa-tty acid esters of the sodium salt of isothionic acid; fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids, e.g., lauric acid amide of taurine, alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18 carbon atoms in the alkyl group, e.g., hexadecyl, alphahydroxy sodium sulfonate. The anionic sur-factant or mixture thereof is used in the form of their alkali or alkaline earth metal salts. The anionic surfactant is prefer-ably of the non-soap type, it being preferred that the soap component be utilized as taught herein. However, minor amounts of soap, e.g., up to about 35% and preferably 20% based on total anionic surfactant can be added, for example, to the crutcher mix.
The concentration of non-soap anionic surfactant should preferably be selected so as to provide an excess with respect to cationic amine softener according to the empirical relationship % concentration _ 1.5X + 5 wherein X is the per cent concentration of cationic amine softener.
This assures the minimum excess of anionic surfactant necessary for optimum overall detergency, softening, etc. performance in the product composition.
Minor amounts of other types of detergents can be in cluded along with the anionic surfactant, their sum in any case not exceeding about 10% and preferably about 2-5% of total detergent, ~2318~7 i.e., such o-ther detergent plus non-soap anionic surfactant. Use-ful here are the nonionic surface active agents which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydra-tion product thereof, polyethylene glycol. Included are the condensation products of C8 to C30 fatty alcohols such as tridecyl alcohol with 3 to 100 moles ethylene oxide; C16 to Of alcohol with 11 to 50 Poles ethylene oxide; ethylene oxide adducts with monoesters of polyhydric alcohols, e.g., hexahydric alcohol; con-densation products of polypropylene glycol with 3 to 100 moles ethylene oxide; the condensation products of alkyl (C6 to C20 straight or branched chain) phenols with 3 to 100 moles ethylene oxide and the like.
Suitable amphoteric detergents generally include those containing both an anionic group and a cationic yroup and a hydro-phobic organic group which is preferably a higher aliphatic radical of 10 to 20 carbon atoms; examples include the N-long chain alkyl aminocarboxylic acids and the N-long chain alkyl iminodicarboxylic acids such as described in United States 3,824,189.
The detergent softener compositions of the parent application preferably include water soluble alkaline to neutral builder salt in amounts of from about 10 to 60% by weight of total composition. Useful herein are the organic and inorganic builders including the alkali metal and alkaline earth metal phosphates, particularly the condensed phosphates such as the pyrophosphates or tripolyphosphates, silicates, borates, carbonates, bicarbon-ates and the like. Species thereof include sodium tripolyphos-phate, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phos-phate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates: Na2O/SiO2 of 1.5:1 to 3.2:1~ sodium carbonate, sodium sulfate, borax (sodium tetraborate ethylene diamine tetraacetic acid tetrasodium salt, trisodium nitrilotriacetate and the like and mixtures of the foregoiny.
Builder salt may be selected so as to provide either phosphate-containing or phosphate-free detergents. As to the la-tter embodi-ments, sodium carbonate is particularly effective. Another material found to provide good detergency effects is metakaolin which is generally produced by heating kaolinite lattice to drive off water producing a material which is substantially amorphous by x-ray examination but which retains some of the structural order of the kaolinite. Discussions of kaolin and metakaolin are found in United States Patent 4,075,280 columns 3 and 4 and Grimshaw, "The Chemistry of Physics of Clays and Allied Ceramic materials,"
(4th ed., Wiley-Interscience), pages 723-727. The metakaolin also appears to have softening utility. As to the latter, the most effective metakaolins appear to be those which behave best in the reaction with sodium hydroxide to form zeolite 4A as described in United States Patent 3,114,603 which refers to such materials as "reactive kaolin." As explained in the referenced sources, meta-k.aolin is an aluminosilicate. The metakaolin and/or a zeolite is included in about the same amounts as the builder salt, and pre-ferably supplemental thereto, e.g., zeo]ite silicate in a ratio of 6:1. A particularly useful form of the metakaolin is that available commercially as Satintone No. 2.
PreEerred optional ingredients in the detergent softener compositions of the parent application include perfume such as Genie* perfume; optical brighteners and bluing agents which may be dyes or pigments, suitable materials in this regard including stilbene and Tinopal* 5 BM brighteners and particularly in combina-tion and Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete*, Brilliant Blue RBL and Cibacete Violet B, Polar Brilliant Blue RAW and Calcocid glue 2G bluing agents. The brightener may be included in amounts ranging up to about 1% of the total composi-tion while bluing agents may range up to about .1% preférably up to about .01% of total composition. Bluing agent, e.g., Polar Brilliant Blue may be included in the soap spaghetti. In either case, the amount need only be minimal to be effective.
Other ingredients of optional significance in the deter-gent softener compositions of the parent application include bleaching agents which may be of the oxygen or chlorine liberating type; oxygen bleaches include sodium and potassium perborate, potassium monopersulfate and the like, while chlorine bleaches are typified by sodium hypochlorite, potassium dichloroisocyanurate, trichloroisocyanuric acid and the like. the latter chlorine-liberating bleaches are representative of the broad class of water soluble, organic, dry solid bleaches known as the N-chloro imides *Trade marks i 2 3 1 ~7 including their alkali metal salts. These cyclic imides have from about 4 to 6 member in the ring and are described in detail in United States Patent 3,325,~14. Each of the oxygen and chlorine type bleaches discussed above are fully compatible with the detergent softener compositions and have good s-tability in the presence of the anionic and cationic components. They are gener-ally used in proportions ranging from about 0.1 to 45% by weight of total solids or from about .05% to about 40% based on total detergent composition.
Yet additional optional ingredients include water soluble and/or dispersible hydrophobic eolloidal cellulosic soil suspending agent. Methyl eellulose, e.g., Methocel is partieular-ly effective. Polyvinyl alcohol is likewise effective and es-pecially in the washing of cotton and synthetic fibers such as nylon, dacron and resin treated cotton. The additional soil sus-pending agent may be included in amounts up to about 2% based on total solids and up to about 4% based on total detergent composi-tion. However, it must be emphasized that the nonionic organic surfactant eomponent of the soap spaghetti supplies at least a major part of the anti-redeposition or soil suspending funetion, its effectiveness in this regard being signifieantly augmented by the soap material as previously explained.
Fillers may also be included in addition to the afore-mentioned ingredients, such as sodium sulfate, sodium chloride and the like. The amount will range up to about ~0% of total com-position.
