GB2164657A - Hot water wash cycle detergent-softener compositions - Google Patents

Abstract

The softening performance of a water-insoluble cationic fabric softener, such as dimethyl distearyl ammonium chloride, in a nonionic surfactant detergent composition is improved by increasing the fabric substantivity of the cationic fabric softener using a polyfunctional additive selected from (i) diquaternary ammonium compounds, (ii) polymers of dimethyldiallyl ammonium chloride, (iii) cationic guar gum, (iv) poly(methylvinylether/maleic acid) and (v) diimidazolinium compounds. An example of a diquaternary ammonium compound is N-tallow pentamethyl propane diammonium chloride. The detergent-softener compositions provide improved softening and cleaning at washing temperatures as high as 60 DEG C to 100 DEG C. Amphoteric surfactants can be included to increase the cloud point of the composition to above the wash water temperature.

Description

SPECIFICATION Hot water wash cycle detergent-softener compositions The present invention relates to a composition and a method for cleaning and softening fabrics in the wash cycle of a laundering operation. More specifically, the present invention relates to softening compositions adapted for use in the wash cycle of a laundering operation, especially using hot water, the composition including a nonionic surfactant, a cationic quaternary ammonium compound softening agent, and a polyfunctional additive for increasing the substantivity of the softening agent.

Compositions useful for treating fabrics to improve the softness and feel characteristics thereof are known in the art.

When used in domestic laundering, fabric softeners are typically added to the rinse water during the rinse cycle which has a duration of only from about 2 to 5 minutes. Consequently, the user is required to monitor the laundering operation or take other precautions so that the fabric softener is added at the proper time.

This requires the user to return to the washing machine either just prior to or at the beginning of the rinse cycle of the washing operation which is obviously burdensome to the user. In addition, special care has to be taken to use a proper amount of the fabric softener so as to avoid overdosage which may render the clothes water repellant by depositing a greasy film on the fabric surface, as well as imparting a certain degree of yellowness to the fabrics.

As a solution to the above-noted problems it has been known to use fabric softeners which are compatible with common laundry detergents so that the softeners can be combined with the detergents in a single package for use during the wash cycle of the laundering operation. Examples of such wash cycle added fabric softening compositions are shown in U.S. Patents 3,351,438, 3,660,286 and 3,703,480. In general, these wash cycle fabric softening compositions contain a cationic quaternary ammonium fabric softener and additional ingredients which render the softening compounds compatible with the common laundry detergents.

It is also known, however, that the cationic softening compounds added to the wash cycle, either as an ingredient in a detergent-softener composition or as a wash cycle softener, interfere with the brightening activity, as well as the cleaning efficiency of the detergent. As a result, it has been sought to offset to some degree this interference in detergent-softening compositions by using non ionic surfactants, higher levels of brightener compounds, carboxymethylcellulose, anti-yellowing compounds, bluing agents, and so forth.

However, little improvement has been made in wash cycle softening compositions using a variety of detergents, most of which are anionic detergents.

There have also, however, been many disclosures in the art relating to detergent compositions containing cationic fabric softening agents, including the quaternary ammonium compound softening agents, and nonionic surface-active compounds as well as other surfactant, e.g. anionics, zwitterionics, and amphoterics.

As representative of this art, mention can be made of U.S. Patents 4,264,457, 4,239,659,4,259,217, 4,222,905, 3,537,993,3,583,912, 3,983,079,4,203,872, 4,264,479,3,951,879, 3,360,470,3,351,483, and 3,644,203.

The following patents disclose nonionic surfactant containing detergents and/or shampoos which include a polyfunctional additive: 3,313,734 (shampoo - quaternary ammonium - containing polymers); 3,351,557 (ethylene/maleic anhydride copolymers - emulsion stabilizers); 3,509,059 (acidic group containing polymer, e.g. polyacrylic acid, formed in situ, i.e. in presence of nonionic surfactant); 3,703,480 (amino polyureylene resins - for compatibilizing cationic fabric softener with anionic surfactant); 3,723,322 (carboxylated polysaccharide - as detergent builder); 3,962,418 (cationic cellulose ether - thickener and hair conditioning agent); 4,213,960 (polyaminoamides and quaternary ammonium homopolymers and copolymers - hair treating agent); 4,371,517 (cationic polymers and anionic polymers).The use of polycationics, polyamines, and polyamides to improve softening of the classical quaternary compound fabric softeners in rinse cycle fabric softeners is known from, for example, U.S. Patent 4,237,016, U.K. Patent Specifications 1,576,326 and 2,041,025A, Belgium Patent 844,122, European Patent 13780 and German Patent DE 2,925,859A1.

While many of these prior art formulations provide satisfactory cleaning and/or softening under many different conditions they still suffer from a variety of defects such as requiring addition in the rinse cycle; not providing adequate softening - e.g. comparable to rinse cycle - added softeners - especially under hot water washing conditions, i.e. at a temperature of 60"C and higher; requiring formation of complexes of the cationic compound; using lower softening performance water-soluble, e.g. monohigher alkyl quaternary ammonium cationic compounds, or being limited to liquid compositions.

Although it is not uncommon for present day laundry detergent compositions and for conventional home automatic washing machines, especially in the United States, to be able to effect washing/cleaning of soiled fabrics using cold or warm wash water, specially for sensitive fabrics, wash-wear fabrics, permanent-press fabrics, and the like, it is nevertheless appreciated that more effective cleaning (soil removal) requires higher washing temperatures. Furthermore, in European and in other countries, the home washing machines operate at hot temperatures of 60"C or more, up to the boiling temperature of the wash water. While these high temperatures are beneficial for soil removal there is not an equal benefit for softening performance.

The present invention is based on the discovery that the softening performance of a detergent system based on a mixture of a nonionic detergent compound and a cationic quaternary ammonium compound fabric softening agent is significantly enhanced by using a limited class of polyfunctional compounds, which increase the substantivity of the water-insoluble cationic fabric softener to the fabric being treated, and hence increase the softening performance.It has been further discovered that softening performance is further improved by using as the nonionic surfactant one which has a cloud point, alone or in combination with an amphoteric surfactant,which is at last about 5"C higher than the washing temperature which is at least about 60"C. Furthermore, this enhancement of the softening performance is achieved without any, or at least without any significant, deterioration in washing (i.e. cleaning) performance.

A relationship between cleaning performance and the cloud point of a nonionic/cationic detergent mixture is known from U.S. Patents 4,222,905 - Cockrell, Jr., and 4,259,217 - Murphy. More particularly, as stated at column 5, lines 40-61 of the Murphy patent: "Processes for laundering fabrics with the compositions of the present invention which provide superior greasy and oily soil removal and fabric care benefits, are taught herein. in these processes, the laundry detergent compositions are used under temperature conditions such that the aqueous laundry solution is either at, or close to (i.e. within about 20"C of) the cloud point (i.e. the temperature at which a phase rich in nonionic surfactant separates in the laundry solution) of the nonionic/cationic surfactant mixture.This can preferably be accomplished by formulating those nonionic/cationic surfactant mixtures so that their cloud point falls between about 0 to 95"C, particularly from about 10 to 70"C, especially between about 20" and 70"C, most especially from about 30 to about 50"C. During the washing operation, the temperature of the laundry solution is held within this temperature range and within 20"C of the cloud pointtemperature.

Performance is improved further where the temperature of the aqueous laundry solution is within about 1 5"C, more preferably within about 10"C, of the nonionic/cationic surfactant mixture cloud point temperature." Apparently, the requirement to operate at washing temperatures at or below the cloud point temperature is based on the premise that the cloud point of the surfactant mixture in the wash water corresponds to the temperature at which micelles of the surface-active agent aggregate to such an extent that these aggregates become so large that they come out of solution, resulting in the observed cloudiness. Further temperature increase will lead to complete phase separation of the water and the nonionic surfactant and as a result detersive action on the soiled fabrics and overall cleaning ability is lost.

However, while it is stated by Murphy that the nonionicicationic mixtures may, "depending on the identity and concentration of the cationic component .... provide the benefits known in the prior art for such cationics, e.g .... softening effects for textile," it is nevertheless clear that there was no recognition or suggestion that the softening effects of the cationics can be significantly improved by using certain nonionics having high cloud point temperatures, per se.That is, whereas Murphy and Cockrell, Jr. teach a relationship between the cloud point of the nonionic/cationic mixture, washing temperature, and cleaning performance, it has now been discovered that it is the relationship between the cloud point of the nonionic alone (or the nonionic and any electrolytes present in the wash water) and the wash temperature which effects the softening performance of the water insoluble cationic quaternary ammonium compound softening agents.In contrast to the requirement of the present invention to use high cloud point temperature nonionics (i.e. those having cloud point temperatures above about 60"C, especially above about 90"C, especially preferably, above about 100"C) each of Murphy and Cockrell, Jr. prefer nonionicsurfactants having relatively low cloud points.

