PT94418A - PROCESS FOR THE PREPARATION OF A CATIONIC TENSION-ACTIVE COMPOSITION FOR FIBER CONDITIONING CONSTITUTED BY COMPOUNDS CONTAINING LONG CHAIN HYDROCARBON GROUPS - Google Patents

Description

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The present invention relates to a process for the preparation of compositions for fiber conditioning. More particularly, the process is to include in said compositions a cationic surfactant for fiber conditioning and a substantially water-insoluble compound which is dispersible in water and has in its formula an exceptionally long chain hydrocarbyl group of at least one preferably at least 25 carbon atoms and which is preferably n-alkyl or alkylene. The combination of such a compound and the cationic surfactant for fiber conditioning enhances the deposition, on aqueous substrates, of fibrous substrates of at least one of those materials, thereby producing a better conditioning of such fibers. In addition to the manufacturing process of these effective fiber conditioning compositions, the invention further relates to methods for applying such compositions in the form of conditioning lotions and " sham-poos " for human hair, laundry detergents for use in the washing cycle and fabric rinse cycle, and laundry detergents which are useful for washing the laundry and at the same time softening it.

Cationic surfactants (cationic surfactants) have been used in aqueous compositions for treatment of fibrous materials namely human hair and articles of clothing. In hair care compositions, in particular lotions and 'shampoos', the cationic surfactants adhere to the hair, even from diluted aqueous media, and help to make it easier to comb and less susceptible of accumulating electro- static. With regard to the laundry, the cationic surfactants improve the softness of the fabrics and reduce the unpleasant electro-static loads of the fabrics, especially the synthetic ones, which result from the drying of the washed laundry in an automatic laundry dryer. -4-

Hydrocarbons, particularly paraffin waxes, petrolatum, petroleum jelly and mineral oil, have been used in hair care preparations that lubricate, shape and brighten hair. Both cationic surfactants and hydrocarbons have been applied to fibrous materials from aqueous media and, in some cases, they have been simultaneously applied with other components of the composition. However, prior to the present invention, their compositions were neither made nor applied to fibrous materials for the purposes of the applicants, and were not recognized as having a better conditioning action due to the presence of the cationic surfactant and the dispersible compound in water (CDA) in those compositions.

According to the present invention a fiber conditioning composition contains a cationic surfactant for fiber conditioning and a water dispersible compound which contains in its formula a long chain hydrocarbyl group having at least 25 carbon atoms (CDA) wherein the ratio of cationic fiber conditioning surfactant to long chain hydrocarbyl containing compound is in the range of 1:20 to 20: 1 in which ratio the presence of both of those materials in the composition improves depositing at least one of them on a fibrous substrate to be conditioned by applying thereto an aqueous medium containing that composition. Among such compositions are "shampoos" and conditioning lotions for human hair, fabric softening detergents in the wash and rinse cycle, and laundry detergents for softening and washing.

In some applications, the water-dispersible compound which contains in its formula a long-chain hydrocarbyl group having at least 25 carbon atoms (CDA) acts as a promoter for the deposition of the cationic surfactant on the fibrous substrate, from relatively dilute aqueous media; in other cases the reverse mechanism is observed, wherein the cationic surfactant promotes the deposition and adhesion of the CDA and, in other times, each promotes the deposition and adherence of the other.

The final results, however, are a better conditioning of the fibrous material to be treated. The invention also encompasses processes for the manufacture of the described compositions, as well as processes as they are used to condition fibrous substrates.

Investigations made in the literature of the prior art have disclosed various patents which may be considered relevant to the present invention. Among these, the most important ones are: U.S. Patents 3,519,562; 3,630,949; 4,184,970; 4,360,437; 4,401,578; 4,426,299; 4,454,049; 4,704,272 and 4,818,523; British Patent Specification 1,601,360 and Japanese Patent 63 08319. U.S. Patent 3,519,562 discloses textile sewing lubricating compositions containing oxidized Pisher-Tropsch waxes, certain cationic quaternary ammonium salt emulsifiers and water. The oxidized Fisher-Tropseh waxes are different from the ASCs of the present invention and are applied differently in the textiles to be treated, and are applied to a different end. U.S. Patent 3,630,949 is directed to a static dispersant material that is depositable from an aerosol composition comprising a quaternary ammonium chloride and 12-hydroxy stearic acid.

The compositions of the patent are not in aqueous media and the hydroxy stearic acid does not contain the required long chain alkyl group of the ASCs of the applicants. 6-

U.S. Patent 4,184,970 discloses an agglomerate of quaternary ammonium compound granules intimately mixed with organic dispersion inhibitors and water, wherein the dispersion inhibitor may be a paraffin wax. Although it is indicated that octacosane can be used as a dispersion inhibitor, the patent compositions are in the form of particles, as opposed to the applicant's liquid compositions, which are mainly aqueous, the function of the dispersion inhibitor may not be possible in the compositions of the applicants and certainly it can not be granulated with the quaternary ammonium compound in the liquid compositions of the applicants. U.S. Patent 4,360,437 relates to textile treatment compositions for use in the rinse cycles of the laundry operation, and such compositions include a cationic fabric softener, a long chain hydrocarbon and mono chain amines specific compounds or compounds derived from the amine. Among the suitable hydrocarbons referred to in the patent are several that are ineffective for the purpose of the applicants and the specifically mentioned paraffins are all of shorter alkyl chains than those of the applicants. U.S. Patent 4,401,578 discloses concentrated fabric softening compositions containing a cationic fabric softener and a viscosity control agent. The viscosity control agent may be a paraffinic material, but those described are all shorter than that required for the efficacy effects of the present invention. U.S. Patent 4,426,299 includes the same disclosure of U.S. Patent 4,401,578. U.S. Patent 4,454,049 relates to textile treatment compositions in the drain cycle for fabric softening and static electricity control. Such compositions include cationic fabric softening agent,

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or water insoluble nonionic elongation, which may be a C q hidro hidro hydrocarbon and an organic solvent, the total of these materials being at least 50% of the product. Although the patent refers to the use of straight or branched C q hidro hidro hydrocarbons it will be appreciated from the rest of the disclosure that those materials with 25 or more carbon atoms in the alkyl chain are not disclosed.

In fact, the patent indicates the advantageous use (for the purpose of the patent) of much shorter chain n-paraffins. The patent also relates to compositions containing substantial proportions of organic solvent, unlike the compositions of the applicants. U.S. Patent 4,704,272 describes "shampoos " which contain synthetic organic surfactant, water insoluble dispersed silicone, quaternary ammonium salt, and suspending agent, in particular xanthan gum. The present invention is different because its CDAs are not silicones and the presence of the silicone in the compositions of the invention is not required. U.S. Patent 4,818,523 discloses hair rinse conditioners, which may include hydrocarbons, namely petrolatum (apparently having a shorter chain length than C25) and mineral oil (which is branched chain), but such materials do not are effective in the present invention and do not result in the best fiber conditioning of the applicants. The disclosure of British Patent 1,601,360 relates to textile treatment compositions containing certain hydrocarbon materials in combination with specific cationic materials for laundry softening and greater ease of ironing and anti-crease effects. Hydrocarbons of 12 to 40 carbon atoms are referred to but are not indicated as being preferred and there is no

in memory of any textile treatment compositions containing the higher chain length CD's of applicants. Japanese Patent No. 63 08 379, according to Chemical Abstracts., 110: 121001, relates to a hair conditioner containing hydrophobic and agentgg cationic ten-sio-actives. The hydrophobic oils referred to include liquid paraffin, which does not satisfy the alkyl chain length requirement of the inventors' invention.

