LU86390A1 - DETERGENT, SOFTENING AND ANTISTATIC COMPOSITION BASED ON NON-IONIC DETERGENT AND METHOD FOR CLEANING AND SOFTENING TISSUES USING THE SAME - Google Patents

Description

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The present invention relates to a detergent-softener composition and a method for cleaning and softening fabrics in the washing cycle of a laundry operation. More particularly, the present invention relates to softening / antistatic compositions intended for use in the washing cycle of a laundering operation, the composition comprising as essential ingredients, a softening agent of the cationic mono (alkyl) compound type. higher) quaternary ammonium dispersible in water, a nonionic surfactant and an anionic detergent of the sulfosuccinamate type.

The compositions useful for treating tissues in order to improve their flexibility and their touch characteristics are known in practice.

When used in home laundry, fabric softeners are usually added to the rinse water during the rinse cycle, which lasts only about 2 to 5 minutes.

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Therefore, the consumer is obliged to monitor the laundering operation or to ensure that the fabric softener is added at the correct time. This forces the consumer to return to the washing machine ^ either immediately before the rinsing cycle of the washing operation, or at the start of this cycle, which is tedious for the consumer. In addition, special care must be taken to use the correct amount of fabric softener so as to avoid an excessive dose which can make garments hydrophobic by depositing a greasy film on the surface of the fabrics, as well as giving them a certain degree of yellowing.

As a solution to the problems mentioned above, it is known to use fabric softeners which are compatible with common laundry detergents so that the fabric softeners can be combined with detergents in a single package for use during the wash cycle of the laundering operation. Examples of such fabric softener compositions added to the wash cycle are described in US Pat. Nos. 3,351,438, 3,660,286 and 3,703,480 and many others. In general, these fabric softener compositions for the wash cycle contain a cationic fabric softener of the quaternary ammonium type and other ingredients which make the fabric softener compounds compatible with common laundry detergents.

It is known, however, that the cationic softening compounds added to the washing cycle, either as an ingredient in a detergent-softening-health composition, or as a softener for the washing cycle, impede the brightening activity as well as the cleaning power of detergent. Thus, attempts have been made to compensate t to a certain extent for this influence in the detergent-softening compositions by using nonionic surfactants, higher proportions of brightening agent, carboxymethylcellulose, anti-yellowing compounds, brighteners etc ... However, little improvement has been achieved in the softening compositions for washing cycles using various detergents, most of which are anionic detergents.

The art is replete with descriptions of detergent compositions containing cationic softeners, including softeners of the quaternary ammonium compound type, and nonionic surfactants. As representative examples of this technical modality, mention may be made of US Pat. Nos. 4,264,457, 4,239,659, 4,259,217, 4,222,905, 3,951,879, 3,360,470, 3,351,483, * '35 3 644 203, etc ... In addition, the US patents T * 3 of America n ° 3 537 993, 3 583 912, 3 983 079, 4 203 872 and 4 264 479 describe in particular combinations of surfactant, non-ionic, cationic fabric softener and another ionic surfactant or modifier such as zwitterionic surfactants, amphoteric surfactants, etc.

= Although many of these formulations of the prior art offer satisfactory cleaning and / or softening under many different conditions, they still have the disadvantages of not providing correct softening, for example comparable to that of fabric softeners added to the rinse cycle.

U.S. Patent No. 3,920 15,565 describes a liquid fabric softener composition for the rinse cycle, containing 2 to 15% of a cationic fabric softener and 0.5 to 4.0% of an alkali metal salt of a fatty acid of 16 to 22 carbon atoms (soap) and optionally up to 2% of a nonionic emulsifier, the remainder being water. Di (higher alkyl) dimethyl ammonium chlorides are the preferred cationic compounds although the mono (higher alkyl) quaternary ammonium compounds are also mentioned.

It is generally recognized in practice that quaternary mono (higher alkyl) ammonium compounds, such as for example stearyl trimethyl ammonium chloride, which are relatively soluble in water, are less effective softeners than fabric softeners quaternary di (higher alkyl) type cationics (see, for example, U.S. Patent No. 4,326,965) and, therefore, it has been suggested to use them in conjunction, for example, with anionic detergents such as as fatty acid soaps with which they can form softening complexes as fabric softeners for the rinse cycle.

The Applicant has previously discovered that stable fabric softening compositions having better dispersibility in cold water when used in the rinse cycle are obtained with a cationic quaternary ammonium compound as the sole softener and a sulfonate anionic at a weight ratio of the cationic compound to the anionic compound of about 80: 1 to 3: 1 (see U.S. Patent No. 3,997,453). This patent describes softening compounds of mono (higher alkyl) and di (higher alkyl) quaternary ammonium and it also describes alkylbenzene sulfonates as an anionic compound. According to this patent, the addition of small amounts of anionic sulfonate to aqueous dispersions of the excess amount of the quaternary softener reduces the viscosity of the dispersion and produces a homogeneous liquid which is easily dispersible in cold water ( i.e. 20 to the rinse cycle of an automatic washing machine).

However, as mentioned above, it has been known for some time that it would be very useful for convenience to use the fabric softening formulation in conjunction with the detergent in the washing cycle of the washing machine. .

U.S. Patent No. 4,222,905 describes laundry detergent compositions which may be in liquid form and which are formulated from certain nonionic surfactants and certain cationic surfactants, including mono compounds (higher alkyl) quaternary ammonium, such as a (tallow alkyl) trimethylammonium halide, at a nonionic / cationic surfactant weight ratio of from 5: 1 to about 1: 1. This patent teaches that the quantity of anion-producing materials must be reduced to a minimum '5 5 and preferably completely avoided, but in any case, anionic materials having a dissociation constant less than 1x10 -5, such as Sodium benzene sulfonate (linear alkyl Cnfg) should be introduced only in amounts up to a maximum of 10% by weight of cationic surfactant.