Therefore, the nonionic surfactants used in the composition described in these Murphy and Cockrell patents are fatty alcohols ethoxylated with at most 12 moles ethylene oxide, preferably at most 9 moles ethylene oxide, and having hydrophilic-lipo-philic balance(HLB) values of from about 5 to 17, preferably from about 6 to 15.

Accordingly, it was totally unexpected that softening performance of the cationic softener would be dramatically improved without diminishing and, in fact improving, cleaning performance of the nonionic surfactant by formulating the detergent-softener composition to have a cloud point above the washing temperature.

The use of nonionic surfactants having cloud points of at least about 60"C and higher than the wash water temperature is disclosed in Colgate-Palmolive Co's copending application entitled "WASH CYCLE DETERGENT-SOFTENER COMPOSITION" filed on or about the same day as this application under agents' reference P12426GB. The use of amphoteric surfactants to raise the cloud point of the nonionic surface active compounds to above the wash water temperature is also disclosed in this application and is described in greater detail in connection with the low cloud point nonionic surfactants in Colgate-Palmolive Co's copending application entitled "HOT WATER WASH CYCLE DETERGENT-SOFTENER COMPOSITION" filed on or about the same day as this application under agents' reference P12424GB. The disclosures of these applications are incorporated herein by reference.

The present invention is based on the discovery that softening performance of the water-insoluble cationic quaternary ammonium compound fabric softeners can be further improved by incorporating in the composition of the nonionic surfactant and cationic fabric softener, a polyfunctional additive which increases the substantivity of the cationic fabric softener to the fabrics being treated. In addition, cleaning performance of the nonionic can also be simultaneously improved.

It was on the basis of this discovery that the present invention was completed.

Accordingly, the invention aims to improve softening performance of detergent compositions containing quaternary ammonium compound softening agents and nonionic detergent compounds without significantly adversely effecting, and in some cases improving, overall cleaning performance.

Thus according to the present invention a laundry detergent composition capable of washing soiled fabrics in an aqueous wash liquid, at an elevated temperature of at least about 60"C up to the boiling temperature of about 1 00"C, includes, by weight, from 1 to 20 parts of a water-soluble nonionic surface active agent, from 2 to 20 parts of a water insoluble quaternary ammonium compound fabric softener, and from 0.5 to 10 parts of a fabric substantivity increasing polyfunctional additive and optionally up to about 10 parts of an amphoteric surfactant.

In a preferred embodiment of the invention, the nonionic has a cloud point temperature above the elevated temperature of the wash water. In an especially preferred embodiment of the invention, the compositions will include both the high cloud point temperature nonionic and an amphoteric surfactant. In each of the preferred embodiments, the detergent composition will include at least one additional detergent additive including detergent builders, thickeners, anti-redeposition agents, corrosion inhibitors, bleaches, enzymes, dyes, bluing agents, optical brighteners, perfumes, and the like.

In one aspect, therefore, the present invention provides a detergent composition for cleaning and softening textile fabrics in an aqueous media, especially at an elevated washing temperature of at least about 60"C, which includes, on a weight basis (a) from about 1 to 20% of a nonionic surfactant, (b) from about 2 to 20% of a water insoluble cationic quaternary ammonium compound fabric softening agent, (c) from about 0.5 to 10% of a polyfunctional additive selected from the group consisting of (i) diquaternary ammonium compounds, (ii) polymers of dimethyldiallyl ammonium chloride, (iii) cationic guar gum, and (iv) poly(methylvinylether/maleic acid), the amount of (b) plus (c) being in the range of about 4 to 22%, the ratio of (b) to (c) being in the range of from about 10:1 to about 1:3.

(d) from 0 to about 10% of an amphoteric surfactant.

(e) from about 25 to 80% of at least one detergent builder, (f) from 0 to about 40% of a bleaching agent, (g) from 0 to about 7% of a bleach activator, (h) from 0 to about 4% of each of soil suspending agents, anti-redeposition agents and thickening agents, (i) from 0 to about 5% of anti-corrosion agents, (j) from 0 to about 1% of organic chelating agents, (k) from 0 to about 2% of colourants, dyes, pigments, bluing agents and optical brighteners, (I) from 0 to about 2% of enzymes, (m) from 0 to about 0.5% perfume, (n) from 0 to about 10% of pH modifiers and buffers, (o) from 0 to about 50% of inert fillers, flow promoting agents and carriers, and (p) from about 2 to about 20% of water.

In accordance with a more preferred embodiment of the invention, there is provided a powder or granular free-flowing detergent softener composition for cleaning and softening soiled textiles fabrics in an aqueous wash water medium at an elevated temperature of from about 60"C to about 100 C, the composition including, on a weight basis, (a) from about 3 to 15% of a nonionic surfactant having a hydrophobic group condensed with sufficient alkylene oxide to increase the cloud point of the nonionic to above the elevated temperature, (b) from about 2 to 20% of a water-insoluble cationic quaternary ammonium compound fabric softener characterised by at least two long chain aliphatic groups of from 16 to 22 carbon atoms, (c) from about 1 to 10% of a polyfunctional additive selected from the group consisting of diquaternary ammonium compounds of the formula

wherein R1 represents a divalent alkyl group of from 2 to 4 carbon atoms which may additionally include an hydroxyl substitutent; each of the R2 groups are the same or different and each represent a lower alkyl group of 1 to 4 carbon atoms, which may optionally have an hydroxyl substituent;; R3 represents a straight or branched, saturated or unsaturated aliphatic hydrocarbon group of from 1 to about 22 carbon atoms, which hydrocarbon may be interrupted by an oxygen or -CONH- group; R4 represents a radical selected from the group consisting of aliphatic hydrocarbon radicals optionally interrupted by an oxygen atom or a -CONH group, having in total from about 8 to about 22 carbon atoms, alkylaryl radicals having from about 8 to 16 carbon atoms in the alkyl moiety, and aryl, and X represents a salt forming anion; and polymers of dimethyldiallyl ammonium chloride (d) 0.1 to 10% by weight of an amphoteric surfactant; and (e) balance, detergent builders, detergent adjuvants, fillers and moisture.

In the above preferred embodiment, it is especially preferred to include about 25 to 50% of detergent builders, from 0 to 5% corrosion inhibitor, from 0 to 1% organic chelating agent, from 0 to 40% oxygen bleach, from 0 to 7% bleach activator, from 0 to 4% thickener and anti-redeposition agent, from 0.2 to 0.5% optical brightener, from 0.7 to 1.3% enzyme, from 0 to 0.5% perfume, and balance, up to about 20% moisture.

Although the reason is not completely understood, the present inventors have discovered that best softening performance of cationic fabric softeners is achieved when the softener is very finely divided in the wash water (in the order of a few microns to submicron diameters) and water insoluble. The finely divided particles, must of course, be uniformly, although randomly, dispersed throughout the wash bath in order to uniformly contact all of the articles of clothing, towels, linens, and other articles being washed. It appears that the softener particles are effectively trapped by the fibres of the fabrics and adhere thereto by a combination of electrical, chemical and physical attraction.

In accordance with the present invention, the substantivity to the treated fabrics is further improved, and the softening performance of the cationic fabric softener proportionately increased, by adding to the detergent-softener composition a polyfunctional additive, preferably a diquaternary compound, polyquaternary compound, or cationic polymer.While these polyfunctional additives may themselves impart softness to the treated fabrics due to their own affinity for fabrics, as is known from the prior art cited above, their mode of operation in the wash cycle detergent-softener compositions of the present invention does not apparently primarily involve any direct softening action, but rather is apparently based primarily on either or both of the following factors: (1) their ability to stabilize the dispersion of the quaternary compound fabric softener; and (2) their ability to improve the contact between the quaternary compound and the fabric. By whatever mode of action the polyfunctional additives function to improve softness, it is a feature of the present invention that softness of the wash cycle treated fabrics is substantially equivalent to conventional rinse cycle added fabric softener treated fabrics.Moreover, it is possible to achieve substantial improvement in cleaning performance when using the preferred compositions of the present invention.

The essential ingredients in the detergent-softener compositions are therefore, the nonionic surfactant, the water-insoluble cationic fabric softener, and the polyfunctional additive. The use of an amphoteric surfactant in addition to the above essential ingredients is highly preferred, especially where the cloud point of the nonionic surfactant is at or below the wash watertemperature.

Although the compositions of the present invention can provide good softening and cleaning performance in cold wash water, e.g. about 20"C to 30"C, or warm wash water, e.g. about 30"C to 40"C or more, the best results are accomplished when the compositions are used with wash water at elevated temperatures of from about 60"C to about 100 C (boiling temperature).