The detergent softener composition of the parent appli-cation is prepared by conventional processing such as spray drying a crutcher mix of surfactan-t, builder, filler etc. with volatile ingredients such as perfume or ingredients otherwise adversely affected by the spray drying process such as peroxygen bleach, e.g., sodium perborate. Ingredients of this type are preferably post blended. As previously mentioned, the soap spaghetti (when used) and cationic amine softener~nonionic surfactant mixture are simply dry blended with the dried detergent in particulate form by simple mechanical mixing which is more than adequate to achieve a homogeneous product. As previously explained, part or all of the soap spaghetti may alternatively be added to the aqueous crutcher mixture. A typical procedure would be as follows: Water is added to a crutcher followed in order by anionic, sodium silicate, optional ingredients where used such as Satintone #2 and filler such as sodium sulfate and builder salt. The crutcher mixture is heated to about 1~0F before addition of builder, e.g., sodium tripolyphosphate and the solids content of the crutched mixture before spray drying is about 55-65%. Spray drying may be carried out in a conventional manner by pumping the hot mixture from the crutcher to a spray tower where the mixture passes through a spray nozzle into a hot evaporative atmosphere. Bleach and other mater-ials remaining to be added are incorporated into the cooled, dried detergent mass by any suitable means such as simple mechanical mixiny.
In use, sufficient of a detergent composition is added 2 3 ~7 to the wash cycle to provide a concentration of cationic amine softener in the wash medium of about 1.5 to 8.0 g/3500g laundry with a range from about 70 to the boil (i.e., about 212F). In this connection it is understood that by "cold" wash is meant a washing tempera-ture of up to 70 F, "warm" is from above 70 F to boiling.
Certain types of aliphatic quaternary ammonium compounds though relatively ineffective as regards softening are neverthe-less quite effective as antistats in the detergent softener com-positions and particularly since they are physically compatible with anionic surfactant in liquid environments. In general, such materials encompass the ethoxylated and/or propoxylated quaternary ammonium compounds of the following formula:
m n wherein R and R represent ethoxy or propoxy, m and n are integers of from l to 50 and may be the same or different and Rg represents alkyl of 14 to 24 carbon. Compounds of this type include (a) methylbis (2-hydroxy-ethyl) coco ammonium chloride a liquid 75%
active ingredient in isopropanol/water solvent and available com-mercially as Ethoquad* c/12, Armak* and Variquat* 63 Sherex Chemical Co.; (b) Ethoquad c/25 - same as in (a) but having 15 *Trade Marks 1 2 1 8 ~7 moles of ethylene oxide (m + no and available as 95% active in-gredient; a methylbis (2-hydroxyethyl) octadecyl ammonium chloride, a liquid 75% active ingredient in isopropanol/~ater solvent available commercially as Ethoquad 18/12, Armak and (d) same as (c) but having 15 moles of ethylene oxide (m n), a liquid 95% active ingredient and available commercially as Ethoquad 18/15 Armak. These materials can be used in amounts ranging up to about 10% by weight of the total composition.
The following examples illustrate the invention of the parent and of this application and are given for purposes of thus tration only and are not intended to limit the invention. All parts and percentages are given by weight.
Example 1 A) 100 g of powdered Arosurf TA (dimethyl distearyl ammon-ium chloride) are heated to 90C and a fluid melt results. To this melt are added 10 go of liquid nonionic Neodol 23-6.5 (C1213 linear alcohol condensed with 6.5 moles of ethylene oxide).
The mixture is stirred well and then cooled to room temperature.
A white solid results. The solid is then ground to a powder (on U.S. #8 Sieve 06 through U.S. #100 Sieve < 10%). The product re-sembles the original Arosurf powder.
B) Part A is repeated except that only 5 g. of nonionic is used.
Example 2 The products of Example 1 as well as powdered cationic alone (same as used for Example 1 to produce the co-melted product), of a particle size the same as that of Example 1, are each tested separately for dispersion uniformity in water by -the following procedure.
In a teryitometer equipped as usual with a reciprocating stirrer there are added to 500 ml of water (hardness of 150 ppm) at 70 (31C) 0.15 g. of a detergent (13.4% alkyl benzene sul-fonate; 24% sodium tripolyphosphate; 30% sodium sulfate; ~.5%
sodium carbonate; 6.3% water-soluble silicate solids; 7~ moisture;
4% soap; minor amounts brightener, methocel and perfume) which also contains 4.5% of the particles of Example 1. The stirrer is operated for 5 minutes at 100 rpm and then the aqueous composition is vacuum filtered through fresh smooth blue denim fabric. In the case of the liquors with the Example 1 - containing detergent there is no visible (i.e., no white spots) evidence of any residue.
When the procedure i5 repeated using identical conditions with the same composition except that in place of 4.5% of Example 1 pro ducts, there is used ~.5~ powdered cationic alone there is a very visible pattern of white spotting on the denim. This is very clear evidence of the outstanding benefits of the Example 1 pro-ducts.
Example 3 When the compositions described in Example 2 are used to wash soiled white towels in a washing machine and then dried in an automatic dryer, the clothes in each instance are acceptably soft although those washed with the detergent containing the Ex-ample 1 softener combination are somewhat softer. In addition, 23 ~7 the towels washed with the detergent containing powdered cationic alone (i.e., not combined with nonionic) have some visible albeit slight spotting (i.e., greasy staining) due apparently to the cationic material whereas the others do not.
Example 4 Example lA lB & 3 are repeated except that the follow-ing nonionics are used in place of the Meodol 23-6.5.
a) Neodol 25-7 (A C12_15 alkyllinear alcohol 7. moles of ethylene oxide) b) Igepal* C0-630 (Nonyl phenol + 10 moles of ethylene oxide) c) Neodol 45-13 (A C14 15 alkyllinear alcohol -I 13 moles of ethylene oxide) Example 5 . .
A spray dried heavy duty detergent having the following composition is provided:
Component Wt. %
Linear tridecylbenzene sulfonate (LTBS) 15 Tripolyphosphate sodium (NaTPP) 33 Silicate 7 Brightener (Stilbene* &
Tinopal* 5BM) .48 O.S. sodium sulfate and water 44.52 100.-00 To 90 g of the above composition are added 4 grams of *Trade marks the cationic-nonionic powder of Example 1 part B. Excellent re-sults are obtained Example 5 Example 3 is repeated except that the detergent also contains a soap spaghetti (4.5% in detergent).
Example 7 _ _ Example 6 is repeated except that the soap spaghe-tti contains 20% by weight of Neodol 25-7.
In Examples 6 & 7 the soap spaghetti is an 85/15 tal3ow/
coco soap.
Example 8 Example 3 is repeated but using a detergent composition having the following proximate analysis.
Component wt. %
Linear Dodecyl benzene sulfonate 23 Na2C3 20 Silicate 15 Borax 3 Nonionic surfactant Soap 2 Carboxymethyl cellulose Brightener* 0.48 Satintone Na~SO4 and water Q.S.
*Stilbene and Tinopal 5BM
To 95 grams of the above composition, 5 gm of the product of Example lB are added.
Example 9 Example 8 is repeated except 5 gm of a soap-nonionic spaghetti (similar to Example 7) is used.