From the above summary of the most recent advances in the art of the art known to applicants, it is found that their invention is novel and not obvious, since there is no actual indication or suggestion in the prior art of employing their alkyl containing CDAs of the longer chain with cationic surfactant of fiber conditioning in aqueous media and there is no acknowledgment of the importance of its discovery of the reaction between such components in the deposition of a greater amount of fiber conditioning materials than would have been expected, even from relatively dilute aqueous media, in the fibers to be treated. The aspect of the process of the present invention is also novel and not self-evident and is important for obtaining the unexpectedly beneficial fiber conditioning actions. Similarly, the uses of the different types of fiber conditioning compositions described herein are also novel and not obvious, and result in unexpectedly beneficial conditioning effects. The cationic fiber conditioning surfactant used may be any t

a suitable one, which has fabric softening properties, hair conditioning and / or anti-static properties. First, those cationic materials which are most useful are those which will be referred to as quaternary ammonium salts, which are those containing at least one higher molecular weight group and one, two or three lower molecular weight groups in a total of four, all attached to a common nitrogen atom to form a cation, and wherein an anion for electrical equilibrium, namely halide, acetate or lower alkoxy sulfate ion, for example chloride, bromide or methosulphate, is present. The higher molecular weight substituent (s) on the nitrogen is / are preferably one or more higher alkyl groups containing 10 or 12 to 22, or 12 to 18 or 20 carbon atoms namely lauryl, cocoalkyl, myristyl , cetyl, stearyl, tallowalkyl, hydrogenated tallowalkyl or substituted higher alkyl, and the lower molecular weight substituents are preferably lower alkyl of 1 to 3 or 4 carbon atoms such as methyl or ethyl, or substituted lower alkyl . One or more of said lower molecular weight substituents may include an aryl moiety or may be substituted by aryl, namely benzyl, phenyl or another suitable substituent.

Preferred quaternary ammonium salts for textile treatment compositions, such as wash cycle additives, rinse cycle additives and softening detergents, include di-lower alkyl-ammonium di-lower alkyl halides, such as di- tallow alkyl dimethyl ammonium and di-tallow hydrogenated alkyl dimethyl ammonium (distearyl dimethyl ammonium chloride or DSDMAC). Although these same quaternary ammonium salts can be used in the hair treatment compositions, including rinsing lotions, conditioners, and shampoos, the preferred quaternary ammonium salts are the corresponding tri-lower alkylammonium monoalkyl halides , namely cetyltrimethylammonium chloride and bromide, lauryltrimethylammonium chloride and stearyltriethylammonium chloride.

However, it is also possible to use at least partially the corresponding mono-lower alkyl ammonium trialkyl halides, namely trilauryl monoethyl ammonium chloride or tricyclic mono methyl ammonium chloride. In addition to the aforementioned cationic compounds, other suitable cationic surfactants include the imidazolinium salts, namely 2-hepta-decyl-1-methyl-1 - [(2-stearoylamido) ethyl] imidazolinium chloride. The corresponding methyl sulfate compound, 2-methyl-1- (2-hydroxyethyl) -1-benzylimidazolinium chloride, 2-coco-1- (2-hydroxyethyl) -1-benzylimidazolinium chloride; 2-coco-1- (2-hydroxyethyl) -1-octadecenylimidazolinium chloride; 2-heptadecenyl-1- (2-hydroxyethyl) -1- (4-chlorobutyl) imidazolinium chloride; and 2-heptadecyl-1- (hydroxyethyl) -1-octadecyl imidazolinium ethyl sulfate. The imidazolinium salts will be readily and preferably halides (preferably chlorides) and lower alkylsulfates (alkosulfates d.

Other quaternary ammonium salts and imidazolinium salts having fabric softening, hair conditioning and anti-static properties may be used in the present invention and a number of other such compounds are described in U.S. Patent 4,000,077, herein incorporated by reference

Cationic fiber conditioning agents may be replaced in the present compositions at least partially by cationic surfactant complexes with cationic surfactants and organic acids, such as citric acid. 11-

Such complexes are described in U.S. patent application Ser. No. 06 / 916,067 and U.S. patent application Serial No. 07 / 189,560, both incorporated herein by reference. The water-dispersible compound (CDA) of the present compositions, which is hereby designated as readily identifiable, is a hydrocarbon, an organic acid, an ester, an amide, an amine, an amine salt, a quaternary ammonium compound or an alcohol , or any mixture thereof, but it is necessary that any of those compounds used in the present compositions, to be effective for the intended purpose, includes in its formula a hydrocarbyl chain of at least 25 carbon atoms.

Preferably, such a chain is a normal alkyl (or alkylene). The applicants' discovery is that when such a chain is present and has a length of at least 25 carbon atoms, it is preferably in the range of (or having on average) 25 to 50 carbon atoms, and times more preferably 25 or 27 to 39 carbon atoms, the fiber conditioning (conditioning) composition made therefrom and with the cationic surfactant, even in the dilution state and in the presence of detergent, satisfactorily condition fibrous materials , namely hair and clothing, making hair easier to pentean and handle, both when it is damp and when it is dry, and making the clothing softer and usually also anti-static. Although the rinse water and the wash water are diluted relative to the cationic surfactant and CDA, in these compositions and in these applications, said composition components deposit into the fibers to be treated in an amount sufficient for obtaining desirable, visible and beneficial effects of conditioning. Such results are surprising because said compounds

(I.e.

The present invention relates to a process for the preparation of fibers in an aqueous medium. The compositions of the present invention also provide improved fiber conditioning and interfere with such conditioning, as would be expected, and this desirable joint action and improved deposition of the components in the fibers is obtained in dilute aqueous media. Although a portion of the CDA and the cationic surfactant can remain in the wash water, at least a significant portion of them settle on the fibers (hair or clothing fibers) to condition them, without undesirable grease.

Among the various compounds of the C 25 -C 25 + type which are useful as CDAs in the practice of the present invention are pentacosane, heptacosane, nonacosane, melene, n-alkane, C ^ n-alkane, ciretic acid, cysteine, cysteine, psyllic acid, C26 n-alcohol, C2-6 alcohols, C-n-alcohols, C2-6 paraffins, C2-C3 petrolatums, myriac-palmitate, myriac-cer- tate, lace-ril-palmitate, myricil-hypogaete, ceryl-2-hydroxy palmitate mono and diamines and amine salts of said hydrocarbons, alcohols of said hydrocarbons and amides of said acids. As will be seen the various said CDAs include all at least one normal alkyl or alkylene group of 25 to 39 carbon atoms, a range which may be considered as more preferred. However, said compounds are listed as representative and not exclusive.

Also, although saturated compounds are preferred, as a rule, at least for stability reasons, the unsaturated materials are also useful.

The various CDAs can be used as pure compounds or in mixtures. They can be synthetic or can be obtained from natural materials. Some have been synthesized and may be used as CDAs in the present compositions, or may be mixed with other synthesized compounds of this type. Alternatively, such compounds may be obtained from natural materials and chemical refinery products, in particular oil refineries. Such materials and products can be processed to produce higher concentrations of more desirable CDAs or can be used directly. Among such sources of CDA which are components of the compositions of the present invention are petrolates, paraffin waxes, beeswax, various waxes from the group consisting of candelabra, wax from Japan, wax tree from the myriac family and wax-montane, and other natural waxes which include said amounts of compounds containing C 25-105 + normal alkyl or normal alkylene. Experimentation has shown that carnaribe wax does not produce the desired results, but microcrystalline waxes, which include secondary branched chains and primary alicyclic chains, in addition to the normal alkane chains, have been shown to be useful, which apparently indicates that some cyclization is branching in an alkyl chain does not seriously interfere with the fiber conditioning action of the compounds containing the C 1-5 alkylphenylalkyl and alkylene.

Accordingly, a branching similar to that of the microcrystalline waxes fits the n-alkane description of the CDA of this invention. Of course, as long as there is a normal C25 chain, branching and the presence of other groups will not lead to the compounds being outside the characteristics of the CDAs described in this invention.

In addition to the cationic surfactant and CDA components of the present composition, the only other component required in the hair conditioning lotion and in the laundry compositions to be used in the wash cycle and the rinse cycle is a V aqueous medium in which the cationic surfactant and CDA are emulsified or dispersed from another atom. When in the form of an emulsion with hydrotrope an emulsifying agent and / or another surfactant is preferably present, in order to have good stability and be highly effective in the conditioning of fibrous materials, the composition should be prepared in accordance with with a certain procedure, which will be described below. The aqueous medium may be water or an aqueous alcoholic medium and may also contain various standard adjuvants, as are used in compositions of the types described. The water used is preferably deionized water, although tap water is also satisfactory. The alcohol used, if any, will usually be denatured alcohol, in particular SD-40, and when present in the fiber conditioning compositions, will usually constitute 3 to 15% final composition, e.g., about 5 %. The synthetic organic detergent component of the present " sharapoo " and the detergent detergent compositions is a synthetic organic anionic detergent or a synthetic organic nonionic detergent, or a mixture thereof (and, of course, it is also possible to use mixtures of anionic detergents and mixtures of nonionic detergents).