- · Detergent compositions with mixed nonionic / cationic surfactants having a nonionic / cationic weight ratio of about 1: 1 to 40: 1 in which the nonionic surfactant belongs to the class having a hydrophilic ratio - lipophilic (RHL) of about 5 to about 17, and the cationic surfactant belongs to the class of mono (higher alkyl) quaternary ammonium compounds in which the upper alkyl group has about 15 to about 30 carbon atoms, are described in U.S. Patent No. 4,239,659. This patent gives a general description of what other additives can be incorporated at their conventional rates of use established in the art as being of about 0 to about 40%. A detailed list of additives is given, including semi-polar, non-ionic, anionic, zwitterionic and ampholytic co-surfactants, detergency builders, dyes, fillers, enzymes, bleaches and many other. There is no example of use, or description, of anionic surfactants; however, it has been established that the co-surfactants must be compatible with the nonionic and cationic surfactants and can be any of the anionic surfactants described in US Pat. No. 4,259,217.

The latter patent describes mixtures of nonionic surfactants having an RHL of about 5 to about 17 and a cationic surfactant, including mono (higher alkyl) quaternary ammonium compounds, at Λ 35 nonionic weight ratio : cationic from 5.1: 1 to about 6,100: 1. According to this patent, the detergent compositions can contain up to approximately 50%, preferably from approximately 1 to approximately 15%, of anionic surfactants and / or zwitterionic surfactants. Anionic surfactants include, but are not limited to (linear alkyl) benzene sulfonates and alkyl ether sulfates. Example XV ^ in column 40 of this patent describes a liquid detergent composition for laundering large laundry, having the following formula: 10 Components% by weight

Sodium sulfate of a C \ 2 C] ^ 5 alcohol ethoxylated with 3 moles of ethylene oxide 5.0

Ethoxylated Cp2 “Cl3 alcohol containing an average 15 of 6.5 moles of ethylene oxide 20.0

Trimethyl ΐ thyl-ammonium (copra) chloride 3,5

Glycine 8.0 rr Sodium toluene-sulfonate 10.0 20 Water and minor additives the rest up to 100

The following liquid detergent composition for washing large laundry is described in Example XVII (column 41): 25 Components% by weight

Condensation product of a C14-C15 fatty alcohol with an average of 7 moles of ethylene oxide 28.5

Triethanolamine salt of a benzene sulfonic acid (linear alkyl) in which the alkyl chain has an average of 11.9 carbon atoms 20.0

(C3-C13 alkyl) dihydroxy-ethyl-methyl-ammonium chloride 1.5 c 35 Ethanol 10.0 J * 7

Diethylene triamine pentamethyl phosphonic acid 0.3

Citric acid 0.2 9: 1 mixture of dimethylpolysiloxane 5 and acrogel silica emulsified in a highly ethoxylated fatty acid (commercially available from Dow Corning under the designation DB31) 0.3

Saturated fatty acid having 16 to 22 carbon atoms in the 0.75 alkyl chain

Proteolytic enzyme 0.4

Minor additives and water the rest up to 100

A liquid laundry detergent and fabric softener composition which contains about 3 to 35% by weight of a nonionic surfactant, about - 3 to 30% by weight of cationic surfactant of the mono (alkyl) compound type higher) quaternary ammonium and a mixture of anionic surfactants comprising (a) 20 (C4-C1Q alcohols) sulfates and (b) (C12-C22 ethoxylated alcohols) ether-sulfates or carboxylates, is described in the patent of the States - United States of America n ° 4 264 457.

The molar ratio of total cationic surfactant to total anionic surfactant can vary between 0.8: 1 and 25: 1. According to this patent, the choice and the proportions of the two particular anionic surfactants to the exclusion of other known anionic surfactants are essential for obtaining the maximum detergent power, flexibility and antistatic properties.

The Applicant has also previously discovered that the softening and antistatic action of a detergent compound and a cationic fabric softening agent of the type consisting of mono (higher alkyl) quaternary ammonium is greatly improved by using 35 cationic softener in the form of an 8 to about 1: 1 complex with an anionic active surfactant which is an aromatic (linear alkyl) sulfonate. This discovery is the subject of patent application in France No. 85 15278 filed on October 15, 1985 in the name of the applicant.

Furthermore, this improvement in the softening / antistatic action is obtained without reducing, and, in some cases, greatly improving, the bleaching and cleaning action.

Although excellent softening and anti-static effects have been obtained by the nonionic liquid detergent compositions, based on the complex of cationic fabric softener and (linear alkyl) benzene sulfonate, it is nevertheless desirable to achieve further improve the overall cleaning action. It is also desirable to be able to form the fabric softener complex of the quaternary mono - (higher alkyl) type fabric with a wider range of commercially available anionic detergents than only anionic detergents of the (linear alkyl) aromatic sulfonate type. .

As a result of other research carried out by the applicant, it has been discovered that the two aims can be achieved very easily by adding to the composition another surfactant which is a sulfosuccinamate. The incorporation of the sulfosuccinamate greatly enhances the detergent power of the nonionic / cationic mixture with or without the other advantages of other anionic surfactants such as a (linear alkyl) benzene sulfonate.

It is on the basis of these findings that the present invention has been developed.

It is therefore an object of the present invention to improve the softening, whitening and antistatic action of detergent compositions containing softening agents of the quaternary ammonium * compound type and non-ionic detergent compounds, while greatly improving the overall cleaning action.

Another object of the present invention is to formulate stable liquid detergent-softener compositions using cationic softeners of the mono (higher alkyl) quaternary ammonium type with non-ionic surfactants and sulfosuccina- ~ mate as main surfactant components and essentials, which compositions are compatible with brightening fluorescent agents, enzymes, soil release agents and other detergent additives.

Yet another object of the invention is to provide a laundry detergent-softener composition for the wash cycle, which can effectively clean a wide range of soils, including clays, oils, greases, etc., and impart flexibility with natural and synthetic fibers and fabrics.

These and other objects of the invention which will become apparent from the following description are achieved by providing a laundry detergent composition capable of washing soiled fabrics in an aqueous washing liquid, which composition comprises a surfactant non-ionic and a sulfosuccinamate type surfactant as essential surfactants, a cationic fabric softener of the type composed of mono (higher alkyl) quaternary ammonium and, optionally an anionic surfactant. In the preferred embodiment, the composition may contain at least one coloring and / or bleaching agent, in particular dyes, whitening agents and optical brightening agents, and mixtures thereof, and other optional additives for detergents, particularly enzymes and soil release agents.

In other useful embodiments, the composition may be formulated with only or mainly a non-aqueous liquid vehicle or a mixture of water and an organic solvent. In yet another embodiment, the composition can be formulated as a paste or liquid of high viscosity.

