GB2163770A - Hot water wash cycle detergent-softener compositions - Google Patents

Abstract

Softening performance of water-insoluble cationic quaternary ammonium compound fabric softeners, such as dimethyl distearyl ammonium chloride, is improved in a surfactant system based on a nonionic detergent having a cloud point below the wash water temperature and an amphoteric surfactant in an amount sufficient to raise the cloud point to above the wash water temperature, especially elevated washing temperatures of from about 60 DEG C to about 100 DEG C (boiling 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 water insoluble cationic quaternary ammonium compound softening agent and a nonionic surfactant having a cloud point below the washing temperature and an amphoteric surfactant to raise the cloud point of the composition to above the wash temperature.

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 nonionic surfactants, higher levels of brightener compounds, carboxymethylcellulose, anti-yellowing compounds, blueing 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 softening agents, including the quaternary ammonium compound softenings agents, and nonionic surface-active compounds. 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, 3,951,879, 3,360,470, 3,351,483, and 3,644,203. In addition, U.S. Patents 3,537,993, 3,583,912, 3,983,079, 4,203,872, and 4,264,479, specifically discloses combinations of nonionic surface-active agent, cationic fabric softener and another ionic surfactant or modifier, such as two zwitterionic surfactants, amphoteric surfactants, and the like.

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 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 Europe 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 inventors have discovered 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 nonionic detergents characterised by having cloud points above the washing temperature. Furthermore, this enhancement of the softening performance is achieved without any, or at least without any significant, deterioration in washing (i.e. cleaning) performance. This discovery forms the basis of applicants' copending application No. 8521761, filed today, entitled WASH CYCLE DETERGENT SOFTENER COMPOSITION.

The present inventors have also discovered that the cloud point of nonionic surfactants having cloud point temperatures of less than 60"C can be raised to above 60"C by incorporating in the detergent composition an amphoteric surfactant. It has also been discovered that the mixed nonionic/amphoteric surfactant mixtures are compatible with water insoluble cationic quaternary ammonium compound fabric softeners, such as dimethyl distearyl ammonium chloride (DMDSAC) and enhance the softening performance of the cationic fabric softeners to the same extent as do the high cloud point nonionic detergents which by themselves have cloud points above the washing temperature.It has also now been discovered that the mixed nonionic/amphoteric surfactant system, even in the presence of a cationic fabric softener, act synergistically to provide unexpectedly better cleaning performance than the same or greater amounts of either of the two surfactants used in the absence of the other.

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 laundery 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 point temperature.Performance is improved further where the temperature of the aqueous laundry solution is within about 15"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 iost.

However, while it is stated by Murphy that the nonionic/cationic 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 nonionic surfactants 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 using a mixed nonionic/amphoteric surfactant system which has a cloud point above the washing temperature.

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 effective overall cleaning performance.

The present invention also aims to boost both softening performance and cleaning performance of a detergent-softener composition containing a water-insoluble cationic fabric softener compound and nonionic surfactants having a cloud point temperature of below 60"C, when used to wash soiled fabrics in water at a temperature of at least 60"C.

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 100"C, includes a nonionic surface active agent having a cloud point below the elevated temperature, a water insoluble cationic quaternary ammonium compound fabric softener and an amphoteric surfactant in an amount sufficient to raise the cloud point of the composition to a temperature higher than the elevated temperature. In the preferred embodiment the detergent composition will include at least one additional detergent additive selected from detergent builders, thickeners, anti-redeposition agents, corrosion inhibitors, bleaches, enzymes, dyes, blueing agents, optical brighteners, perfumes, and the like.

The nonionics which are contemplated have to have appropriate water solubility and a cloud point temperature as specified above.

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 12 to 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 3 moles of alkylene oxide per mole of hydrophobe up to about 14 moles of alkylene oxide per mole of hydrophobe will provide the required water solubility, cleaning performance and cloud point temperatures of less than about 60"C.

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 3 to 14, preferably 4 to 12, espcially 6 to 11; or

wherein R' represents a primary or secondary alkyl chain of from 4 to 12 carbon atoms, and m is an average of 3 to 14, preferably 4 to 12, especially 6 to 11.