Amphoteric, ampholytic, zwitterionic and even cationic detergents and surfactants (surfactants) may be present in the compositions of the invention in addition to the cationic surfactants for fiber conditioning. Various suitable detergents which may be used are listed in McCutcheon's Detergents and Smulsifiers, U.S.A., 1984, which is hereby incorporated by reference. 15-

Of these compounds, the preferred anionic detergents are of the sulfated and / or sulfone types, which may be termed " sulfated " attached ". Such detergents are water-soluble salts of a sulfophilic or sulfonic lipophilic acid. The lipophilic fraction of that acid will usually be from 8 to 30 carbon atoms and will preferably include an alkyl group, preferably a chain of 8 to 22 or 10 to 18 or 20 carbon atoms, more preferably 10 to 14 or 16 carbon atoms, e.g., about 12 carbon atoms. Among those anionic detergents may be mentioned, for example, the higher alkyl sulphates, the higher linear alkyl benzene sulphonates, the paraffin sulfonates, the olefin sulphonates, the monoglyceride sulphates and the higher fatty alcohol lower alkoxy sulphates . Such a higher fatty alcohol or higher alkyl-lower alkoxy sulfates are preferably 10 to 14 or 16 carbon atoms in the higher fatty alcohol or its alkyl moiety and up to 20 moles of lower alkoxy per mole, namely 1 to 20 , more preferably 2 to 4 or 2 to 6, e.g., 23 (the lower alkoxy being usually ethoxy, but sometimes also including up to 3056 propoxy) and these are preferred detergents for " shampoos ". A particularly preferred higher sulfate fatty alcohol is lauryl sulfate and a particularly preferred higher polyalkoxy lower sulfate fatty alcohol is one in which the higher fatty alcohol is lauryl alcohol, which is triethoxylated. For the detergents softeners, the most preferred anionic detergents are linear higher alkyl benzene sulphonates, namely dodecyl linear benzene sulphonate. For " shampoos " the anionic detergents are usually ammonium and / or triethanolamine salts or mixtures of one or more of them and sodium salts, and for the softening detergents the salts are usually sodium, in particular the sodium salts of the above detergents.

Although the detergent compositions of the invention are preferably anionic, they may also be nonionic or mainly nonionic, in which case the major nonionic detergent component will normally be alkoxy (lower) alcohol or phenol, (the phenol may be substituted by an alkyl group, usually a chain of 8 to 10 carbon atoms). The lower alkoxy is usually ethoxy, but may also be at least partially propoxy (up to 30% of the alkoxy). Preferably the nonionic detergent will be a condensation product of a higher fatty alcohol of 8 to 15 carbon atoms with 5 to 12 moles of lower alkylene oxide, more preferably having the higher fatty alcohol 8 to 12 carbon atoms and condensed with 6 to 10 mol of lower alkylene oxide. Similarly, when the ethylene oxide is condensed with alkyl phenol, the number of moles of ethylene oxide used will be in the similar ranges per mole of phenol as per mole of alcohol. For both the ethoxylated fatty alcohols and the ethoxylated alkyl phenols, it is preferred that they are of the narrow gamma ethoxylate type (EGE) although the EGL (broad) ones are also useful.

Although we can manufacture " sham-poo " and softening detergent compositions which use only nonionic detergent as the detersive surfactant, it is often preferred to incorporate some anionic detergent into those compositions, in that the nonionic detergents are normally of poor foaming and it is usually desirable that the detergent compositions have the ability to produce foam, in particular to wash hair with " shampoo ". While any of the above-mentioned anionic detergents herein may be used in addition to the nonionic detergent when a nonionic detergent is present, it has been found to be preferable to use a non-

which is of the sulfate or sulphonate type, but preferably an alkyl fatty sulphate of 8 to 18 or 10 to 16 carbon atoms, for example ammonium lauryl sulphate or triethanolamine (LSATG).

Various adjuvants may be used together with the required components of the compositions of the invention because of the properties which they transmit to them. In all liquid compositions of the invention, there may be included ethanol and / or other normally polar cosolvent, and dyes and perfumes can usually also be incorporated, foam modifying agents, opacifying agents, thickening agents and perlaceous agents are optional.

For hair conditioning compositions, in particular lotions, fatty higher alcohols, such as cetyl alcohol, which has a strong effect, thickening agents such as hydroxy ethyl cellulose and neutralizing agents and buffer solutions may also be present , such as sodium borate. With regard to laundry cycle additives for fabric softening and laundry rinse additives, it has been found that small portions of sequestering salts, in particular sodium citrate, and lower alkylene glycols, such as propylene glycols, help to improve the rheology of the liquid product, acting as a preparation that makes it more fluid. For " shampoos " the adjuvants may include thickeners and opacifiers, namely cetyl alcohol, stearyl stearate and ethylene glycol distearate, other thickeners, namely xanthan gum, " Natrosol " (methylcellulose), and sodium chloride, sequestering antioxidant preservatives, and lower alkylene glycol-based solubilizers and fluidizers, in particular propylene glycol. for the cleansing detergents, the additional useful adjuvants include fluorescent brighteners, namely distethenes brighteners, preservatives such as formalin-18-

and neutralizing agents, including triethanolamine. In addition to the adjuvants mentioned, other known in the art may also be present for use in the liquid compositions of the types described in this invention and when solid particulate compositions are made, components suitable for such compositions may also be used, flow promoting agents, anti-redeposition agents, fabric softening powders such as bentonite, builders such as polyacetal carboxylate, zeolite, sodium tripolyphosphate and sodium carbonate, bleaching agents such as sodium perborate, bleach activators and / or stabilizers and soil release promoting agents such as polyethylene terephthalate-polyoxyethylene terephthalate copolymers (TPE-TPOE copolymers).

The various proportions of the components required in the described compositions are important for obtaining the best properties of the compositions described herein. For all compositions of the invention, the ratio of cationic surfactant to CDA fibers should be such that the presence of both of those materials in the compositions improves the deposition of at least one of them on a fibrous substrate to be conditioned by application therein of an aqueous medium containing the composition of the invention. This proportion of said two components has been found to be typically in the range of 1:20 to 20: 1, preferably in the range of 1: 3 to 20: 1 and most preferably in the range of 1: 2 to 20: 1. Expressed differently, such ranges are from 0.05: 1 to 20: 1, 0.33: 1 to 20: 1 and 0.5: 1 to 20: 1, respectively. In percentages, the aqueous emulsion compositions of the invention, which are preferably based on quaternary ammonium salt as the surface active agent,

will usually comprise 0.1 to 20% of that quaternary ammonium salt and 0.1 to 10% of CDA, which is often and preferably an n-alkane.

For conditioning lotions for human hair, usually for use after washing with " shampoo " the percentages of quaternary ammonium salt, DCA and aqueous medium will normally be in the ranges of 0.2 to 10%, 0.1 to 5% and 75 to 99%, respectively, preferably 0.2 to 5 , 0.1 to 2%, and 85 to 98%, more preferably 0.3 to 2%, 0.1 to 1% and 90 to 97% and more preferably still 0.4 to 1.2% 1 to 0.5% and 95 to 97%. The remaining part, if any, will consist of adjuvants, which also constitute the remaining part of the other compositions of the invention, which are hereinafter described. In the described compositions, the preferred aqueous medium is water, the most preferred quaternary ammonium halide is higher alkyl halide fatty-tri-lower alkyl ammonium, wherein the higher alkyl has 12 to 18 carbon atoms and the lower alkyls have 1 to 3 carbon atoms and the DCA is selected from the group consisting of alkanes, carboxylic acids, esters of carboxylic acids and alcohols of alkyl chains of at least 25 carbon atoms, and mixtures thereof. For the most preferred compositions of all, the quaternary ammonium halides are cetyltrimethylammonium chloride, dicetyl dimethylammonium chloride and distearyl dimethyl ammonium chloride and DCA is beeswax, normal petroleum lithium , paraffin wax or microcrystalline wax or is an approximately equal mixture of a petrolatum having an average of 27 to 33 carbon atoms in the respective n-alkanes and beeswax. -20-

For " shampoos " the proportions of synthetic organic detergent, quaternary ammonium salt, CDA and aqueous medium are typically in the ranges of 5 to 25%, 0.2 to 10%, 0.1 to 5% and 65% to 94% respectively, said ranges being preferably 8 to 20%, 0.2 to 5%, 0.1 to 3% and 70 to 90%, more preferably 10 to 18%, 0.3 to 2%, 0 , 1 to 1.5% and 75 to 85%, and most preferably 12 to 18%, 0.4 to 2.0%, 0.1 to 2.0% and about 80%.

