This invention relates to fabric softening compositions. More particularly, it relates to particulate fabric softening compositions and to particulate fabric softeningdetergent compositions.

It has long been well known that although synthetic organic detergent compositions are excellent washing agents they tend to leave washed laundry feeling "hard" to the touch. Consequently, fabric softening compositions have been employed in therinse to treat the washed laundry and soften it. In recent years such fabric softening agents have been incorporated in detergent compositions so that the laundry could be both washed and softened in the same operation, obviating a separate trip to thewashing machine to add fabric softener to the rinse water. Among the fabric softening materials employed in detergent compositions have been the smectite clays, of which montmorillonites and especially bentonites have been most successful. In parentapplications Ser. Nos. 07/638,945, now U.S. Pat. No. 5,126,060, 07/755,965 and 07/756,030 fabric softening and fabric softening detergent compositions have been described in which pentaerythritol compounds (PEC's) have been employed in conjunctionwith swellable bentonites to increase fabric softening activities in both fabric softening compositions and detergent compositions. The increase in fabric softening obtainable made such compositions the equal of quaternary ammonium salt based fabricsoftening rinses, and allowed one to make such compositions without the disadvantages associated with such "quats". However, although the bentonite/PEC compositions are effective fabric softeners in hot water washing, leaving the washed laundry soft andfree of any bentonite deposition, it has been found that when such fabric softening compositions or fabric softening detergent compositions are employed in cold water, such as water at a temperature of 45.degree. C. or lower, e.g., 40.degree. C., theremay be a tendency for the bentonite/PEC combinations to deposit on the laundry, which is especially objectionable when the laundry is dark in color because it is given a whitish cast. Such defect of the bentonite/PEC compositions has been cured by thepresent invention.

In accordance with this invention a particulate agglomerated fabric softening composition of improved fabric softening action and reduced tendency to objectionably discolor dark colored laundry washed in cold wash water in which the fabricsoftening composition is present, comprises a fabric softening clay powder agglomerated into particles with a normally solid co-melt of a mixture of pentaerythritol compound and nonionic surfactant, with the melting point of the mixture being in therange of 30.degree. to 45.degree. C. Also within the invention are a process for manufacturing the described fabric softening compositions, and fabric softening detergent compositions that include them.

The closest art known to applicants, other than the parent patent applications previously mentioned, include U.S. Pat. Nos. 3,928,212; 4,126,562; 4,142,978; 4,152,272; 4,162,984; and 4,214,038; EPO Specification 276999-A; German Specification3613479-A; and Japanese Specifications 0247370 and 4821353. Although these references disclose that pentaerythritol compounds and other esters of polyhydric alcohols have been suggested for fabric softening applications, often in conjunction withquaternary ammonium salt and other cationic softeners, and although bentonite is a known fabric softener in detergent compositions and rinse preparations and some nonionic surfactants are known detergents, such do not make the present invention obviousbecause nowhere in the prior art is it disclosed or suggested that a fabric softening composition should be made by co-melting PEC with nonionic surfactant and then agglomerating bentonite powder with the co-melt, which is of a melting point in the30.degree. to 45.degree. C. range. Neither is there any suggestion in the art of the significant advantages that are obtained from the present invention, including increased fabric softening action, little or no chalky residue on dark laundry itemsthat are washed or treated in cold water, and better cleaning, especially of oily soils, because of the additional cleaning power of the nonionic surfactant in the fabric softening composition.

The clays that are useful components of the invented compositions are those which cooperate synergistically with the PEC's to soften laundry better than would be expected from such a mix of components, whether in particulate fabric softeningcompositions or whether in particulate fabric softening detergent compositions. Such clays include the montmorillonite-containing clays which have swelling properties (in water) and which are of smectite structure, so that they deposit on fibrousmaterials, especially cotton and cotton/synthetic blends, such as cotton/polyester, to give such fibers and fabrics made from them a surface lubricity or softness. The best of the smectite clays for use in the present invention is bentonite and the bestof the bentonites are those which have a substantial swelling capability in water, such as the sodium and potassium bentonites, or which are swellable in the presence of sodium or potassium ions, such as calcium bentonite. Such swelling bentonites arealso known as western or Wyoming bentonites, which are essentially sodium bentonite. Other bentonites, such as calcium bentonite, are normally non-swelling and usually are, in themselves, unacceptable as fabric softening agents. However, it has beenfound that such non-swelling (but swellable) bentonites exhibit even better fabric softening in combination with PEC's than do the swelling bentonites, providing that there is present in or with the softening composition a source of alkali metal or othersolubilizing ion, such as sodium (which may come from sodium hydroxide, added to the composition, or from sodium salts, such as builders and fillers, which may be functional components of the composition). This utility of the normally non-swellingbentonite is surprising and the superiority of such in the invented compositions (when a source of sodium is present) over normally swelling bentonite, such as sodium bentonite, is even more surprising. Among the preferred bentonites are those of sodiumand potassium, which are normally swelling, and calcium and magnesium, which are normally non-swelling, but are swellable. Of these it is preferred to utilize calcium (with a source of sodium being present) and sodium bentonites. The bentonitesemployed are not limited to those produced in the United States of America, such as Wyoming bentonite, but also may be obtained from Europe, including Italy and Spain, as calcium bentonite, which may be converted to sodium bentonite by treatment withsodium carbonate, or may be employed as calcium bentonite. Also, other montmorillonite-containing smectite clays of properties like those of the bentonites described may be substituted in whole or in part for the bentonites described herein and similarfabric softening results will be obtained.

