CA1223405A - Detergent softener composition - Google Patents

Abstract

DETERGENT SOFTENER COMPOSITIONS

ABSTRACT OF THE DISCLOSURE

The present invention provides particulate heavy duty detergent compositions, particularly for imparting improved softness and detersive effects to fabrics laundered therewith said composition including in addition to conventional builder and principally anionic surfactant components, particulate cationic softener of the di-lower-di-higher alkyl quaternary ammonium and/or heterocyclic imide type, e.g., imidazolinium, in admixture with nonionic surfactant and optionally a mixture of fatty acid soap and nonionic organic surfactant, the weight ratio of soap to softener being about 8:1 to 1:3 preferably 5:1 to 1:2, more preferably 3:2:2:3, e.g., about unity. The soap-nonionic surfactant mixture as well as the cationic softener-nonionic mixture are in the form of a spaghetti, flake, or other shape and is present in the product composition as substantially homogeneously dispersed, discrete particles. A
process of laundering fabrics using the above-mentioned compos-ition is also disclosed.

Description

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This invention relates to detcrgent compositions and in particular to detergent-softe]ler compositions capable of imparting improved softness, detersive effects 9 soil anti-redeposition and antistatic properties -to fabrics treated therewith and particularly in a machine laundering p-rocess.
The detergent compositions of this invention are also outstanding in that they result in less greasy staining (due to the catiollic 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 qua~ernary ammonium type, is likewise well recognized in the patent literature.
Such interaction often results in the formation of unsightly pre-cipitates which become entrapped within or otherwise deposited upon the fabric being washed. Discoloration or other aesthetical displeasing effects are for the most part inevitable. The net result is often a depletion in the effective amount of anionic available for useful purposes since the loss of anionic is the primary consequence.
Remedial techniques heretofore proposed to abate the aforedescribed cationic-anionic problem though divergent as to approach seem convergent as to result namely, less than satisfactory.

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Thus, although the most effective types of cationic quaternary ammonlum softeners, as exemplifiecl by the aforementioned di-higher alkyl type quats, such as clistearyl dimethyl ammonium chloride, can function in the wash cycle in the presence of anionic, builder, etc., the quantity needed to achieve effective softening is usually coterminous with amounts promotive of undesired cationic-anionic interaction. As a general rule, at least about twice as much cationic is required fo~ sof-tening as for antistat.
In U.S. 3,325,4]4, dealing primarily with detergents of controlled foam or sudsing capability, the cationic-anionic problem and attendant detrimental effects are discusedd in detail. The patent additionally points out that certain quater-nary ammonium compounds, amoung 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 being correspondinglv limitedO Cationics 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. U.S. 3,~7~,338 is representative, this patent teaching the use of anionic softener referred to as "branched-chain carboxylic acids," as fabric softener. Presumably, anionic detergent would be stable in the presence of the anionic softener.

~ZZ34~i As the foregoing demonstrates, the remedies proposed necessitate the discarding of softeners and principally those of the di-higher-di~lower a1kyl 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.
The problem of cationic incompatibility in anionic detergents is also acknowledged in U.S. 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 inhibitors is a maximum water solubility at 25C of 50ppM.
Similar disclosures may also be found U.S. Patents 4,113,630;
4,196,104 and 4,272,385. In U.S. Patent No. 4,230,590 to Wixon heavy duty detergents comprising conventional builder, princi-pally 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 U.S. Patent No. 4,298,480 to Wixon heavy duty detergents having compositions similar to that described in the preceeding paragraph with the exception that cellulose ether is excluded therefrom are disclosed.
In U.S. Patent 4,329,237 to Wixon having duty deter-gents also similar to those in the preceeding 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 properties, it has been found that optimum softening without spot staining may not be attained.