For the most preferred conditioning compositions, in the form of " shampoo " the synthetic anionic organic detergent is a mixture of at least two different sulfated anionic synthetic organic detergents, at least one of which is an ammonium, sodium or triethanolammonium salt, the quaternary ammonium halide is a higher trialkyl chloride < lower alkyl ammonium or a tri-lower alkyl di-lower alkyl ammonium chloride, wherein the higher alkyl has 12 to 22 carbon atoms and the lower alkyl has 1 to 3 carbon atoms and the CDA is selected from the group consisting of alkanes, carboxylic acids, esters of carboxylic acids and alcohols, alkyl chains of at least 25 carbon atoms and mixtures thereof. The most preferred compositions comprise 5 to 15% ammonium and / or sodium lauryl sulfate and 10% sodium and / or sodium lauryl diethoxy sulphate, and the CDA is in a paraffin wax of 25 to 30 atoms of carbon and / or a petrolatum having an average of 27 to 33 carbon atoms in said n-alkanes, and / or beeswax.

Laundry detergents for wash cycle and rinse cycle laundry will usually have percentages of quaternary ammonium salt or equivalent, CDA and aqueous (or water) medium in the ranges of 1 to 20%, 0.1 to 5% and 70 to 97.9%, preferably 1.5 to 10%, 0.1 to 2%, and 80 to 97.9% and more preferably 1.5 to 1% di-alkyl superior fatty acid di lower alkyl ammonium, wherein the higher alkyl has 12 to 22 carbon atoms and the lower alkyls have 1 to 3 carbon atoms 0.1 to 2% of CDA, which is selected from the group consisting of alkanes, carboxylic acids , esters of carboxylic acids and alcohols, of alkyl chains of at least 25 carbon atoms, and mixtures thereof, and 85 to 95% water. Most preferably, such compositions will comprise 2 to 856 of distearyl dimethyl ammonium chloride, 0.1 to 156 of CDAA, found in beeswax, petrolatum and / or paraffin wax and 90 to 95% water more adjuvants if any.

The softening detergents will usually be comprised of a detersive proportion of synthetic organic detergent, which will normally be an anionic detergent, nonionic detergent or a blend thereof, 0 to 7556 of detergent builder (s), 2 to 2056 of ammonium salt quaternary for softening of fabrics or equivalent, 0.1 to 256 of CDA, 0 to 7556 of water (with lower percentages of water for particulate softening detergents) and the remainder, if any, of adjuvant (s). Preferably, the softening detergent compositions will comprise 10 to 3556 of synthetic organic detergent, 2 to 1556 of quaternary ammonium salt or a complex of quaternary ammonium salts or a blend thereof, 0.1 to 256 of CDA and 50 to 9256 of water, the remainder being water. More preferably, such a softening detergent may contain 10 to 2556 of a nonionic detergent, which is a condensation product of one mole of higher fatty alcohol of 10 to 16 carbon atoms with 3 to 11 moles of ethylene oxide, 2 to 1056 of an anionic detergent which is a linear higher alkyl benzene sulphonate, wherein the higher alkyl has 10 to 16 carbon atoms, 7 to 1356 of di-alkyl superior fatty di-lower alkyl ammonium- 22-

wherein the higher alkyl has 12 to 22 carbon atoms and the lower alkyls have 1 to 3 carbon atoms, or a respective citric acid complex, or a mixture thereof 0.1 to 1% of CDA, which is selected from group consisting of alkanes, carboxylic acids, esters of carboxylic acids and alcohols of alkyl chains of at least 25 carbon atoms, and mixtures thereof, and 60 to 75% water, any remaining part consisting of aqueous, preferably water. The most preferred detergent cleansing compositions contain 12 to 20% of a nonionic detergent which is a condensation product of one mole of an upper fatty alcohol of 12 to 15 carbon atoms with 5 to 9 moles of ethylene oxide , 3 to 7% of an anionic detergent which is a linear alkyl benzene sulfonate, wherein the alkyl has 10 to 14 carbon atoms, 1 to 5% distearyl dimethyl ammonium chloride, 7 to 11 % of a citric acid complex of di-stearyl-methyl amine, 0.1 to 0.5% of the CDA, from a petrolatum having an average length of 27 to 33 carbon atoms in its n-alkanes, and 65 to 70% water, any remainder consisting of adjuvant (s).

In the art, various processes for the manufacture of oil-in-water emulsions, which can be used to prepare the fiber conditioning compositions of the present invention (when in liquid form) are well known. However, to ensure that the emulsion made will have a better stability and that the fiber conditioning activity is maximized and reproducible at such maximum activity, it has been found desirable to utilize a specific manufacturing process which forms a part of the present invention. One such process is to form a fused cationic surfactant component of the fiber conditioning composition and the CDA at an elevated temperature in order to heat the aqueous medium which should be the continuous phase of an emulsion which may contain components hydrophilic properties to a temperature

and the resulting lipophilic and hydrophilic materials are blended together at about the same elevated temperature, thereby producing the fiber conditioning composition in the form of an emulsion with improved stability and efficacy. The temperature at which the cationic surfactant and the CDA are heated will normally be in the range of 70 to 95 or 100 ° C, preferably 70 to 90 ° C and most preferably about 80 ° C, e.g. 80 ° C. The aqueous medium, preferably containing any stable hydrophilic components of the composition, will be heated to the same temperature and the lipophilic melt will be gradually added with mixing to the aqueous medium until an emulsion is formed which will sometimes be a microemulsion . The emulsion is gradually cooled to room temperature, usually for a period of five minutes to one hour, with continuous mixing, to avoid any breakage of the emulsion and any heat-sensitive adjuvants are added with mixing. The product at room temperature is a stable liquid in the form of an emulsion.

If it separates after a long storage at elevated temperatures, it can be reconstituted by shaking. When the fiber conditioning emulsion or other form of the composition is dissolved or dispersed in water as in a wash water or rinse water, both the cationic surfactant and the CDA are deposited on fibrous substrates in such water, resulting therefrom effective and beneficial conditioning of the treated fibers.

When used, the compositions of this invention are dissolved or dispersed in water at a concentration in the range of 0.01 to 10%. In some cases, such as " shampoos " and hair lotions they can be applied at their maximum power,

in water at a concentration of 10 to 50%, preferably 20 to 30%. On the other hand, the laundry preparations will be used in higher dilutions, namely 0.05 to 2%, eg, 0.1 to 0.5% and 1%. The temperature of normal use is in the range of 10 to 60 ° C, depending on the type of fibrous substrate to be treated, and depending on the type of composition to be used. Preferably, for most applications, the water temperature will be in the range of 10 to 40 ° C and more preferably such a range will be 25 to 40 ° C especially for treatment of human hair on the head. The fibrous material to be conditioned, whether human hair, cotton or synthetic fibers, namely polyester or polyester cotton blends, will be maintained in contact with the aqueous solution or dispersion of the fiber conditioning composition for 1 or 1 to 30 minutes, e.g., about 2 minutes, and during that time, the cationic surfactant and CDA will both deposit onto the fibrous substrate and serve to condition it. Often the CDA promotes deposition of the cationic surfactant, but sometimes the reverse also occurs. In the case of human hair, in which the said active components are applied in the form of " shampoo " or conditioning lotion, the important and improved conditioning effect assessed by scoreboards is a significantly greater ease in combing both wet and dry hair both after application of a conditioning lotion of the invention and after washing with a "; shampoo " conditioning compositions of the invention. The mechanism of absorption or deposition of the composition containing both the cationic surfactant for conditioning fibers with the CDA but has been explained but is clearly more complicated than the mere deposition of the components of the composition because these components are removed by the fibrous materials from a dilute aqueous solution

and not retained in the fibrous substrate despite the dilution and consequent water rinsing of the solution or dispersion of the fiber conditioning composition from the conditioning of fibers from the fibrous material. Likewise, it is an effective conditioning portion of the active conditioning agents that remains in the fibrous material after rinsing. Since the uptake of the active conditioning components is best in the absence of significant builder portions for the synthetic organic detergent, " shampoos " which do not contain such a builder may have lower cationic conditioning agent and CDA contents than those desirably incorporated in the softening detergents of the invention.