The nonionic surfactants which are contemplated can generally be any of the nonionic surfactants known to be useful as detergents for cleaning soiled tissue.

Suitable nonionic surfactants are commercially available and come from the condensation of an alkylene oxide or equivalent reactant and a hydrophobic compound with reactive hydrogen. Hydrophobic organic compounds can be aliphatic, aromatic or heterocyclic, although the first two classes are preferred. The preferred types of hydrophobic compounds are aliphatic-higher alcohols and alkyl-phenols, although others may be used such as carboxylic acids, carboxamides, mercaptans, sulfonamides, etc. The products (I condensation ethylene oxide with (higher alkyl) phenols or higher fatty alcohols represent preferred classes of nonionic compounds. In general, the hydrophobic portion should contain at least about 6 carbon atoms, and preferably at least About 8 carbon atoms, and it can contain up to about 50 or more carbon atoms, a preferred range being from about 8 to 22 carbon atoms, in particular from 10 to 18 carbon atoms for aliphatic alcohols and 12 to 20 carbon atoms for the (higher alkyl) 50 phenols The amount of alkylene oxide varies considerably depending on the hydrophobic compound, but is generally about 3 moles of alkylene oxide up to '' at around 200 moles per mole of hydrophobic compound, preferably about 3 to 50 moles, and more preferably 55 5 to 20 moles of alkylene oxide per mole of hydrophobic compound 11 will provide sufficient cleaning action and necessary compatibility with other components.

Preferred classes of nonionic surfactants are represented by the formulas: ° 5 RO (CH2CH20) nH (I) in which R is a primary or secondary alkyl chain of about 8 to 22 carbon atoms and n is on average equal to 5-50, preferably 5-20, especially 6-13; and 10 R1-Ç) ^ - 0- (CH2CH20) mH (II) in which r! is a primary or secondary alkyl chain of 4 to 12 carbon atoms, and m is on average equal to 5-50, preferably 5-20, in particular 6-13.

Preferred alcohols from which the compounds of formula (I) are prepared include lauryl, myristylic, cetyl, stearyl - and oleyl alcohols, and mixtures thereof. Particularly preferred radicals R are C 1 to C 6 alkyl groups, with C 12 to C 15 alkyl groups and mixtures thereof being particularly preferred.

The radicals R1 preferred in formula (II) are Cg groups to Cg and C9 groups, including octyl, isooctyl and nonyl groups, being particularly preferred.

Representative examples of the nonionic compound of formula (I) are lauryl alcohol condensed with 5 or 7 or 11 moles of ethylene oxide. Representative examples of the nonionic compound of formula (II) include isooctylphenol or nonylphenol condensed with 3 to 8 moles of ethylene oxide.

Other non-ionic compounds which can be used include polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil acids, acids from petroleum oxidation products , 12 etc ... These esters generally contain about 10 to about 22 carbon atoms in the acid portion and about 3 to about 30 moles of ethylene oxide or its equivalent.

* 5 Still other non-ionic active surf s are the condensation products of alkylene oxide with the amines and amides of higher fatty acids. The fatty acid group generally contains about 8 to about 22 carbon atoms and is condensed with about 10 3 to about 30 moles of ethylene oxide as a preferred example. The corresponding carboxamides and sulfonamides can also be used as equivalent sensitive.

Although ethylene oxide has been given as an example of the alkylene oxide group present in nonionic surfactants, the invention also contemplates using nonionic active surfaces formed with the oxide. propylene, preferably a mixture of ethylene oxide ... and propylene oxide. For example, the nonionic active surfactants sold in the well known Plurafac series such as Plurafac B-26, the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. In the higher alkanols alkoxylated by a poly (lower alkoxy) chain, to obtain the best ratio of the hydrophilic and lipophilic portions, the number of lower alkoxy groups generally represents 40% to 100% of the number of carbon atoms of the alcohol higher, preferably 40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of such a higher poly (lower alkoxy) alkanol. Higher molecular weight alkanols and various other normally solid detergents and nonionic surfactants can contribute to gelation of liquid detergent formulations 13 and therefore will be omitted or used in limited amounts in the present liquid compositions, although minor proportions can be used for their cleaning properties, etc., and may be advantageous in paste formulations or more highly viscous. With respect to both preferred and less preferred nonionic detergents, the alkyl groups contained therein are most preferably linear, although a minor degree of branching can be tolerated, for example at the level of the neighboring carbon atom or, separated by two carbon atoms from the terminal carbon atom of the straight chain and opposite the ethoxylated chain, provided that such a branched alkyl group is not of length more than three carbon atoms.

Normally, the proportion of carbon atoms in such a branched configuration is minor and rarely exceeds 20% of the carbon atom content of the alkyl group. Similarly, although the linear alkyl groups which are terminally linked to the ethylene oxide chains are very preferred and required to provide the best combination of detergency, biodegradability and non-gelling characteristics, it can there may be a minor or secondary junction in the chain with ethylene oxide. There is generally only a minor proportion of such alkyl groups, generally less than 50%, but, as is the case for example with Tergitol, this proportion may be higher. Also, when the lower alkylene oxide chain contains propylene oxide, this generally represents less than 20% and preferably less than 10% of this chain, although more can be used. high percentages, as in some Plurafac.

The amount of nonionic surfactant is generally the minimum amount which, when added to the wash water, provides a suitable cleaning action. In general, amounts of from about 1 to about 50%, preferably from about 10 to about 40%, and more preferably from about 12 to 35% by weight of the composition, can be used.

