GB2133813A - Detergent softener composition - Google Patents

Abstract

Particulate heavy duty detergent compositions, particularly for imparting improved softness and detersive effects to fabrics laundered therewith, comprise 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 composition is also described.

Description

SPECIFICATION Detergent softener compositions The present invention relates to detergent compositions and in particular to detergent-softener compositions capable of imparting improved softness, detersive effects, soil antiredeposition and antistatic properties to fabrics treated therewith and particularly in a machine laundering process. The detergent compositions of the present invention are also outstanding in that they result in less greasy staining (due to the cationic softener) of the laundered and dried clothes.

Compositions for simultaneously achieving detergency and an appreciable level of softness in the machine laundering of fabrics, and thus suitable for use in the wash cycle, are well-known and widely available commercially. The fugitive interaction between anionic surfactant, perhaps the most commonly used of the available types of surfactants, and cationic softeners particularly those of the dilower-di-higher alkyl quaternary ammonium type, is likewise well recognized in the patent literature.

Such interaction often results in the formation of unsightly precipitates which become entrapped within or otherwise deposit upon the fabric being washed. Discolouration or other aesthetically displeasing effects are form the most part inevitable. The net result is often a depletion in the effective amount of anionic surfactant available for useful purposes since the loss of anionic surfactant is the primary consequence of this interaction.

Remedial techniques heretofore proposed to abate the aforedescribed cationic-anionic problem though divergent as to approach seem convergent as to result in that they are less than satisfactory.

Thus, although the most effective types of cationic quaternary ammonium softeners, as exemplified by the aforementioned di-higher alkyl type quaternary compounds, such as distearyl dimethyl ammonium chloride, can function in the wash cycle in the presence of anionic surfactant, builder, etc., the quantity needed to achieve effective softening is usually coterminous with amounts promotive of undesired cationic-anionic interaction. As a general rule, at least about twice as much cationic surfactant is required for softening as for antistatic activity.

In U.S.P. 3,325,414, which deals primarily with detergents of controlled foam or sudsing capability, the cationic-anionic problem and attendant detrimental effects are discussed in detail. The patent additionally points out that certain quaternary ammonium compounds, among the class of cationic agents, are generally unstable when heated and when in contact with alkaline builders, the instability being manifested by the development of strong amine odours and undesirable colour. The compositions of that patent are limited to the use of quaternary ammonium halides having but one higher alkyl group, the given structural formula for the cationic material being correspondingly limited.

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 tacitally avoid the use of cationic softeners altogether proposing the use of, for example, anionic materials as softening agents. U.S. 3,676,338 is representative, this patent teaching the use of anionic softeners referred to as "branched-chain carboxylic acids", as fabric softeners. Presumably, anionic detergent would be stable in the presence of the anionic softener.

As the foregoing discussion demonstrates, the remedies proposed necessitate the discarding of softeners and principally those of the di-higher-di-lower alkyl quaternary ammonium salt and cyclic imide types, these having been determined by experience to be among the most effective softeners thus far developed in the art.

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 250C of 50ppM. Similar disclosures may also be found in U.S. Patents 4,113,630; 4,196,104 and 4,272,386. In U.S. patent No. 4,230,590 to Wixon heavy duty detergents comprising conventional builder, principally anionic surfactant components, cationic softener and a mixture of fatty acid soap and cellulose ether are disclosed. The soap-cellulose ether mixture is in the form of 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 heavy duty detergents 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.

The present invention provides stable detergent softener compositions capable of providing improved softness without staining, detergency, antistatic and soil antiredeposition properties to fabrics treated therewith in a laundering process in cold or hot water. The compositions generally comprise by weight from about 5 to 40% of a water-soluble, non-soap, anionic surfactant, from about 10 to 60% of water-soluble, neutral to alkaline builder salt, from about 2 to 20% of cationic softener selected from (a) aliphatic, di-(lower) C1-C4 alkyl, di-(higher) C14-C24 alkyl quaternary ammonium salts, tb) heterocyclic compounds, and mixtures of (a) and (b), the said cationic softener being in intimate admixture with a water-soluble anionic surfactant (preferably 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 form, the weight ratio of soap (when used) to softener being from about 8:1 to 1:3 preferably 5:1 to 1 :2, more preferably 2:3 to 3:2 e.g. about unity, the percent concentration of anionic surfactant being at least about (1 .5x+5), x representing the percent concentration of the softener, the soap being substantially homogeneously dispersed throughout the said composition preferably as discrete particles.