However, a very significant advantage of the present invention is that in laundry detergents and " shampoos " as well as in hair conditioning lotions and laundry cycle additives and laundry rinse cycle, whether for human hair treatment or for clothing, the use of both the cationic fiber conditioning agent and the CDA, results in a significantly better conditioning action, which thus allows the use of a smaller amount of the conditioning agent thereby saving the respective costs. The products made are also of better stability which is important since the consumer does not like to have to stir liquid products before using them to disperse their components and because the stable emulsions are much more attractive in the selling places than those that present separation and must be re-emulsified. Various advantages of the present composition and processes have been set forth above, but a specific advantage deserves further enhancement. It is the significant advance in the conditioning action obtained with the combination of the cationic surfactant of 26-

It has been observed that when human hair is rinsed with compositions of this invention, there are significant increases in the conditioning effects, namely the ease of combing, compared to the effects obtained after using compositions which are identical , but in which there is no CDA. in addition, the conditioning obtained is comparable to that of commercial conditioning compositions based on cationic surfactant conditioning, but containing more of these compounds. The "shampoos " hair conditioning compositions of the invention, while containing more active conditioning agents than lotions, may contain less than " shampoos " of commercial hair conditioning, and yet are often more effective than these commercial products. What is even more surprising, and is regarded as a victory in the art, is the fact that " shampoos " of the invention can be as effective as commercial conditioning lotions. Until now it has always been considered impossible the ability to obtain from a " shampoo " a conditioning similar to that of a conditioning lotion. Similar types of improved conditioning effects have been found for the corresponding rinse and rinse cycle conditioners and cleansing detergents of the invention.

Preferred compositions of this invention are in liquid form and preferably have the form of a stable emulsion or microemulsion. However the compositions of the invention, in particular the softening detergents may be converted to the particulate solid or solid form, when a substantial portion of the entire aqueous medium is replaced with a solid carrier or solid adjuvants such as bentonite, sodium sulfate , zeolites, sodium tripolyphosphate, sodium carbonate and other builders. Thus, for example, the water content of a liquid softening detergent can be replaced by 27-

a builder or carrier so that it constitutes up to 75% or more of the composition, and the physical form of the product can be altered accordingly.

The following examples illustrate but do not limit this invention. Unless otherwise noted, all parts are by weight in the examples in the specification and the appended claims, and all temperatures are in ° C. -28-

EXAMPLE tn tn o m CN 1 O o CN o 'b b 1 o b o o H H c e o <T> The compound of the formula: ## STR1 ## wherein R 1, R 2, R 2, R 2, R 3 and R 4 are as defined hereinbefore. o tn o E β σν o 0 a 1-4 0 E tn tn t t bd) Q o CN o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o 0 P d Ό o tn o O tn o β o &gt; (1) or (2) or (2) may be prepared by reacting a compound of the formula: ## STR1 ## wherein R 1 is H or H or H or H; Η Η Η Η Η * Η Η Η Η Η Η Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό ρ σ &gt; (b) (b) and (b), and (b), and (c), the following equation is obtained: '' '' '' '' '' 'Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο * Λ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ Ρ * * * * XJ β d) w H 0 • rl XJ N • rl O d) 1 d) iH Ό rl &quot; Λ XJ 0 Λ HP • H w β ο d) d &gt; (B) (b) (b) (b) (b) (b) (b) (b) and (b). r-4 O XJ &gt; 0 β P 0 a 0 PG Ρ a ρ d) (0 P 0) or β β 0 β S 0 b P XJ d) or P β υ Ο 0 H d) • H w rj 0 Cn u υ * υ E < ; m * c * 29-

The hair conditioning lotions of the above formulas were made by fusing together the lipophilic components (cetyltrimethylammonium chloride, petrolatum, beeswax and cetyl alcohol) at 80Â ° C, and emulsifying the melt in the remainder of the formula in the aqueous medium, which is also at 80 ° C, after which the emulsion formed was cooled to ambient temperature for about 20 minutes for each formula. Standard human hair braids (3 g per braid) were treated with one gram each of the conditioning lotions for one minute, after which they were rinsed and wet combed. One panel of reviewers rated the ease of combing wet hair on a scale of 1 to 5, ranging from difficult to easy and 12 classifications were given for each braid, with mean scores being calculated for each. Subsequently, in separate tests, after rinsing the braids, they were dried with hair and were combed.

Using the same scale, the ease of combing was again evaluated by the panel and the means were calculated. The following table summarizes these averages. 30-

k (0 Q) Pc <Daoc a> rs ta Ό • H • H O m fc. w o r H H H H H H H H H H H H H H H H H H H H H H H H H cm cm cm cm cm cm cm cm cm cm cm cm cm tr tr tr tr tr.

w m • H Ό '<D S o tn * M · tn t &quot; rr

H

TABLE &lt;

CM 00 tn &lt; j &gt; CM% CM

k d) 03 m 0 H d) rQ ta o 0 Tf 0 Tf O m tf d> (tf P-a to <t w a Tf • rfε oo o>

From the results of these experiments it is evident that the presence of the CDAs in the compositions of the invention substantially increases the ease in combing, which is considered to be tightly bound to the overall maneuverability and conditioning of the human hair braids treated with the compositions of the invention, with a control composition (IA) which did not contain such a CDA. In the experiments reported, the best results (corresponding to the best conditioning) were obtained with experiment 1B, wherein the single CDA is obtained from beeswax, although the formula of the experiment 1D produces satisfactory results and is economically advantageous, compared to that of 1B. In vivo tests ("live-in-use" practice tests) attest to these results, as with other in-vitro tests, in which the braids are contacted with diluted rinse emulsion (composition: water diluted 1: 1, 1: 2 and 1: 3).

In similar tests, when a mineral oil was used instead of the CDA, a much weaker conditioning resulted, and sometimes the braids were live oily, which is usually inconvenient. The braids of Formulas 1A-1G did not appear oily after treatment. When carnauba wax is used in place of the CDA, the hair conditioning effect is less than the effects of the compositions of the invention because of their aromatic content, although the microcrystalline wax is effective.

Although the costs of such cationic surfactants are currently prohibitive, when using heptacosyl trimethyl ammonium chloride or hentriacosyl trimethyl ammonium chloride at a concentration of 1% or 0.5% instead of cetyl-trimethyl-ammonium in the present formulas, without any of said CDA, those cationic surfactants,

will also act as CDA, and the effects of hair conditioning will be better, as in the experimental formulas recorded.

In other variations of the formulas of this example, cetyltrimethylammonium chloride is replaced by cetyltrimethylammonium bromide or by lauryl trimethylammonium chloride, the cetyl alcohol is replaced by myristyl alcohol and the petrolatum is replaced by a C25 paraffin, and better results are obtained. Likewise, the ratio of cetyl alcohol to cetyltrimethylammonium chloride can range from 3: 1 to 1: 1 in the 2: 1 examples, with the desired cetyl alcohol lubricating effect continuing to be obtained.