A second essential ingredient in the formulations of the present invention is the cationic fabric softener. Softeners are used to make fabrics or textiles flexible, and the terms "softening" and "softener" refer to touch, hand, or feel; this is the tactile impression offered by fabrics or textiles on the hands or body and this represents an aesthetic or commercial criterion of importance. The cationic fabric softeners used in the present invention are quaternary mono (higher alkyl) ammonium compounds i represented by the following formula: R2 ^ .R3 '+ 20 m ·' X "^^ R3 (III) in which R2 is a long chain alipathic radical; having 10 to 22 carbon atoms, and the three symbols R2 represent, independently, alkyl or hydroxy-lower alkyl radicals and X is anion forming a water-soluble salt, for example a halide, it is ie chloride, bromide, iodide, a sulfate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or a similar organic or inorganic radical of solubilization. The carbon chain of the aliphatic radical containing 10 to 22 atoms of carbon, in particular 12 to 20, preferably 12 to 18, and better still 16 to 18 carbon atoms, can be straight or branched, and saturated or unsaturated. The lower alkyl radicals have β 35 1 to 4 carbon atoms, preferably 1 or 2 atoms 15 of c arbone, and better still, these are methyl groups, and they may contain a hydroxyl radical. Preferably, the long carbon chains are obtained from long chain fatty acids, for example those derived from tallow and soybean oil. The terms "soy" and "tallow," etc., as used herein, refer to the source from which the long chain fatty alkyl chains originate. Mixtures of fabric softeners of the quaternary ammonium compound type can be used. The preferred ammonium salt is a mono (higher alkyl) trimethyl ammonium chloride in which the alkyl group is from tallow, hydrogenated tallow or stearic acid. Particular examples of softening agents of the quaternary ammonium type of formula 15 (III) suitable for use in the composition of the present invention include the following: tallow chloride-trimethyl ammonium, (hydrogenated tallow chloride) trimethyl ammonium , trimethyl stearyl ammonium chloride, triethyl stearyl ammonium chloride, trimethyl cetyl ammonium chloride, soy trimethyl ammonium chloride, stearyl dimethyl ethyl ammonium chloride, tallow diisopropyl methyl chloride ammonium, sulfates, methosulfates, ethosulfates, bromides and hydroxides, correspondents, etc.

Another useful class of commercially available tissue softening quaternary ammonium compounds are the ethoxylated compounds of formula (IV): 'R3 1 + R2-N- (CH2CH20) XH X “30 (CH2CH20) yH ( IV) in which X, R2 and R3 are as defined for formula (III) and x and y each represent positive numbers of at least 1 and the sum x + y is from 2 to 15.

A particularly preferred compound of formula 16 (IV) is sold by Armak under the trade name Ethoquad 18/12 (r3 = CH3 ~, R.2 = C] _g alkyl, x + y = 12).

The amount of the cationic fabric softener of the quaternary monoalkyl type fabrics can generally be between approximately 1 and approximately 20%, preferably between approximately 4 and approximately 16%, and in particular between approximately 5 and 10% by weight of the composition. .

The weight ratio of the nonionic surfactant to the cationic fabric softener can be between about 1: 1 and 15: 1, preferably between about 1.5: 1 and 10: 1, and better still between about 2: 1 and 8: 1.

The surfactant sulfosuccinamate is the third essential active ingredient in the compositions of the invention. These compounds are characterized by the fact that they have a C à to ouverte open chain hydrocarbon substituent. C22 linked to the nitrogen atom of the carbonamide group (-CON <^) present at a carboxy terminal group of the succinamate portion, and by the fact that the sulfonyl group 20 (-SO3-) is linked to l 'one of the carbon atoms in alpha or beta position with respect to the carbonamide group.

Examples of the sulfosuccinamate include disodium N-octadecyl sulfosuccinamate (available under the designation Alkasurf SS-ΤΑ from Alkaril Chemicals, 25 or ASTROMID 18 from Alco Chemical Corp.), N-oleyl sulfosuccinamate disodium (available from Alkaril Chemicals under designation Alkasurf SS-OA), N- (1,2-dicarboxyethyl) -N-octadecyl-sulfosuccinamate tetra-sodium (available under the designation ASTROMID 22 from 30 Alco Chemical Corp., or under the designation Monawet SNO-35 from Mona Industries, Inc.).

In general, however, the sulfosuccinamates can be represented by the following general formula (V): 4 O 4 -R4 CH2-C-N4 ^^ (V); Z-O3-S-CH-COOZ r5 *! ” 17 in which Z is a monovalent cation forming a salt, such as an alkali metal, ammonium or amine, is hydrogen, a lower alkyl group, carboxy (lower alkyl), or 1,2-dicarboxy (lower alkyl) and 5 r5 is an open chain hydrocarbon residue of 10 to 22 carbon atoms.

As the alkali metal, sodium, potassium or lithium are preferred, sodium being particularly preferred.

The monovalent amine salt-forming cation can be, for example, a mono-, di- or tri (lower alkanol) -amine, for example mono-, di- or triethanolamine.

The "lower alkyl" group can have 1 to 5, preferably 1 to 3, and more preferably 1 or 2 carbon atoms.

The open chain hydrocarbon residue represented by r5 may be saturated or unsaturated, and may be a straight chain or branched chain group, preferably an alkyl or alkenyl group of 14 to 18 carbon atoms, in particular from 16 to 18 carbon atoms, such as tallow, hydrogenated tallow, fractionated tallow, oleyl, octadecyl, stearyl, etc.

When is a carboxy (lower alkyl) or 1,2-dicarboxy (lower alkyl) group such as carboxymethyl, carboxyethyl, carboxypropyl, 2-carboxy-2-methylethyl, 1,2-dicarboxyethyl, etc., the group or the carboxyl groups may be in the form -C00Y where Y is the group Z or a lower alkyl group; preferably Y is Z, more preferably sodium.

The amount of the sulfosuccinamate should be chosen with care depending on factors such as the nature and amount of the nonionic surfactant and the cationic fabric softener, the particular sulfosuccinamate, as well as the intended washing conditions, "including for example the type of fabrics, the type of soiling, the washing temperature, the hardness of the water, etc. In general, however, a maximum cleaning action is achieved when the quantities of sulfosuc-cinamate, nonionic surfactant and fabric softener for cationic tissues with a mono (higher alkyl) group are each within the following ranges - in parts by weight based on the total composition.

Broad Preferred (a) Nonionic surfactant 10-50 12-35 10 (b) Quaternary monoalkyl compound 1-10 2-6 (c) Sulfosuccinamate 1-10 2-6

In the above ranges, the weight ratios of (a) :( b), (a) :( c) and (b) :( c) are also important, although again the optimal values may differ for different compounds and different washing conditions. However, in most cases, the ratios (a) :( b) and (a) :( c) range from about 15: 1 to 1: 1, preferably from 10: 1 to 1.5: 1, better still 20 from 8: 1 to 2: 1. The weight ratio (b) :( c) should generally be about 3: 1 to 1: 3, preferably about 2: 1 to 1: 2, more preferably about 1.3: 1 to 1: 2. In addition, the weight ratio (a) :( b) + (c) is about 10: 1 to 1: 1, preferably 6: 1 to 1.5: 1.