Example 10 Example 6 is repeated except that the soap spaghetti used also contains 4% by weight of carboxymethyl cellulose.
Example 11 The following heavy duty detergent composition is pre-pared.
Components Wt.
Linear alkyl benzene sulfonate 9 Alcohol ether sulfate 8 Nonionic surfactant 2 Tripolyphosphate sodium 24 Zeolite A 17 Na2SO4, brightener, water Q.S.
To this composition is added 5.0 g of the cationic pro-duct of Example lB.
Example 12 Example 11 is repeated except that the soap/nonionic sur-factant spaghetti of Example 6 is added to give 4% in the deter-gent.
Example 13 An unperfumed powder detergent composition having the following formulation is prepared.
1 2~ ~a7 Component Wt. %
Linear tridecylbenzene sulfonate 14.8 Tripolyphosphate sodium 26.5 Silicate 6.9 Brightener (Stilbene* and Tinopal* 5 BM) 0.47 Sodium carbonate 4.9 Carboxymethyl cellulose 0.25 Methocel* 0.6 Sodium sulfate, moisture Q.S.
To 90.6 parts by weight of the above unperfumed powder detergent are added:
Cationic-Nonionic mixture of Ex lB 4.0 parts Soap spaghetti (90% tallow/coco 85/15; 10% Neodol 25-7 (Shell Chemical Co.), spaghetti length =
15 mm, diameter = 0.5mm 4.0 parts Borax Pentahydrate 0.7 parts Nonionic surfactant 0.5 parts (Neodol ~5-7) Perfume 0.2 parts The following Examples illustrate the production and use of the cationic-nonionic combination in prilled form.
Example 14 Eive hundred kilograms of dimethyl distearyl ammonium chloride containing about 4% water is heated to 90C and forms a melt. To 'chis hot melt are added 25 kilograms of Neodol 23-6.5.
This co-melt is then sprayed downwardly from the top of a 75-foot (about 24 meters) tower - 16 foot diameter (about 5 meters).
*Trade mark 2 3 1 8~7 At the same time cool air at about 50~F (10C) is passed upwardly to countercurrent to the falling spray) at a rate of about 30,000 cubic feet per minute (cfm). The congealed product is col-lected at -the bottom of the tower. The produc-t particle is white in appearance, free~flowing generally spherical and solid. It has a porous surface (pock-marked appearance). The bulk density of the prill is about 0.37 (g/cc).
Example 15 To 95.5 g. of the detergent of Example 2 (without EX-ample l particles) are added 4.5 I. of the pills of Example 14.
Example 16 Example 5 through 13 are each repeated except that thecationic-nonionic mixture used in those examples are replaced by the prills of Example 14.
Example 17 Each of the previous examples is repeated except that the nonionic .in the cationic-nonionic mixture is used in amounts of 2%; 7%; 12%; 15%; 20%.
Example 18 Each of the previous examples is again repeated except that the cationic softener of the cationic-nonionic mixture is replaced by the following:
(a) dimethyl di-tallow ammonium methosulfate (b) dimethyl, di-hydrogenated tallow ammonium chloride (c) methyl-l-tallow amido ethyl-2-tallow imidazolinium metho-sulfate (d) me-thyl-l-oleylamidoethyl-2-oleyl imidazolinium metho-sulfate Example l9 In each of the foregoing examples where the cationic-nonionic particles are used in admix1ure with the detergent, the amount of the cationic-nonionic is varied to provide 2%; 7% and ]0% thereof based on the weight of the detergent & softener par-t-icles.
Among the nonionics which are useful in the cationic-nonionic combination it is clear that there is a wide range of melting point. Thus Neodol 23-6.5 is a liquid nonionic as is Igepal C0-630 (nonyl phenol plus lO moles of ethylene oxide) where-as Neodol 25-7 is a somewhat pasty solid and Neodol 25-12 a soft white solid. At higher ethylene oxide content (i.e. > 15 moles of ethylene oxide) the product becomes more solid and somewhat waxy in feel and appearance.
Particularly where it is desired to use higher levels (i.e., above about 5 to 10%) of nonionic in the cationic co-melt, it is often advantageous to use a mixture of a liquid nonionic and a solid nonionic. In addition to the ethoxylated solid nonionics one may also use other solid or pasty nonionics such as the glycer-ol mono and di-fatty glycerides. Of particulax value in this regard are glycerol mono-stearate, glycerol mono oleate and gly-cerol palmitate.
Example 20 Example lo is repeated except that half of the Neodol nonionic is replaced by glycerol monostearate. In the test pro-cedure of Example 2 this product performs on a par with the Example 1 23 8~7 lA material.
_xample 21 Example 3 is repeated using the prvduct of Example 20 in place of the cationic materials of Example 3. Excellent resul-ts are obtained.
Fxample 22 Example 7 is repeated except that the detergent contains the tertiary softener combina-tion of Example 20 in place of the binary combinations of Example 1. The results are similarly excellent as those of Exarnples 3 and 7.
Example 23 Example 22 is repeated except that the nonionic used is Neodol 45--11 (a C14 15 linear alkanol plus 11 moles of ethylene oxide Example 24 Example 6 is repeated except that the soap spaghetti is replaced by an equal weight of Carbowax* (MW-3000-8000) crystals.
Example 25 Example 24 is repeated except that the amount of Carbo-wax is varied as follows (I in detergent):
(a) 0.5 ~b) 1.0 (c) 2.0 (d) 4.0 Example 26 Examples 6, 7, 9, 10, 12, 13, 16, 17, 18, 19, 21, 22 *Trade mark 1 8~7 and 23 are each repeated except where soap spaghetti is used it is replaced by the Carbowax used in Examples 24 and 25 in the amounts indicated (% based on weight of detergent).
(a) G r 2 (b) 0.4 (c) 0.8 (d) 1.0 (e) 2.0 (f) 3.0 (g) 5.0 Ex~nple 27 Examples 24, 25 and 26 are repeated using in place of Carbowax the following:
(A) Pluronic F-108 crystals (B) Soap-spaghetti of high water solubility containing (a) 10% sodium xylene sulfonate; (b) 20% sodium xylene sulfonate; (c) 40~ sodium xylene sulfonate.
The carbowax product of Examples 24 to 26 is a poly-ethylene glycol. The Pluronic F-108 of Example 27 is a polyoxy propylene-polyoxyethylene block copolymer containing 20% polyoxy propylene groups as the hydrophobe and 80~ polyoxyethylene groups.
The base hydrophobe has a MW of 3250~
The Pluronic E`-108 is also illustrative of the water-soluble nonionics which are useful in the cationic-nonionic co-melts of this invention. Of particular value are the liquid Pluronics containing up to about 50% polyoxyethylene groups and a base hydrophobe molecular weight of the polyoxypropylene moiety i 2 3 ~7 of from about 950 to 4000. Where combinations of, for example, Neodol 23-6.5 and Pluronics are used, it may be preferred to use pasty or solid Pluronics. These contain generally from 25% to of polyoxyethylene groups. Illustrative of liquid Pluronics are Pluronic L-61, Pluronic L-64, Pluronic L-72 and Pluronic 101;
of the pasty Pluronics, we find Pluronic P85 and Pluronic P105 among others; of the solid products we may mention Pluronic F-87 and Pluronic F27.