EXAMPLE ο ο 1 ο ιη 1 1 1 ιη ιη ΡΟ ιη Ο ** kkktkk 1 k ιη Η m <Ν Ο Ο CM ο Ο ιη ιη 1 ιη ο ιη σ C5 <3 ιη Cm «* kk I kk 1 k k Γ Γ Γ Γ Γ Γ Γ η η η η η η η η Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν η η η η η η 0) Γ Γ Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η 'C-C J Ν Ν Ν CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS CS. ιη ιη β υ ιη ιη ο Wf Γ ~ ιη ιη ιη CM ιη ιη © 1 k 1 • k k V Μ &gt; 1 0 Μ φ CN Η CM Ο Ο Ο η η Γ Γ Γ mm mm mm mm mm mm mm Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Γ Κ Κ Κ Κ Κ Κ Κ Κ Κ Κ Κ Κ Κ Κ Κ Ο Ο Η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η. Γ • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • ε k k Η Η Ή Ή Ή Ή Ή Ή Ή Ή Ή Ή Ή Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β β - μ ο 0 μ μ υ © Ο Ο Ο Η β β Φ 2 -μ β β < • Η Φ Ο Η Ό Ό Ό Ό Ό Ό μ μ μ μ μ μ μ μ μ μ μ μ μ μ-----------------------μ μ μ μ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ. C Η Η Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο 3 0 * * * * * «« «« «« «« «« «« «« «« «« «« «« «. ο * υ ο Ο υ 34

EXAMPLE 2 (Cont'd) The composition of the invention is shown in the following table: EXAMPLE 2 (Cont'd) (0 dl a LO nd * 00 O n EQ *.% 0) O ι Γ Γ HE HE HE HE HE HE HE HE HE HE HE HE HE HE HE P P P P (b) a compound of the formula: ## STR1 ## wherein R 1 is hydrogen or C 1-6 alkyl; a H CH • H 0'01 trd • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 N E -w td) 0 n G μ di 0 c E μ • r) 0 0 c 01 0 O a a d) a> G E Ό 0 3 He a tw rd E L 3 0 d) σ »u CU * c 35-

Control emulsion (A) and the emulsions of the invention (B-G) were all made by the method described in Example 1 and were tested in the same manner. In addition, the evaluators recorded their overall impressions regarding hair conditioning (which included handling, appearance and touch considerations) as well as wet hair styling and dry hair assessments. These classifications are given in Table 2 below. -, - 36-

O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o

W ε o o 0 · * m oo 00

Q

(ti Ή V 'Φ S • υ m PO X »h m 00 • in IO 0 X Γ0 P0 w

N

TABLE m &lt;

ox M O% d • o • sl * <u + »c Φ + &gt; CQ • H X d)

C3 H

Ό 0 '' '' '' '' 'm m J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J J Ϋ́ Τ Τ Τ Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Η Η Η Η Η Η Η Η Η (ti X (ti CJ ϋ ϋ 0 ο Μ> 0 (0 (0 <u Cu 0 &amp; ο *

From the above data, it is evident that the resulting improvements in human hair conditioning result from the presence in &quot; shampoo &quot; of the small proportions of the CDAs of this invention together with the hair conditioning compound based on cationic surfactant (quaternary ammonium halide) and such improved conditioning is evidently due to the presence of the CDA given the control formula A which does not contain CDA, but contains the cationic conditioning agent, is much lower in the conditioning effect, compared to compositions BG, which are all within the scope of the invention.

The results described are verified by in vivo tests, which consist of normal head hair washes with the described compositions.

In variations of the formulas tested, there may be substitutes for the detergent systems described where those active detergent components are triethanolammonium lauryl sulfate, ammonium olefin sulfonates, ammonium paraffin sulfonates, or mixtures thereof, and may also be present in such nonionic and amphoteric detergent compositions. The conditioning cationic surfactant may also be altered as in Example 1, and CDA may be obtained from other materials, including wax-montane and candelilla wax, synthetic beeswax and wax from Japan, and may also be incorporated microcrystalline waxes in the compositions. Similarly, the CDAs may be pure compounds, in particular hydrocarbons, alcohols, carboxylic acids and carboxylic esters, or from fractions of CDA sources, such as beeswax, and may be alcohols, amines, amine salts and quaternary ammonium salts -

of the hydrocarbons and amides of such carboxylic acids, and the compositions in the form of "shampoo" will also exhibit improved hair conditioning activity.

In another variation of the &quot; shampoo &quot; a relatively small percentage of nonionic detergent, namely, (R) cool fatty upper-polyethoxylate, such as &quot; Neodol &quot; 25-3, 23-6, 5 or 25-7 in addition to the anionic detergent (to improve the removal of oil, and previously deposited conditioning agents from the hair and scalp). Typically 1 to 10% of such a nonionic detergent, preferably 2 to 5%, e.g., about 3% may be present.

EXAMPLE 3 Component Percent (by weight) Distearyl dimethyl ammonium chloride 6.0 6.0 3.0 Amine citrate complex mm 3.0 Beeswax (yellow) 0.5 0.5 * Petrolate 0.1 0.1 Sodium citrate 0.090-0.05 Propylene glycol 0.1 0.1 0.1 Deionized water 93.85 93.25 93.3 100.0 100.0 100.0 contains 60 % of n-alkanes with a mean of 27 to 33 carbon atoms, with their peak in the distribution curve in that range. pre-prepared complex obtained by mixing distearyl-methyl amine and citric acid in a molar ratio of 1: 1. -40-

The fabric conditioning compositions to be used in the washing cycle and rinse cycle of this example which are useful for the treatment of clothes, usually in an automatic washing machine are made according to the process described in Example 1, the materials lipophilic melts together and being added, with mixing, to the hydrophilic components in the aqueous medium, and being cooled to room temperature.

Control compositions (3A) and those of the invention (3B and 3C) are each tested in wash cycle and rinse cycle applications using different commercial detergents at wash water concentrations suggested by the respective manufacturers. In the washing cycle tests, the water is of a hardness of about 125 ppm in the form of CaCO 3 and is at a temperature of 32øC, the laundry load is large, the washing time is 14 minutes and rinsing is cold.

Commercial detergents in which the additive is added in the wash cycle are &quot; Tide &quot;

Ir) powder (with phosphate based builder), &quot; FRESH START &quot; Tide &quot; liquid and &quot; WISK &quot; and the concentrations of the wash cycle additive in the wash water vary so that about 4 to 9% of the conditioning components are present at that stage, based on the detergent composition used (or 75 to 150 g of the composition of conditioning by 68 liters of washing water, representing 0.1 to 0.2%). Test additives, which are blended with standard 5 pound (2.688 kg) ballast of different types of fabrics, include knitted nylon, cotton knit, &quot; Dacron &quot; (R) plain knit &quot; , &quot; Dacron &quot; mixtures

Go) from &quot; Dacron / cotton 65/35) and &quot; Banlon &quot; (for evaluation of static electricity accumulations), and 41- *

velvet hand towels, for softness assessments). The washed materials are dried for 60 minutes using the raised and weighed set point of an automatic laundry dryer, and the complete washing and drying operations are repeated twice, after which the test fabrics are evaluated for the static (synthetic) adhesion power and softness (velvet towels). The evaluation of adhesion caused by static electricity is effected immediately after the dryer has been switched off after the third drying operation. The humidity in the test room is in the range of 44 to 56% R.H. for both static and softness tests. The velvet towels are hung on a clothes hanger after they have been removed from the dryer and are left there for about twelve hours before being evaluated for softness. At all concentrations of the active conditioning components which were tested and in washing the test fabrics with all the detergent compositions in the wash water containing the wash cycle additives 3B and 3C, there was a lower adhesion due to the static electricity of the than when composition 3A was used.

The differences of this adhesion are visible even to a casual observer. With regard to tissue softness, the results are similar favorable to the compositions of the invention both when the evaluations are performed by a perltíè of long experience in such techniques, as when the observations are made by unqualified observers.

A very important result observed is that the use of the compositions of the invention as wash cycle softeners produces a washing-

even better fabric softening at lower adhesion due to static electricity than that observed when a commercial rinse cycle softener (&quot; Downy &quot;) was used as the wash cycle additive in an amount equal in content active conditioning ingredient.

The same type of results are obtained in applications in the rinse cycle, using the same process, except that only one washing operation and one drying operation are used. The theory which has been advanced to explain the superiority of the detergent compositions of the invention over those of ontrol and those of the commercially available fabric softener in the wash cycle is that the Applicants CDA acts in a manner to "protect &quot; the cationic surfactant of the reaction with the anionic compounds in the wash water, thus allowing all of its tissue conditioning capabilities to function. This theory is supported by conductance and Zeta potentials measurements of the experimental and control compositions, and turbidity measurements of the compositions of the invention and wash water controls containing commercial anionic detergent compositions, although this is not reliable.