For example, according to a preferred embodiment of the invention in which the non-ionic surfactant is a C 2 -C 25 alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of alcohol (such as the product from Shell Oil Co., Neodol 25-7) in an amount of about 15 to 25% by weight of the total composition, the fabric softener of the quaternary monoalkyl compound type is tallow-trimethyl ammonium chloride , and the sulfosuccinamate is N- (1,2-dicarboxyethyl) -N-octadecyl-sulfosuccinamate tetrasodium (e.g. * 35 Monawet SNO-35), the preferred ratios of the nonionic surfactant to the quaternary compound and the quaternary compound to sulfosuccinamate are approximately 12: 1 to 4: 1 and approximately 1: 1 to 1: 2, respectively under conventional washing conditions, for example at 49 ° C, at a product concentration of 0.2% , 100 ppm of hardness ions, for a wide range of fabrics and soils.

Another optional, but preferred, component of the detergent composition of the invention is an anionic surfactant. Thus, as described in patent application 85 15278 mentioned above, the softening and antistatic action of the mixture of nonionic surfactant and fabric softening agent of the type composed of mono (higher alkyl) quaternary ammonium is greatly improved by the use of a detergent of the aromatic (linear alkyl) sulfonate type, preferably in the form of a 1: 1 molar complex with the quaternary fabric softener.

Examples of suitable anionic detergents include water-soluble salts, for example sodium, potassium, ammonium and alkylolammonium salts of (linear higher alkyl) aromatic sulfonates containing from about 8 to 26 carbon atoms, preferably 10 to 22 carbon atoms, in the alkyl radical. (The term "alkyl" embraces the alkyl portion of the higher acyl radicals).

Preferred examples of the aromatic (linear alkyl) sulfonates are those containing 10 to 16 carbon atoms in the linear alkyl radical, for example the sodium, potassium and ammonium salts of (higher alkyl) benzene sulfonates, of (higher linear alkyl ) toluene sulfonates, (upper linear alkyl) phenol sulfonates and (higher linear alkyl) naphthalene sulfonates. (Upper linear alkyl) -benzene sulfonates such as (CpQ-55 Cpg alkyl) -, in particular (C 1 -C 4 to C 14 alkyl) -, for example * 20 (C 12 alkyl (n - <^ ° âécyle)) -benzene-sulfonates, are particularly preferred anionic surfactants.

In addition to aromatic (linear alkyl) sulfonates, another preferred class of anionic surfactants which can enhance the overall action, in particular antistatic and softening, of the detergent compositions of the invention includes the alkyl ethersulfates of formula R ^ 0 ( CH2CH20) p-SO3M, in which is a higher alkyl group having 8 to 20, in particular 10 10 to 18 carbon atoms, M is a cation forming a solubilization salt, such as an alkali metal ion, a alkaline earth metal, ammonium ion, ammonium ion substituted by 1 to 3 lower alkyl groups, or mono-, di- and trialkanolamines having 2 or 3 carbon atoms in the alkanol group (s), and p is a number from 2 „to 8, preferably from 2 to 6 (in particular equal to 1/5 to 1/3 or 1/2 of the number of carbon atoms in R ^). A preferred detergent of the polyethoxylated alcohol type sulfate 20 is available from Shell Chemical Company and is marketed under the designation Neodol 25-3S. This material, the sodium salt, is normally sold as a product with 60% active ingredient in an aqueous solvent medium. Although Neodol 25-3S is the sodium salt, it is also possible to use the potassium salt and other suitable soluble salts of triethenoxy sulfate (higher alcohol of 12 to 15 carbon atoms) and other compounds of this type. types described herein, such as those already designated and those described below, in partial or total replacement of the sodium salts. As in the case of the various materials of the compositions of the present invention, they can be used as a mixture.

Examples of (higher alcohol) - polyethenoxy sulfates which can be used as a component of the anionic detergent of the present liquid detergents 21 or include a partial replacement thereof: (mixed normal or primary C1-C15 alkyls) -tri-thénoxy-sulfate, sodium salt; myristyl-triethenoxy-sulfate, potassium salt; n-decyl-diethenoxy-sulfate, diethanolamine salt; lauryl-diethenoxy-sulfate, ammonium salt; palmityl-tetraethenoxy-sulfate, sodium salt; (primary normal Cl4-Cl5 alkyl mixed) -tr ± -and tetraethenoxy sulfates, sodium salt; stearyl-pentaé-thénoxy-sulfatef trimethylamine salt; and (mixed normal C10- <318 alkyls) - triethenoxy sulfate, potassium salt. Minor proportions of the corresponding branched chain and middle alkoxylating detergents such as those described above can be used, but modified so that the ethoxylation is at a mid carbon atom, for example located at four carbon atoms at the end of the chain,, and the carbon content in the higher alkyl is the same. Similarly, the junction of normal alkyl may be at a secondary carbon atom, or spaced two carbon atoms from the end of the chain. In either case, as previously indicated, only small proportions should be present, for example 10 or 20%, in the general case.

As is the case with preferred nonionic detergents, the present poly (lower alkoxy) sulfates-higher alkanols are readily biodegradable and have better detergency when the fatty alkyl is linked at the end to the poly ( oxyalky-50 lower lene), which is connected at the end to the sulfate. Here again, as is the case with nonionic detergents, a small proportion, for example not exceeding 10%, of branched components and having a median junction are tolerable. In general, it is preferable that the alkyl group contained in the alkoxylated anionic detergent, 22 as in the nonionic detergent, is a mixture of different chain lengths, such as chains of 11, 12, 13, 14 and 15 carbon atoms or 12 and 13 carbon atoms instead of being made up of a single chain length. Nevertheless, the invention applies to liquid detergents containing pure nonionic and anionic components.