Suitable nonionic surface active agents are commercially available and are derived from the condensation of an alkylene oxide or equivalent reactant and a reactive-hydrogen hydrophobe. The hydrophobic organic compounds may be aliphatic, aromatic or heterocyclic, although the first two classes are preferred. The preferred types of hydrophobes are higher aliphatic alcohols and alkyl phenols although others may be used such as carboxylic acids, carboxamides, mercaptans, and sulphonamides. The ethylene oxide condensates with higher-alkyl phenols or higher fatty alcohols represent preferred classes of nonionic compounds.

Usually, the hydrophobic moiety should contain at least about 6 carbon atoms, and preferably at least about 8 carbon atoms, and may contain as many as about 50 carbon atoms or more, a preferred range being from about 8 to 22 carbon atoms, especially from 10 to 18 carbons for the aliphatic alcohols, and 1 2to 20 carbons for the higher alkyl phenols. The amount of alkylene oxide will vary considerably depending upon the hydrophobe, but as a general guide and rule, at least about 15 moles of alkylene oxide per mole of hydrophobe up to about 30 moles of alkylene oxide per mole of hydrophobe should be used in order to obtain cloud point temperatures of at least about 60"C or higher.

Accordingly, the preferred nonionic surfactants can be represented by the formulae: RO(CH2CH20)nH (I) wherein R represents a primary or secondary alkyl chain of from about 8 to 22 carbon atoms and n is an average of from 15 to 30; or

where R' represents a primary or secondary alkyl chain of from 4 to 12 carbon atoms, and m is an average of 15 to 30.

The preferred alcohols from which the compounds of formula I are prepared include lauryl, myristyl, cetyl, stearyl and oleyl alcohol and mixtures thereof. Especially preferred examples of the R group are C10 to C18 with the C12 to C15 alkyls and mixtures thereof being especially preferred.

The preferred examples of the R' group are from C6to C12, with C8 and Cg, e.g. octyl, isooctyl and nonyl being especially preferred.

Atypical example of a nonionic compound of formula (I) is lauryl alcohol condensed with 15 moles ethylene oxides. A typical example of a nonionic compound of formula II is isooctyl phenol condensed with 30 moles ethylene oxide.

Other nonionic compounds which may be used include the polyoxyalkylene esters of the organic acids such as the higher fatty acids, the resin acids, tall oil acids, and acids from petroleum oxidation products.

These esters will usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 3 to about 12 moles of ethylene oxide or its equivalent.

Still other nonionic surfactants are the alkylene oxide condensates with the higher fatty acid amides. The fatty acid group will generally contain from about 8 to about 22 carbon atoms and this will be condensed with about 3 to about 12 moles of ethylene oxide as the preferred illustration. The corresponding carboxamides and sulphonamides may also be used as substantial equivalents.

It is also within the scope of the invention to replace all or part of the above described high cloud point nonionics with the corresponding low cloud point nonionics, that is, the same hydrophobe group but condensed with only from about 3 to 14 moles ethylene oxide. However, when using the low cloud point temperature nonionics, it is essential to also include one of the amphoteric surfactants, as described in more detail below, to ensure a sufficiently high cloud point of the composition. Preferably, no more than 50%, especially no more than 30%, and most preferably no more than about 20% of the total nonionic is a low cloud point compound.

The amount of the nonionic in the composition will generally be the minimum amount which when added to the wash water with or without the amphoteric surfactant will provide adequate cleaning performance.

Generally, amounts ranging from about 2 to about 20%, preferably from about 3 to about 10%, and especially preferably from about 4 to 9% by weight of the composition, provide good cleaning performance.

As used herein, the term "cloud point" means the temperature at which a graph which plots the light scattering intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, underthefollowing experimental conditions: The light scattering intensity is measured using a Model VM-12397 Photogoniodiffusometer, manufactured by Societe Francaise d'instruments de controle et d'analyses, France (the instrument being hereinafter referred to as (SOFICA). The SOFICA sample cell and its lid are washed with hot acetone and allowed to dry.

The surfactant mixture is made and put into solution with distilled water at a concentration of 1000 ppm.

Approximately a 15 ml sample of the solution is placed into the sample cell using a syringe with a 0.2 micron nucleopore filter. The syringe needle passes through the sample cell lid so that the cell interior is not exposed to atmospheric dust. The sample is left in a variable temperature bath, and both the bath and the sample are subject to constant stirring. The bath temperature is heated using the SOFICA's heater and cooled by the addition of ice (heating rate = 1 OC/minute); the temperature of the sample is determined by the temperature of the bath. The light scattering (90 angle) intensity of the sample is then determined at various temperatures, using a green filter and no polarizer in the SOFICA.

In the present invention, cloud point measurements are made for both solutions of the nonionic/ amphoteric (at 1% by weight) in distilled water and in water containing 10% NaCI, although the latter generally far exceeds the amounts of salts and electrolytes actually experienced in normal usage. Therefore, if the nonionic/amphoteric cloud point measured in 10% NaCI solution satisfies the cloud point requirement of the present invention, then there will be no problem in formulating compositions containing very high concentrations of builder salts and other electrolytes, for example, up to about 85% of the composition.

In this regard, it is known that the cloud point temperature for a given composition in the wash solution depends upon the physical and chemical properties (such as critical micelle concentration (CMC) and solubility) of the cationic, nonionic/amphoteric and additional components included in that composition, and will be lowered by increasing the alkyl chain lengths of the nonionic surface-active compound, by decreasing the degree of ethoxylation of the nonionic component, or by adding electrolytes, such as phosphates, polyphos-phates, perborates, carbonates, sulphonates, particularly in relatively low amounts (such as from about 1 to about 15% of a given composition).

Because water insoluble cationic softening compounds are used in the present invention the cationics will have substantially no effect on the cloud point of the total composition. Actually, because the softening cationic compounds used in the present invention are water insoluble the cloud point temperature of the total formulation is very difficult to measure since the mixtures are naturally somewhat cloudy. Therefore, the cloud point of the nonionic, and nonionic/amphoteric mixture, with or without addition of electrolytes, is determined in the absence of the cationic compound, and this provides a sufficiently accurate measure of the cloud point of the total composition including the cationic.

For washing temperatures of from about 60 to 70"C, all of the EO 15-30 nonionic surfactants described above, especially those of formulae I and II, should provide cloud points in excess of the washing temperature.

However, for higher washing temperatures of 71 0C to 100"C, especially 80" to 100"C, it is necessary to use the more highly ethoxylated surfactants, for example 25 to 30 moles ethylene oxide per mole of hydrophobe.

For these more highly elevated washing temperatures the most preferred nonionic surfactants are the C8-C9 alkyl phenols ethoxylated with from 25 to 30 moles, especially from 28 to 30 moles, and especially preferably about 30 moles, ethylene oxide.

Alternatively, and as discussed in greater detail in the above mentioned copending applications [agents' references P12426G B and P12424GB], it has also now been discovered that for any of the nonionics the cloud point can be raised by as much as about 40"C, generally about 5 to 20"C by adding to the composition an amphoteric surface-active compound, for example, a carboxyethylated higher fatty alkyl (e.g. coco) imidazoline amphoteric compound, generally in an amount of from about 0.5 to 10%; preferably 1 to 4%, especially preferably from about 1 to 3%, by weight of the composition.

Therefore, in a preferred embodiment of the invention which is especially useful for washing soiled fabrics in an aqueous wash water an an elevated temperature in the range of from about 80"C to 1 00"C, the detergent composition includes in addition to (a) the nonionic surfactant of formula I or formula II, (b) the water insoluble cationic quaternary ammonium compound fabric softener of formula (III) or formula (IV), given below, (c) the polyfunctional additive and (d) an amphoteric surfactant in an amount sufficient to raise the cloud point of the composition to above the elevated temperature of 80"C to 1 00"C, especially preferably above about 105"C.

The second essential ingredient of the formulations of the present invention is the cationic fabric softener.

Softening agents are used to render fabrics or textiles soft, and the terms "softening" and "softener" refer to the handle, hand, touch or feel; this is the tactile impression given by fabrics or textiles to the hand or body and is of aesthetic and commercial importance. Generally, the cationic fabric softeners consist of at least one hydrophilicfunctional group bearing a negative charge and a hydrophobic group containing a quaternary ammonium atom which is positively charged.

In order to impart sufficient softness to the treated fabrics, it is essential that the cationic compound is water-insoluble. As used herein, a compound is considered water insoluble if its solubility in water at the washing temperature is less than about 1%, preferably less than about 0.5%.