In the soap-nonionic surfactant mixture, the nonionic desirably constitutes from about 2 to about 50%, preferably from about 5 to about 40%, more preferably from about 8 to about 30%, and most preferably from about 8 to about 20%, all percentages being by weight. The total nonionic 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 both the processes of formulating and using the aforedescribed compositions.

Adding the cationic material in intimate admixture with nonionic organic surfactant in flakes, gra'nules and the like form, has the advantage that the spot staining of the clothes after drying is substantially mitigated. In addition, the softness in the fabrics laundered is generally unexpectedly enhanced. The nonionic surfactant also contributes to soil antiredeposition, especially in nonphosphate 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 may be included in the post-added cationic which leads to a significant improvement in the flowability of the detergent composition.

In the embodiments of the present invention utilizing soap particles with or without cellulose ether or nonionic surfactant as taught in the above-described Wixon patents the useful fatty acids include generally those derived from natural or synthetic fatty acids having from 10 to 30 carbon atoms in the alkyl chain. Preferred are the alkali metal, 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 preferably in the mutual proportions respectively of 1 5/85. 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 are obtained when 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, walnut, poppyseed, sunflower, maize, rapeseed, mustardseed, apricot kernel, almond, castor and olive.

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 include, without necessary limitation, 80/20 capric-lauric, 80/20 capric-myristic, 50/50 oleic-capric, 90/10 capric-palmitic and the like.

The nonionic surfactancts useful in the soap particles and in admixture with the cationic may conveniently be known material 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 name 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 the molecule as a whole and the liquid character of the product is retained up to the point where the 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 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrobase constituted by the reaction product of ethylene diamine and excess propylene oxide, the 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 22 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.

4. Nonionic surfactants including 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 1 5 moles of ethylene oxide per mole of alcohol and the condensation product of about 1 5 moles of ethylene opde with one mole of tridecanol.

Other examples include dodecylphenol condensed with 1 2 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 1 5 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 ethylene oxide per mole of myristyl alcohol: lauramide condensed with 1 5 moles of ethylene oxide per mole of lauramide; and di-iso-octylphenol condensed with 1 5 moles of ethylene oxide.

Among the above-listed nonionic surfactants, the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms with ethylene oxide is preferred. Typical examples of such non-ionic surfactants are Neodol 25-7, a product of Shell Chemical Co., which comprises the condensation product of a C12~l5 alcohol with 7 moles of ethylene oxide, and Neodol, 23-6.5 which is the product of a C12~l3 alcohol with 6.5 moles of ethylene oxide.

Cationic softeners useful herein are conveniently known materials and are of the high-softening type. Included are the N1N-di-(higher) C14-C2 N'N-di-(lower) C1-C4 alkyl quaternary ammonium salts with water solubilizing anions such as halide, e.g. chloride, bromide and iodide; sulphate, methodsulphate and the like and the heterocyclic imides such as imidazolinium compounds.

For convenience, the aliphatic Iquaternary ammonium salts may be structurally defined as follows:

wherein R and R1 each represent an alkyl group of 14 to 24 and preferably 14 to 22 carbon atoms; R2 and R3 each represent a lower alkyl group of 1 to 4 and preferably 1 to 3 carbon atoms, X represents an anion capable of imparting water solubility or dispersibility including the aforementioned chloride, bromide, iodide, sulphate and. methosulphate anions. Particularly preferred species of aliphatic quaternary compounds include: distearyl dimethylammonium chloride, di-hydrogenated tallow di methyl ammonium chloride, di-tallow dimethyl ammonium chloride, distearyl dimethyl ammonium methyl sulphate, and di-hydrogenated tallow dimethyl ammonium methyl sulphate.