The swellable bentonites and similarly operative clays are of ultimate particle sizes in the micron range, e.g., 0.01 to 20 microns and of actual particle sizes less than 100 or 150 microns, such as 40 to 150 microns or 45 to 105 microns. Suchsize ranges also apply to the zeolite builders, which will be described later herein. The bentonite and other such suitable swellable clays may be agglomerated to larger particle sizes too, such as up to 2 or 3 mm. in diameter but such agglomerates arenot preferred unless they include the PEC and nonionic surfactant, too.

Another component of the invented particulate compositions of the present invention, which is usually the main fabric softening compound therein, other than the fabric softening clay, such as bentonite, is preferably a higher fatty acid ester ofa pentaerythritol compound, which term is used in this specification to describe higher fatty acid esters of pentaerythritol, higher fatty acid esters of pentaerythritol oligomers, higher fatty acid esters of lower alkylene oxide derivatives ofpentaerythritol and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers. Pentaerythritol compound may be abbreviated as PEC herein, which description and abbreviation may apply to any or all of pentaerythritol,oligomers thereof and alkoxylated derivatives thereof, as such, or more preferably and more usually, as the esters, as may be indicated by the context.

The oligomers of pentaerythritol are preferably those of two to five pentaerythritol moieties, more preferably 2 or 3, with such moieties being joined together through etheric bonds. The lower alkylene oxide derivatives thereof are preferably ofethylene oxide or propylene oxide monomers, dimers or polymers, which terminate in hydroxyls and are joined to the pentaerythritol or oligomer of pentaerythritol through etheric linkages. Preferably there will be one to ten alkylene oxide moieties ineach such alkylene oxide chain, more preferably 2 to 6, and there will be one to ten such groups on a PEC, depending on the oligomer. At least one of the PEC OH groups and preferably two, are esterified by a higher fatty acid or other higher aliphaticacid, which can be of an odd or even number of carbon atoms.

The higher fatty acid esters of the pentaerythritol compounds are preferably partial esters and more preferably there will be at least two free hydroxyls thereon after esterification (on the pentaerythritol, oligomer or alkoxyalkane groups). Frequently the number of such free hydroxyls is two or about two but sometimes it may be one, as in pentaerythritol tristearate, or as many as eight, as in pentapentaerythritol tetrapalmitate.

The higher aliphatic or fatty acids that may be employed as esterifying acids are those of carbon atom contents in the range of 8 to 24, preferably 12 to 22 and more preferably 12 to 18, e.g., lauric, myristic, palmitic, oleic, stearic andbehenic acids. Such may be mixtures of such fatty acids, obtained from natural sources, such as tallow or coconut oil, e.g., pentaerythritol ditallowate (the tallow acids diester of pentaerythritol, PEDT) or from such natural materials that have beenhydrogenated. Synthetic acids of odd or even numbers of carbon atoms may also be employed. Of the fatty acids lauric, stearic, coco and tallow acids are often preferred (and such preference may depend on the pentaerythritol compound being esterified).

Examples of some esters (PEC's) within the present invention follow:

______________________________________ MONOPENTAERYTHRITOL ESTERS ______________________________________ ##STR1## MONOPENTAERYTHRITOL DILAURATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.10 COO R.sub.2 = CH.sub.3 (CH.sub.2).sub.10 COO R.sub.3 = OHR.sub.4 = OH MONOPENTAERYTRITOL MONOSTEARATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.2 = OH R.sub.3 = OH R.sub.4 = OH ______________________________________ DIPENTAERYTHRITOL ESTERS ______________________________________ ##STR2## DIPENTAERYTHRITOL TETRALAURATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.10 CO R.sub.2 = CH.sub.3 (CH.sub.2).sub.10 CO R.sub.3 = CH.sub.3 (CH.sub.2).sub.10 CO R.sub.4 = CH.sub.3 (CH.sub.2).sub.10 CO DIPENTAERYTHRITOL TETRASTEARATE R.sub.1 = CH.sub.3(CH.sub.2).sub.16 CO R.sub.2 = CH.sub.3 (CH.sub.2).sub.16 CO R.sub.3 = CH.sub.3 (CH.sub.2).sub.16 CO R.sub.4 = CH.sub.3 (CH.sub.2).sub.16 CO MONOPENTAERYTHRITOL DISTEARATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.2 = CH.sub.3(CH.sub.2).sub.16 COO R.sub.3 = OH R.sub.4 = OH MONOPENTAERYTHRITOL TRISTEARATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.2 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.3 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.4 = OH MONOPENTAERYTHRITOLMONOBEHENATE R.sub.1 = CH.sub.3 (CH.sub.2 ).sub.20 COO R.sub.2 = OH R.sub.3 = OH R.sub.4 = OH MONOPENTAERYTHRITOL DIBEHENATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.20 COO R.sub.2 = CH.sub.3 (CH.sub.2).sub.20 COO R.sub.3 = OH R.sub.4 = OH ______________________________________ PENTAERYTHRITOL 10 ETHYLENE OXIDE ESTER ______________________________________ ##STR3## with n + n' = 10 MONOPENTAERYTHRITOL 10 ETHYLENE OXIDE DISTEARATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.2 =CH.sub.3 (CH.sub.2).sub.16 COO ______________________________________ PENTAERYTHRITOL 4 PROPYLENE OXIDE ESTERS ______________________________________ ##STR4## MONOPENTAERYTHRITOL 4 PROPYLENE OXIDE MONOSTEARATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.16COO R.sub.2 = OH MONOPENTAERYTHRITOL 4 PROPYLENE OXIDE DISTEARATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.16 COO R.sub.2 = CH.sub.3 (CH.sub.2).sub.16 COO MONOPENTAERYTHRITOL 4 PROPYLENE OXIDE MONOBEHENATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.20 COO R.sub.2 = OH MONOPENTAERYTHRITOL 4 PROPYLENE OXIDE DIBEHENATE R.sub.1 = CH.sub.3 (CH.sub.2).sub.20 COO R.sub.2 = CH.sub.3 (CH.sub.2).sub.20 COO ______________________________________

Although in the formulas given herein some preferred pentaerythritol compounds that are useful in the practice of this invention are illustrated it will be understood that various other such pentaerythritol compounds within the descriptionthereof herein may be employed too, including such as pentaerythritol di-hydrogenated tallowate, pentaerythritol distearate (PEDS), pentaerythritol dipalmitate, and dipentaerythritol tetratallowate. Also, in this specification when reference is to acompound of a class, unless it is indicated otherwise therein it is to be considered that the employment of mixtures of compounds of such class are intended to be included (commercial compounds are often mixtures). For example, a technicalpentaerythritol ditallowate (tallow acids diester of pentaerythritol, sometimes called the distearate) comprises about 18% monoester, about 38% diester, about 32% triester and about 8% tetraester, with about 4% of unreacted pentaerythritol and tallowacids. It is desirable to minimize or limit the proportions of triester and tetraester present to avoid unduly high melting points for the PEC's.

The PEC's utilized in this invention can have fabric softening effects of their own but such activities are remarkably increased when a montmorillonite clay (bentonite) is also present. In the absence of such bentonite the PEC may besubstantially undispersed in wash and rinse waters. It has been found that better dispersed PEC has greater softening activity. When undispersed, PEC could be in solid form when cold or in molten form when hot, in neither of which states does it act aseffectively to soften fabrics (and in both of which cases it can deposit objectionably on treated materials to produce somewhat greasy spotting thereof). The bentonite acts to disperse the PEC to make it more effective as a softener, and at the sametime such "dispersing agent" also acts as a softener, which avoids the undesirable dilution of softening action by an ordinary dispersing agent, and it synergistically improves fabric softening. However, despite the utility of bentonite as a dispersantit is often inadequate alone to disperse the PEC sufficiently in cold water (of a temperature lower than about 45.degree. C.), which led to the present invention.

The nonionic surfactant which serves in the co-melt to lower the melting or softening point of the PEC (when a mix softens instead of melting sharply its softening or pour point will be considered as equivalent to its melting point) may be anysuitable nonionic surfactant that has such ability to lower the melting point of the PEC/nonionic surfactant co-melt to the 30.degree. to 45.degree. C. range. Normally, cold water washing will be effected in that temperature range, so to obtain bestdispersion of the fabric softening composition components it is desirable to lower the melting point of the PEC/nonionic surfactant co-melt to such range. Still, it is desirable that the co-melt solidify at room temperature (normally 20.degree. to25.degree. C.) to avoid having it bleed liquid. Although the known nonionic surfactants, as listed in McCutcheon's Detergents and Emulsifiers Annuals, e.g., that for 1981, may be used, if of desired melting points, it is preferable to employ thosewhich are condensation products of a higher alcohol with a lower alkylene oxide of 2 to 4 carbon atoms, preferably ethylene oxide. Desirably, the higher alcohol is a long chain alcohol of 11 to 18 carbon atoms and preferably it is of 12 to 15 carbonatoms, e.g., 12 to 14 carbon atoms, on the average, and it will be a fatty or Oxo alcohol. The molar ratio of ethylene oxide to higher alcohol in the condensation product will usually be in the range of 1 to 10 or 11 moles of ethylene oxide per mole ofalcohol, preferably 2 to 7, e.g., 2, 7, and preferably will be 7 or about 7, with seven moles of EtO per mole of C.sub.12-15 fatty alcohol. Such nonionic surfactant has a pour point of 21.degree. C. and it has been found that about three parts of itper two parts of PEDT will lower the melting point of the mix to 40.degree. C. and make the invented fabric softening composition well dispersed in cold wash or rinse water. A condensation product of two moles of ethylene oxide per mole of C.sub.12-15fatty alcohol solidifies at 7.degree. C. and two parts thereof will lower the melting point of three parts of PEDT to about 40.degree. C.