It is generally desired that the cationic softening compound be included in the composition in a form to ensure a high dispersibility in the wash liquid and therefore maximum attachment to the treated fabric. Such dispersed particle sizes in the wash liquid range from about less than 10 to about 50 microns, preferably from about less than 10 to about 20 microns can be used for the cationic softening compound to achieve this effect.

Suitable water insoluble quaternary ammonium compound fabric softeners which are commercially known may be represented by the following formula:

wherein R1 and R2 and R5 and Re each represent, independently, a long chain aliphatic radical having from 16 to 22 carbon atoms, R3 and R4 and R7 each represent, independently, lower alkyl radicals, or R6 may be the group.

wherein R8 represents a long chain aliphatic radical having from 16 to 22 carbon atoms, and R9 represents a divalent alkyl group of 1 to 3 carbon atoms, and X represents a water soluble salt forming anion such as a halide, i.e. chloride, bromide, iodide; or a sulphate, acetate, hydroxide, methosulphate, ethosulphate, or similar inorganic or organic solubilizing mono- or dibasic radical. The carbon chain of the aliphatic radical containing 16 to 22 carbon atoms, especially 16 to 20 carbon atoms, may be straight or branched, and saturated or unsaturated. The lower alkyl radicals have from 1 to 4 carbon atoms and may contain a hydroxy radical. Preferably, the carbon chains are obtained from long chain fatty acids such as those derived from tallow and soyabean oil.Terms such as "disoya", and "di-tallow", as used herein refer to the source from which the long chain fatty alkyl chains are derived. Mixtures of the above, as well as other water insoluble quaternary ammonium surface active agents may also be used if desired. The preferred ammonium salt is a dialkyl dimethyl ammonium chloride wherein the alkyl group is derived from hydrogenated tallow or stearic acid, our a dihigheralkyl imidazolinium chloride.Specific examples of quaternary ammonium softening agents of formula (II) above suitable for use in the compositions of the present invention include the following: hydrogenated ditallow dimethyl ammonium chloride, dimethyl distearyl ammonium chloride, dimethyl stearyl cetyl ammonium bromide, dimethyl dicetyl ammonium chloride, di-soya dimethyl ammonium chloride, and the corresponding sulphate, methosulphate, ethosulphate, bromide and hydroxide salts thereof.

Examples of quaternary ammonium softening agents of formula (IV) above include 1-methyl-1 ,2-dihepta- decyl imidazolinium chloride (bromide or methosuiphate), 1,2-dieicosylalkylamidoethyl-1-methyl imidazolinium chloride (bromide or methosulphate), 2-hexadecyl-1-methyl-1 [(2-dodecoyl amido)ethyl] imidazolinium methylsulphate, 2-heptadecyl-1 -methyl-1 [(2-stearoyl amido)ethyl] imidazolinium methylsulphate, 2 nonadecyl/heneicosyl-1 -[(2-eicosoyl/docosoyl imido) ethyl] imidazolinium methyl chloride.

Dimethyldistearyl ammonium chloride is especially preferred in view of its superior softening performance, biodegradability, low water solubility, availability and cost.

The amount of the cationic fabric softener can generally range from about 2 to about 20%, preferably from about 3 to about 16%, and especially preferably from about 6 to 15%, by weight of the composition.

The weight ratio of the nonionic surface active agent to the cationic fabric softener can be within the range offrom 1:10to5:1, preferably from aboutl:5to4:1,especiallypreferablyfrom 1:2to3.5:1.

The polyfunctional additives which are used to increase the fabric substantivity of the water insoluble cationic quaternary ammonium compound fabric softeners include (i) diquaternary ammonium compounds, (ii) polymers of dimethyldiallyl ammonium chloride, (iii) cationic guar gum, (iv) poly(methylvinylether/maleic acid), and (v) diimidazolinium compounds.

The diquaternary ammonium compounds are especially preferred and may be generally represented by compounds of the formula

wherein R1 represents a divalent alkyl group of from 2 to 4 carbon atoms which may optionally have an hydroxyl substituent; R2 represents the same or different lower alkyl groups of 1 to 4 carbon atoms, which may optionally have an hydroxyl substituent; R3 represents an aliphatic hydrocarbon group of from 1 to about 22 carbon atoms, which hydrocarbon may optionally be interrupted with an oxygen or -CONH- group; R4 represents a radical selected from the group consisting of aliphatic hydrocarbon radicals, optionally interrupted with an oxygen atom orthe group -CONH-, having in total from about 8 to 22 carbon atoms, alkyl aryl radicals having from about 8 to about 16 carbon atoms in the alkyl moiety, and aryl;; and X represents a salt-forming anion, especially, Cl-, Br-, CH2SO3-, or CH2CH2SO3-.

One class of diquaternary compounds which can be used in the present invention are the compounds represented by the formula

wherein R5 represents an alkyl radical containing from 6 to about 20, preferably 10 to 14, carbon atoms, R6 and R7 each represent methyl, ethyl, or hydroxyethyl, and X represents chloride or bromide. Specific examples include tetramethyl-di-(octoxy--hydroxyprnpyl)-i8-hydroxy-prnpylene-diammoniu m dichloride, tetramethyl-di-(ss-hydroxydodecyl)-ss-hydroxypropylene-diammonium dibromide, tetramethyl-di-(ss- hydroxytetradecyl)-ss-hydroxypropylene-diammonium dichloride, tetraethyl-di(dodecyloxy-P hydroxypropyl)-ss-hydroxypropylene-diammonium dichloride. These compounds are disclosed in U.S.

Patent 3,983,079 at columns 3 and 4.

An especially preferred class of diquaternary compounds are the N-mono higher alkyl-penta-lower alkyl-lower alkane-diammonium salts, such as the compounds represented by the following formula

wherein R3 represents a long chain aliphatic radical of from 12 to 22 carbon atoms, preferably 14to 20 carbon atoms, R9 represents a divalent alkyl of from 2 to 4 carbon atoms, and R10 and R11, and R12 each represent lower alkyl of 1 to 4 carbon atoms, and X- represents a salt-forming anion, such as chloride, bromide, iodide, sulphate, methylsulphate, ethylsulphate, or nitrate. As a specific example mention can be made of the compound sold under the trademark Adogen 477, a product of Sherex, which is N-tallow pentamethylpropane diammonium chloride.

The polymers of dimethyldiallyl ammonium dichloride include both homopolymers and copolymers. The comonomers in the copolymers include, for example, acrylic acid, methacrylic acid, styrene, vinyl acetate, vinyl propionate, acrylamide, methacrylamide, and similar copolymerizable monomers. Acrylamide and methacrylamide are preferred, and acrylamide is especially preferred.

As an example of the diimidazolinium compound mention can be made of the compounds of the formula

wherein R3 represents a straight or branched, saturated or unsaturated aliphatic group having 12-18 carbon atoms, R' represents a divalent aliphatic hydrocarbon group having 2-5 carbon atoms, R3 represents a lower alkyl group having 1-4 carbon atoms, and X represents a salt forming anion.

As a specific example, mention can be made of 1-ethylene-bis(2-tallow-1 methyl-imidazolinium methyl sulphate).

The polymerization can be carried out by standard techniques well known in the art. The degree of polymerization is not particularly critical and satisfactory results are obtained with polymers having molecular weights of from about 500 to about 107.These polymers, as well as the cationic guar gums and poly(methylvinylether)maleic acid) are commercially available.

The amount of the polyfunctional additive will generally range from about 0.5 or 2 to about 10%, preferably from 2 to about 8% of the total composition. It is also preferred that, within the above described amounts, the cationic fabric softener (b) and polyfunctional additive (c) are used at a (b) : (c) weight ratio of from about 10:1 to 1:3, preferably from about 6:1 to 1:2, especially from about 4:1 to 1:1.

As mentioned above, in the preferred embodiment ofthe invention, the composition further includes (d) an amphoteric surfactant.

One specific class of useful amphoteric surfactants are the complex fatty amido surfactants of the general formula (V)

wherein R represents a straight or branched, saturated or unsaturated aliphatic group having 12-18 carbon atoms (such as alauryl, tridecyl, tetradecyl, pentadecyl, palmityl, heptadecyl, stearyl, tallow, coco, soya, oleyl, or linoleyl group), R1 and R2 each represent, independently, a divalent aliphatic hydrocarbon group having 2-5 carbon atoms, (e.g. a methylene, ethylene, propylene, butylene, 2-methyl-butylene, or pentylene group), and M represents a hydrogen atom or an alkali metal ion (e.g. sodium, potassium, caesium or lithium).Examples of compounds of formula V which are commercially available include

available as Miranol CM (liquid) and Miranol DM (paste) from Miranol Chemical Co.; Soromine AL and Soromine AT from GAF Corporation and the Deriphat compounds from General Mills.