Heterocyclic imide softeners of the imidazolinium type may also, for convenience, be structurally defined as follows:

wherein R4 represents a lower alkyl group of 1 to 4 and preferably 1 to 3 carbons; R5 and R6 each represent substantially linear higher alkyl groups of about 1 3 to 23 and preferably 13 to 19 carbons and X has the aforedefined significance.Particularly preferred species of imidazoliniums include: 1 -methyl-1 -tallow amido ethyl-2-tallow imidazolinium methyl sulphate; available commercially from Sherex Chemical Co. under the tradename Varisoft (Registered Trade Mark) 475 as a liquid, 75% active ingredient in isopropanol solvent, 1-methyl-1-oleyl amido ethyl-2-oleyl imidazolinium methyl sulphate; available commercially from Sherex Chemical Co. under the tradename Varisoft (Registered Trade Mark) 3690, 75% active ingredient in isopropanol solvent.

It is preferred in 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 surfactant 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 techniques, until it is sufficiently "doughy" or plastic to be in suitable form for, preferably, extrusion or other process, e.g. pelleting, granulation, stamping or pressing. Working may be effected, for example, by roll mi)ling, although this is not essential, followed by extrusion in a conventional soap plodder with the desired type of extrusion head. The latter is selected in accordance with the shape, 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 average length of from about 2 to 20 mm with about 95% thereof within a tolerance of 0.5 to 20 mm and an average diameter or width of from about 0.2 to 2.00 mm with a range of 0.4 to 0.8 mm being preferred. The bulk density of the spaghetti will usually, having referred 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 0.2 mm in thickness, pellets have a cross-section of 2.5 mm while tablets have a cross-section of 2.5 mm and thickness of 2.5 mm.

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 liquified mixture of the cationic and the nonionic. In the most preferred embodiment a liquid nonionic is used (e.g. Neodol 23-6.5) and this is added to the melted cationic. A typical cationic is Arosurf TA-1 00 (1 dimethyl distearyl ammonium chloride) and as supplied this material forms a very fluid liquid when melted and heated to 900 C. The liquid mixture of cationic and nonionic 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% by weight of nonionic based on the weight of the cationic softener is contemplated. Preferably the nonionic should be used in amounts of from 5 to 1 5% with about 1 0% 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 in heavy duty detergents 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 SO4H, SO3H, COOH and PO4H and an alkyl or alkyl group having about 8 to 22 carbon atoms 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 sulphated and sulphonated 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 sulphonates having from about 8 to 1 8 carbon atoms in the alkyl group which may have a straight (preferred) or branched chain structure.Preferred species include, without necessary limitation: sodium lineartridecylbenzene sulphonate, sodium linear dodecyl benzene sulphonate, sodium linear decyl benzene sulphonate, lithium or potassium pentapropylene benzene sulphonate; alkali metal salts of sulphated condensation products of ethylene oxide, e.g. containing 3 to 20 and preferably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 1 8 carbon atoms or with alkyl phenols having alkyl groups containing 6 to 1 8 carbon atoms, e.g. sodium nonyl phenol pentaethoxamer sulphate and sodium lauryl alcohol triethoxamer sulphate; alkali metal salts of saturated alcohols containing from about 8 to 1 8 carbon atoms, e.g. sodium lauryl sulphate and sodium stearyl sulphate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulphonic acids e.g. fatty acid esters of the sodium salt of isethionic acid; fatty ethanolamide sulphates; fatty acid amides of amino alkyl sulphonic acids, e.g.

lauric acid amine of taurine; alkali metal salts of hydroxy alkane sulphonic acids having 8 to 18 carbon atoms in the alkyl group, e.g. hexadecyl, alphahydroxy sodium sulphonate. The anionic surfactant or mixture thereof is desirable used in the form of its alkali or alkaline earth metal salts. The anionic surfactant 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 anionic can be added, for example, to the crutcher mix.

The concentration of non-soap anionic surfactant should preferably be selected so as to provide an excess with respect to cationic-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 surfactant, their sum in any case not exceeding about 10% and preferably about 25% 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 condensation products of C8 to C30.

fatty alcohols such as tridecyl alcohol with 3 to 100 moles ethylene oxide; C16 to C18 alcohols with 11 to 50 moles of ethylene oxide; ethylene oxide adducts with monoesters of polyhydric, e.g. hexahydric alcohol; condensation products of polypropylene glycol with 3 to 100 moles of ethylene oxide; the condensation products of alkyl (C6 to C20 straight or branched chain) phenols with 3 to 100 moles of ethylene oxide and the like.