Example 28 As an illustration of the anti-stain benefits of the present invention, several different soiled, white materials are laundered at both 70F and 120F using the detergent containing ca~ionic alone, (A) on the one hand and the cationic-nonionic prill of Example 14 on the other hand (B). The detergent is that described in Example 2.
All of the white materials are equally soiled and the reflectance values of laundered materials are measured. The follow-ing are the reflectance values (Rd).
7_ 120F
(A) (B) (A) (B) Spun Dacron* 77.7 79.0 64.7 66.5 Dacron*/Cotton (65/35) 81.4 81.5 73.9 76.1 Cotton 87.8 87.8 87.3 87.3 Nylon 84.1 85.2 84.1 84.5 The above clearly demonstrates that even after only one washing there is significant improvement on Spun Dacron at *Trade Marks both laundering temperature, on Da~rorl/Cotton at 120F and on Nylon at 70 I. A difference of 0.5 Rd units is significant in the sense that this difference is visually discernible.
2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000 are satisfactory.
3. The condensation product of aliphatic alcohols having from 8 to 30 carbon atoms, in eithex straight chain or branched chain configuration, with from 2 to 100 moles of ethylene oxide e.g., a coconut alcohol-ethylene oxicle condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.
Nonionic surfactants include nonyl phenol condensed with either about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol with an average of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.
Othex examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol con densed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; bis-(N-2-hydroxyethyl) lauramide; nonyl phenol condens-ed with 20 moles of ethylene oxide per mole of nonyl phenol;
myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide; and di-iso-octylphenol condensed with 15 moles of ethylene oxide.
Among the above-listed nonionic surfactants, the con-densation product of aliphatic alcohols having from 8 to 22 carbon atoms with ethylene oxide is preferred. Typical examples of such nonionic surfactants are Neodol* 25-7, a product of Shell Chemical CoO, which comprises the condensation product of C~2 15 alcohol with 7 moles of ethylene oxide, and Neodol* 23-6.5 which is the *Trade marks ~23~8n7 product of a C12 13 alcohol with 6.5 moles of ethylene oxide.
Cationic amine softeners useful herein are known materials and are of the hiyh-softening type. Included are the N,N-di-(higher) C14 - C24, N,N-di~(lower) Cl - C4 alkyl quaternary ammonium salts with water solubilizing anions such as halide, e.g~, chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.
For convenience, the aliphatic quaternary am~onium salts may be structurally defined as fo]lows:
R N R X
wherein R and Rl represent alkyl of 14 to 24 and preferably 14 to 22 carbon atoms; R2 and R3 represent lower alkyl of 1 to 4 and preferably 1 to 3 carbon atoms, X represents an anion capable of imparting water solubility or dispersibility including the afore-mentioned chloride, bromide, iodide, sulfate and methosulfate.
Particularly preferred species of aliphatic quats include:
di-hydrogenated tallow dimethyl ammonium chloride di-tallow dimethyl ammonium chloride distearyl dimethyl ammonium methyl sulfate di-hydrogenated tallow dimethyl ammonium methyl sulfate ~eterocyclic imide softeners of the imidazolinium type may also, for convenience, be structurally defined as follows:
_ 9 t 7 R -CY
wherein R4 is lower alkyl of 1 to 4 and preferably 1 to 3 carbons;
R5 and R6 are each substantially linear higher alkyl groups of about 13 to 23 and preferably 13 to 19 carbons and x has the afore-defined significance. Particularly preferred species of imidazo-liniums include:
methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trade mark 10Varisoft 475 as a liquid, 75% active ingredient in isopropanol solvent, methyl-l-oleyl amido ethyl-2 oleyl imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trade mark Varisoft 3690, 75% active ingredient in isopropanol solvent.
The cationic-nonionic mixture may be first mixed in the desired amounts to form a substantially homogeneous mass which can be worked, according to well known technique, until it is suffi-20ciently "doughy" or plastic to be in suitable form for, preferably, extrusion or other process, e.g., pelleting, granulation, stamping and pressing. Working may be effected, for example, by roll mill-ing, although this is not essential, followed by extrusion in a conventional soap plodder with the desired type of extrusion head.
The latter is selected in accordance with the shape, to geo-metric form, desired in the extrudate. Extrusion in the form oE
spaghetti or noodles is particularly preferred. Other shaped forms such as flakes, tablets, pellets, ribbons, threads and the like are suitable alternatives. Special extruders for the fore-going purposes are well known in the art and include or example Elanco* models EXD-60; EXCD-100; EX-130 and EXD-180, a suhler*
extruder and the like. Generally, the spaghetti extrudate is a form-retaining mass, i.e., semi-solid and essentially non-tacky at room temperature requiring in most cases no further treatment such as water removal. If necessary, the latter can be effected by simple drying techniques. The spaghetti should have an average length of from about 2 to 20 mm. with about 95% thereof within a tolerance of 0.5 to 20 mm. and an average diameter or width of from about 0.2 to 2.0 mm. with a range of 0.4 to 0.8 mm. being prefer-red. The bulk density of the spaghetti will usually, having reference to the type of cationic amine softener and nonionic surfactant used, be from about 0.9 to 1.3 g/cm3. Flakes will measure about 4 mm. in length and breadth and 0.2 mm. in thickness, pellets have a cross section of 2.5 mm. while tablets have a cross section of 2.5 mm. and thickness of 2.5 mm.
It is preferred however to use the mixture in prilled form. The pr7 lls are produced by spray cooling a liquefied mixture *Trade marks I 3 ~7 of the cationic amine softener and the nonionic surfactant. In the most preferred embodiment a liquid nonionic surfactant is used (e.g., Neodol* 23-6.5) and this is added to melted cationic amine softener. A typical cationic amine softener is Arosurf* TA-100 (dimethyl dis-tearyl ammonium chloride) and as supplied this mater-ial forms a very fluid liquid when melted and heated to 90C.
The liquid mixture of cationic and nonionic may in another prefer-red embodiment may be allowed to cool to room temperature or as necessary to solidify. The solid may then be yround to desired particle size and post added to other detergent ingredients.
Generally, from 2 to 20~ by weight of nonionic surfact~
ant based on the weight of the cationic amine softener-nonionic surfactant mixture is contemplated. Preferably the nonionic should be used in amounts of from 5 to 15% with about 10% being particular-ly preferred in the case of Neodol 23-6.5.