Frequently the particulate fabric softening composition of the invention will consist of only the three components described but in some instances compatible adjuvants may also be present. Among such may be named: supplementary fabric softeners,such as quaternary ammonium salts, where permissible; perfumes; stabilizers; fillers; enzymes; and fluorescent brighteners. Examples of such adjuvants are given in the art previously mentioned herein, all of which is hereby incorporated by reference. Quaternary ammonium salts and other cationic softeners will usually be omitted from the compositions because of their detrimental effects on aquatic organisms, but limited quantities of them may sometimes be tolerable, when the ecotoxicity thereof iswithin the limits permitted by law and regulations. Any adjuvants present should be water soluble or dispersible or should be meltable in the composition at a temperature in the range of 30.degree. to 45.degree. C., or should be present in smallenough quantity so as not to cause a deposition problem on the laundry.

The previous description of the components of the invented compositions is directed to those in the fabric softening compositions that are intended for addition to non-softening detergent compositions to give them fabric softening properties. Alternatively, the fabric softening compositions may be employed as additives to wash waters or rinse waters. In all such cases, when the bentonite is a swelling bentonite, such as a sodium or potassium bentonite, there will be no need for the presenceof any other material with the described compositions but when the bentonite is a swellable one, which should be converted to swelling form by reaction with a source of solubilizing ion, such as sodium or potassium, such a source should be present, too Asuitable source of solubilizing ions is found in built detergent compositions that are built with alkali metal builder salts, such as sodium carbonate, sodium bicarbonate, sodium tripolyphosphate, borax, sodium citrate and/or sodium silicate, which mayalso be in the wash water or in the rinse water, or may be added to the rinse water, or to the fabric softening composition. Normally the proportion of ionizable sodium or potassium should be at least 50% of the gram equivalent of calcium or magnesiumin the calcium or magnesium bentonite, and preferably it will be at least 100% and more preferably in 100% excess or more.

When the fabric softening composition is incorporated in a detergent composition to make it into a fabric softening detergent composition the active detergent will desirably be either an anionic detergent or a nonionic detergent or a mixture ofthe two. Even when the detergent composition is solely anionic the final product will have nonionic detersive characteristics because of the presence in the fabric softening composition component of nonionic surfactant. When the detergent compositionincludes nonionic detergent the amount thereof included in the formula can often be decreased because of the presence of the nonionic surfactant in the fabric softening composition component.

Among the nonionic detergents those which are most preferred are ethylene oxide condensates with higher fatty alcohols or with alkyl phenols, such as condensation products of 1 to 20, 5 to 15, 6 to 12 or 7 to 11 moles of ethylene oxide withhigher fatty alcohols of 10 or 12 to 18 or 13 to 17 or 12 to 15 carbon atoms or with alkyl phenols of 7 to 10 carbon atoms in the alkyl groups, e.g., Dobanol.RTM. 25-7, Synperonic.RTM. A7, Neodol.RTM. 25-3, Neodol 25-7, Neodol 45-11, and C.sub.12-15or C.sub.13-17 alcohols condensed with 7 or 11 moles of ethylene oxide per mole. Although the improved softening obtained when bentonite is employed with a PEC is noticeable in anionic, nonionic and anionic/nonionic detergent compositions, such increasein softening action is even more surprising in the case of nonionic detergent compositions because PEC alone (without bentonite) has no fabric softening action at all in nonionic detergent compositions (but does have some such action in anionicdetergents).

The anionic detergents are normally of the water soluble sulfate and/or sulfonated lipophile type, which may be designated "sulf(on)ated", and which include lipophile and sulf(on)ate moieties, but analogous phosph(on)ates may also be utilized. Of the synthetic anionic organic sulf(on)ated detergents those preferred are higher alkyl (preferably linear alkyl) benzene sulfonates, higher fatty alcohol sulfates, higher fatty alcohol ethoxylate sulfates, olefin sulfonates and paraffin sulfonates. Usually such compounds are water soluble alkali metal salts, such as sodium salts, and include higher fatty alkyl or other aliphatic moieties, which serve as lipophilic moieties, and which increase detergency, especially against greasy soils. Suchhigher alkyl or higher aliphatic moieties will normally be of 8 to 22 carbon atoms, preferably 10 or 12 to 16 or 18 carbon atoms and more preferably, especially for the more preferred alkyl sulfates and alkylbenzene sulfonates, the alkyl moieties will beof 10 or 12 to 14 carbon atoms. The higher fatty alcohol ethoxylate sulfates that are useful will normally be of 1 to 20 ethoxy groups per mole, preferably 3 to 10 or 15, e.g., 3 or 7. As representatives of anionic detergents there may be mentionedsodium linear dodecylbenzene sulfonate, sodium linear tridecylbenzene sulfonate, sodium lauryl alcohol sulfate, sodium coco alcohol triethoxylate sulfate, sodium C.sub.16 paraffin sulfonate and sodium olefin sulfonate derived from C.sub.14 olefin.