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 C8 to C12, with C8 and Cg, e.g. octyl, isooctyl and nonyl being especially preferred.

Typical examples of a nonionic compound of formula (I) are lauryl alcohol condensed with 5 or 7 or 11 moles ethylene oxides. Typical examples of a nonionic compound of formula II are isooctyl phenol or nonyl phenol condensed with 3 to 8 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 acids 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.

The amount of the nonionic in the composition will generally be the minimum amount which when added to the wash water with the amphoteric surfactant will provide adequate cleaning performance. Generally, amounts ranging from about 0.5 to about 20%, preferably from about 1 to about 15%, and especially preferably from about 1 to 10% by weight of the composition, can be used.

The compositions of the present invention are primarily intended for use in connection with those home and commercial laundry washing machines which operate at elevated washing temperatures, especially at water temperatures in excess of about 60"C (140"F), preferably in excess of 80"C (176"F), and especially preferably at-the-boil, i.e. at 1000C (212"F) or more.

Naturally, however, these compositions, while being particularly effective when used at these elevated washing temperatures, can also exert their improved softening performance at lower temperatures below 60"C down to about 20"C or lower.

When the compositions are formulated for use at wash temperatures over a broad range of say, for example, 20"C to 60"C, as well as higher temperatures in order to be most useful for a broad range of fabrics including delicate natural and synthetic fibres, as well as more temperature insensitive fabrics such as cottons, etc., the nonionic amphoteric combination and ratio can be selected to provide a cloud point temperature which exceeds the wash water temperature by at least about 20"C, for example, a cloud point temperature of the composition in the range of 80" to 90"C. Where, however, the formulation is designed for the principal intended use at elevated washing temperatures of 60"C or more, such as is generally the case in Europe, as well as when using industrial washing machines, then the composition will have substantially higher cloud points, for example, up to about 50"C above the washing temperature. Thus, for a washing temperature of 60"C, the nonionic/amphoteric should have a cloud point of at least about 65"C, preferably at least about 70"C and up to about 90"C, preferably in the range of the from about 70"C to 850C. For wash water temperatures of 100"C, the composition cloud point is chosen in the range of from about 105"C to about 1500C, preferably 105"C to 1200C.

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, under the following 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 C/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, sulphates, 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 formulations is very difficult to measure since the mixtures are natually 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 nonionic surfactants described above, but which are ethoxylated with at least 15 moles ethylene oxide, generally 15 to 30 moles ethylene oxide, will provide cloud points in excess of the washing temperature, and can provide enhanced softening performance without the amphoteric surfactant.

However, for higher washing temperatures of 71"C to 100"C, especially 80" to 100"C, only the more highly ethoxylated surfactants, for example 25 to 30 moles ethylene oxide per mole of hydrophobe, for example, the C8-Cg alkyl phenols ethoxylated with from 25 to 30 moles, especially from 28 to 30 moles, and especially preferably about 30 moles, ethylene oxide, have sufficiently high cloud points to provide improved softening without the amphoteric.

While detergent compositions based on the high cloud point nonionic surfactants can provide improved softening as disclosed in the aforementioned copending application No. 85217161 these compositions often suffer from a mild deterioration of cleaning performance. In addition, the highly ethoxylated nonionics are more expensive and less readily commercially available than the low cloud point temperature nonionics used in the present invention.

These drawbacks of our other discovery are avoided in the present invention since the addition of the amphoteric surfactant permits the use of the less expensive and readily commercially available nonioncs characterised by cloud points of below 60"C, and by hydrophilicliphophilic balances (HLB) of from about 5 to about 17; requires substantially lower amounts of total surfactants to achieve equivalent or superior cleaning performance; and raises the cloud point of the composition to above the selected washing temperature to boost the softening performance of the cationic fabric softener.

It has 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 1 to 20%, preferably 1 to 15%, especially preferably from about 1 to 10%, 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 at an elevated temperature in the range of from about 80"C to 100"C, the detergent composition includes in addition to the nonionic surfactant of formula I or formula II and the water insoluble cationic quaternary ammonium compound fabric softener of formula (XIV) or formula (XV) (set out below) an amphoteric surfactant in an amount sufficient to raise the cloud point of the composition to above the elevated temperature of 80"C to 100"C, especially preferably above about 105"C.