Suitable amphoteric detergents generally include those containing both an anionic group and a cationic group and a 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 soluble alkaline to neutral builder salt in amounts of from about 10 to 60% by weight of total composition. Useful herein are the organic and inorganic builders including the alkali metal and alkaline earth metal phosphates, particularly the condensed phosphates such as the pyrophosphates or tripolyphosphates, silicates, borates, carbonates, bicarbonates and the like.Species thereof include sodium tripolyphosphate, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates e.g. with Na2O/SiO2 ratios of 1.6:1 to 3.2:1, sodium carbonate, sodium sulphate, borax (sodium tetraborate), ethylene diamine tetraacetic acid tetrasodium salt, trisodium nitrilotriacetate and the like and mixtures of the foregoing. The 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 substantially amorphous by x-ray examination but which retains some of the structural order of the kaolinite. Discussions of kaolin and metakaolin are found in U.S. Patent 4,075,280 columns 3 and 4 and Grimshaw, "The Chemistry and Physics of Clays and Allied Ceramic materials", (4th edition, Wiley-lnterscience), pages 723-727. Metakaolin is also the subject of U.S.

Patent applications Serial Nos. 905,622 and 905,718, the relevant disclosures of which are herein incorporated by reference. The metakaolin also appears to have softening utility. As to the latter, the most effective metakaolins appear to be those which behave best in the reaction with sodium hydroxide to form zeolite 4A as described in U.S. Patent 3,114,603 which refers to such materials as "reactive kaolin". As explained in the referenced sources, metakaolin is an alumino-silicate. The metakaolin and/or a zeolite is included in about the same amounts as the builder salt, and preferably 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 blueing 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 blueing agents. The brightener may be included in amounts raning up to about 1% of the total composition while blueing agents may range up to about 0.1% preferably up to about 0.01: of total composition. Blueing agents, 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 liberating type; oxygen bleaches include sodium and potassium perborate, potassium monopersulphate and the like, while chlorine bleaches are typified by sodium hypochlorite, potassium dichloroisocyanurate, trichloroisocyanurate acid and the like. The latter chlorine-liberating bleaches are representative of the broad class of water soluble, organic, dry solid bleaches known as the N-chloro imides 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 presenc 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 0.05% 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 (Registered Trade Mark) is particularly effective. Polyvinyl alcohol is likewise effective and especially in the washing of cotton and synthetic fibres 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 emphasised 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 aforementioned ingredients, such as sodium sulphate, 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. without volatile ingredients such as perfume or ingredients otherwise adversely affected by the spray drying process such as peroxygen bleach, e.g. sodium perborate. Ingredients of this type are preferably post blended. As previously mentioned, the soap spaghetti (when used) and cationic 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 surfactant, sodium silicate, optional ingredients where used such as Satintone #2 and filler such as sodium sulphate and builder salt. The crutcher mixture is heated to about 1 400F (600C) before addition of builder, e.g. sodium tripolyphosphate and the solids content of the crutched mixture before spray drying is about 5565%. 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 9/3500 g laundry with a range from about 700F (21 0C) to the boil (i.e. about 2120F (1000C)). In this connection it is understood that by "cold" wash is meant a washing temperature of up to 700F (21 OC), "warm" is from about 700F (21 OC) to boiling.

Certain types of aliphatic quaternary ammonium compounds though relatively ineffective as regards softening are nevertheless quite effective as antistatic agents in the compositions herein and particularly since they are physically compatible with anionic surfactants in liquid environments. In general, such materials encompass the ethoxylated and/or propoxylated quaternary ammonium compounds of the following formula:

wherein R7 and R8 each represent an ethoxy or propoxy group, m and n are integers of from 1 to 50 and may be the same or different and R9 represents an alkyl group of 14 to 24 carbon atoms.Compounds of this type include (a) methylbis (2-hydroxy-ethyl) coco ammonium chloride, a liquid 75% active ingredient in isopropanol/water solvent and available commerically as Ethoquad (Registered Trade Mark) c/i 2, Armak and Variquat (Registered Trade Mark) 638, Sherex chemical Co.; (b) Ethoquad c/25-same as in (a) but having 1 5 moles of ethylene oxide (each of R7 and R8-m and n each=1 5) and available as 95% active ingredient; (c) methylbis (2-hydroxyethyl) octadecyl ammonium chloride, a liquid, 75% active ingredient in isopropanol/water solvent available commercially as Ethoquad 18/12, Armak and (d) same as (c) but having 1 5 moles of ethylene oxide (each of R7 and R8-m and n each=1 5), 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 present invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples in which all parts and percentages are by weight.