In the detergent softener compositions of toe parent application utilizing soap particles with or without cellulose ether or nonionic surfactant as taught in the above-described Wixon patents the useful fatty acids include generally those derived from natural or synthetic fatty acids having from 10 to 30 carbons in the alkyl chain. Preferred are the alkali metals, e.g., sodium and/or potassium soaps of C10 - C24 saturated fatty acids, a particularly preferred class being the sodium and/or potassium salts of fatty acid mixtures derived from coconut oil and tallow, e.g., the combination of sodium coconut soap and potassium tallow soap in the mutual proportions respectively of 15/85. As is known *Trade marks as the molecular weight of the fatty acid is increased, the more pronounced becomes its foam inhibiting capacity. Thus, fatty acid selection herein can be made having reference to the foam level desired with the product composition. In general, effective results obtain wherein at least about 50% of the fatty acid soap is of the C10 - C18 variety. Other fatty acid soaps useful herein include those derived from oils of palm grounclnut, hardened fish, e.g., cod liver and shark, seal, perilla, linseed, candlenut, hempseed, walnut, poppyseed, sunflower, maize, rapeseed, mustard-seed, apricot kernel, almond, castor and olive, etc. Other fatty acid soaps include those derived from the following acids: oleic, linoleic, palmitoleic, palmitic, linoleic, ricinoleic, capric, myristic and the like, other useful combinations thereof including, without necessary limitation, 80/20 capric-lauric, 80/20 capric-myristic, 50/50 oleic-capric, 90/10 capric-palmitic and the like.
The nonionic surfactants useful in admixture with the cationic amine softener are also useful in the soap particles.
Where the soap and nonionic surfactant are used in combination, the soap is used with at most equal and preferably minor quantity of nonionic surfactant, e.g., from about 2% to about 50% of the mixture preferably from about 5% to about 40%, more preferably from about 8 to about 30%, and most preferably from about 8 to about 20%, based on the total soap-nonionic surfactant admixture for incorporation into the final detergent composition, usually by post blending of both soap and the cationic-nonionic mixture with dried detergent.
1 23 ~07 Although surfactants of conventional type can be used in the detergent softener compositions of the parent application, it is preferred that at least about 9G% and preferably at least about 95~ of the total surfactant or detergent be of the anionic type, these materials being particularly beneficial in heavy duty detergent for fabric washing. Suitable anionic surfactants gener-ally include the water soluble salts of organic reaction products having in their molecular structure an anionic solubilizing group such as SO4H, SO3H, COOH and PO4H and an alkyl or alkyl group hav-ing about 8 to 22 carbon in the alkyl group or moiety. Suitable detergents are anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as: water soluble sulfated and sul-fonated anionic alkali metal and alkaline earth metal and detergent salts containing a hydrophobic higher alkyl moiety, such as salts of higher alkyl mono- or poly-nuclear aryl sulfonates having from about 8 to 18 carbon atoms in the alkyl group which may have a straight preferred or branched chain structure, preferred species including, without necessary limitation: sodium linear tridecyl-benzene sulfonate, sodium linear dodecyl benzene sulfonate, sodium linear decyl benzene sulfonate, lithium or potassium pentapropylene benzene sulfonate; alkali metal salts of sulfated condensation products of ethylene oxide, e.g., containing 3 to 20 and prefer-ably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 18 carbon atoms or with alkyl phenols having alkyl groups containing 6 to 18 carbon atoms, e.g., sodium nonyl phenol pentaethoxamer sulfate and sodium lauryl alcohol triethoxamer sulfate; alkali metal salts of saturated alcohols containing from about to 18 carbon atoms, e.g./ sodium lauryl sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acid, e.g., fa-tty acid esters of the sodium salt of isothionic acid; fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids, e.g., lauric acid amide of taurine, alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18 carbon atoms in the alkyl group, e.g., hexadecyl, alphahydroxy sodium sulfonate. The anionic sur-factant or mixture thereof is used in the form of their alkali or alkaline earth metal salts. The anionic surfactant is prefer-ably of the non-soap type, it being preferred that the soap component be utilized as taught herein. However, minor amounts of soap, e.g., up to about 35% and preferably 20% based on total anionic surfactant can be added, for example, to the crutcher mix.
The concentration of non-soap anionic surfactant should preferably be selected so as to provide an excess with respect to cationic amine softener according to the empirical relationship % concentration _ 1.5X + 5 wherein X is the per cent concentration of cationic amine softener.
This assures the minimum excess of anionic surfactant necessary for optimum overall detergency, softening, etc. performance in the product composition.
Minor amounts of other types of detergents can be in cluded along with the anionic surfactant, their sum in any case not exceeding about 10% and preferably about 2-5% of total detergent, ~2318~7 i.e., such o-ther detergent plus non-soap anionic surfactant. Use-ful here are the nonionic surface active agents which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydra-tion product thereof, polyethylene glycol. Included are the condensation products of C8 to C30 fatty alcohols such as tridecyl alcohol with 3 to 100 moles ethylene oxide; C16 to Of alcohol with 11 to 50 Poles ethylene oxide; ethylene oxide adducts with monoesters of polyhydric alcohols, e.g., hexahydric alcohol; con-densation products of polypropylene glycol with 3 to 100 moles ethylene oxide; the condensation products of alkyl (C6 to C20 straight or branched chain) phenols with 3 to 100 moles ethylene oxide and the like.
Suitable amphoteric detergents generally include those containing both an anionic group and a cationic yroup and a hydro-phobic organic group which is preferably a higher aliphatic radical of 10 to 20 carbon atoms; examples include the N-long chain alkyl aminocarboxylic acids and the N-long chain alkyl iminodicarboxylic acids such as described in United States 3,824,189.
The detergent softener compositions of the parent application preferably include water soluble alkaline to neutral builder salt in amounts of from about 10 to 60% by weight of total composition. Useful herein are the organic and inorganic builders including the alkali metal and alkaline earth metal phosphates, particularly the condensed phosphates such as the pyrophosphates or tripolyphosphates, silicates, borates, carbonates, bicarbon-ates and the like. Species thereof include sodium tripolyphos-phate, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phos-phate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates: Na2O/SiO2 of 1.5:1 to 3.2:1~ sodium carbonate, sodium sulfate, borax (sodium tetraborate ethylene diamine tetraacetic acid tetrasodium salt, trisodium nitrilotriacetate and the like and mixtures of the foregoiny.