The amphoteric compounds disclosed in columns 3 and 4 of U.S. Patent 4,203,872 to Flanagan can also be used. These include the following seven groups of compounds (VIto XII).

(1) Betaine detergents having the formula

A suitable example is

(2) Alkyl bridged betaine detergents having the formula

A suitable example is

(3) Imidazoline detergents having the formula

A suitable example is

(4) Alkylimino propionate detergents having the formula

(5) Alkyliminodipropionate detergents having the formula

(6) Ether bridged alkyliminodipropionate detergents having the formula

(7) Cocoimidazoline based amphoteric detergents having the formula

Mixtures of any of the amphoteric detergents with one another and with the amine oxide detergents listed above may also be used.

In the above groups of compounds of formulae VI to XII, R1 represents a straight or branched, saturated or unsaturated aliphatic radical containing from about 7 to about 20, preferably from about 8 to 18, especially preferably from about 10 to 14 carbon atoms, R2 and R3 each represent lower alkyl groups of C1 to C4, preferably methyl or ethyl, especially preferably ethyl, R4 represents a divalent C1-C4 alkyl group, preferably methylene or ethylene, especially preferably ethylene.

A particularly preferred group of amphoteric compounds are the carboxyethoxylated higher fatty alkylimidazoline compounds of the formula (XIII)

where R' represents a straight or branched, saturated or unsaturated aliphatic group of from 7 to 20 carbon atoms, preferably of 8 to 18 carbon atoms, especially preferably of 10 to 14 carbon atoms, and R4 represents a divalent lower alkyl group of 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Preferred R' groups include coco, tallow, heptadecyl, oleyl, decyl and dodecyl, especially coco (i.e. derived from coco fatty acid).

The preferred R4 group is ethylene (-CH2CH2-). The compound carboxyethylated cocoimidazoline is available as Rexoteric CSF, a trademarked product of Rexolin on a 100% active ingredient basis, or as a 45% active ingredient solution.

The open chain carboxyethylated higher fatty alkyl amine derivatives are another preferred class of amphoteric compound. These include compounds of the above formulae (IX), (X) and (Xl) i.e. the alkyliminopropionate and ether bridged alkylimino-propionate detergents. Carboxyethylated octyl amine which is available as Rexoteric OASF from Rexolin is an especially preferred member of this group.

Other classes of amphoteric surfactants such as the sarcosines, taurines, isothionates and the like can also be used.

Although there are no firm guidelines for selecting combinations of nonionic surfactants and amphoteric surfactants or the appropriate amounts of each to give the necessary cloud point temperature in excess of the washing temperature to promote the softening performance of the cationic fabric softener it is usually sufficient to use the amphoteric - with the amount of nonionic surfactant specified above - in an amount of from about 0.1 to 10%, preferablyfrom about 0.5 to about 14%, especially from about 1 to about 3%, based on the total weight of the composition.Generally ratios of nonionic: amphoteric within the above-mentioned amounts are in the range of from about 1 Sto 10:1, preferably 1:3 to 6:1, especially 1 :2to 4:1, will provide the desired high cloud point and enhanced softening performance, especially in combination with the polyfunctional compound.

The detergent compositions of the present invention are preferably provided as free flowing powders but may also be in liquid form.

The detergent composition of the present invention may also and generally does include water soluble builder salts. Water-soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and diorthosphosphate, and potassium bicarbonate. The alkali metal silicates are useful builder salts which also function to make the composition anti-corrosive to washing machine parts.Sodium silicates of Na2/SiO2 ratios of from 1.6:1 to 1:3.2 especially about 1:2 to 1:2.8 are preferred. Potassium silicates of the same ratios can also be used.

Another class of builders useful herein are the water-insoluble aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeolites (i.e. alumino-silicates) are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are hereby incorporated by reference for such descriptions. An example of amorphous zeolites useful herein can be found in Belgium Patent 835,351 and this patent too is incorporated herein by reference. The zeolites generally have the formula: (M2O)x. (Al203)y.(SiO2)z.WH20 wherein xis 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium.A typical zeolite is type A or similar structure, with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milli-equivalents per gram or greater, e.g. 400.

Other materials such as clays, particularly of the water-insoluble types, may be useful adjuncts in compositions of the present invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminium silicate in which about 1/6th of the aluminium atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable for detergents invariably contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 milliequivalents calcium per 100 g of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1,2,3 and 4 by Georgia Kaolin Co.Bentonites, such as those called Wilkinite, are known to soften textiles as described in British Patent 401,413 to Marriott and British Patent 461,221 to Marriott and Dugan.

Examples of organic alkaline sequestrant builder salts which can be used alone with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate, sodium and potassium nitrilotriacetates and triethanolammonium N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these poly carboxylates are also suitable.

Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates.

Of special value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in U.S.P. 4,144,226; 4,315,092 and 4,146,495. Other U.S. patents on similar builders include 4,141,676; 4,169,934; 4,201,858; 4,204,8524,224,420; 4,225,685; 4,226,960; 4,233,422; 4,233,423; 4,302,564 and 4,303,777. Also relevant are European Patent Application Nos. 0015024; 0021491 and 0063399.

Various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose; optical brighteners, e.g. cotton, amine and polyester brighteners, for example, stilbene,triazole and benzidine sulphone compositions, especially sulphonated substituted triazinyl stilbene, sulphonated naphthotriazole stilbene, and benzidine sulphone; most preferred are stilbene and triazole combinations.

Bluing agents such as ultramarine blue; enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes; bactericides, e.g. tetrachlorosalicy lanilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives; ultra-violet absorbers; anti-yellowing agents, such as sodium carboxymethyl cellulose, complex of C12 to C22 alkyl alcohol with C12 to C18 alkysulphate; pH modifiers and pH buffers; colour safe bleaches; perfume; and anti-foam agents or suds-suppressors, e.g. silicon compounds can also be used.

The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches.

Chlorine bleaches are typified by sodium hypochlorite (NaOCI), potassium dichloroisocyanurate (59% available chlorine), and trichloroisocyanuric acid (85% available chlorine). Oxygen bleaches are represented by sodium and potassium perborates and potassium monopersulphate. The oxygen bleaches are preferred.

Bleach stabilizers and/or activators, such as, for example, tetraacetylethylene diamine, can also be included.

The proportions of components which may be present in the preferred total care compositions, in percent by weight (of actives) based on the total weight of the final product are as follows: (a) nonionic detergent 2% to about 20%, preferably about 3% to about 10%, especially 4% to 9%; (b) quaternary ammonium salt about 2% to about 20%, preferably about 3% to about 16%, especially preferably about 6 to 15%; (c) polyfunctional additive - from about 0.5 to 10%, preferably about 3 to 8%; (d) amphoteric surfactant - from 0 to about 10%, preferably from 0.1 to 5%, especially 0.5 to 4%, and most especially from about 1 to 3%; (e) alkali metal builder salts - about 25% to about 80% and preferably about 25% to about 70%, and especially preferably about 25 to 50%, the balance being detergent additives, fillers and moisture. Suitable ranges of the detergent additives are: enzymes - 0 to 2%, especially 0.7 to 1.3%; corrosion inhibitors - about 0 to 5%, and preferably 0.1 to 2%; anti-foam agents and suds-suppressors - O to 4%, preferably 0 to 3%, for example 0.1 to 3%; soil suspending or anti-redeposition agents and anti-yellowing agents - 0 to 4%, preferably 0.5 to 3%; colourants, perfumes, brighteners and bluing agents total weight 0% to about 2% and preferably 0% to about 1%; pH modifiers and pH buffers - 0 to 5%, preferably 0 to 2%; bleaching agent - 0% to about 40% and preferably 0% to about 25%, for example 2 to 20%; bleach stabilizers and bleach activators 0 to about 15%, preferably 0 to 10%, for example, 0.1 to 8%. In the selection of the adjuvants, they will be chosen to be compatible with the main constituents of the detergent composition.

While the high cloud point nonionics are preferably the sole surface-active detergent compounds used in the compositions of this invention, small amounts of other surface-active compounds, including, for example, anionics, and zwitterionics can also be used, preferably in amounts up to 20% by weight, especially up to 10% by weight, and especially preferably up to 5% by weight.

Examples of suitable anionic detergents include the water-soluble salts, e.g. the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing about 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms.

Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g. tallow, grease, coconut oil, tall oil and mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, e.g. sodium coconut soap and potassium tallow soap.