, 3~15 The present invention provides stable detergent softener composi-tions capable of providing improved softness without stainillg, detergency, antistatic and s~il antiredeposition properties to fabrics treated ~herewith therewith in a laundering process in cold or hot water.
According to the present invention, there is provided a particu-late detergent softener composition capable of imparting improved softness, detergency, antistatic and nonstain properties to fabrics treated therewith in a laundering process 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 dis-persible fatty acid soap or a mixture thereof with nonionic organic surfac-tant, the nonionic constitu~ing from about 2 to about 50% by weight of the said soap mixture,wherein the ca~ionic-nonionic mixtureis substantially homogeneously dispersed in said composition as discrete particles.
In another aspect, the invention 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 invention also 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 surfactant active compound.
The compositions generally comprise by weight from about 5 to 40%
of a water-soluble, non-soap, anionic surfactant, fromabout 10 to 60% of water soluble, neutral ~o alkaline builder salt, from about 2 to 20% of cationic softener selected rom (a) aliphatic, di-(lower) Cl - C4 alkyl, di-(higher) C14 - C24 a]kyl quaternary ammonium saltsJ (b) heterocyclic compounds, and mixtures of (a) and (b), said cationic in intimate admixture with a water-soluble nonionic (2 to 50% by weight based on weight of cationic), and from about 0 to 20% of a mixture of water soluble or dispersible fatty acid soap and nonionic organic surfactant in spaghetti-like or other shaped, discrete 3~5 form, the weight ratio of soap (when used) to softener being from about 2:3 to 3:2, the per-cent concentration of anionic surfactant being at least about ].5 x + 5, x representing the per-cent concentration of softener, wherein the soap is substantially homogeneously dispersed throughout said composition preferably as discrete particles.
In the soap-nonionic surfactant mixture, the nonionic constitutes from about 2 to about 50%, preferably from about 5 to about 40%, more pre-ferably from about 8 to about 30%, and most preferably from about 8 to about 20%, all percentages being by weight. The totalnonionic surfactant content in the soap mixture will vary from about 0.04% to about 10%, preferably from about 0.1% to about 8%, and more preferably from about 1.6 to about 6%, and most preferably from about 1.6% to about 4%, all percentages being by weight and based on the weight of the detergent composition.
In certain other aspects~ the invention includes using the afore-described compositions.
According to the present invention by adding the cationic material in intimate admixture with nonionic organic surfactant in flakes, granules and the like form, the spot staining of the clothes after drying is substan-tially mitigated. In addition, the softness in the fabrics laundered is generally unexpectedly enhanced. The nonionic surfactan~ also contributes to soil antiredeposition, especially in non-phosphate formulas.
The inclusion of the nonionic organic surfactant in the cationic softener composition has the following additional 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 in the post-added cationic whichleads to a significant improvement in the flowability of the detergent composition.

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In the embodiments of the present invention utiliziny soap particles with or without cellulose ether or non-ionic 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 metalsr 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 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 groundnut, hardened fish, e.g., cod liver and shark, seal, perilla, linseed, candlenut, hempseed, wainut, poppyseed, sunflower, maize, rapeseed, mustardseed, 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 the soap particles and in admixture with the cationic are known materials. Such nonionic surfactants may be broadly defined as water-soluble compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic 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 between 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". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of 'he molecule as a whole and the li~uid character of the product is retained up to the point where polyoxyethylene content is 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.

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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 ethyl-ene 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 either straight chain or branched chain configuration, with from 2 to 100 moles of ethylene oxide e.g., a coconut alcohol-ethylene oxide 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.
Other 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 condensed with 20 moles of ethylene oxide per mole of nonyl phenol; myristyl alcohol condensed with 10 moles of ethyl-ene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide; and di-iso-_ g ~ 223~

octylphenol condensed with 15 moles of ethylene oxide.
Among the above-listed nonionic surfactants, the condens-ation 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 Co., which comprises the condensation pr~duct of C12 15 alcohol with 7 moles of ethylene oxide, and Neodol*23-6.5 which is the product of a C12 13 alcohol with 6.5 moles of ethyl-ene oxide.
Cationic softeners useful herein are known materials and are of the high-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 ammonium salts may be structurally defined as follows:

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 includ-ing the aforementioned chloride, bromide, iodide, sulfate and methosulfate. Particularly preferred species of aliphatic * Trade Marks 10 ~L2;~34~S
quats include:
di-hydrogenated tallow dimethyl ammonium chloride di-tallow dimethyl ammoni.um chloride distearyl dimethyl ammonium methyl sulfate di-hydrogenated talllow dimethyl ammonium methyl sulfate Heterocyclic imide softeners of the imidazolinium type may also, for convenience, be structurally defined as follows:

N ~ !H

R4 CH2C~2NH -C X

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 imidazoliniums include:
methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trade mark Varisoft 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.