Builder salt may be selected so as to provide either phosphate-containing or phosphate-free detergents. As to the la-tter embodi-ments, sodium carbonate is particularly effective. Another material found to provide good detergency effects is metakaolin which is generally produced by heating kaolinite lattice to drive off water producing a material which is substantially amorphous by x-ray examination but which retains some of the structural order of the kaolinite. Discussions of kaolin and metakaolin are found in United States Patent 4,075,280 columns 3 and 4 and Grimshaw, "The Chemistry of Physics of Clays and Allied Ceramic materials,"
(4th ed., Wiley-Interscience), pages 723-727. The metakaolin also appears to have softening utility. As to the latter, the most effective metakaolins appear to be those which behave best in the reaction with sodium hydroxide to form zeolite 4A as described in United States Patent 3,114,603 which refers to such materials as "reactive kaolin." As explained in the referenced sources, meta-k.aolin is an aluminosilicate. The metakaolin and/or a zeolite is included in about the same amounts as the builder salt, and pre-ferably supplemental thereto, e.g., zeo]ite silicate in a ratio of 6:1. A particularly useful form of the metakaolin is that available commercially as Satintone No. 2.
PreEerred optional ingredients in the detergent softener compositions of the parent application include perfume such as Genie* perfume; optical brighteners and bluing agents which may be dyes or pigments, suitable materials in this regard including stilbene and Tinopal* 5 BM brighteners and particularly in combina-tion and Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete*, Brilliant Blue RBL and Cibacete Violet B, Polar Brilliant Blue RAW and Calcocid glue 2G bluing agents. The brightener may be included in amounts ranging up to about 1% of the total composi-tion while bluing agents may range up to about .1% preférably up to about .01% of total composition. Bluing agent, e.g., Polar Brilliant Blue may be included in the soap spaghetti. In either case, the amount need only be minimal to be effective.
Other ingredients of optional significance in the deter-gent softener compositions of the parent application include bleaching agents which may be of the oxygen or chlorine liberating type; oxygen bleaches include sodium and potassium perborate, potassium monopersulfate and the like, while chlorine bleaches are typified by sodium hypochlorite, potassium dichloroisocyanurate, trichloroisocyanuric acid and the like. the latter chlorine-liberating bleaches are representative of the broad class of water soluble, organic, dry solid bleaches known as the N-chloro imides *Trade marks i 2 3 1 ~7 including their alkali metal salts. These cyclic imides have from about 4 to 6 member in the ring and are described in detail in United States Patent 3,325,~14. Each of the oxygen and chlorine type bleaches discussed above are fully compatible with the detergent softener compositions and have good s-tability in the presence of the anionic and cationic components. They are gener-ally used in proportions ranging from about 0.1 to 45% by weight of total solids or from about .05% to about 40% based on total detergent composition.
Yet additional optional ingredients include water soluble and/or dispersible hydrophobic eolloidal cellulosic soil suspending agent. Methyl eellulose, e.g., Methocel is partieular-ly effective. Polyvinyl alcohol is likewise effective and es-pecially in the washing of cotton and synthetic fibers such as nylon, dacron and resin treated cotton. The additional soil sus-pending agent may be included in amounts up to about 2% based on total solids and up to about 4% based on total detergent composi-tion. However, it must be emphasized that the nonionic organic surfactant eomponent of the soap spaghetti supplies at least a major part of the anti-redeposition or soil suspending funetion, its effectiveness in this regard being signifieantly augmented by the soap material as previously explained.
Fillers may also be included in addition to the afore-mentioned ingredients, such as sodium sulfate, sodium chloride and the like. The amount will range up to about ~0% of total com-position.
The detergent softener composition of the parent appli-cation is prepared by conventional processing such as spray drying a crutcher mix of surfactan-t, builder, filler etc. with volatile ingredients such as perfume or ingredients otherwise adversely affected by the spray drying process such as peroxygen bleach, e.g., sodium perborate. Ingredients of this type are preferably post blended. As previously mentioned, the soap spaghetti (when used) and cationic amine softener~nonionic surfactant mixture are simply dry blended with the dried detergent in particulate form by simple mechanical mixing which is more than adequate to achieve a homogeneous product. As previously explained, part or all of the soap spaghetti may alternatively be added to the aqueous crutcher mixture. A typical procedure would be as follows: Water is added to a crutcher followed in order by anionic, sodium silicate, optional ingredients where used such as Satintone #2 and filler such as sodium sulfate and builder salt. The crutcher mixture is heated to about 1~0F before addition of builder, e.g., sodium tripolyphosphate and the solids content of the crutched mixture before spray drying is about 55-65%. Spray drying may be carried out in a conventional manner by pumping the hot mixture from the crutcher to a spray tower where the mixture passes through a spray nozzle into a hot evaporative atmosphere. Bleach and other mater-ials remaining to be added are incorporated into the cooled, dried detergent mass by any suitable means such as simple mechanical mixiny.
In use, sufficient of a detergent composition is added 2 3 ~7 to the wash cycle to provide a concentration of cationic amine softener in the wash medium of about 1.5 to 8.0 g/3500g laundry with a range from about 70 to the boil (i.e., about 212F). In this connection it is understood that by "cold" wash is meant a washing tempera-ture of up to 70 F, "warm" is from above 70 F to boiling.
Certain types of aliphatic quaternary ammonium compounds though relatively ineffective as regards softening are neverthe-less quite effective as antistats in the detergent softener com-positions and particularly since they are physically compatible with anionic surfactant in liquid environments. In general, such materials encompass the ethoxylated and/or propoxylated quaternary ammonium compounds of the following formula:
m n wherein R and R represent ethoxy or propoxy, m and n are integers of from l to 50 and may be the same or different and Rg represents alkyl of 14 to 24 carbon. Compounds of this type include (a) methylbis (2-hydroxy-ethyl) coco ammonium chloride a liquid 75%
active ingredient in isopropanol/water solvent and available com-mercially as Ethoquad* c/12, Armak* and Variquat* 63 Sherex Chemical Co.; (b) Ethoquad c/25 - same as in (a) but having 15 *Trade Marks 1 2 1 8 ~7 moles of ethylene oxide (m + no and available as 95% active in-gredient; a methylbis (2-hydroxyethyl) octadecyl ammonium chloride, a liquid 75% active ingredient in isopropanol/~ater solvent available commercially as Ethoquad 18/12, Armak and (d) same as (c) but having 15 moles of ethylene oxide (m n), a liquid 95% active ingredient and available commercially as Ethoquad 18/15 Armak. These materials can be used in amounts ranging up to about 10% by weight of the total composition.
The following examples illustrate the invention of the parent and of this application and are given for purposes of thus tration only and are not intended to limit the invention. All parts and percentages are given by weight.
Example 1 A) 100 g of powdered Arosurf TA (dimethyl distearyl ammon-ium chloride) are heated to 90C and a fluid melt results. To this melt are added 10 go of liquid nonionic Neodol 23-6.5 (C1213 linear alcohol condensed with 6.5 moles of ethylene oxide).
The mixture is stirred well and then cooled to room temperature.
A white solid results. The solid is then ground to a powder (on U.S. #8 Sieve 06 through U.S. #100 Sieve < 10%). The product re-sembles the original Arosurf powder.