The anionic class of detergents also includes the water-soluble sulphated and sulphonated synthetic detergents having an alkyl radical of 8 to 26, and preferably about 12 to 22 carbon atoms, in their molecular structure. (The term alkyl includes the alkyl portion of the higher acyl radicals.) Examples of the sulphonated anionic detergents are the higher alkyl mononuclear aromatic sulphonates such as the higher alkyl benzene sulphonates containing from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, e.g. the sodium, potassium, and ammonium salts of higher alkyl benzene sulphonates, higher alkyl toluene sulphonates, higher alkyl phenol sulphonates, and higher naphthalene sulphonates.A preferred sulphonate is linear alkyl benzene sulphonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers, i.e. wherein the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4,5,6 or7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low. Particularly preferred materials are set forth in U.S. Patent 3,320,174.

Other suitable anionic detergents are the olefin sulphonates, including long-chain alkene sulphonates, long-chain hydroxyalkane sulphonates or mixtures of alkene-sulphonates and hydroxyalkane-sulphonates.

These olefin sulphonate detergents may be prepared in a known manner by the reaction of sulphur trioxide (soy) with long-chain olefins containing 8 to 25, preferably 12-21, carbon atoms and having the formula RCH-CHR1 where R represents a higher alkyl group of 6 to 23 carbons and R1 represents an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene-sulphonic acids which is then treated to convert the sultones to sulphonates. Other examples of sulphate or sulphonate detergents are paraffin sulphonates containing about 10-20, preferably about 15-20 carbon atoms, e.g. the primary paraffin sulphonates made by reacting long-chain alpha olefins and bisulphites and paraffin sulphonates having the sulphonate groups distributed along the paraffin chain as shown in U.S.Patents 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Patent 735,096; sodium and potassium sulphonates of higher alcohols containing 8 to 18 carbon atoms, such as sodium lauryl sulphate and sodium tallow alcohol sulphate; sodium and potassium salts of an alpha-sulphofatty acid ester containing about 10 to 20 carbon atoms in the acyl group, e.g. methyl alpha-sulphomyristate and methyl-alpha-sulpho-tallowate, ammonium sulphates of mono- or diglycerides of higher (C10-C18) fatty acids, e.g. stearic monoglyceride monosulphate; sodium and alkylolammonium salts of alkyl polyethenoxy ether sulphates produced by condensing 1 to 5 moles of ethylene oxide with one mole of higher (C8-C18) alcohol; sodium higher alkyl (C10-C18) glyceryl ether sulphonates; and sodium or potassium alkyl phenol polyethenoxyethersulphateswith about 1 to 6 oxyethylene groups per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.

The suitable anionic detergents include also the C8-C18 acyl sarcosinates (e.g. sodium lauroyl sarcosinate), sodium and potassium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid, and sodium and potassium salts of the C8-C18 acyl N-methyl taurides, e.g. sodium cocoyl methyl taurate and potassium stearoyl methyl taurate.

Examples of zwitterionic surfactants include the derivatives of quaternary ammonium compounds containing an aliphatic straight chain group of 14to 18 carbon atoms and a sulphate or sulphonate anionic solubilizing group. Specific examples include 3-(N,N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1 - sulphonate, 3-(N,N-dimethyl-N-tallowyl ammonio)-2-hydroxypropane-1 -sulphonate, 3-(N,N-dimethyl-Ntetradecyl ammonio)-propane-1 -sulphonate, and 6-N,N-(dimethyl-N-hexadecyl ammonio) hexanoate.

In addition to the so-called active materials of these compositions other important constituents are filler salt(s) and moisture. A filler salt helps to improve the mechanical properties of the product, usually improving the flow rate and countering any tendency toward tackiness. It may also aid in promoting ready solution of the product in wash water. Among useful filler salts the best is sodium sulphate, preferably in the anhydrous state. However, other fillers, including sodium chloride, sodium acetate, and the alkali metal salts of such acids, may also be used, as may be starches, talcs, silicas and various other fillers which perform a carrying or supporting function.The proportion of filler or mixture thereof will be within the 5 to 50% range, preferably being 10 to 30% and most preferably about 20%, especially when sodium sulphate, an hydrous, is the filler salt. The percentages of moisture will normally be from 1 to 15%, preferably 5 to 12% and most preferably about 8%. When such proportions are used a satisfactorily flowing particulate, pulverulent or granular product results, which, by control of particle size and moisture content, can be prevented from being excessively dusty.

Whatever the form of the laundry detergent, its use in the washing process is essentially the same. The particulate composition is usually added to wash water in an automatic washing machine so that the concentration thereof in the wash water may range from about 0.05 to 1.5%, usually 0.1 to 1.2%. The water to which it is added will preferably be of medium or low hardness, e.g. from 30 to 120 parts per million of hardness, as calcium carbonate, but both softer and harder water may be usefully employed. The water temperature can be from 20"C to 100"C and is preferably from 60 to 1000C in those cases where the textile or laundry is capable of withstanding high temperatures without deterioration or fading of dyes.When low temperature laundering is desired, the temperature may be held at 20 to 400C, under which conditions good cleaning and softening are the result, although the product may not be as clean as when washed at the higher temperatures. At the concentrations of detergent compositions mentioned the pH of the wash water will usually be from 7 to 11, preferably from 8 to 10. At such pH's the composition is effective as a detergent, not unduly harsh to the material being washed nor to human skin and effectively cleans and softens. The laundry:wash water weight ratio will usually be about 1:4 to 1:30 or 1:10 to 1:30.

The compositions of the present invention provide significantly improved softening performance, at washing temperatures of at least 60"C, as compared, for example, to formulations which are otherwise identical, except that the nonionic has a cloud point below 60"C, for example a straight chain higher fatty, e.g.

C12-C15, alcohol with 7 to 13 ethylene oxide units. This effect could not have been predicted from the prior art since there was no known correlation between the nonionic surfactant cloud point and softening performance.

Cloud point values ("C) for various nonionic surfactants at 1% by weight concentrations, and mixtures of nonionic/amphoteric surfactants at 1% weight concentrations were measured as described above in distilled water and in 10% NaCI are given in Table 1 below.

TABLE 1 Distilled Nonionic Surfactant Water 10% NaCI A. C12-C15fatty alcohol EO7:1 43+2 < 25 B. C12-C1fatty alcohol EO 11:1 85be2 59+2 C12-C15 fatty alcohol EO 15:1 > 100 > 60 isoctylphenol EO 30:1 > 100 > 60 nonyl phenol EO 20:1 > 100 72 nonyl phenol EO 15:1 91 70 nonyl phenol EO 8:1 45 < 30 A.+ Rexoteric OASF (1:2) 75~2 50rut2 A. + RexotericOASF(4:1) 58+2 28 2 A.+ RexotericCSF(4:1) 55t2 42+2 B.+ Rexoteric OASF (1:2) > 100 90~2 B.+ RexotericOASF(4::1) 95t2 85rut2 B.+ RexotericCSF(4:1) > 100 80r2 The 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 on a weight basis: Examples 1 to 3 These are concerned with the production of a powdery detergent softener composition in accordance with the invention.

The following compositions set out in Table 2 are prepared: TABLE 2 Example 1(%) 21%) 3(0/01 Ingredients Proportions Nonylphenol EO 20:1 15.0 C12-C15fattyalcohol EO 11:1 10.0 7.5 Rexoteric CSF (100% actives) 2.5 Sodium tripolyphosphate 42.0 42.0 42.0 Dimethyldistearyl ammonium 6.45 6.45 6.45 chloride (93% actives) N tallow pentamethyl propane 3.0 3.0 3.0 diammonium dichloride (Adogen 477) (50% actives) Minors & miscellaneous (e.g. Bal- Bal- Bal optical brighteners, perfume, ance ance ance moisture, etc.) Using 100 grams of each of the Compositions of Examples 1, 2 and 3 bath towels and hardened cotton terry cloth are washed in about 20 litres ofwaterat60"C.

The washed fabrics are evaluated for softness by a panel of 4 expert judges on multiple replicates after cummulative washing. Each of the compositions are graded on a scale of 1 to 10 with "10" being the highest grading and representing the degree of softness obtained with a rinse cycle added softener (dimethyl distearyl ammonium chloride). On this scale, the Composition of Examples 1 and 2 each received a rating of 8-10. The composition of Example 3 received a rating of 4-5.

Furthermore, each of the Compositions of Examples 1 and 2 are evaluated for overall soil and stain removal on 10 different types of soiled fabrics and are found to give comparably excellent cleaning performance.

Examples 4 to 7 Each of the following compositions as set out in Table 3 are compared for softening performance under the same conditions described in Examples 1 to 3.