While not wishing to be bound by any particular theory of operation, it is hypothesized that the amphoteric and nonionic surfactants form mixed micelles which are, more soluble than micelles formed from the nonionics alone. It is postulated that these mixed micelles provide greater resistance to forming sufficiently large aggregates to come out of solution, thereby increasing the cloud point temperature.

Substantially any of the known amphoteric surfactants can be used to raise the cloud point of the nonionic surfactant cationic fabric softener composition.

Examples of suitable amphoteric detergents are those containing both an anionic and a cationic group in addition to a hydrophobic organic group, which is advantageously a higher aliphatic radical, e.g. about 10-20 carbon atoms. Among these are the N-long chain alkyl amino carboxylic acids (e.g. of the formula RR2NR'COOM);N-long chain alkyl imino di-carboxylic acids (e.g. of the formula RN(R'COOM)2) and the N-long chain alkyl betaines (e.g. of the formula RR2R4N±R'- COO-) where R represents a long chain alkyl group, e.g. of about 10-20 carbons, R' represents a divalent radical joining the amino and carboxylic portions of an amino acid (e.g. an alkylene radical of 1-4 carbon atoms), M represents a hydrogen atom or a salt forming metal, R2 represents a hydrogen atom or another monovalent substituent (e.g. methyl or other lower alkyl), and R3 and R4 represent monovalent substituents joined to the nitrogen atom by carbon-tonitrogen bonds (e.g. methyl or other lower alkyl substituents).Example of specific amphoteric detergents are N-alkyl-beta amino propionic acids; N-alkyl-beta-imino dipropionic acids and Nalkyl, N,N-dimethyl glycine; the alkyl group may be for example that derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol (or a lauryl-myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl or blends of such alcohols. The substituted amino propionic and imino dipropionic acids are often supplied in the sodium or other salt forms which may likewise be used in the practice of the present invention.Examples of other amphoteric detergents are the fatty imidazolines such as those made by reacting a long chain fatty acid (e.g. of 10-20 carbon atoms) with di-ethylene triamine and monohalo carboxylic acids having 2-6 carbon atoms, e.g. 1-coco-5hydroxyethyl-5-carboxyethyi imidazoline; betaines containing a sulphonic group instead of a carboxylic group; betaines in which the long chain substituent is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of 2-trimethylamino fatty acids such as 2trimethylaminolauric acid, and compounds of any of the previously mentioned types in which the nitrogen atom is replaced by phosphorous.

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 lauryl, tridecyl, tetradecyl, pentadecyl, palmityl, heptadecyl, stearyl, tallow, coco, soya, oleyl, or linoleyl group), R' 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 (VI to XII).

(1) Betaine detergents having the formula

A suitable example is

(1) 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 Ci-C4 alkyl group, preferably methylene or ethylene, especially prefera bly 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 R1 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 (XI) i.e. the alkyliminopropionate and ether bridged alkyliminopropionate 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 combination 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 1 to 20%, preferably from about 1 to about 15%, especially from about 1 to about 10%, based on the total weight of the composition. Suitable ratios of nonionic: amphoteric within the above-mentioned amounts are in the range of from about 1:5 to 10:1, preferably 1:3 to 6:1, especially 1:2 to 4:1.

However, some general guidelines and rules with respect to the factors effecting cloud point, such as longer alkyl chain groups in the amphoteric will generally lower the cloud point of the composition, have been described above. Accordingly, it can be appreciated that within the above general ranges, the amount and nature of the amphoteric may vary widely, depending on the specific nature and intended operating temperature of the formulation, as well as on the nature and amounts of the other ingredients, especially the nonionic surfactant and electrolytes.