In variations of the given examples, the various components, but not the cationic conditioning surfactant and the CDA, may be omitted, and the results recorded will be essentially the same. Also, the components of Example 3 may be replaced by the various cationic components and sources of CDA mentioned in the specification and other working examples, giving rise to similar and significant differences in the anti-static and fabric softening action in favor of the compositions of the invention. Thus, for example, higher monoalkyl trialkyl halides may be used

Lower alkyl ammonium and higher trialkyl mono-lower alkyl ammonium halides, such as other of the above CDAs. -44-

EXAMPLE 4

Component Percent (by weight) AB DodeciX linear sodium benzene sulphonate 5.0 5.0 Sodium sulphate (accompanying the anionic detergent) 1.7 1.7 *** Neodol 25-7 15.0 15 , Distearyl dimethyl ammonium chloride 6.0 6.0 Petrolatum 0.5 Citric acid (50% aqueous solution) 9.0 9.0 Triethanolamine 0.3 0.3 Formalin 0.2, 2 Fluorescent (Tinopal, (R) 5BM, Extra Cone.) 0.2 0.2 Dye (0.5% aqueous solution) 1.0 1.0 Perfume 0.4 0.4 Deionized water 61 , 60, 7, 100, 100, 0

It contains 60% n-alkanes having a mean of 27 to 33 carbon atoms, with the peak of the distribution curve in that range. -4-

***

Nonionic detergent which is a product of the condensation of one mole of fatty alcohol of 12-15 carbon atoms with 7 moles of ethylene oxide.

A control softening detergent composition (4A) and the composition of the invention (4B) are both used to wash both cotton and synthetic test fabrics according to the process described in Example 3 with a single washing and drying, and the fabrics are then evaluated for adhesion due to static electricity and softness by the methods described in Example 3.

The results obtained are also similar to those recorded in Example 3 for fabric conditioning compositions to be used in the wash cycle which would be expected, given that the present cleansing detergent composition produces substantially the same type of wash water, as is apparent from the addition of the corresponding wash cycle conditioning composition to a wash water containing detergent composition. As in Example 3, when practicing multiple washes and drying of the test tissues, the best conditioning effects on the compositions of the invention increase.

In changes to the formula of

The detergent component may be either anionic or all nonionic, and the anionic and nonionic detergents may be substituted by others previously described in these examples in the foregoing description. Distearyl dimethyl ammonium chloride may be substituted by other salts of quaternary ammonium complexes such as those mentioned above, or other quaternary ammonium and amine complexes as mentioned above. Likewise, CDA-46-

may be replaced by other CDAs of the types which have been described above. Such a change or such series of changes continues to result in the compositions of the invention which will have improved tissue conditioning properties including static softening and / or anti-static properties compared to control compositions that do not contain the required CDA. A further advantage of the invention is that several CDAs are all safe for use in the described proportions (many having already been accepted or approved for oral ingestion) and do not therefore require testing for governmental toxicity and authorization. EXAMPLE 5

In the formulas and compositions described in the previous examples, variations of the components may be made by substituting one or more of them with others described in the specification as equivalents or substitutes. The proportions of components may vary, typically at -10%, -20% and -50%, provided they remain within the ranges indicated in the specification. The liquid compositions may be converted into particulate solids by replacing water with particulate carrier materials, in particular structurers and fillers. In some cases, it may be desirable to separately add to the rinsing or rinsing water the melt blend of cationic fiber conditioning surfactant and CDA, preferably in liquid form, either in molten form or in appropriate organic solvent, namely isopropanol, or in admixture with a 4-

powder vehicle. The individual cationic surfactant for tissue conditioning and the CDA may also be added to the wash water or rinse water, but, as previously indicated, the desired tissue conditioning effects will not be obtained from such a simple mixing in a stretch as large as when these components are first fused together. Furthermore, it is highly preferred that they are presented in the form of an emulsion, when introduced into the rinsing and rinsing waters. To an extent of the invention, where the work is now pending, the various CDAs, including those which are quaternary ammonium salts, are used to promote deposition or absorption by substrates, such as clothing and hair fibers, of relatively insoluble materials namely fluorescent brighteners, colorants, soil release promoting perfumes, bactericidal fungicides, insect repellents, soil repellents, anti-wrinkle chemicals, which can be incorporated into rinse lotions, additives and appropriate detergent compositions. The invention has been described with respect to its working examples, illustrations and embodiments, but is not to be construed as being limited thereto, since it is apparent that one skilled in the art of the disclosure herein may use substitutes and the like , without departing from the invention.

Claims (2)