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It is preferred ln one aspect of the present invention where the soap and nonionic surfactant are used in combination that the soap be 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 surfac-tant admixture for incorporation into the final detergent composition, usually by post blending of both soap and the cationic-nonionic mixture with dried detergent. The soap and nonionic surfactant when combined 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 sufficiently "doughy" or plastic to be in suitable form for, preferably, extrusion or other process, e.g., pelleting, gran-ulation, stamping and pressing. Working may be effected, for example, by roll milling, although this is not essential, fol-lowed by extrusion in a conventional soap plodder with the desired type of extrusion head. The latter is selected in accordance with the shape, i.e., geometric form, desired in the extrudate. Extrusion in the form of 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 foregoing purposes are well known in the art and include for example Elanco*
models EXD-60; EXCD-100; EX-130 and EXD-180, a Buhler* 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 * Trade Marks - 12 -~L~3~S

average length of from about 2 to 20 mm. with about 95-- thereof within a tolerance of 005 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 preferred. The bulk density of the spa~hetti will usually, having reference to the type of fatty acid soap 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 6.2 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.

The cationic-nonionic mixture may be prepared similarly as for the soap-nonionic mixture. It is preferred however to use the mixture in prilled form. The prills are produced by spray cooling a liquefied mixture of the cationic and the non ionic. In the most preferred embodiment a liquid non-ionic is used (e.g., Neodol*23-6.5) and this is added to melted cationic. A typical cationic is Arosurf*TA-100 (dimethyl distearyl ammonium chloride) and as supplied this material forms a very fluid liquid when melted and heated to 90C. The liquid mixture of cationic and nonionic may in another preferred embodiment may be allowed to cool to room temperature or as necessary to solidify. The solid may then be ground to desired particle size and post added to the other detergent ingredients.
Generally, from 1 to 20% be weight of non-ionic based on the weight of the cationic softener is contemplated.
Preferably the nonionic should be used in amounts of from 5 to 15% with about 10% being particularly preferred in the case of Neodol 23-6.5.
Although surfactants of conventional type can be used herein, it is preferred that at least about 90% and preferably at least about 95% of the total surfactant or detergent be of the anionic type, these materials being particularly beneficial * Trade Marks - 13 -~3~

in heavy duty detergent for fabric washing. Anionics for use herein generally include the water soluble salts of organic reaction products having in their molecular structure an anionic solubilizing group such as S04~1, S03H, COOH and P04H and an alkyl or alkyl group having 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 sulfonated 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 preferably 3 to 10 moles of ethylene oxide, with aliphati~
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 8 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., fatty acid esters of the sodium salt of isethionic acid;
fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids, e.g., lauric acid amide of taruine; 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 or mixture thereof is used in the form ~l.Z23~

oi their alkali or alkaline earth metal salts. The anionic is preferably 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 anionlc can be added, for example, to the crutcher mix.
The concentration of non-soap anionic should preferably be selected so as to provide an excess with respect to cationic-softener according to the empirical relationship % concentration - 1.5X + 5 wherein X is the per cent concentration of cationic softener.
This assures the minimum excess of anionic necessary for optimum overall detergency, softening, etc. performance in the product composition.
Minor amounts of other types of detergents can be included along with the anionic, their sum in any case not exceeding about 10% and preferably about 2-5% of total detergent, i.e., such other detergent plus non-soap anionic. Useful 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 polyhydration product thereof, polyethylene glycol. Included are the condens-ation products of C8 to C30 fatty alcohols such as tridecyl alcohol with 3 to 100 moles ethylene oxide; C16 to Cl~ alcohol with 11 to 50 moles ethylene oxide; ethylene oxide adducts with monoesters of polyhydric alcohols, e.g., hexahydric alcohol;
condensation 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 group and a ~23a~05 hydrophobic 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 U.S. 3,824,189.
The compositions herein preferably include water solu~le 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, bicarbonates and the like.
Species thereof include sodium tripolyphosphate, trisodium phos-phate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates: Na2O/SiO2 of 1.6:1 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 foregoing.

Builder salt may be selected so as to provide either phosphate-containing or phosphate-free detergents. As to the latter embodiments, 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 sub-stantially 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 4,075,230 col-umns 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 ~2~34~S