Typical examples to show the cloud point raising effect of the amphoteric can be seen from the experimental data, (set out in the following Table 1), which is obtained by measuring cloud point temperature ("C) by the method described above for solutions of 1 % of actives in either distilled water or in a saline solution (10% NaCI): TABLE 1 Cloud Point Distilled Surfactant (weight ratio) H90 10% NaCl A. C12-C15 alkyl alcohol EO 7:1 43+2 25 A. + Rexoteric OASF (1:2) 75+2 50+2 A. + Rexoteric OASF (4:1) 58+2 28+2 A. + Rexoteric CSF (4:1) 55+2 42+2 B.C12-C15 alkyl alcohol EO 11:1 85+2 59+2 B. + Rexoteric OASF (1:2) 100 85+2 B. + Rexoteric OASF (4:1) 95+2 70+2 B. + Rexoteric CSF (4:1) 100 80+2 Isooctyl phenol EO 30:1 100 Nonyl phenol EO 20:1 100 72 Nonyl phenol EO 15:1 91 Table 1 also shows for comparison the cloud point values of some more highly ethoxylated alkyl phenol nonionic surfactants.

An essential ingredient of the detergent softener 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 textile to the hand or body and is of aesthetic and commercial importance. Generally, the cationic fabric softeners consist of at least one hydrophilic functional 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 R' and R2 and R5 and R8 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 R5 may be the group

wherein R8 represents a long chain aliphatic radical having frpm 16 to 22 carbon atoms, and R8 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, or a dihigheralkyl imidazolinium chloride.Specific examples of quaternary ammonium softening agents of formula (III) above suitable for use in the compositions of the present invention include the following: hydrigenated 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-diheptadecyl imidazolinium chloride (bromide or methosulphate), 1 ,2-dieicosylalkylaminidoe- thyl-1-methyl imidazolinium chloride (bromide or methosulphate), 2-hexadecyl-1-methyl-1[(2-dode- coyl amideo)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 1 to about 20%, preferably from about 4 to about 16%, and especially preferably from about 6 to 9%, by weight of the composition.

The weight ratio of the nonionic surface active agent to the cationic fabric softener can be within the range of from 1:10 to 5:1, preferably from about 1:8 to 4.5:1.

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, phophates, 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 diorthophophate, 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 Na2O/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-insolubie 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). (Al20,)y.(SiO2)z.WH2O wherein x is 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 milliequivalents 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 building salts which can be used along 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 polycarboxylates are also suitable.

Other suitable builders of the organic type include carboxylmethylsuccinates, tartronates and glycollates. Of specical 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; 4,204,852; 4,224,420; 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. tetrachlorosalicylanilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives, ultraviolet absorbers; anti-yellowing agents, such as sodium carboxymethyl cellulose, complex of C12 to C22 alkyl alcohol with C,2 to Cl8 alkylsulphate; 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: nonionic detergent-about 0.5% to about 20%, preferably about 1% to about 15%, especially 1% to 10%; amphoteric surfactant-about 2 to 20%, preferably 1 to 15%, and especially from 1 to 10%; quaternary ammonium salt-about 1% to about 20%, preferably about 4% to about 16%, especially preferably about 6 to 9%; alkyli metal builder salts-about 20% to about 85% and preferably about 35% to about 80%, and especially preferably about 60 to 75%, the balance being detergent additives, fillers and moisture.Suitable ranges-of the detergent additives are: enzymes to 2%, especially 0.7 to 1.3%; corrosion inhibitors-about 0 to 40%, and preferably 5 to 30%; anti-foam agents and suds-suppressors-0 to 15%, preferably 0 to 5%, for example 0.1 to 3%; soil suspending or anti-redeposition agents and anti-yellowing agents-0 to 10%, preferably 0.5 to 5%; colourants, perfumes, brighteners and bluing agents total weight 0% to about 2% and preferably 0% to about 1%; pH modifiers and pH buffers 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 nonionics and amphoterics are preferably the sole surface-active detergent compounds used in the compositions of this invention, small amounts of other surface-active compounds, including other nonionics, 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 other nonionics include all those mentioned above but which have, for example, more than 15 moles alkylene oxide per mole of hydrophobe, for example 15 to 30 moles ethylene oxide per mole of hydrophobe.