Examples 1A and 1B A) 100 g of powdered Arosurf TA (dimethyl distearyl ammonium chloride) are heated to 900C 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. A white solid results. The solid is then ground to a powder (on U.S. No. 8 Sieve 0% through, U.S. No.100 Sieve less than 10% through; a No. 8 sieve has openings 2.38 mms across, a 100 sieve 149 microns across). The product resembles the original Arosurf powder.

B) Example 1 A is repeated except that only 5 g of nonionic is used.

Example 2 The products of Examples 1 A and 1 B as well as powdered cationic material alone (Example 1 C) (the same as that used for Example 1A to produce the co-melted product), of a particle size the same as that of Example 1 A, are each tested separately for dispersion uniformity in water by the following procedure.

In a tergitometer equipped as is usual with a reciprocating stirrer there are added to 500 ml of water (hardness of 150 ppm) at 700F (31 OC) 0.15 g of a detergent (13.4 alkyl benzene sulphonate; 24% sodium tripolyphosphate: 30% sodium sulphate; 4.5% sodium carbonate; 6.3% water-soluble silicate solids; 7% moisture; 4% soap; minor amounts brightener, methocel and perfume) which also contains 4.5% of the particles of Examples 1 A, 1 B and 1 C. The stirrer is operated for 5 minutes at 100 rpm and then the aqueous composition is vacuum filtered through fresh smooth blue denim fabric. In the case of the liquors with the Examples 1 A and 1 B-containing detergent there is no visible evidency of any residue (i.e. no white spots).When the procedure is repeated using identical conditions with the same composition except that in place of 4.5% of the Example 1 A and 1 B products, there is used 4.5% of the powdered cationic alone there is a very visible pattern of white spotting on the denim. This is very clear evidence of the outstanding benefits of the Examples 1 A and 1 B products.

Example 3 When the detergent compositions described in Example 2 are used to wash soiled white towels in a washing machine and then dried in an automatic dryer, the clothes in each instance are acceptably soft although those washed with the detergent containing the Examples 1 A and 1 B softener combination are somewhat softer. In addition, the towels washed with the detergent containing powdered cationic alone (Example 1 C) (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 Examples 1 A, 1 B and 3 are repeated except that the following nonionics are used in place of the Neodol 23-6.5.

a) Neodol 25-7 (A C1218 alkyl linear alcohol+7 moles of ethylene oxide).

b) Igepal C0-630 (Nonyl phenol+ 0 moles of ethylene oxide) c) Neodol 45-13 (A C14~15 alkyl linear alcohol+13 moles of ethylene oxide).

Example 5 A spray dried heavy duty detergent having the following composition is provided: Component Weight % Linear tridecyl benzene sulphonate (LTBS) 1 5 Sodium tripolyphosphate (NaTPP) 33 Silicate 7 Brightener (Stilbene and Tinopal 5BM) 0.48 Q.S. sodium sulphate 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 B. Excellent results are obtained.

Example 6 Example 3 is repeated except that the detergent also contains a soap spaghetti (4.5% in detergent), the soap spaghetti being an 85/15 tallow/coco soap.

Example 7 Example 6 is repeated except that the soap spaghetti contains 20% by weight of Neodol 25-7.

Example 8 Example 3 is repeated but using a detergent composition having the following approximate analysis: Component Weight % Linear dodecyl benzene sulphonate 23 Na2CO3 20 Silicate 15 Borax 3 Nonionic surfactant 1 Soap 2 Carboxymethyl cellulose 1 Brightener (Stilbene and Tinopal 5BM) 0.48 Satintone 1 Na2SO4 and water Q.S.