In addition to the above examples of suitable anionic and nonionic detergents, extensive listings of such detergents that are useful may be found in standard textbooks relating to synthetic organic detergents, such as the McCutcheon texts,previously cited, which are incorporated herein by reference.

Of the water soluble builders for the anionic and nonionic detergents it is preferred to employ water soluble salts, such as sodium or potassium salts, more preferably sodium salts, and of these the carbonates, silicates, borates, bicarbonatesand phosphates, especially the polyphosphates, are preferred, such as sodium carbonate, sodium bicarbonate, sodium silicate of Na.sub.2 O:SiO.sub.2 ratio in the range of 1:1.6 to 1:3, preferably 1:2 to 1:3, e.g., about 1:2, 1:2.35 or 1:2.4, sodiumtripolyphosphate, tetrasodium pyrophosphate and borax, but sodium sesquicarbonate and sodium sesquisilicate may also be used, as may be the corresponding potassium and other soluble salts, when suitable. Of the water insoluble builders, which buildersalso have water softening properties, the most preferred are the zeolites, especially the hydrated zeolites. Such zeolites include crystalline, amorphous and mixed crystalline and amorphous zeolites of both synthetic and natural origins, which are ofsatisfactorily quick and sufficiently effective activities in counteracting calcium hardness ions in wash waters. Preferably the zeolites employed are characterized as having high exchange capacities for calcium ions, which exchange capacity is normallyfrom about 200 to 400 milligram equivalents of calcium carbonate per gram of the zeolite. Although other ion exchanging zeolites may also be utilized, often the zeolite will be of the formula

wherein x is 1, y is from 0.8 to 1.2, z is from 1.3 to 3.5 and w is from 0 to 9, and preferably is 2.5 to 6. Of the crystalline zeolites that are useful those preferred include Zeolites A, X and Y, with A being more preferable, and the mostpreferred of these is Zeolite 4A. These zeolites are preferably in finely divided state when added to the crutcher with the synthetic detergent prior to drying, and are of ultimate particle diameters and actual sizes like those previously described forthe bentonites. Other builders that may be utilized include organic compounds, which are often sequestrants for hardness ions. Such compounds include organic acids, especially hydroxy and amino polycarboxylic acids, such as citric and gluconic acidsand ethylene diamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), all usually as their water soluble salts, e.g., sodium salts. Additional useful builders are the organic-phosphorus chelating agents, such as the Dequests.RTM., e.g., Dequest2046, which are manufactured by Monsanto Co.

Filler or bodying salts are often also present in the detergent compositions. Although various such salts can be employed that which is most commonly and most successfully utilized is sodium sulfate. Finally, various adjuvants may be present,too, including: enzymes, such as proteases, amylases and cellulases; antioxidants; stabilizers; fluorescent brighteners; anti-redeposition agents; foaming agents; anti-foams, such as silicone oils; colorants; buffers; pigments, such as titanium dioxide;bleaching agents; such as sodium perborate; bleach activators, such as TAED; and sequestrants and chelating agents.

The proportions of components in the fabric softening compositions of the invention will normally include 50 to 90% of the bentonite, 5 to 30% of the PEC and 5 to 45% of the nonionic surfactant, with such ranges preferably being 50 to 80%, 10 to30% and 10 to 40%, respectively. When the PEC is a higher fatty acid ester of pentaerythritol, as is preferred, the preferred esters are the mono- and di-esters and the content of the diester will be at least 30% of the total PEC. Technical mixtures ofthe esters may be used and in many cases only technical mixtures will be available commercially. Pure diesters and monoesters can be employed, too, although often the results will not warrant the additional expense. For fabric softening compositionsconsisting of calcium or sodium bentonite, pentaerythritol ditallowate (technical) and C.sub.12-15 fatty alcohol . 7 EtO nonionic detergent the most preferred proportions are about 65%, about 20% and about 15%, respectively. When the nonionicsurfactant in the formula is C.sub.12-15 fatty alcohol . 2 EtO instead, less of it needs to be used and the most preferred proportions will be changed to about 65%, about 20% and about 15%, respectively.

The detergent composition that is made fabric softening by being blended or formulated with the invented fabric softening composition is one which normally comprises 4 to 35% of synthetic organic detergent, 50 to 92% of builder for the detergentor a combination of builder and filler, with the builder being more than half thereof, and 3 to 15% of water. Preferably, such percentage ranges are 5 to 20%, 65 to 90% and 5 to 15%, respectively and the builder content will be more than 2/3 of thetotal of builder and filler. When the detergent composition contains sodium perborate as a bleaching agent, and includes pentaerythritol ditallowate and C.sub.12-15 fatty alcohol . 7 EtO nonionic detergent, the more preferred proportions are 5 to 15%of synthetic detergent (anionic and/or nonionic), 50 to 85% of builder or combination of builder(s) and filler (sodium sulfate, anhydrous), 5 to 20% of sodium perborate (anhydrous basis) and 5 to 15% of water. In such compositions the preferred rangesfor the fabric softening composition components are 55 to 75% of bentonite (preferably calcium bentonite), 10 to 20% of pentaerythritol ditallowate, and 15 to 30% of nonionic surfactant.