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 alkylincludes the alkyl portion of the higher acyl radical.) 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 napthalene 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 or 7) 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 detegents may be prepared in a known manner by the reaction of sulphur trioxide (SO2) 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 Rl 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 sulphates 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 alphasulphofatty acid ester containing about 10 to 20 carbon atoms in the acyl group, e.g. methyl alphasulphomyristate and methyl-alpha-sulpho-tallowate, ammonium sulphates of mono- or diglycerides of higher (C10-Cl8) 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-Cl8) alcohol; sodium higher alkyl (ClO-C,8) glyceryl ether sulphonates; and sodium or potassium alkyl phenol polyethenoxy ether sulphates with 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 potasium stearoyl methyl taurate.

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

It has further been discovered that the nonionic/amphoteric surfactant mixture has unexpectedly improved cleaning performance as compared to an equal weight of the same nonionc alone or as compared to the corresponding nonionic ethoxylated with sufficient ethylene oxide to yield the same cloud point. For example, using carboxyethylated higher fatty alkyl imidazoline as the amphoteric about 50 to 90% of the nonionic can be replaced with only about 10 to 40% of the amphteric to achieve the same or superior softening (depending on washing temperature) and the same or superior cleaning performance.

Since the amphoteric can act synergistically with the nonionic with respect to cleaning performance the total amount of nonionic and amphoteric in the detergent formula can be greatly reduced, for example, to 3 to 20%, especially to 5 to 10% of the composition. The ratio of nonionic to amphoteric is not particularly critical but for a given weight of nonionic the cloud point will increase as the amount of the amphoteric increases. Generally, ratios of nonionic to amphoteric of from about 1:5 to 10:1, preferably 1:3 to 6:1, especially preferably 1:2 to 4:1, will provide improved cleaning performance, as well as softening performance (where necessary to increase the cloud point of the nonionic to above the washing temperature).Furthermore, within the above amounts and ratios, the mixed nonionic/amphoteric surfactant mixture will be fully compatible with the cationic quaternary ammonium softening compound.

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, anhydrous, 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 waters may be usefully employed. The water temperature can be from 20"C to 100"C and is preferably from 60 to 100"C in those cases where the textiles 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 40"C, 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 amphoteric is not used to raise the cloud point to above 60"C. 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.

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: EXAMPLE 1 to 16 These are concerned with the production of a powdery detergent softener composition in accordance with the invention.

Compositions were made up having the components and proportions set out in Table 2 below.

TABLE 2 Example 1 2 3 4 Ingredients Proportions (a) Nonionic C12-C15 fatty alcohol EO 11:1 2.0 8.0 - C12-C15 fatty alcohol EO 30:1 15.0 Nonyl phenol EO 20:1 15.0 (b) Softener Dimethyl distearylammonium 8.0 8.0 8.0 8.0 chloride (938 AI) (c) Amphoteric Rexoteric OASF 45 (45% A.I.) 8.9 - 8.9 8.9 Builder Sodium metasilicate 8.0 8.0 8.0 8.0 Sodium tripolyphosphate 28.0 28.0 28.0 28.0 Sodium pyrophosphate 10 H20 24.0 24.0 24.0 24.0 Sodium orthophosphate 0.5 0.5 0.5 0.5 Nitrilotriacetate (NTA), 8.0 8.0 8.0 8.0 Na salt minors and miscellaneous Balance (e.g. perfume, optical brighteners, moisture) (a):(b) 1:4 (a):(c) 1::4.45 Soiled fabrics are washed at 60"C in about 20 litres of water containing 7 grains hardness ions per gallon (US) using about 100 grams of the composition given in Table 2.

The washed fabrics are evaluated for softness by a panel of 4 expert judges on multiple replicates after cumulative washing. For comparison, the identical composition is prepared except that the Rexoteric OASF is not used and the amount of C12-C18 fatty alcohol EO 11;1 is increased to 8% (Example 2-a comparative example), or about 15% of Cl2-Cl5 fatty alcohol EO 30:1 (Example 3-a reference example) or 15% of nonyl phenol EO 20:1 (Example 4-a reference example) is used in place of the nonionic and amphoteric used in Example 1, and each of these compositions are evaluated in the same way as the composition of Example 1.Each of the compositions are graded on a scale of 1 to 10 with "10" being the highest grading and representing the same detergent composition (without cationic softener) and a rinse cycle added softener (dimethyldistearyl ammonium chloride). On this scale the composition of Examples 1, 3 and 4 achieved a rating of 5-6 and equal cleaning performance. The composition of Example 2 received a rating of only 2-3.