To 95 grams of the above composition, 5 gm of the product of Example 1 B are added.

Example 9 Example 8 is repeated except 5 gm of a soap-nonionic spaghetti (similar to Example 7) is used.

Example 10 Example 6 is repeated except that the soap spaghetti used also contains 4% by weight of carboxymethyl cellulose.

Example 11 The following heavy duty detergent composition is prepared: Component Weight % Linear alkyl benzene sulphonate 9 Alcohol ether sulphate 8 Nonionic surfactant 2 Sodium tripolyphosphate 24 Zeolite A 17 Na2SO4, brightener, water Q.S.

To this composition is added 50 g of the cationic product of Example 1 B.

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 Weight % Linear tridecylbenzene sulphonate 14.8 Sodium tripolyphosphate 26.5 Silicate 6.9 Brightener (Stilbene and Tinopal 5BM) 0.47 Sodium carbonate 4.9 Carboxymethyl cellulose 0.25 Methocel 0.6 Sodium sulphate, moisture Q.S.

To 90.6 parts by weight of the above unperfumed powder detergent are added: Parts Cationic-Nonionic mixture of EX. 1 B 4.0 Soap spaghetti (90% tallow/coco 85/15; 10% Neodol 25-7 (Shell Chemical Co.), spaghetti length=15 mm, diameter=0.5 mm 4.0 Borax Pentahydrate 0.7 Nonionic surfactant (Neodol 25-7) 0.5 Perfume 0.2 The following examples illustrate the production and use of the cationic-nonionic combination in prilled form.

Example 14 Five hundred kilograms of dimethyl distearyl ammonium chloride containing about 4% water is heated to 900C and forms a melt. To this hot melt are added 25 kilograms of Neodol 23-6.5. This comelt is then sprayed downwardly from the top of a 75-foot (about 24 metres) tower of 1 6 foot diameter (about 5 metres). At the same time cool air at about 500F (1 00C) is passed upwardly (i.e.

countercurrent to the falling spray) at a rate of about 30,000 cubic feet per minute (cfm). The congealed product is collected at the bottom of the tower. The product 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 Examples 5 to 13 are each repeated except that the cationic-nonionic mixture used in those examples are replaced by the prills of Example 1 4.

Example 17 Each of the previous examples is repeated except that the nonionic in the cationic-nonionic mixture is used in amounts of 2%; 7%; 12%, 1 5% and 20%.

Example 18 Each of the previous examples is again repeated except that the cationic softener of the cationicnonionic mixture is replaced by the following: (a) dimethyl di-tallow ammonium methosulphate; (b) dimethyl, di-hydrogenated tallow ammonium chloride; (c) 1 -methyl-1 -tallow amido ethyl-2-tallow imidazolinium methosulphate; (d) 1 1-methyl- 1 -oleylamidoethyl-2-oleyl imidazolinium methosulphate.

Example 19 In each of the foregoing examples where the cationic-nonionic particles are used in admixture with the detergent, the amount of the cationic-nonionic is varied to provide 2%; 7% and 1 09/0 thereof based on the weight of the detergent and 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 nonionic 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. greater than or equal to 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 non-ionic in the cationic co-melt, it is often advantageous to use a mixture of a liquid nonionic and a solid nonionic. In addition to the ethoxylated solid nonionics one may also use other solid or pasty nonionics such as the glycerol mono and di-fatty glycerides. Of particular value in this regard are glycerol mono-stearate, glycerol mono-oleate and glycerol palmitate.

Example 20 Example 1 A 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 1 A 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 contains the tertiary softener combination of Example 20 in place of the binary combinations of Example 1. The results are similarly excellent as those of Examples 3 and 7.

Example 23 Example 22 is repeated except that the nonionic used in 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.

Examples 25A to 25D Example 24 is repeated except that the amount of Carbowax is varied as follows (% in detergent): (a) 0.5 (b) 1.0 (c) 2.0 (d) 4.0 Examples 26A to 26G Examples 6, 7, 9, 10, 12, 13, 16, 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 (9) 5.0 Example 27 Examples 24, 25 and 26 are repeated using in place of Carbowax the following: (A) Pluronic F-108 crystals.