TABLE 3 Example 4t%) 5(0/0) 6(0/0) 70%) Ingredients Proportions Nonyl phenol EO 20:1 15.0 Sodium metasilicate - 8.0 Sodium tripolyphosphate s 28.0 Sodium pyrophosphate 10H2O 23.0 Sodium orthophosphate v 0.S Nitrilotriacetate, Na salt 8.0 Dimethyl distearyl ammonium 8.0 8.0 6.45 8.0 chloride (93% actives) Copolymer (dimethyldiallyl - 7.6 - ammonium chloride/acrylamide) (40% actives) Adogen 477 (50% actives - - 3.0 6.0 Minors & miscellaneous ------)Balance The following results are reported for softening performance on bath towels and hardened cotton terry cloth: Example 5 significantly better than Example 4; Example 7 significantly better than Example 4; Example 6 directionally better than Example 4; Example 5 directionally better than Example 7; Example 7 directionally better than ExampleS; Example 6 directionally better than Example 4.

Example 8 A preferred formulation of a built full performance powder or granular composition according to the present invention is shown in Table 4 below along with broad ranges: TABLE 4 Ingredients Range % Ex. 8 % C12-C15fattyalcohol EO 11:1 3-15 6.0 Rexoteric CSF (100% actives) 0-3 1.5 Sodium tripolyphosphate 25-50 42.0 Sodium silicate (1::2) (40% actives) 0-5 3.0 Ethylenediamine tetraacetic acid 0-1 0.45 Sodium perborate monohydrate 0-15 13.0 (NaBO3.H2O) Perborate Activator (TAED) 0-7 2.8 Sodium carboxymethyl cellulose 0-4 2.6 Optical Brightener (Tinopal) 0.2-0.5 0.33 Enzyme (Alcalase 2T-from NOVA) 0.7-1.3 1.0 Dimethyl stearyl ammonium 5-15 8.6 dichloride N-tallow pentamethyl profane1 1-5 3.4 diammonium chloride Inert carrier and flow promoter 0-5 3.0 Perfume 0-1 0.4 Water Balance Balance The method for making the composition described herein are generally well known in the art and in particular reference is made to U.S.Patent 4,269,722 of Joshi, wherein relatively high density, built nonionic powders are produced from spray dried base beads which are over-sprayed with nonionic detergent (which may contain other minor conventional additives such as colour, perfume, brightener, or bleach). This entire patent disclosure is incorporated by reference.

Thus a typical procedure disclosed in USP 4269722 (and the corresponding GB 1584410) for making spray dried detergent beads is as follows.

An aqueous slurry is prepared consisting of 14.5 parts of pentasodium tripolyphosphate powder (anhydrous), 15.2 parts of 50% aqueous solution of sodium silicate (Na2O:SiO2 = 1:2.4) and 21 parts of deionized water. The slurry is brought to a temperature of about S0C and is mixed well in a crutcherto form the hexahydrate salt of pentasodium tripolyphosphate. The preliminary crutcher mix thus made is then heated to 88"C and is maintained between that temperature and 93"C to prevent hydration of the anhydrous sodium tripolyphosphate powder to be added subsequently.The full crutcher mix is then made by addition, at a temperature in the mentioned 88 to 93"C range, of 28.3 parts of pentasodium tripolyphosphate powder (anhydrous) and 21 parts of deionized water. The mix resulting contains from about 45 to 50% of solids by weight, due to hydration of some of the anhydrous tripolyphosphate and evaporation of some moisture.

The crutcher mix is pumped to a countercurrent spray drying tower, which is 8ft. high, and is sprayed at a manifold temperature of 82"C and at a pressure of about 750 p.s.i.g. (54 kg/cm2 absolute) through a "Whirljet 15-1" spray nozzle into drying air having an initial temperature, as it enters the spray tower, of about 31 5"C.

The spray dried base beads produced are of internal structure and outer surface characteristics like those of the bead shown in Figures 6 and 7, being rounded solid particles of irregular configuration having sponge-like porous outer surfaces and skeletal internal structures, in contrast to conventional spray dried detergent beads which have substantially continuous outer surface and a hollow core.

The spray dried base beads contain 77% of sodium tripolyphosphate, 13% of sodium silicate and 10% of moisture. The bulk density is 0.55 g/cc, the flowability is 86% of that of dry sand and the product is completely non-tacky. A sieve analysis shows: 1% on a No.20 screen; 19% through No.20, on No.40; 50% through No.40, on No.60; 20% through No.60, on No.80; 6% through No.80, on No.100; 3% through No.100, on No.200; and 1% through No.200.

The base beads are introduced into a batch rotary drum blender and are post-sprayed at 49"C with "Neodol 25-7" and minor proportions of colouring agent, perfume and brighteners to produce a final product consisting of 78% of the base bead, 19.7% of "Neodol 25-7" and 2.3% of the minor components. In other experiments the liquids (the "Neodol 25-7" and the minor components or aqueous solutions or dispersions of them) are sprayed in the forms of fine droplets or mists onto the tumbling base beads in "Patterson-Kelley" twin shell and "Zig-Zag" blenders.

The compositions resulting are of a bulk density of 0.68 g/cc and a flowability of 79% and are completely non-tacky. They analyze: 1% on a No.20 screen; 20% on No.40; 52% on No.60; 20% on No.80; 5% on No.100; 2% on No.200; and 0% through No.200.

Claims (48)

1. A detergent composition comprising a non-ionic surfactant, a cationic quaternary ammonium compound fabric softening agent and at least one additive selected from (i) diquaternary ammonium compounds; (ii) polymers of dimethyldiallyl ammonium chloride; (iii) cationic guar gum; (iv) poly(methylvinylether/maleic acid); and (v) diimidazolinium compounds.

2. A composition as claimed in Claim 1 further comprising an amphoteric surfactant.

3. A composition as claimed in Claim 1 or 2 wherein the said surfactant or combination of the said surfactants is such that the composition, when added to wash water at a concentration of 1% by weight, has a cloud point above 60"C.

4. A composition as claimed in Claim 1, 2 or 3, wherein the weight ratio of the amount of non-ionic surfactant to the amount of fabric softening agent is from 1:20 to 10:1.

5. A composition as claimed in any one of Claims 1 to 4, wherein the weight ratio of the amount of non-ionic surfactant to the amount of additive is from 1:10 to 40:1.

6. A composition as claimed in any one of Claims 1 to 5, wherein the weight ratio of the amount of fabric softening agent to the amount of additive is from 1:5 to 40:1.

7. A composition as claimed in Claim 2, wherein the weight ratio of the amount of non-ionic surfactant to the amount ofamphoteric surfactant is up to 1:10.

8. A composition as claimed in any one of Claims 1 to 7 which comprises, on a weight basis from 1 to 15% of the non-ionic surfactant.

9. A composition as claimed in any one of Claims 1 to 8, which comprises, on a weight basis, from 2 to 20% of the water insoluble cationic quaternary ammonium compound fabric softening agent.

10. A composition as claimed in any one of Claims 1 to 9, which comprises, on a weight basis, from 0.5 to 10% of the additive.

11. A composition as claimed in any one of Claims 1 to 10, wherein the combined amount of the fabric softening agent and the additive is in the range of from about 5 to 22%.

12. A composition as claimed in any one of Claims 1 to 10, wherein the ratio of the amount of the fabric softening agent to the amount of the additive is in the range of from 10:1 to 1:3.

13. A composition as claimed in Claim 2 comprising up to 10% of the amphoteric surfactant.

14. A composition as claimed in any one of Claims 1 to 14 comprising at least one detergent builder.

15. A composition as claimed in Claim 14, wherein the detergent builder is present in an amount of from 25 to 80% by weight.

16. A composition as claimed in any one of Claims 1 to 15, comprising from 0 to 40% of a bleaching agent.

17. A composition as claimed in any one of Claims 1 to 16 comprising from 0 to 7% of a bleach activator.

18. A composition as claimed in any one of Claims 1 to 17 comprising from 0 to 4% of each of soil suspending agents, anti-redeposition agents and thickening agents.

19. A composition as claimed in any one of Claims 1 to 18 comprising from 0 to 5% of anti-corrosion agents.

20. A composition as claimed in any one of Claims 1 to 19 comprising from 0 to 1% of organic chelating agents.

21. A composition as claimed in any one of Claims 1 to 20 comprising from 0 to 2% of colourants, dyes, pigments, blueing agents and optical brighteners.

22. A composition as claimed in any one of Claims 1 to 21 comprising from 0 to 2% of enzymes.

23. A composition as claimed in any one of Claims 1 to 22 comprising from 0 to 0.5% perfume.

24. A composition as claimed in any one of Claims 1 to 23 comprising from 0 to 10% of pH modifiers and buffers.

25. A composition as claimed in any one of Claims 1 to 24 comprising from 0 to 50% of inert fillers, flow promoting agents and carriers.