In the fabric softening detergent compositions, which may be made by mixing together the detergent composition and the fabric softening composition or may be made by formulating the composition from scratch, the proportions of the compositionsgiven herein are based on mixings of the two types of compositions, but "scratch" formulas may be easily calculated from them. The proportion of fabric softening composition that is mixed with the detergent composition is any suitable proportion toresult in an acceptable fabric softening detergent composition that will wash well and soften the washed laundry. Thus, the composition will include a detersive proportion of a built detergent composition and a fabric softening proportion of a fabricsoftening composition. Usually the percentage of the fabric softening composition in the final product will be in the range of 10 to 40%, preferably 20 to 35% and most preferably 25 to 35%. The compositions will be of particle sizes in the ranges of100 microns to 3 mm., preferably 150 microns to 2 mm. in diameter, and they will be evenly mixed together.

To make the invented fabric softening compositions is relatively easy but it is important that the PEC and the nonionic surfactant be co-melted, after which the co-melt is deposited on the clay. The co-melt is of such a composition that itsmelting point (or softening or pour point) is in the range of 30.degree. to 45.degree. C., so that it will satisfactorily disperse when the fabric softening composition is in cold wash or rinse water. Preferably the co-melt melting point will be nohigher than 43.degree. C. and more preferably will be no higher than 40.degree. C. The co-melt will be made by raising the temperatures of both the PEC and the nonionic surfactant to a temperature at which they are both liquid, which temperature mightbe in the range of 50.degree. to 70.degree. C., for example, often 55.degree. to 65.degree. C., such as 60.degree. C. or about 60.degree. C., for PEDT and similar pentaerythritol esters. Normally the PEC will be chosen on the basis of its fabricsoftening activity in conjunction with bentonite and nonionic surfactant, and on the basis of its melting point. For example, one will usually avoid employing a PEC that has a melting point in excess of 70.degree. C. and often one will also avoid thoseof melting point above 65.degree. or 60.degree. C. because it might be difficult to lower the co-melt melting point sufficiently (ideally to 35.degree. or 40.degree. C.) to obtain the excellent dispersing that results in no "chalking" of dark coloredlaundry treated with the fabric softening composition.

The co-melt may be made in any suitable manner, as by heating the nonionic surfactant and the PEC together or by heating them separately to the co-melting temperature and mixing the melts together. The PEC is solid and the C.sub.12-15 alcohol . 7 EtO nonionic surfactant is a paste at room temperature (20.degree. to 25.degree. C.). The co-melt is also normally solid at such temperature, but the co-melted mixture, after solidification at room temperature, will melt or soften at a "cold" waterwashing temperature, such as 40.degree. C. or thereabout. When the co-melt is made from the PEDT and the 7 EtO nonionic surfactant the surfactant is melted at 30.degree. C. and the PEDT is melted at 60.degree. C. and they are mixed together and thenthe mix is heated to 60.degree. C. When the 2 EtO nonionic surfactant is co-melted with the PEDT the normally liquid nonionic is mixed with the 60.degree. C. PEDT and the liquid mix is then heated to 60.degree. C.

After the co-melt is made, and while it is still hot, e.g., at about 60.degree. C., it is sprayed onto a moving bed of the finely divided bentonite powder (at room temperature) which is thereby agglomerated to larger particles held together bythe solidified co-melt. The mixing or tumbling of the particles may be controlled to regulate the particle sizes of the agglomerate made. Alternatively, the co-melt may be mixed with the bentonite powder to form a pasty mass, which may then be sizereduced by conventional means to desired particle size range. When the benonite is calcium or magnesium bentonite there may be mixed with it a suitable proportion of a sodium potassium salt, as a source of alkali metal ion, preferably sodium ion, andsuch proportion can be in the range of 1/5 to 20 times or 1/2 to 10 times that of the bentonite, with enough being present to give the bentonite swelling characteristics. Alternatively, such alkali metal salt may be in the detergent composition employedor may be added to the rinse water.

The following examples illustrate but do not limit this invention. All parts and percentages in the examples, specification and claims are by weight and all temperatures are in .degree.C. unless otherwiseindicated.

EXAMPLE 1

______________________________________ Component Percent (by weight) ______________________________________ *Pentaerythritol distearate, technical 15.0 **Fatty alcohol ethylene oxide condensate 21.2 nonionic surfactant Calcium bentonite63.8 100.0 ______________________________________ *18.2% Pentaerythritol monostearate, 38.2% pentaerythritol distearate, 31.9% pentaerythritol tristearate, 8.3% pentaerythritol tetrastearate and 3.4% of unreacted pentaerythritol and tallow acid,available from Hoechst A.G. **C.sub.12-15 Oxo alcohols.7 EtO (Oxo alcohols from crached wax olefins). The alcohol may be replaced by C.sub.13-14 Alfol .RTM. 1412H or by C.sub.13-15 Oxo alcohols from Ziegler olefins.