(B) Soap-spaghetti of higher water solubility containing (a) 10% sodium xylene sulphonate; (b) 20% sodium xylene sulphonate; (c) 40% sodium xylene sulphonate.

The Carbowax product of Examples 24 to 26 is a polyethylene glycol. The Pluronic F-108 of Example 27 is a polyoxypropylene-polyoxyethylene block polymer containing 20% polyoxypropylene groups as the hydrophone and 80% polyoxyethylene 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-nonionic comelts of the present invention. Of particular value are the liquid Pluronics containing up to about 50% polyoxyethylene groups and a base hydrophobe with the molecular weight of the polyoxypropylene moiety being from about 950 to 4000. Where combinations of, for example, Neodol 23-6.5 and Pluronics are used, it may be preferred to use pasty or solid Pluronics. These contain generally from 25% to 80% of polyoxyethylene groups. Illustrative of liquid Pluronics are Pluronic L-61, Pluronic L-64, Pluronic L-72 and Pluronic 101; the pasty Pluronics include Pluronic P85 and Pluronic P 105 among others; and the solid products include Pluronic F-87 and Pluronic F27.

Example 28 As an illustration of the anti-stain benefits of the present invention, several different soiled, white materials are laundered at both 700F (21 OC) and 1200F (490C) using the detergent containing cationic alone (Example 1 C) on the one hand (Example 28A) and the cationic-nonionic prill of Example 14 on the other hand (Example 28B). The detergent is that described in Example 2.

All of the white materials are equally soiled and the reflectance values of laundered materials are measured. The reflectance values (Rd) are given in Table 1 below.

Table 1 700F (2l0C) 120 F (490C) Detergent (A) (B) (A) (B) Fabric Spun Dacron 77.7 79.0 64.7 66.5 Dacron/Cotton (65/35) 81.4 81.5 73.9 76.1 Cotton 87.8 87.8 87.3 87.3 Nylon 84.1 85.2 84.1 84.5 The above clearly demonstrates that even after only one washing there is significant improvement on Spun Dacron at both laundering temperatures, on Dacron/Cotton at 1 200F (490C) and on Nylon at 700F (21 OC). A difference of 0.5 Rd units is significant in the sense that this difference is visually discernible.

Claims (30)

Claims

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 about 0 to 20% of water-soluble or dispensible fatty acid soap or a mixture thereof with nonionic organic surfactant, the nonionic constituting from about 2 to about 50% by weight of the said soap mixture, wherein the cationic-nonionic mixture is substantially homogeneously dispersed in the said composition as discrete particles.

2. A composition as claimed in Claim 1 in which the said cationic is a quaternary ammonium halide and the nonionic is a water-soluble ethoxylate.

3. A composition as claimed in Claim 1 or Claim 2, in which the said nonionic comprises from about 2 to 20% of the said mixture, and the mixture comprises from about 2 to about 15% of the said detergent.

4. A composition as claimed in Claim 3 in which the said nonionic comprises from about 2% to about 1 5% by weight of the said cationic-nonionic mixture and the said mixture comprises from about 2 to about 10% of the said detergent.

5. A composition as claimed in Claim 1, 2, 3 or 4 in which the said nonionic comprises from about 3 to about 1 0% by weight of the said cationic-nonionic mixture.

6. A composition as claimed in any one of Claims 1 to 5 in which the said cationic-nonionic mixture is the finely ground product of a comelt of the cationic and nonionic component.

7. A composition as claimed in any one of Claims 1 to 6 in which the cationic-nonionic mixture is a prill.

8. A composition as claimed in Claim 8 in which the said prill is a generally spherical, poroussurfaced solid cored particle.

9. A composition as claimed in any one of Claims t to 8 in which the said cationic is a di-short chain alkyl, di-long chain alkyl quaternary ammonium halide, and the 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.

10. A composition as claimed in any one of Claims 1 to 8 in which the said cationic is a di C, to C4 alkyl, di C,4 to C,8 alkyl ammonium halide, and the said nonionic is an ethoxylated C8 to C18 linear aliphatic alcohol containing from about 3 to about 50 moles of ethylene oxide.