26. A composition as claimed in any one of Claims 1 to 25 comprising water.

27. A composition as claimed in Claim 26, wherein the water is present in an amount of from 2 to 20%.

28. A composition as claimed in any one of Claims 1 to 27, which is in the form of a free-flowing powder or granules.

29. A composition as claimed in any one of Claims 1 to 28, which comprises from 3 to 15% of the non-ionic surfactant, which has a hydrophobic group condensed with alkylene oxide.

30. A composition as claimed in any one of Claims 1 to 29, which comprises from 2 to 20% of the water-insoluble cationic quaternary ammonium compound fabric softener, which has at least two long chain aliphatic groups of from lSto 22 carbon atoms.

31. A composition as claimed in any one of Claims 1 to 30, which comprises from 1 to 10% of the additive, which is selected from diquaternary ammonium compounds of the formula

wherein R' represents a divalent alkyl group of from 2 to 4 carbon atoms which may optionally include a hydroxyl substituent; each of the R2 groups independently represents a lower alkyl group of 1 to 4 carbon atoms, which may optionally have a hydroxyl substituent; R3 represents a straight or branched, saturated or unsaturated aliphatic hydrocarbon group of from 1 to 22 carbon atoms, which hydrocarbon may be interrupted by an oxygen atom or a -CONH- group;; R4 represents a radical selected from aliphatic hydrocarbon radicals optionally interrupted by an oxygen atom or a -CONH- group, having in total from 8 to 22 carbon atoms, alkylaryl radicals having from 8 to 16 carbon atoms in the alkyl moiety, and aryls; and X represents a salt forming anionic; and polymers of dimethyldiallyl ammonium chloride.

32. A composition as claimed in Claim 1 comprising 0.1 to 10% by weight of an amphoteric surfactant, the amount of the amphoteric surfactant being sufficient to increase the cloud point of the non-ionic surfactant to above the elevated temperatures at which the composition is to be used.

33. A composition as claimed in any one of Claims 1 to 32, comprising from 25 to 50% of detergent builders, from 0 to 5% corrosion inhibitor, from 0 to 1 % organic chelating agent, from 0 to 40% oxygen bleach, from 0 to 7% bleach activator, from 0 to 4% thickener and anti-redeposition agent, from 0.2 to 0.5% optical brightener, from 0.7 to 1.3% enzyme, from 0 to 0.5% perfume, and balance, up to 20%, moisture.

34. A composition as claimed in any one of Claims 1 to 33, wherein the fabric softening aagent is a compound represented by one of the following formulae:

wherein each of R1, R2, R5 and R6 independently represents a C16 to C22 long chain aliphatic radical, each of R3, R4 and R7 represents a lower alkyl radical, or R6 may represent a group

wherein R8 represents a long chain aliphatic radical having from 16 to 22 carbon atoms, and R9 represents a divalent alkyl radical of from 1 to 3 carbon atoms, and X represents a salt forming anion.

35. A compound as claimed in any one of Claims 1 to 34, wherein the ratio, by weight, of the non-ionic surfactant to the cationic compound is in the range of 1:10 to 5:1.

36. A composition as claimed in any one of Claims 1 to 35, wherein the non-ionic surfactant is at least one compound represented by the following formulae RO(CH2CH2O)nH (I) wherein R represents a primary or secondary alkyl chain of from 8 to 22 carbon atoms and n is a number which is, on average, from 3 to 30; and

wherein R1 represents a primary or secondary alkyl chain offrom 7 to 12 carbon atoms, and m is a number which is, on average, from 3 to 30.

37. A composition as claimed in Claim 36, R represents an alkyl of from 12 to 15 carbon atoms and R1 represents an alkyl of from 8 to 9 carbon atoms, and m and n are each numbers which are, on average, from 15 to 30.

38. A composition as claimed in any one of Claims 1 to 37, wherein the fabric softening agent is dimethyl distrearyl ammonium chloride.

39. A composition as claimed in Claim 1 which further comprises at least one detergent additive selected from inorganic detergent builder salts, organic detergent builder salt, soil suspending agents, antiredeposition agents, fatty amides, suds-suppressor agents, anti-foaming agent, optical brighteners, dyes, pigments, blueing agents, anti-yellowing agents, enzymes, corrosion inhibitors, pH modifiers, pH buffers, bacteriocides, fungicides, preservatives, bleaching agents, bleach stabilisers, bleach activators, prefumes, and water.

40. A composition as claimed in Claim 2, comprising from I to 20 parts of the non-ionic surfactant and at least 0.1 part of the amphoteric surfactant.

41. A composition as claimed in Claim 2 or 40, wherein the amphoteric surfactant is a compound having one ofthefollowing structures: (1) Betaine detergents having the formula

(2) Alkyl bridged betaine detergents having the formula

(3) Imidazoline detergents having the formula

(4) Alkyliminopropionate detergents having the formula

(5) Alkyliminodipropionate detergents having the formula

(6) Ether bridged alkyliminodipropionate detergents having the formula

(7) Cocoimidazoline based amphoteric detergents having the formula

(8) Carboxyethylated higher fatty alkyl imidazoline based amphoteric detergents having the formula

and mixtures thereof, wherein R1 represents an aliphatic radical of from 7 to 20 carbon atoms, each of R2 and R3 independently represents a lower alkyl group of from 1 to 4 carbon atoms, and R4 represents a divalent lower alkyl radical of from 1 to 4 carbon atoms

42. A composition as claimed in any one of Claims 1 to 41, wherein the fabric softening agent is finely divided and water-insoluble.

43. A laundry detergent-softener composition for cleaning and softening soiled fabrics in the wash cycle of a washing operation using wash water at an elevated temperature of at least 60 C up to the boiling point of the washer water, the composition comprising (a) from 1 to 20 parts by weight of a non-ionic surface active agent; (b) from 2 to 20 parts by weight of a water-insoluble cationic quaternary ammonium compound fabric softener; (c) from 0.5 to 10 parts by weight of a fabric substantivity increasing polyfunctional additive selected from (i) diquaternary ammonium compounds, (ii) polymers of dimethyldiallyl ammonium chloride, (iii) cationic guar gum, and (iv) poly(methylvinylether/maleic acid and (v) diimidazolinium compounds;; (d) up to 10 parts by weight of an amphoteric surfactant, with the proviso that the non-ionic surface-active agent (a) alone or the combination of the non-ionic surface-active agents (a) and the amphoteric surfactants (d) results in the composition, when added to the wash water at a concentration of 1 % by weight, having a cloud point above the elevated temperature of the wash water.

44. A detergent composition for washing and softening soiled fabrics in an aqueous wash liquid at an elevated temperature in the range of 60 to 100 C, the composition comprising (a) from 0.1 to 20% of at least one water-soluble non-ionic surface active compound of formula I or II RO(CH2CH20)nH (I)

where R represents a primary or secondary alkyl chain of from 8 to 22 carbon atoms, R1 represents a primary or secondary alkyl chain of from 7 to 12 carbon atoms, and n and m are each, on the average, a number of from 3 to 30; (b) from 2 to 20% of at least one water-insoluble cationic quaternary ammonium compound of formula Ill or IV;;

wherein each of R1, R2, R5 and R6 independently represents a C15 to C22 long chain aliphatic radical, each of R3, R4 and R7 independently represents a lower alkyl radical, or R6 represents a group

aliphatic radical of from IS to 22 carbon atoms, and R9 represents a divalent alkyl radical of from 1 to 3 carbon atoms, and X represents a salt-forming anion; (c) from 0.5 to 10% of a polyfunctional additive selected from diquaternary ammonium compounds of the formula

wherein R8 represents a straight or branched, saturated or unsaturated aliphatic hydrocarbon group of from 12to 22 carbon atoms; R9 represents a divalent alkyl group of from 2 to 4 carbon atoms;; each of the groups R'O, R'1 and R12 independently represents a lower alkyl group of 1 to 4 carbon atoms; and X represents a salt forming anion; and polymers of dimethyldiallyl ammonium chloride; (d) at least one amphoteric surfactant in an amount offrom 0.1 to 10%, such that the composition has a cloud point above the elevated temperature; and (e) balance, detergent builders, detergent adjuvants, inerts and water.

45. A method of cleaning and softening soiled fabrics in an aqueous wash water at a temperature of at least about 60"C which comprises washing the fabrics in an aqueous solution of a composition as claimed in any one of Claims 1 to 44, the aqueous solution being heated to a temperature of at least 600C.

46. A method as claimed in Claim 45 wherein the wash water temperature is about 100C and wherein the non-ionic surfactant is a Cs-Cs alkyl phenol condensed with from 25 to 30 moles ethylene oxide.

47. A detergent composition substantially as herein described with reference to any one of the Examples.

48. A method of cleaning and softening soiled fabrics comprising washing the fabrics in an aqueous solution of a composition substantially as herein described with reference to any one of the Examples.