B) Part A is repeated except that only 5 g. of nonionic is used.
Example 2 The products of Example 1 as well as powdered cationic alone (same as used for Example 1 to produce the co-melted product), of a particle size the same as that of Example 1, are each tested separately for dispersion uniformity in water by -the following procedure.
In a teryitometer equipped as usual with a reciprocating stirrer there are added to 500 ml of water (hardness of 150 ppm) at 70 (31C) 0.15 g. of a detergent (13.4% alkyl benzene sul-fonate; 24% sodium tripolyphosphate; 30% sodium sulfate; ~.5%
sodium carbonate; 6.3% water-soluble silicate solids; 7~ moisture;
4% soap; minor amounts brightener, methocel and perfume) which also contains 4.5% of the particles of Example 1. The stirrer is operated for 5 minutes at 100 rpm and then the aqueous composition is vacuum filtered through fresh smooth blue denim fabric. In the case of the liquors with the Example 1 - containing detergent there is no visible (i.e., no white spots) evidence of any residue.
When the procedure i5 repeated using identical conditions with the same composition except that in place of 4.5% of Example 1 pro ducts, there is used ~.5~ powdered cationic alone there is a very visible pattern of white spotting on the denim. This is very clear evidence of the outstanding benefits of the Example 1 pro-ducts.
Example 3 When the compositions described in Example 2 are used to wash soiled white towels in a washing machine and then dried in an automatic dryer, the clothes in each instance are acceptably soft although those washed with the detergent containing the Ex-ample 1 softener combination are somewhat softer. In addition, 23 ~7 the towels washed with the detergent containing powdered cationic alone (i.e., not combined with nonionic) have some visible albeit slight spotting (i.e., greasy staining) due apparently to the cationic material whereas the others do not.
Example 4 Example lA lB & 3 are repeated except that the follow-ing nonionics are used in place of the Meodol 23-6.5.
a) Neodol 25-7 (A C12_15 alkyllinear alcohol 7. moles of ethylene oxide) b) Igepal* C0-630 (Nonyl phenol + 10 moles of ethylene oxide) c) Neodol 45-13 (A C14 15 alkyllinear alcohol -I 13 moles of ethylene oxide) Example 5 . .
A spray dried heavy duty detergent having the following composition is provided:
Component Wt. %
Linear tridecylbenzene sulfonate (LTBS) 15 Tripolyphosphate sodium (NaTPP) 33 Silicate 7 Brightener (Stilbene* &
Tinopal* 5BM) .48 O.S. sodium sulfate and water 44.52 100.-00 To 90 g of the above composition are added 4 grams of *Trade marks the cationic-nonionic powder of Example 1 part B. Excellent re-sults are obtained Example 5 Example 3 is repeated except that the detergent also contains a soap spaghetti (4.5% in detergent).
Example 7 _ _ Example 6 is repeated except that the soap spaghe-tti contains 20% by weight of Neodol 25-7.
In Examples 6 & 7 the soap spaghetti is an 85/15 tal3ow/
coco soap.
Example 8 Example 3 is repeated but using a detergent composition having the following proximate analysis.
Component wt. %
Linear Dodecyl benzene sulfonate 23 Na2C3 20 Silicate 15 Borax 3 Nonionic surfactant Soap 2 Carboxymethyl cellulose Brightener* 0.48 Satintone Na~SO4 and water Q.S.
*Stilbene and Tinopal 5BM
To 95 grams of the above composition, 5 gm of the product of Example lB are added.
Example 9 Example 8 is repeated except 5 gm of a soap-nonionic spaghetti (similar to Example 7) is used.
Example 10 Example 6 is repeated except that the soap spaghetti used also contains 4% by weight of carboxymethyl cellulose.
Example 11 The following heavy duty detergent composition is pre-pared.
Components Wt.
Linear alkyl benzene sulfonate 9 Alcohol ether sulfate 8 Nonionic surfactant 2 Tripolyphosphate sodium 24 Zeolite A 17 Na2SO4, brightener, water Q.S.
To this composition is added 5.0 g of the cationic pro-duct of Example lB.
Example 12 Example 11 is repeated except that the soap/nonionic sur-factant spaghetti of Example 6 is added to give 4% in the deter-gent.
Example 13 An unperfumed powder detergent composition having the following formulation is prepared.
1 2~ ~a7 Component Wt. %
Linear tridecylbenzene sulfonate 14.8 Tripolyphosphate sodium 26.5 Silicate 6.9 Brightener (Stilbene* and Tinopal* 5 BM) 0.47 Sodium carbonate 4.9 Carboxymethyl cellulose 0.25 Methocel* 0.6 Sodium sulfate, moisture Q.S.
To 90.6 parts by weight of the above unperfumed powder detergent are added:
Cationic-Nonionic mixture of Ex lB 4.0 parts Soap spaghetti (90% tallow/coco 85/15; 10% Neodol 25-7 (Shell Chemical Co.), spaghetti length =
15 mm, diameter = 0.5mm 4.0 parts Borax Pentahydrate 0.7 parts Nonionic surfactant 0.5 parts (Neodol ~5-7) Perfume 0.2 parts The following Examples illustrate the production and use of the cationic-nonionic combination in prilled form.
Example 14 Eive hundred kilograms of dimethyl distearyl ammonium chloride containing about 4% water is heated to 90C and forms a melt. To 'chis hot melt are added 25 kilograms of Neodol 23-6.5.
This co-melt is then sprayed downwardly from the top of a 75-foot (about 24 meters) tower - 16 foot diameter (about 5 meters).
*Trade mark 2 3 1 8~7 At the same time cool air at about 50~F (10C) is passed upwardly to countercurrent to the falling spray) at a rate of about 30,000 cubic feet per minute (cfm). The congealed product is col-lected at -the bottom of the tower. The produc-t particle is white in appearance, free~flowing generally spherical and solid. It has a porous surface (pock-marked appearance). The bulk density of the prill is about 0.37 (g/cc).
Example 15 To 95.5 g. of the detergent of Example 2 (without EX-ample l particles) are added 4.5 I. of the pills of Example 14.
Example 16 Example 5 through 13 are each repeated except that thecationic-nonionic mixture used in those examples are replaced by the prills of Example 14.
Example 17 Each of the previous examples is repeated except that the nonionic .in the cationic-nonionic mixture is used in amounts of 2%; 7%; 12%; 15%; 20%.
Example 18 Each of the previous examples is again repeated except that the cationic softener of the cationic-nonionic mixture is replaced by the following:
(a) dimethyl di-tallow ammonium methosulfate (b) dimethyl, di-hydrogenated tallow ammonium chloride (c) methyl-l-tallow amido ethyl-2-tallow imidazolinium metho-sulfate (d) me-thyl-l-oleylamidoethyl-2-oleyl imidazolinium metho-sulfate Example l9 In each of the foregoing examples where the cationic-nonionic particles are used in admix1ure with the detergent, the amount of the cationic-nonionic is varied to provide 2%; 7% and ]0% thereof based on the weight of the detergent & softener par-t-icles.