11. A composition as claimed in any one of Claims 1 to 8 in which the cationic amine softener is selected from the group consisting of di C, to C4 alkyl, di C14 to C,8 quaternary ammonium salts, imidazolinium salts and mixtures thereof and the nonionic in the cationic-nonionic mixture is a C8 to C,8 linear aliphatic alkanol containing from about 6 to about 20 moles of ethylene oxide.

12. A composition as claimed in any one of Claims 1 to 11 in which the said non-soap detergent comprises an alkyl benzene sulphonate, and the said builder comprises a phosphate.

13. A composition as claimed in any one of Claims 1 to 12 in which the surfactant is a C8 to C18 linear alkyl benzene sulphonate.

14. A composition as claimed in any one of Claims 1 to 8 in which the said cationic is a di-short chain alkyl, di-long chain alkyl quaternary ammonium halide, the 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; the said nonionic comprises from about 2% to about 15by weight of the said cationic-nonionic mixture and the said mixture comprises from about 2 to about 10% of the said detergent.

1 5. A composition as claimed in any one of Claims 1 to 8 in which the said non-soap detergent comprises an alkyl benzene sulphonate, the said builder comprises a phosphate, the said cationic is a di Ca to C4 alkyl, di Ca4 to C,8 alkyl ammonium halide, the said nonionic is an ethoxylated C8 to C,8 linear, aliphatic alcohol containing from about 3 to about 50 moles of ethylene oxide and the said nonionic comprises from about 3 to about 10% by weight of the said cationic-nonionic mixture.

16. A composition as claimed in any one of Claims 1 to 8 in which the surfactant is a C8 to C18 linear alkyl benzene sulphonate, the cationic amine softener is selected from the group consisting of di Cg to C4 alkyl, di C4 to C,8 quaternary ammonium salts, imidazolinium salts and mixtures thereof and the nonionic in the cationic-nonionic mixture is a C8 to C,8 linear aliphatic alkanol containing from about 6 to about 20 moles of ethylene oxide.

1 7. A composition as claimed in any one of Claims 1 to 15 in which the nonionic is a liquid nonionic and constitutes from about 210% by weight of the cationic-nonionic mixture.

18. A composition as claimed in any one of Claims 1 to 1 7 including as an adjuvant a glycol or glycerol mono- or di-ester of a C8 to C,8 fatty acid.

1 9. A composition as claimed in Claim 1 8 in which the adjuvant is glycerol monostearate.

20. A composition as claimed in Claim 18 or 19 in which the amount of the adjuvant is from about 1 to about 20% based on the weight of the cationic-nonionic mixture and is included as a component thereof.

21. . A process for preparing a composition as claimed in any one of Claims 1 to 20 which comprises spray drying the non-soap organic surfactant and builder salt and, to the spray-dried material, post adding the balance of the ingredients.

22. A composition as claimed in Claim 1 substantially as specifically described herein with reference to any one of Examples 2 to 28.

23. A particulate softener composition comprising an intimate blend of a cationic amine softener and from 2 to 20% based on the weight of the said mixture of a water-soluble nonionic ethoxylate surface active compound.

24. A particulate softener composition comprising an intimate blend of a cationic amine softener and from 2 to 20% based on the weight of the said mixture of a water-soluble nonionic ethoxylate surface active compound formed from a melt of the said materials.

25. A spray cooled softener composition comprising an intimate blend of a cationic amine softener and from 2 to 20% based on the weight of the said mixture of a water-soluble nonionic ethoxylate surface active compound.

26. A composition as claimed in Claim 23, 24 or 25 in which the ethoxylate is a C8 to C,8 linear aliphatic alcohol and the amount of combined ethylene oxide is from about 5 to about 100 moles.

27. A composition as claimed in Claim 23, 24, 25 or 26 in which the amount of nonionic ranges from about 2 to about 10%.

28. A composition as claimed in any one of Claims 23 to 27 which includes from about 2 to 20% of a glycol or glycerol mono- or di-ester of a C8 to C,8 fatty acid.

29. A composition as claimed in Claim 28 which contains from about 2 to about 10% glycerol mono-stearate.

30. A composition as claimed in Claim 23 substantially as specifically described herein with reference to any one of Examples 14, 17 or 18.