When in the composition of Example 1, the Cl2-Cl5 fatty alcohol EO 11:1 is replaced by an equal amount of nonyl phenol EO 4:1 (Example 5) or nonyl phenol EO 8:1 (Example 6) or, Cl2-Cl5 fatty alcohol 7:1 (Example 7) or Cl4-Cl6 fatty alcohol EO 5:1 (Example 8), a rating of 5-6 is also achieved.

Similarly good results are obtained by replacing dimethyl distearly ammonium chloride in the composition of Example 1 with dimethyl hydrogenated ditallow ammonium chloride (Example 9), diethyl disoya ammonium chloride (Example 10), dimethyl stearyl cetyl ammonium chloride (Example 11) or 2-hexadecyl- 1-methyl- 1 [(2-dodecoyl amido)ethyl] imidazolinium methylsulphonate (Example 12), and the corresponding bromide, sulphate, and hydroxide salts, thereof.

Similarly good results are obtained by replacing Rexoteric OASF in the composition of Example 1 with Rexoteric CSF (Example 13), Miranol DM (Example 14),

(Example 15)

(Example 16) It is a particular advantage of the detergent-softener compositions of the present invention that since they can provide better cleaning performance with lower total amounts of surfactants more highly concentrated formulations can be prepared and packaged for use by the consumer.

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 oversprayed 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 (Na20:SiO2=1:2.4) and 21 parts of deionized water. The slurry is brought to a temperature of about 60"C and is mixed well in a crutcher to 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 315"C.

The spray dried base beads produced are of internal structure and outer surface characteristics like those of the bead shown in Figs. 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 a 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 flow-ability 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 (21)

1. A composition of matter useful in formulating laundry detergent compositions comprising a blend of (A) a water soluble nonionic surfactant and (B) an amphoteric surfactant in an amount sufficient to raise the cloud point of the blend of (A) and (B) at 1% by weight concentration in distilled water or at 1% concentration in water containing 10% by weight sodium chloride or in both cases to a value of at least 5"C above, the cloud point of the nonionic surfactant at 1% by weight concentration in distilled water and at 1% concentration in water-containing 10% by weight sodium chloride respectively, the weight ratio of (A) to (B) being in the range 1:5 to 10:1.

2. A composition as claimed in Claim 1 in which the ratio of (A) to (B) is in the range 1:3 to 6:1.

3. A composition as claimed in Claim 1 or Claim 2 in which the ratio of (A) to (B) is in the range 1:2 to 4:1.

4. A composition as claimed in Claim 1, 2 or 3 in which the cloud point of the blend at 1% concentration in distilled water is at least 53"C.

5. A composition as claimed in any one of Claims 1 to 4 in which the cloud point of the blend at 1% concentation in distilled water is at least 60"C.

6. A composition as claimed in any one of Claims 1 to 5 in which the nonionic surface active agent is a compound of the formulae I or II or a mixture thereof, RO(CH2CH2O)nH (1)

wherein R represents a primary or secondary, straight or branched alkyl group of 8 to 22 carbon atoms, R' represents a primary or secondary alkyl group of 7 to 12 carbon atoms, and each of n and m are numbers having a value of from 4 to 14.

7. A composition as claimed in any one of Claims 1 to 6 in which the amphoteric surfactant is selected from the group consisting of (1) Betaine detergents having the formula

(2) Aikyl 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) Carboxyethylate higher fatty alkyl imidazoline based amphoteric detergents having the formula

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

8. A composition as claimed in Claim 1 substantially as specifically described herein with reference to any one of Examples 1, 5, 6, 7, 8, 13, 14, 15 or 16.

9. A laundry detergent composition characterised by the presence of a composition as claimed in any one of Claims 1 to 8.