The pentaerythritol distearate is melted by being heated to 60.degree. C., the nonionic surfactant is melted by being heated to 30.degree. C. and the two are mixed together, after which the co-melt resulting is heated to 60.degree. C. and theheated co-melt is mixed with the calcium bentonite powder, which is of a nominal particle size of about 150 microns in diameter and is at room temperature. The mixing is effected in a Hobart.RTM. mixer and is continued for five minutes, until theco-melt is evenly dispersed in the bentonite. Then the mix is allowed to cool to room temperature, about 21.degree. C., at which it forms a solid cake, which is then size-reduced to particle sizes in the range of 150 microns to 2 mm. in diameter,averaging about 0.5 to 1 mm. in diameter. The particles resulting are of improved particle strength and are satisfactorily flowable, and are capable of being automatically fed by washing machine feeding mechanisms to the wash water or the rinse waterto soften laundry.

In an alternative process for manufacturing the fabric softening composition described the co-melt is sprayed onto tumbling bentonite particles in a Lodige.RTM. mixer until the bentonite is agglomerated to the desired size range mentioned above,during which agglomeration the particles are allowed to cool to room temperature. The resulting agglomerated particles are the equivalent of those made by size reducing the cake of fabric softening composition.

The processes described above are maintained the same but instead of employing calcium bentonite a sodium bentonite is substituted (Wyoming bentonite) of essentially the same particle size range. The fabric softening composition resulting is ofessentially the same physical characteristics as that of the formula based on calcium bentonite but because the bentonite is swellable without the presence of alkali metal ion it is not required that there be present with the bentonite any source ofalkali metal ions. While the alkali metal ion source for the calcium bentonite may be included in a detergent composition, the wash water or the rinse water in which the fabric softening composition is used, it may also be incorporated in the fabricsoftening composition with the calcium bentonite, as by admixing with the calcium bentonite an equivalent weight proportion of ionizable alkali metal salt, such as sodium carbonate, sodium sulfate or sodium tripolyphosphate, which will be sufficient tomake the bentonite swellable.

Although the prime object of this invention is the making of particulate fabric softening products, aqueous and aqueous alcoholic emulsions and dispersions of the fabric softening compositions may be made by emulsifying or dispersing theparticulate compositions (which may be further size reduced beforehand) in appropriate liquid media (in which the liquid medium of the continuous phase will be 40 to 95%, preferably 60 to 90%). For such emulsions and dispersions there will normally alsobe present 0.5 to 10%, preferably 1 to 5%, of an emulsifying agent, hydrotrope and/or dispersant, such as an ethoxylated lower alkyl amine, sodium toluene sulfonate and/or polymeric electrolyte, and such products may also include a source of sodium orpotassium ions when the bentonite present is calcium or magnesium bentonite. The liquid products made exhibit the same type of superior fabric softening properties as the particulate products, and do not objectionably whiten treated laundry despite thetreatment being conducted in cold water, at about 40.degree. C.

EXAMPLE 2

______________________________________ Component Percent (by weight) ______________________________________ Sodium linear C.sub.10-13 alkylbenzene sulfonate, 6.0 technical Zeolite 4A (hydrated) 19.0 Sodium silicate (Na.sub.2 O:SiO.sub.2 =1:2) 3.5 Sodium maleate methacrylate copolymer 1.1 Ethylene diamine tetra(methylene 0.5 phosphonate) sodium salt Sodium carboxymethyl cellulose 0.4 Stilbene fluorescent brightener 0.2 Sodium sulfate, anhydrous 13.54 Sodium carbonate,anhydrous 10.0 Sodium perborate, monohydrate 9.0 Tetraacetyl ethylene diamine 1.8 Hydroxylamine sulfate 0.5 Enzyme blend 0.36 Sodium aluminosilicate (Tixolex 28) 0.4 Perfume 0.55 Calcium bentonite or calcium 18.0 montmorillonite (swellablein presence of sodium) Pentaerythritol distearate, technical 4.25 Nonionic surfactant (C.sub.12-15) 6.0 fatty alcohol.7 EtO) Water 4.9 100.0 ______________________________________

The first eight components of the formula are mixed together with water in a crutcher at a temperature of about 63.degree. C., with the water content of the crutcher mix being about 50%, and the crutcher mix is spray dried in a countercurrentspray drying tower, with the inlet and exit air temperatures being 320.degree. C. and 130.degree. C., respectively. The spray dried base beads resulting are of a moisture content of about 10% and are of a particle size distribution such that less than1% are larger than 1.7 mm., less than 25% are larger than 800 microns, less than 50% are larger than 500 microns, and at least 90% are larger than 150 microns, in diameter.