Of course, ethylene oxide is the preferred lower alkylene oxide of the alkoxylated anionic detergent, as well as the nonionic detergent, and its proportion in polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic detergent and, in more preferred compositions, 2 to 4 moles will be present, the most preferred amount being three moles, particularly when the alkanol is greater than 12 or 13 carbon atoms or 11 or 12 to 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic ratio, when the carbon atom content of the alkyl chain is in the lower part of the range of 10 to 18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about two moles per mole, while when the higher alkanol has 16 to 18 carbon atoms, in the upper part of the range, the number of ethylene oxide groups can be increased to 4 or 5 and, in some cases, up to 8 or 9. Similarly, the salt-forming cation can be modified to obtain the best solubility. It may be any suitable metal or solubilization radical, but most often an alkali metal such as sodium, or ammonium. If an alkylamine or lower alkanolamine is used, the alkyl and alkanol groups generally contain 1 to 4 carbon atoms and the amines and alkanolamines can be mono-, di- and trisubstituted, as in monoethanolamine,

'J

23 t diisopropanolamine and trimethylamine.

Aromatic (higher alkanol) -poly (lower alkoxy) sulfates and (linear alkyl) sulfonates are highly preferred complementary detergents in the compositions of the present invention, but other anionic detergents can be used with them or in combination therewith. place such compounds. In particular, alpha-olefin sulfonates, paraffin sulfonates and (higher alcohol) sulfates can be used. 10 Olefin sulfonates generally contain long chain alkenyl sulfonates or long chain hydroxyalkane sulfonates (the OH group being located on the carbon atom which is not directly linked to the carbon atom carrying the group - SO3H). The olefin sulfonate type detergent generally comprises a mixture of such types of compounds in varying amounts, often with long chain disulfonates or sulfate sulfonates. Such olefin sulfonates are described in numerous patents such as U.S. Patents 2,061,618, 3,409,637, 3,332,880, 3,420,875, 3,428,654, 3,506,580 and British Patent No. 1,129,158. The number of carbon atoms in the olefin sulfonate is generally in the range of 10 to 25, more commonly 10 to 20, or 12 to 18, for example a mixture mainly of C] _2 / C] _4 and C ^ g, having an average of about 14 carbon atoms, or a mixture mainly of C14, C] _g and having an average of about 16 carbon atoms.

Another class of useful anionic detergents is that of (higher paraffin) sulfonates. They are primary or secondary paraffin sulfonates obtained by reacting long chain alpha-olefins and bisulfites, for example sodium bisulfite, or paraffin sulfonates whose sulfonate groups are distributed along the paraffin chain, by * mf 24 example the products obtained by reacting a long chain paraffin with sulfur dioxide and oxygen under ultraviolet light, then by neutralizing with sodium hydroxide or other suitable base (as in United States patents 2,503,280, 2,507,088, 3,260,741, 3,372,188 and German patent no. 735,096).

Paraffin sulfonates contain from 13 to 17 carbon atoms and are normally monosulfonates, but if desired, they may be di-, tri- or poly-sulfonates. In general, the di- and poly-sulfonates are used in admixture with a corresponding monosulfonate, for example in the form of a mixture of mono- and disulfonates containing up to about 30% of the disulfonate. Their hydrocarbon substituent is preferably linear, but if desired, branched chain paraffinsulfonates can be used, although they are not as satisfactory with regard to biodegradability. The paraffin sulfonate can be sulfonated at the end or the substituted tallow onate can be linked to carbon atom 2 or other carbon atom of the chain, and, similarly, the sulfonate groups of any di- or poly -sulfonate used can be distributed over different carbon atoms of the hydrocarbon chain.

Paraffin sulfonates and olefin sulfonates are used in the form of their alkali metal salts, for example sodium and potassium, ammonium, or mono-, di- and tri (lower alkanol) amines, or their mixtures. Triethanolamine is the preferred alkanamine salt forming cation. (Linear alkyl) benzenesulfonates and alkyl ether sulfates are particularly preferred as an anionic surfactant.

These anionic surfactants can not only - react with the quaternary mono (higher alkyl) compound * • - f + 25 to improve the softening and antistatic action, but they also have the function of causing more effective deposition on the tissues in progress. laundering various other optional detergent builders, as described in detail below, in particular optical brighteners.

Although no particular rule can be applied to each combination of ingredients and for all washing conditions, it has been noted that as a general rule, between the two preferred classes of anionic surfactants, the (linear alkyl) benzene sulfonates are generally slightly more effective than alkyl ether sulfates in softening action, but slightly less in cleaning action - although the addition of any anionic active surf does not provide often only slight improvements in cleaning action compared to the same composition without anionic surfactant. It is naturally possible to use mixtures of two or more anionic surfactants.

Since the anionic surfactant probably forms a complex with the cationic softener to improve the softening / antistatic action without hampering, or slightly improving, the cleaning action of the nonionic surfactant and the brightening agent , in the detergent formula, the ratio of the cationic compound to the anionic surfactant is particularly decisive, since strong excess of one or the other component could disturb the overall yield. Therefore, ratios of the cationic compound to the anionic surfactant from about 1.3: 1 to 1: 1.5, preferably from 1.2: 1 to 1: 1.2, more preferably from 1.1: 1 at 1: 1.1, and in particular about 1: 1 will give better softening and anti-static effects, as well as a better whitening and perhaps cleaning effect.

* 9 * t, * ** "> i 26

The total amount of the cationic / anionic softener mixture in the composition is generally between about 2 and 20%, preferably between 5 and 15% by weight based on the total composition.

In addition, the total amount of cationic softener and anionic surfactant is generally between about 20 and 100%, preferably between 30 and 80% by weight, based on the nonionic surfactant. In addition, in the above amount and ratio ranges, the cationic / anionic softening mixture is compatible with the nonionic surfactant, sulfosuccinamate and optical brightener, etc.

The vehicle for the liquid detergent composition of the invention is preferably an aqueous vehicle, and it may be water alone or water with other solvents added to dissolve the particular ingredients, as is well known in the art. Due to the availability of water and its low price, it is preferable to use water as the main solvent. However, certain amounts of other solvents can be used, generally up to 20%, and preferably up to a maximum of 15% of the total content. In general, such a complementary solvent is either a lower alkanol or a lower diol or polyol, for example ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol, etc. use ethereal polyols such as diethylene glycol and those known as cellosolves.

In addition to the complementary solvent, it is also generally preferable to include a hydrotropic material in the formulation in order to maximize the compatibility of all active ingredients and to make the liquid formulation more homogeneous and stable. Examples of suitable hydrotopes include the alkali metal aryl sulfonates such as sodium benzenesulfonate, sodium toluene sulfonate, sodium xylene sulfonate and the corresponding potassium salts. hydrotope can be used in amounts up to about 15%, preferably 10% by weight of the total composition, for example 1 to 8%, or 2 to 6%.