10. A laundry detergent composition capable of washing and softening soiled fabrics in an aqueous wash liquid at an elevated temperature of at least 60"C, the said composition comprising (a) a water-soluble nonionic surface-active agent having a cloud point below the elevated temperature; (b) a water-insoluble cationic quaternary ammonium compound fabric softening agent, and being selected from the group consisting of the compounds of formulae XIV and XV::

wherein R' and R2 and R8 and R8 each represent, independently, long chain aliphatic radicals of 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 of 16 to 22 carbon atoms, and R9 represents a divalent alkyl radical of 1 to 3 carbon atoms, and X represents a salt-forming anion; and (c) an amphoteric surfactant in an amount sufficient to raise the cloud point of the composition to a temperature higher than the elevated temperature.

11. A composition as claimed in Claim 10 in which the nonionic surface-active agent (a) is a compound of the formulae I or II or a mixture thereof, RO(CH2CH2O)0H (1)

wherein R represents a primary or secondary, straight or branched alkyl group of 8 to 22 carbon atoms, R' represents a primary or secondary alkyl group of 7 to 12 carbon atoms, and each of n and m are numbers having a value of from 4 to 14.

12. A composition as claimed in Claim 10 or Claim 11 in which the amphoteric surfactant is selected from the group consisting of (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) Cocimidazoline based amphoteric detergents having the formula

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

and mixtures thereof, wherein Rl represents an aliphatic radical of from 7 to 20 carbon atoms, R2 and R3 each represent a lower alkyl group of 1 to 4 carbon atoms, and R4 represents a diavelent lower alkyl radical of 1 to 4 carbon atoms.

13. A composition as claimed in Claim 10, 11 or 12 which comprises, on a weight basis of active ingredients based on the total weight of the composition about 0.5 to about 20% of the nonionic detergent, component (a), about 1 to about 20% of the softening agent, component (b), about 1 to about 20% of the amphoteric, component (c), and balance detergent adjuvants, fillers and moisture.

14. A composition as claimed in Claim 13 in which the ratio of components (a):(b) is from 1:10 to 5:1.

15. A composition as claimed in Claim 13 or Claim 14 in which the ratio of components (a):(c) is from 1:5 to 10:1.

16. A composition as claimed in any one of Claims 10 to 15 which further comprises at least one detergent additive selected from the group consisting of inorganic detergent builder salts, organic detergent builder salts, soil suspending agents, anti-redeposition agents, fatty amides, suds-suppressor agents, anti-foaming agents, optical brighteners, dyes, pigments, bluing agents, anti-yellowing agents, enzymes, corrosion inhibitors, pH modifiers, pH buffers, bactericides, fungicides, preservatives, bleaching agents, bleach stabilizers, bleach activators, perfumes, and water.

17. A composition as claimed in any one of Claims 10 to 1.6 which comprises, on an active weight basis, (a) from about 0.5 to about 20% of the nonionic surface-active agent; (b) from about 1 to about 20% of the cationic softening agent; (c) from about 1 to about 20% of the amphoteric surfactant; (d) from about 20 to about 85% of detergent builder salts; (e) O to about 40% of corrosion inhibitors; (f) O to about 40% of bleaching agents and activators; (g) O to about 10% of soil suspending or anti-redeposition agents; (h) O to about 10% of anti-yellowing agents; (i) O to about 2% of each of optical brighteners, colourants, bluing agents, bactericides, fungicides, and enzymes; (j) O to about 15% of anti-foam agents or suds-suppressors; (k) O to about 5% of each of pH modifiers and pH buffers; and (I) balance water.

18. A composition as claimed in any one of Claims 10 to 17 which comprises about 1 to 10% of component (a), about 6 to 9% of component (b), about 1 to 10% of component (c), and (d) balance, detergent adjuvants, fillers and moisture, wherein the ratio of components (a):(b) is from 1:8 to 4.5:1 and the ratio of components (a):(c) is from 1:2 to 4:1.

19. A composition as claimed in Claim 10 substantially as specifically described herein with reference to any one of Examples 1 or 5 to 16.

20. A method for 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 9 to 19.

21. A method as claimed in Claim 20 in which the wash water temperature is about 100"C.