CLAIMS: 2. A process for the preparation of a fiber conditioning composition comprising a fiber conditioning cationic tensioactive agent and a water dispersible compound which contains in its formula a hydrocarbonyl group of at least 25 carbon atoms (CDA) wherein the ratio of the fiber conditioning cationic surfactant to long chain hydrocarbon containing compound is in the range of 1:20 to 20: 1, ratio wherein the presence of both of those materials in the composition improves the deposition of at least one of them on a fibrous substrate to be conditioned by applying thereto an aqueous medium containing that composition. 2ã. A process according to claim 1, characterized in that the cationic surfactant of fiber conditioning is a quaternary ammonium salt and the CDA is a hydrocarbon, an acid an ester, an amide, an amine, a salt of amine, a quaternary ammonium salt, or an alcohol or a mixture thereof, the composition is aqueous, the proportion of that quaternary ammonium salt for that CDA is in the range of 0.5: 1 to 20: 1, and the deposition of at least one of said compounds on a substrate to be conditioned is on human hair or clothing. 3ã. A process as claimed in claim 2 wherein the quaternary ammonium salt and CDA are in an aqueous emulsion in which the ratio of quaternary ammonium salt is in the range of 0.1 to 20% and the ratio of CDA is in the range of 0.1 to 10%. -4- 4ã. A composition according to claim 3, characterized in that said composition is applied as a conditioning lotion for human hair after washing with &quot; shampoo &quot; and comprises 0.2 to 10% quaternary ammonium salt, 1 to 5% CDA, 75 to 99% aqueous medium and the remaining part, if any, consisting of adjuvant (s). 5i. A process according to claim 4, characterized in that 0.2 to 5% of quaternary ammonium halide, 0.1 to 2% of CDA, 85 to 98% of water are included in said composition, and the remaining part is if any, of adjuvant (s). 6ã. A process according to claim 5, characterized in that 0.3 to 2% of the alkyl superior fatty alkyl tri-lower alkyl ammonium halide, or di-alkyl-higher fatty acid halide, dialkyl and lower-ammonium halide or tri-lower alkyl fatty acid-lower alkyl ammonium halide, wherein the higher alkyl is 12 to 22 carbon atoms and the lower alkyls are 1 to 3 carbon atoms, 0.1 to 1 % of CDA, selected from the group consisting of carboxylic acid esters of carboxylic acids and alcohols and alkyls with at least 25 carbon atoms, and mixtures thereof 90 to 97% water, and the balance, if any, of adjuvant (s). 71. A process according to claim 6, characterized in that 0.4 to 0.2% cetyl trimethyl ammonium chloride, dicetyl dimethyl ammonium chloride or diethyaryl dimethyl ammonium chloride are included in said composition, and 0.1 to 0.5% of CDA, which is in an approximately equal mixture of a petrolatum containing an average of 27 to 33 carbon atoms in the respective n-alkanes, 95 to 97% water and the remainder if any, of adjuvant (s). 8ã. 3. A composition according to claim 3, wherein the composition is applied as a &quot; shampoo &quot; for conditioning of human hair and include 5 to 25% of synthetic organic detergent, 0.2 to 10% of quaternary ammonium salt, 0.1 to 5% of CDA, 65 to 94% of aqueous medium and the remainder, if desired. to the adjuvant (s). 9a. A process according to claim 8, characterized in that 20% synthetic anionic organic detergent is included in said composition 8, 0.2 to 5% quaternary ammonium halide, 0.1 to 2% CDA, 70 to 90% water and the remainder, if any, of adjuvant (s). 10â. A process according to claim 9, characterized in that the composition comprises 10 to 18% of a mixture of at least two different sulfated anionic synthetic organic detergents, at least one of which is an ammonium, sodium or triethanolamine salt; , 3 to 2% trialkyl chloride higher fatty mono-lower alkyl ammonium, wherein the higher alkyl is 12 to 22 carbon atoms and the lower alkyl is 1 to 3 carbon atoms, 0.1 to 1.5 % of CDA, which is selected from the group consisting of alkanes, carboxylic acids, carboxylic acid esters, alcohols, amides, amines, amine salts and quaternary ammonium salts with alkyl chains of at least 25 carbon atoms, and mixtures thereof 75 to 85% water, and the remainder, if any, of adjuvant (s), 11æ. 11. A process as claimed in claim 10, Composition 5 to 1556 of ammonium and / or sodium lauryl sulfate, 1 to 1056 of sodium and / or sodium lauryl-diethoxy sulfate, 0.4 to 2.0 of tri-cetylmethyl-araonium chloride, , 1 to 2.0% of CDA, which is in a petrolatum having an average of 27 to 33 carbon atoms in its n-alkanes, a paraffin wax containing a mean of 25 to 30 carbon atoms and / or in the wax of the bees, about 30% water, and the remaining part, if any, of adjuvant (s). 12ã. A composition as claimed in claim 3, wherein the composition is applied as a fabric softener in the wash cycle or the rinse cycle and includes 1 to 20% of a quaternary ammonium salt for fabric softening, cationic amine , quaternary ammonium salt complex with anionic surfactant, or cationic amine complex or any mixture thereof, 0.1 to 5% CDA, 70 to 97.9% aqueous medium and the remainder, if desired, if any, of adjuvant (s). 13§. A process according to claim 12, characterized in that from 1.5 to 10% quaternary ammonium quaternary ammonium salt 0.1 to 2% CDA, 70 to 97.9% water is added to said composition and remaining part, if there is any adjuvant (s). 14ã. A process according to claim 13, characterized in that 1,5 to 7% of di-lower alkyl di-lower alkyl ammonium halide is included in said composition, wherein the higher alkyls are 12 to 22 atoms carbon and the lower alkyls are 1 to 3 carbon atoms, 0.1 to 2% CDA, which is selected from the group consisting of alkanes, carboxylic acids, carboxylic acid esters, amines or amine salts, amides, quaternary ammonium, and alkyl chain alcohols of at least 25 carbon atoms and mixtures thereof, 85 to 95% water and the remainder, if any, of adjuvant (s). 15ã. A process according to claim 14, characterized in that in said composition 2 to 856 of distearyl dimethyl ammonium chloride, 0.1 to 1% of CDA, which is contained in beeswax, petrolatum and / or paraffin wax, 90 to 95% water and the remainder, if any, of adjuvant (s). 16ã. A composition according to claim 3, characterized in that said composition is applied as a laundry detergent and includes a detergent proportion of a synthetic organic detergent, 0 to 75% builder (s) for the detergent, to 20% of a quaternary ammonium salt for fabric softening, cationic amine, quaternary ammonium salt complex, anionic surfactant, cationic amine complex, or any mixture thereof, 0.1 to 2% of CDA, 0 to 75% water and the remaining part, if any, of adjuvant (s). 17ã. A process according to claim 15, characterized in that 10 to 35% of a synthetic organic detergent selected from the group consisting of anionic and nonionic detergents and mixtures thereof is included in said composition, 2 to 15% of a quaternary ammonium salt or a quaternary ammonium salt complex, or a mixture thereof 0.1 to 2% CDA, 50 to 2% water and the remainder, if any, of the adjuvant (s). 18a. A process according to claim 17, characterized in that 10 to 25% of a nonionic detergent is included in said composition which is the product of condensation of an alcohol of higher fatty alcohol of 1 to 16 carbon atoms with 3 to 11 mol • -53- AJ of ethylene oxide, 2 to 10% of an anionic detergent which is a higher alkyl linear benzenesulfonate, wherein the higher alkyl is 10 to 16 carbon atoms, 7 to 13% di-lower alkyl fatty acid halide di-lower alkylammonium, wherein the higher alkyls are 12 to 18 carbon atoms and the lower alkyls are 1 to 3 carbon atoms, or a citric acid complex thereof, or a mixture thereof, 1 to 1% CDA, which is selected from the group consisting of alkanes, carboxylic acids, esters of carboxylic acids and alcohols, alkyls with chains of at least 25 carbon atoms, and mixtures thereof, 60 to 75% water, and the remaining part, if any, of adjuvant (s). 19ã. A process according to claim 18, wherein in said composition is added 20 to 20% of a nonionic detergent which is a condensation product of one mole of a higher fatty alcohol of 12 to 15 carbon atoms with 5 to 9 mol of ethylene oxide, 3 to 7% of an anionic detergent which is linear alkyl benzene sulfonate, wherein the alkyl is 10 to 14 carbon atoms, 1 to 5% distearyl dimethyl ammonium chloride , 7 to 11% of a distearyl-methyl amine citric acid complex, 0.1 to 0.5% of CDA, which is in a petrolatum containing a chain having an average length of 27 to 33 carbon atoms in the res -containing n-alkanes, 65 to 70% water, and the remaining part if there is adjuvant (s). 20ã. A process according to claim 1 for the preparation of a fiber conditioning composition in the form of a stable emulsion consisting of forming a melt of the cationic tensioactive agent and of the CDA at an elevated temperature in the range from 70 to 90 ° C, with other heat stable lipophilic components of the conditioning composition of? -54- to a temperature in the range of 70 to 90 ° C, and mixing the resulting liquids at the same temperature, approximately to obtain the fiber conditioning composition in the form of a stable emulsion. 21ã. A process according to claim 20, characterized in that the lipophilic liquid components and the hydrophilic liquid components of the liquid conditioning composition of fibers are mixed together at a temperature of about 80 ° C and cooled to room temperature with stirring which are mixed with any heat-sensitive components. 22ã. A process for the treatment of a fibrous material by conditioning it comprising applying to said fibrous material a fiber conditioning composition prepared according to claim 1 as a dispersion in water at a concentration of 0.01 to 50% for 1 to 30 minutes at a temperature in the range of 10 to 40 ° C and in rinsing the solution or dispersion of the fiber conditioning composition of the fibrous material, wherein at least some of the cationic conditioning agent of fibers or of the CDA of the fiber conditioning composition, or both. 23ã. A composition according to claim 22, characterized in that the fiber conditioning composition is a rinse composition for human hair and comprises 0.2 to 10% quaternary ammonium salt, 0.1 to 5% CDA, 75 to 99% aqueous medium and the remainder, if any, of adjuvant (s) and the rinsing composition is in the form of a dispersion in water at a concentration of 10 to 50%. -55- $ 24a. A composition according to claim 22, characterized in that the fiber conditioning composition is a hair conditioning shampoo (11) and includes 5 to 25% synthetic organic detergent, 0.2 to 10% quaternary ammonium salt , 1 to 5% of CDA, 65 to 94% of aqueous medium, and the remaining part, if any, of adjuvant (s) and &quot; shampoo &quot; be in the form of a solution or dispersion in water at a concentration of 10 to 50%. 25â. 11. A composition according to claim 22, wherein the fiber conditioning composition is a fabric softener for use in the laundry cycle or laundry rinse cycle, and wherein said composition comprises 20 to 20% of a salt of quaternary ammonium for tissue indentation, cationic amine, complex with anionic surfactant, or cationic amine complex, or any mixture thereof 0.1 to 5% CDA, 70 to 97.9% aqueous medium, and the remaining part of the adjuvant (s) and fabric softener to be used in the wash cycle or rinse cycle is in the form of a solution or dispersion in water at a concentration of 0.05 to 2%. 26i. A composition according to claim 22, characterized in that the fiber conditioning composition is a softening detergent and includes a detersive ratio of a synthetic organic detergent, 0 to 75% of a detergent builder, 2 to 20% of a salt of quaternary ammonium for fabric softening, cationic amine, quaternary ammonium salt complexes with anionic surfactant, cationic amine complex, or any mixture thereof, 0.1 to 0.5% of CDA, 0 to 75% water, and the remaining part, if any, of adjuvant (s) and the &quot; sweetener &quot; be in the form of a solution or dispersion in wash water at a concentration of 0.1 to 2%. Lisbon, June 19, 1990 J, PEREIRA DA CRUZ Agent of the Prepriesatía linuntrls! street viCTGR c © F © m 10-a, u * 1200 U6BOÀ