Although aqueous vehicles are preferred, non-aqueous liquid vehicles such as the above-mentioned organic cosolvents can be used as the sole liquid vehicle or as the primary liquid vehicle, i.e., non-aqueous liquid vehicles aqueous can represent about 50 to 100% by weight of the liquid vehicle, the optional residue consisting of water and / or a hydrotropic material. It is also possible to use mixtures of two or more organic solvents.

In addition, it is possible to formulate the detergent composition consisting of the three essential ingredients: nonionic surfactant, compound of mono (higher alkyl) quaternary ammonium, and detergent sulfosuccinamate, plus an optional anionic surfactant, and any adjuvants of detergents, in the form of very viscous compositions, for example gels, pastes, etc., using for example conventional thickeners and well known with the liquid vehicle. Examples of suitable thickeners include, for example, cellulose ethers such as hydroxyethyl cellulose, hydroxymethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose, etc., xanthan gum, mineral clays, etc. As a variant, the compositions can also be prepared directly in the form of pastes, or in the form of very viscous liquids, simply by mixing the various ingredients in the absence of liquid vehicle, or in the presence of only minor quantities, for example reaching a maximum of about 20% by weight, of liquid vehicle, preferably water or a water / organic solvent mixture.

The water intended for the formulation of the present liquid or paste detergents can come from the starting materials themselves, for example solutions or suspensions of the various adjuvant salts, or it can: be added. In the latter case, it is preferable to use deionized water or water of low hardness, for example containing less than 50 ppm of hardness salts, expressed as calcium carbonate, preferably less than 10 ppm of CaCO3 · However, although it is disadvantageous to use hard water, it can be used and satisfactory products can be obtained from water having hardnesses as high as 200 ppm, but in general the use such water is avoided as much as possible.

Various selected compatible adjuvants may also be present in the detergent composition to give it other advantageous properties, functional or aesthetic. Thus, enzymes can be included in the formulation, for example proteases, amylases, lipases, etc., and mixtures thereof; bleaching agents; bleach activators and bleach stabilizers; soil suspending or anti-redeposition agents, for example polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl methylcellulose; soil release agents, for example Polymer QCJ from Alkaril Chemical for the removal of engine oil, etc .; dyes, brighteners, pigments, optical brighteners, for example cotton brighteners, polyamide and polyester; bactericides, for example hexachlorophene; preservatives, for example methyl "parasept" or sodium benzoate; ultraviolet absorbers; pH modifiers, for example amines, pH buffers; opacifiers, for example behenic acid, polystyrene suspensions, etc., and perfumes. The adjuvants, of course, will be chosen so as to be compatible with the main constituents of the detergent formulation.

5 Among the adjuvants mentioned, perhaps the most important for the functional effect are the optical brightening agents because the modern housewife now requires that the washed clothes are not only clean and white, but also that they have an appearance brilliant. Optical brighteners are substantive for washed textiles (this substantivity can be selective) and sometimes have comparatively low solubilities. Therefore, it is important that they are kept in solution in the liquid detergent composition and, more importantly, they should be dispersed immediately in the wash water so as to avoid formation on the laundry. visible shiny spots, instead of a uniform shiny appearance. In this case, the choice of brightening agent to obtain the best results can be determined by the specialist. It has been found that relatively small amounts of brightening agents should be used so as not to exceed the solubility limits. Also, in the class of these materials, it has been found that certain brightening agents dissolve particularly easily, and as they were suitable to be incorporated into these products. Fortunately, such preferred brightening agents include brightening agents for cotton and amide-polyester blends, making them suitable for use with laundry containing various synthetic and natural materials. Among the optical brightening agents which are used in the present system, there may be mentioned Tinopal UNPC, Tinopal CBS (Ciba-Geigy), Arctic White CC (Hilton Davis) and the following Phorwhite £ 35 from Verona: BKL, BUP, BBC in solution, BRV in ', 30

J

solution, DCR liquid, DCBVF, EV liquid, DBS liquid and ANR.

Other types of optical brighteners which give superior whitening effects are the components which do not have sulfonate moieties. The preferred class of brightening agents for use in the present invention includes 2- (4-styrylphenyl) -2H-naphtholCl, 2-d3triazoles, 4,4'-bis (1,2,3-triazole -2-yl) stilbenes, 4,4'-bis (styryl) -10 bisphenyls and ^ '- aminocoumarins. Particular examples of these brightening agents include 4-methyl-7-diethylaminocoumarin, 1,2-bis (benzimidaole-2-yl) ethylene and 1,3-diphenyl-phrazolines, as well as 2,5- bis (benzoxazole-2-yl) -thicphene, 2-styryl-15 naphth-Cl, 2-dQoxazole and 2- (stilbene-4-yl) -2H-naphtho £ l, 2-d} triazole.

The content of optical brightener in the liquid composition is normally from about 0.2% to about 3.0% and preferably from 0.25 to 2.7%. Such concentrations are soluble in the liquid detergents described and are effective in adequately brightening the washed laundry. As mentioned above, the presence of anionic surfactant can improve the uniformity of the deposition of the optical brightening agent.

Yet another class of optional builders are organic detergency builders other than nitrilotriacetates, and sequestering agents. Representative examples of the class of detergency builders and sequestering or chelating agents are sodium citrate, potassium gluconate, polyacrylic acids, ethylenediaminetetraacetic acid, and their alkali metal salts, of alkaline earth metal, amine, alkanolamine and ammonium, etc. It is generally preferable, and often necessary, to completely avoid mineral detergency builders, particularly those of the phosphate type. However, when not prohibited by environmental regulations, minor amounts of mineral phosphate-type detergency builders may be included in the compositions.

The content of other adjuvants is preferably maintained at less than 5%, preferably less than 3% by weight of the product. The use of higher proportions of such compounds than those described can often significantly alter the properties, for example the stability, of the liquid detergent, and therefore should be avoided.

Although the liquid detergent softener composition of the present invention is a stable, transparent single-phase liquid, a compatible opacifying agent can be added to impart a creamy appearance to the formulation.