The calcium bentonite, pentaerythritol distearate and nonionic surfactant are made into a particulate fabric softening composition in the manner described in Example 1, of particle sizes like those of the base beads. Then the sodium carbonate,fabric softening composition, sodium perborate monohydrate, TAED, hydroxylamine sulfate, enzyme blend, and Tixolex 28 are blended in with the base beads and the perfume is oversprayed onto the particulate mixture. The finished fabric softening detergentcomposition is of a moisture content of about 4.9% and of particle sizes like those of the base beads, as previously described.

The fabric softening detergent composition is tested against a control composition of the same formula, with the only difference between the products being in the experimental having a co-melt of PEDS and nonionic surfactant being mixed in liquidstate with the bentonite powder while the control has the PEDS mixed with the bentonite, with the liquid state nonionic surfactant being after-sprayed onto the balance of the formula, with or separate from the perfume. Testing is by actual multiple (3)washings of laundry in a Miele Model 718 automatic tumbler type washing machine in 40.degree. C. water of 400 p.p.m. Ca.sup.++ /Mg.sup.++ (4:1) hardness, using 1% of detergent composition, and the washed specimens are compared after line drying toevaluate cleaning and fabric softening actions of the test composition and the control. Surprisingly, it is found that the experimental product washes better and the washed product feels softer to an evaluation jury. Similar results are obtained whensimilar comparisons are made to leading commercial fabric softening detergent compositions and fabric softening action is considered to be equivalent to or better than with such products. Such results are also obtained when the testing is in wash waterat more elevated temperatures, such as 60.degree. C.

An important improvement found in the invented compositions is in the lack of deposition of bentonite and PEDS on the washed laundry, washed in cold water (40.degree. C.), which is considered to be a significant detriment of the controlbentonite/PEDS detergent composition that has the nonionic detergent post-sprayed onto it. Such negative effects are objectionably visible when the laundry washed is dark colored, because the color becomes lightened and chalky in appearance, rather thanclear and bright. Such problem with the control is not noted at elevated temperatures, of 60.degree. C. and higher, but because much washing is done at lower temperatures the advantage for the invented compositions is significant.

The laundry washed with the invented product is of such improved fabric softening and cleaning power that the PEDS content thereof could be lowered to 4.25% in the fabric softening agglomerate component thereof, from the 6% that had beenconsidered as desirable previous to the present invention. Such improvements are attributable to the presence of the nonionic surfactant in the co-melt with the PEDS. Such decrease in the content of the PEDS is believed to lessen any tendency towardobjectionable whitening of dark colored laundry but such improvement in color integrity of washed laundry is also obtained when the PEDS is present in the detergent composition at a 6% concentration and when its content in the fabric softeningcomposition is increased accordingly.

Other advantages that result from the present invention include the ability to spray dry stronger and higher density base beads because of the post-addition of the bentonite/PEDS/nonionic surfactant softening composition, the decrease intackiness of the detergent composition because the nonionic detergent is not over-sprayed onto the beads near the end of the manufacturing process, and the obtaining of the detersive properties of the nonionic surfactant as a bonus (because it performsdual functions in the product).

EXAMPLE 3

The composition of Example 2 is modified by utilizing 18% of the bentonite, 4.25% of the PEDS and 2.8% of C.sub.12-15 fatty alcohol . 2 EtO condensate nonionic surfactant in the agglomerated fabric softening component of the detergentcomposition. It is found that that agglomerate also is an excellent fabric softening agent and converts the basic detergent composition to one that is also fabric softening, and which cleans and softens laundry washed or treated in cold water(40.degree. C.) without objectionably whitening dark colored laundry items. The difference of 3.2% in the product formula is compensated for with post sprayed or crutcher added nonionic detergent or surfactant or alternatively, in some instances,sodium sulfate or other detergent composition component(s) may be increased.

EXAMPLE 4

In other variations of the detergent composition and fabric softening composition formulas of Examples 1 and 2, instead of the calcium bentonite being utilized sodium bentonite (Wyoming bentonite) is substituted for it part for part. Theproducts resulting will exhibit the same improved detergency, fabric softening and lack of objectionable whitening of dark laundry items that was described above. Additionally, because the bentonite employed is an alkali metal bentonite, which isswellable, there is no need for the presence of any alkali metal ion source in the fabric softening composition.

EXAMPLE 5

The detergent composition of Example 2 is what is described as a non-phosphate composition, which is based on a combination of anionic and nonionic synthetic organic detergents/surfactants. However, where permitted, sodium tripolyphosphate maybe substituted for the zeolite of the formula, the synthetic detergent component may be solely anionic or nonionic, and the builders and adjuvants may be varied accordingly, and the same desirable results attributable to the described invention will beobtainable.

EXAMPLE 6

In the foregoing examples of both the fabric softening and fabric softening detergent compositions there may be substituted others of the equivalent components mentioned in the foregoing specification and the proportions and percentages may bevaried within the ranges given and .+-.10% or .+-.25% from those of the formulas. The resulting compositions will possess the desired characteristics previously noted and will be within the present invention.

This invention has been described with respect to various illustrations and working embodiments thereof but it is not to be limited to those because it is evident that those of skill in the art, with the present specification before them will beable to utilize substitutes and equivalents without departing from the invention.

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