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, metakaolin is an aluminosilicate. The metakaolin and/or a zeolite is included in about the same amounts as the builder salt, and preEerably supplemental thereto, e.g., zeolite silicate in a ratio of 6:1.
A particularly useful form of the metakaolin is that available commercially as Satintone No. 2.
Preferred optional ingredients useful herein 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* 5BM brighteners and particularly in combination and Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete*, Brilliant Blue RBL and Cibacete Violet B, Polar Brilliant Blue RAW and Calcocid Blue 2G bluing agents. The brightener may be included in amounts ranging up to about 1% of the total composition while bluing agents may range up to about .1% preferably 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 optimal significance include bleaching agents which may be of the oxygen or chlorine libera-ting type; oxygen bleaches include sodium and potassium perbor-ate, potassium monopersulfate and the like, while chlorine bleaches are typified by sodium hypochlorite, potassium dichloro-isocyanurate, trichloroisocyanuric acid and the like. The latter chlorine-liberating bleaches are representative of the broad class of water soluble, organic, dry solid bleaches known * Trade Marks - 17 -~22:39~5 as the N-chloro imides including their alkali metal salts. These cyclic imides have from about 4 to 6 members in the ring and are described in detail in U.S. Patent 3,325,414. Each of the oxygen and chlorine type bleaches discussed above are fully compatible with the compositions herein and have good stability in the presence of the anionic and cationic components. They are generally 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 colloidal cellulosic soil suspending agent. Methyl cellulose, e.g., Methocel is particularly effective. Polyvinyl alcohol is likewise effective and especially in the washing of cotton and synthetic fibers such as nylon, dacron and resin treated cotton. The additional soil suspending agent may be included in amounts up to about 2% based on total solids and up to about 4% based on total detergent composition. However, it must be emphasized that the nonionic organic surfactant component of the soap spaghetti supplies at least a major part of the anti-redeposition or soil suspending function, its effectiveness in this regard being significantly 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 40% of total composition.
The detergent composition is prepared by conventional processing such as spray drying a crutcher mix of surfactant, builder, filler etc. with volatile ingredien-ts such as perfume or ingredients otherwise adversely affected by the spray drying ~L2~3~

process such as peroxygen bleach, e.g., sodium perborate. In-gredients of this type are preferably post blended. As pre viously mentioned, the soap spaghetti (when used) and cationic softener-nonionic 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 140F 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 materials remaining to be added are incorporated into the cooled, dried detergent mass by any suitable means such as simple mechanical mixing.
In use, sufficient of the detergent composition is added to the wash cycle to provide a concentration of cationic 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 temperature of up to 70F, "warm" is from above 70F

to boiling.

Certain types of aliphatic quaternary ammonium com-pounds though relatively ineffective as regards softening arenevertheless quite effective as antistats in the compositions herein and particularly since they are physically compatible -- lg --~2~34~S
with anionic surfactant in liquicl environments. In general, such materials encompass the ethoxylated and/or propoxylated quaternary ammonium compounds of the following formula:

R ~ R~ X

wherein R7 and R8 represent ethoxy or propoxy, m and n are integers of from 1 to 50 and may be the same or different and R~ 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 avilable commercially as Ethoquad* c/12, Armak* and Variquat*
638, Sherex Chemical Co~; (b) Ethoquad c/25 - same as in (a) but having 15 moles of ethylene oxide (m+n) and available as 95% active ingredient; (c) methylbis (2-hydroxyethyl) octadecyl ammonium chloride, a liquid~ 75% active ingredient in isopro-panol/water 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 are given for purposes of illustration only and are not intended to limit the invention.
All parts and percentages are given by weight.

* Trade Marks - 20 -~.2~3~5 Example 1 A) 100 g. of powdered Arosurf TA (dimethyl distearyl ammonium chloride~ are heated to 90C and a fluid melt results.
To this melt are added 10 g. of liquid nonionic Neodol 23-6.5 (C12 13 linear alcohol condensed with 6.5 moles of ethylene oxide). The mixture is stirred well and then cooled to room temperature. ~ white solid results. The solid is then ground to a powder (on U.S. ~8 Sieve 0% through U.S. #100 Sleve < 10%).
The product resembles 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 tergitometer equipped as usual with a recipro-cating stirrer there are added to 500 ml of water (hardness of 150 ppm) at 70F (31C) 0.15 g. of a detergent (13.4% alkyl benzene sulfonate; 24% sodium tripolyphosphate; 30% sodium sul-fate; 4.5% sodium carbonate; 6.3% water soluble silicate solids;
7% moisture; ~% 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 Example 1 -containing detergent there is no visible (i.e., no white spots) evidence of any residue. When the procedure is repeated using identical conditions with the same composition except that in place of 4.5% of Example 1 products, there is used 4.5% powdered cationic alone there is a very visible pattern of white spotting ~2~3~

on the denim. This is very clear evidence of the outstanding benefits of the Exarnple 1 products.
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 accept-ably soft although those washed with the detergent containing the Example 1 softener combination are somewhat softer. In addition, 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 following non-ionics are used in place of the Neodol 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 + 13 moles of ethylene oxide) - Example 5 A spray dried heavy duty detergent having the following composition is provided:

* Trade Marks - 22 -~L2;~3~

Component Wt. %
-Linear tridecylbenzene sulfonate (LTBS) 15 Tripolyphosphate sodium (NaTPP) Silicate 7 Brightener (Stilbene* &
Tinopal* 5BM) .48 Q.S. sodium sulfate and water 44.52 100 . 00 To 90 g of the above composition are added 4 grams of the cationic-nonionic powder of Example 1 part B. Excellent results are obtained.
Example 6 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 spaghetti contains 20% by weight of Neodol 25-7.
In Examples 6 & 7 the soap spaghetti is an 85/15 tallow/coco soap.
Example 8 Example 3 is repeated but using a detergent composi-tion having the following proximate analysis.

* Trade Marks - 23 -~Z~3~L~5 Component Wt.
Linear dodecyl benzene sulfonate 23 Silicate 15 Borax 3 Nonionic surfactant Soap 2 Carboxymethyi cellulose Brightener * 0.48 Satintone Na2SO4 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 celluloseO
Example 11 The following heavy duty detergent composition is prepared.
Component Wt. %
_.
Linear alkyl benzene sulfonate 9 Alcohol ether sulfate 8 Nonionic surfactant 2 Tripolyphosphate sodium 24 Zeolite A 17 Na~SO4, brightener, water Q.S.
To this composition is added 5.0 g of the cationic * Trade Marks - 24 -~2~3at05 product of Example lB.
Example 12 Example 11 is repeated except that the soap/nonionic surfactant spaghetti of Example 6 is added to give 4% in the detergent.
Example 13 An unperfumed powder detergent composition having the following formulation is prepared.
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.~5 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 (Neodol 25-7) 0.5 parts Perfume 0.2 parts The following Examples illustrate the production and use of the cationic-nonionic combination in prilled form.

*Trade Marks - 25 -34~5 Example 14 Five hundred kilograms of dimethyl distearyl ammonium chloride containing about 4% water is heated to 90C and forms a melt. To this 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). At the same time cool air at about 50F (10C) is passed upwardly (i.e., countercurrent to the falling spray) at a rate of about 30,000 cubic feet per minute (cfm). The con-gealed product is collected at the bottom of the tower. Theproduct 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 Example 1 particles) are added 4.5 g. of the prills of Example 14.
Example 16 Example 5 through 13 are each repeated except that the cationic-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 th~ 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:

3L;2~3~

(a) dimethyl di-tallow ammonium methosulfate (b) dimethyl, di-hydrogenated tallow ammonium chloride (c) methyl-l-tallow amido ethyl-2-tallow imidazolinium methosulfate (d) methyl-l-oleylamidoethyl-2-oleyl imidazolinium methosulfate Example 19 In each of the foregoing examples where the cationic nonionic particles are used in admixture with the deteryent, the amount of the cationic-nonionic is varied to provide 2%;
7% and 10% thereof based on the weight of the detergent softener particles.
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 non-ionic as is Igepal C0-630 (nonyl phenol plus 10 moles of ethylene oxide) whereas 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 liauid non-ionic and a solid nonionic. In addition to the ethoxylated solid noniOnics, one may also use other solid or pasty non-ionics such as the glycerol mono and di-fatty glycerides. Of particular value in this regard are glycerol mono-stearate, glycerol mono-oleate and glycerol palmitate.

~3~

Example 20 Example lA is repeated except that half of the Neodol nonionic is replaced by glycerol monostearate. In the test procedure of Example 2 this product performs on a par with the Example lA material.
Example 21 Example 3 is repeated using the product of Example 20 in place of the cationic materials of Example 3. Excellent results are obtained.
Example 22 Example 7 is repeated except that the detergent con-tains the tertiary softener combination of Example 20 in place of the binary combinations of Example 1. The results are simllarly excellent as those of Examples 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 Carbowax is varied as follows (~ in detergent):
ta) 0.5 (b) 1.0 (c) 2.0 (d) 4.0 * Trade Marks - 28 -34C9~