Among the nonionics which are useful in the cationic-nonionic combination it is clear that there is a wide range of melting point. Thus Neodol 23-6.5 is a liquid nonionic as is Igepal C0-630 (nonyl phenol plus lO moles of ethylene oxide) where-as Neodol 25-7 is a somewhat pasty solid and Neodol 25-12 a soft white solid. At higher ethylene oxide content (i.e. > 15 moles of ethylene oxide) the product becomes more solid and somewhat waxy in feel and appearance.
Particularly where it is desired to use higher levels (i.e., above about 5 to 10%) of nonionic in the cationic co-melt, it is often advantageous to use a mixture of a liquid nonionic and a solid nonionic. In addition to the ethoxylated solid nonionics one may also use other solid or pasty nonionics such as the glycer-ol mono and di-fatty glycerides. Of particulax value in this regard are glycerol mono-stearate, glycerol mono oleate and gly-cerol palmitate.
Example 20 Example lo is repeated except that half of the Neodol nonionic is replaced by glycerol monostearate. In the test pro-cedure of Example 2 this product performs on a par with the Example 1 23 8~7 lA material.
_xample 21 Example 3 is repeated using the prvduct of Example 20 in place of the cationic materials of Example 3. Excellent resul-ts are obtained.
Fxample 22 Example 7 is repeated except that the detergent contains the tertiary softener combina-tion of Example 20 in place of the binary combinations of Example 1. The results are similarly excellent as those of Exarnples 3 and 7.
Example 23 Example 22 is repeated except that the nonionic used is Neodol 45--11 (a C14 15 linear alkanol plus 11 moles of ethylene oxide Example 24 Example 6 is repeated except that the soap spaghetti is replaced by an equal weight of Carbowax* (MW-3000-8000) crystals.
Example 25 Example 24 is repeated except that the amount of Carbo-wax is varied as follows (I in detergent):
(a) 0.5 ~b) 1.0 (c) 2.0 (d) 4.0 Example 26 Examples 6, 7, 9, 10, 12, 13, 16, 17, 18, 19, 21, 22 *Trade mark 1 8~7 and 23 are each repeated except where soap spaghetti is used it is replaced by the Carbowax used in Examples 24 and 25 in the amounts indicated (% based on weight of detergent).
(a) G r 2 (b) 0.4 (c) 0.8 (d) 1.0 (e) 2.0 (f) 3.0 (g) 5.0 Ex~nple 27 Examples 24, 25 and 26 are repeated using in place of Carbowax the following:
(A) Pluronic F-108 crystals (B) Soap-spaghetti of high water solubility containing (a) 10% sodium xylene sulfonate; (b) 20% sodium xylene sulfonate; (c) 40~ sodium xylene sulfonate.
The carbowax product of Examples 24 to 26 is a poly-ethylene glycol. The Pluronic F-108 of Example 27 is a polyoxy propylene-polyoxyethylene block copolymer containing 20% polyoxy propylene groups as the hydrophobe and 80~ polyoxyethylene groups.
The base hydrophobe has a MW of 3250~
The Pluronic E`-108 is also illustrative of the water-soluble nonionics which are useful in the cationic-nonionic co-melts of this invention. Of particular value are the liquid Pluronics containing up to about 50% polyoxyethylene groups and a base hydrophobe molecular weight of the polyoxypropylene moiety i 2 3 ~7 of from about 950 to 4000. Where combinations of, for example, Neodol 23-6.5 and Pluronics are used, it may be preferred to use pasty or solid Pluronics. These contain generally from 25% to of polyoxyethylene groups. Illustrative of liquid Pluronics are Pluronic L-61, Pluronic L-64, Pluronic L-72 and Pluronic 101;
of the pasty Pluronics, we find Pluronic P85 and Pluronic P105 among others; of the solid products we may mention Pluronic F-87 and Pluronic F27.
Example 28 As an illustration of the anti-stain benefits of the present invention, several different soiled, white materials are laundered at both 70F and 120F using the detergent containing ca~ionic alone, (A) on the one hand and the cationic-nonionic prill of Example 14 on the other hand (B). The detergent is that described in Example 2.
All of the white materials are equally soiled and the reflectance values of laundered materials are measured. The follow-ing are the reflectance values (Rd).
7_ 120F
(A) (B) (A) (B) Spun Dacron* 77.7 79.0 64.7 66.5 Dacron*/Cotton (65/35) 81.4 81.5 73.9 76.1 Cotton 87.8 87.8 87.3 87.3 Nylon 84.1 85.2 84.1 84.5 The above clearly demonstrates that even after only one washing there is significant improvement on Spun Dacron at *Trade Marks both laundering temperature, on Da~rorl/Cotton at 120F and on Nylon at 70 I. A difference of 0.5 Rd units is significant in the sense that this difference is visually discernible.
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A spray cooled softener composition comprising an inti-mate mixture of a cationic amine softener and from 2 to 20% based on the weight of said mixture of a water-soluble nonionic ethoxy-late surface active compound.
2. A composition as defined in claim 1 wherein the ethoxy-late is a C8 to C18 linear aliphatic alcohol and the amount of combined ethylene oxide is from about 5 to about 100 moles.
3. A composition as defined in claim 2 wherein the amount of nonionic ranges from about 2 to about 10%.
4. A composition as defined in claim 3 which includes from about 2 to 20% of a glycol or glycerol mono- or di-ester of a C8 to C18 fatty acid.
5. A composition as defined in claim 4 which contains from about 2 to about 10% glycerol monostearate.
6. A composition as defined in claim 1 wherein the cationic amine softener is selected from (a) aliphatic, di-(lower) Cl -C4 alkyl, di-(higher) C14 - C24 alkyl quaternary ammonium salts, (b) heterocyclic compounds, and mixtures of (a) and (b).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000527364A CA1231807A (en) | 1982-11-05 | 1987-01-14 | Detergent softener composition |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US43965282A | 1982-11-05 | 1982-11-05 | |
| CA000440506A CA1223405A (en) | 1982-11-05 | 1983-11-04 | Detergent softener composition |
| CA000527364A CA1231807A (en) | 1982-11-05 | 1987-01-14 | Detergent softener composition |
| US439,652 | 1989-11-20 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000440506A Division CA1223405A (en) | 1982-11-05 | 1983-11-04 | Detergent softener composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231807A true CA1231807A (en) | 1988-01-26 |
Family
ID=25670203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000527364A Expired CA1231807A (en) | 1982-11-05 | 1987-01-14 | Detergent softener composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1231807A (en) |
-
1987
- 1987-01-14 CA CA000527364A patent/CA1231807A/en not_active Expired
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