Example 26 . . .
Examples 6, 7, 9, 10, 12, 13, 15, 17, 18, 19, 21, 22 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) 0.2 (b) 0.4 (c) 0.8 (d) 1.0 (e) 2.0 (f) 3.0 (g) 5.0 Example 27 Examples 24, 25 and 26 are repeated using in place of Carbowax the following:
(A) Pluronic F-10~ crystals (B) Soap-spaghetti of high water solubility contain-ing (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 polyethylene glycol. The Pluronic E-10~ of Example 27 is a polyoxy propylene-polyoxyethylene block polymer containing 20%
polyoxy propylene groups as the hydrophobe and 80~ polyoxyethyl-ene groups. The base hydrophobe has a MW of 3250.
The Pluronic F-108 is also illustrative of the water-soluble nonionics which are useful in the cationic-r.onionic 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 of from about 950 to 4000. Where combinations of, for ~Zq~3~

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 80% of polyoxyethylene groups. Illustra-tive 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.
~xample 28 As an illustratiion of the anti-stain benefits of the present invention, several different soiled, white materials are laundered at both 70F and 120F using the detergent con-taining cationic alone, (A) on the one hand and the cationic-nonionic prill of Example 14 on the other hand (B). The deter-gent is that described in Example 2.
All of the white materials are equally soiled and the reflectance values of laundered materials are measured. The following are the reflectance values (Rd).

(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 8502 84.1 84.5 The above clearly demonstrates that even after only one washing there is significant improvement on Spun Dacron at both laundering temperatures, on Dacron/Cotton at 120~F and on Nylon at 70F. A difference of 0.5 Rd units is significant in the sense that this difference is visually discernible.

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A particulate detergent softener composition capable of imparting improved softness, detergency, antistatic and non-stain properties to fabrics treated therewith in a laundering process 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 0 to about 20% of water-soluble or dispersible fatty acid soap or a mixture thereof with nonionic organic surfactant, the nonionic consti-tuting from about 2 to about 50% by weight of the said soap mixture, wherein the cationic-nonionic mixture is substantially homogeneously dispersed in said composition as discrete particles.

2. A composition according to claim 1 wherein said cationic amine softener is a quaternary ammonium halide and the nonionic is a water-soluble ethoxylate.

3. A composition according to claim 2 wherein said non-ionic comprises from about 2 to 20% of said cationic amine softener-nonionic mixture, and the mixture comprises from about 2 to about 15% of said detergent.

4. A composition according to claim 3 wherein said cationic is a di-short chain alkyl, di-long chain alkyl quater-nary ammonium halide, said nonionic is an ethoxylate of a C8 to C30 aliphatic alcohol, thiol amide or amine or an alkylated phenol, or thiophenol containing from about 3 to 100 moles of ethylene oxide; said nonionic comprising from about 2% to about 15% by weight of said cationic-nonionic mixture and said mixture comprising from about 2 to about 10% of said detergent.

5. A composition according to claim 4 wherein said non-soap detergent comprises an alkyl benzene sulfonate, said builder salt comprises a phosphate, said cationic is a di Cl to C4 alkyl, di C14 to C18 alkyl ammonium halide, said nonionic is an ethoxylated C8 to C18 linear, ali-phatic alcohol containing from about 3 to about 50 moles of ethylene oxide and said nonionic comprises from about 3 to about 10% by weight of said cationic-non-ionic mixture.

6. A composition according to claim 5 wherein said cationic-nonionic mixture is a prill.

7. A composition according to claim 5 wherein said cationic-nonionic mixture is the finely ground product of a co-melt of the cationic and nonionic component.

8. A composition according to claim 5 wherein said prill is a generally spherical, porous-surfaced solid core particle.

9. A composition according to claim 3 wherein the surfactant is a C8 to C18 linear alkyl benzene sulfonate, the cationic amine softener is selected from the group consisting of di Cl to C4 alkyl, di C14 to C18 quaternary ammonium salts, imidazolinium salts and mixtures thereof and the non-ionic in the cationic-nonionic mixture is a C8 to C18 linear aliphatic alkanol containing from about 6 to about 20 moles of ethylene oxide.

10. A composition according to claim 9 wherein the nonionic is a liquid non-ionic and it constitutes from about 2-10% by weight of the cationic-nonionic mixture.

11. A composition according to claim 10 including as an adjuvant glycol or glycerol mono-or di-ester of a C8 to C18 fatty acid.

12. A composition according to claim 11 wherein the adjuvant is glycerol monostearate.

13. A composition according to claim 12 wherein the amount of the glycerol monostearate is from about 1 to about 20% based on the weight of the cationic-nonionic mixture and is included as a component thereof.

14. A process for preparing the composition of claim 1 which comprises spray drying the non-soap organic surfactant and builder salt and to the spray-dried material post adding the balance of ingredients.

15. A method of cleaning and softening laundry which comprises washing said laundry in an aqueous medium containing the composition of claim 1.