Another optional ingredient, but very! Preferred, detergent compositions of the present invention is an ethoxylated fatty amine such as those from the Ethomeeri © series of compounds from Armak Company, and the Varonic® series from Ashland Chemicals. These compounds can be represented by the general formula: ^^ (ch2ch2o) xh

25 R7-N

CH2CH20) yH

wherein R7 is a fatty alkyl group of about 10 to 22, preferably 12 to 18 carbon atoms, and the sum x + y is about 2 to about 15. The group R7 may be saturated or unsaturated, and , for example, it can come from coconut fatty acid, oleic acid, soy fatty acid, tallow fatty acid, stearic acid, or mixtures of these acids.

The ethoxylated amines help to improve cleaning, softening and anti-static properties. In general, the amounts of ethoxylated amine reaching a maximum of about 15%, preferably about 10%, for example from 1 to 10% or 1 to 8%, in particular 2 to 8% by weight of the composition „5 total liquid are satisfactory.

To promote dissolution of detergents and optical brighteners which may be present in liquid detergents, a small proportion of an alkaline material or mixture of such materials is often included in the present formulations.

Suitable alkaline materials include mono-di- and trialkanolamines, alkylamines, ammonium hydroxide and alkali metal hydroxides. Among these materials, those which are preferred are alkanolamines, preferably trialkanolamines, and, among them, triethanolamine is particularly preferred. The pH of the final liquid detergent containing such a basic material is generally neutral or slightly basic. Satisfactory pH ranges are 7 to 10, preferably about 7.5 to 9.5, but because a pH reading of the liquid detergent using a glass electrode and an electrode Reference to calomel may be imprecise since the detergent system is often essentially non-aqueous, a better indication is obtained by measuring the pH of a 1% solution of the liquid detergent in water. Such a pH is normally also in the range of about 7 to 10, preferably 7.5 to 9.5. In wash water, the pH is generally within this range or it may be slightly more acidic, for example 0.5 to 1 pH unit, due to the organic acid content of the soiled laundry. For liquid formulations, the viscosity at 25 ° C is between 40 and 120 mPa.s, preferably between 40 and 100 mPa.s, better still between 70 and 100 mPa.s, i 35 and in particular between 80 and 95 mPa.s, according to measures at "

V

c "33 carried out using a Brookfield viscometer at room temperature using a spindle No. 1 at 12 revolutions per minute.

The liquid composition is generally added to the washing water in an automatic washing machine of the top or front loading type, so that its concentration in the washing water can be between about 0.05 and 1.5%, generally between 0.1 and 1.2%. In general, depending on the type of machine and the degree of loading with soiled fabrics, the amount of liquid formulation to be added will be between about 1/4 cup and about 1 1/4 cup, the typical amount being about 1/2 scoop (120 milliliters).

The wash water used can be fairly soft water or water of reasonable hardness, and it will generally, and preferably, be used at elevated temperature, in particular at about 38 ° C or more, for example 49 to 82 ° C or more. The composition of the present invention is also useful for laundering clothing in very hard water and at lower temperatures. Thus, the hardness of the water can range from 0 to more than 300 parts per million, calculated as calcium carbonate, and the washing temperatures can range from 4.4 to 49 ° C or more. The washing is carried out in an automatic washing machine in which the washing is followed by a rinsing and by cycles or spinning operations by rotation, dripping or twisting. Of course, the detergent composition can also be used for washing clothes by hand, in which case it can sometimes be used pure on certain stains of the laundry, or the laundry can be soaked in a solution with a higher concentration of detergent before washing.

Washing operations will generally take three minutes to one hour, depending on the fabrics being washed and the degree of soiling. At the end of washing and spinning operations 34 by rotation, dripping or twisting, it is preferable to dry the laundry in an automatic dryer immediately after, but it can also be dried on a cord.

The softening detergent composition of the present invention dissolves very easily whether the wash water is warm or cold, and it cleans, softens and eliminates static charges very effectively on laundry and other items to be bleached without imparting a hydrophobic primer. It can be used in washing machines with top or front loading, and it can be adjusted advantageously to foam to the correct degree. The product is a stable, transparent, attractive liquid which retains its activity and uniformity for a long period of time. In tests in which the effects of its use are compared with those obtained using commercial liquid laundry detergents, it is evaluated very favorably.

This product can be prepared by simply mixing the various ingredients at room temperature with stirring to ensure their dissolution in the aqueous medium. The order of addition of the ingredients and the mixing temperatures can vary without adversely affecting the formation of the single phase transparent liquid product of the present invention. Much more viscous formulations or pastes can be similarly prepared by conventional techniques.

The detergent-softener composition of the present invention has many advantageous features with respect to physical properties and performance in use. With regard to their physical properties, the liquid compositions can be poured and flow freely from the container, as manufactured, and after aging. They exhibit a high degree of storage stability at normal room temperature of the order of about 21 ° C for many months without appreciable precipitation. As a result, the consumer can use them in a conventional manner, by adding very small portions to the laundry bath, and the detergent and softener are present in constant composition in each portion. Although compatible additives can be added to make the final product translucent or opaque, at will, the need for a single-phase solution of the main ingredients ensures effective washing and softening power. with each serving and 15 promotes stability and consistency of the product. The composition can be packaged in any suitable container or packaging material, for example metal, plastic, or glass.

The following specific and nonlimiting examples illustrate various embodiments of the present invention.

In order to test the cleaning action of the detergent compositions, several different formulations were prepared and used in standard test procedures on various soils and on different fabrics at different rates and proportions of active ingredients. All cleaning tests were carried out under the same conditions (unless otherwise specified) in identical washing machines 30 (Terg-O-tometer): 49 ° C, 100 ppm Ca ++, 64 liters of washing water, concentration 0.2% product (1/2 scoop.

The fabrics tested included "Nylon", cotton and a polyester (Dacron) / cotton blend (65/35). The test soils included a mixed soiling (TF) from Test: 35 Fabrics Co., Piscataway clay (PC) and an oily soiling (on cotton) (EMPA) from Test Fabrics Co. The action of cleaning was measured by reflectance readings (Rd) as a measure of whiteness and these readings are correlated to obtain a total soil removal value (ES) in which the values

Rd for the different soiled fabrics are multiplied ^ each by a coefficient, which has been determined for each artificially soiled fabric so as to make the correlation existing between the cleaning action on the artificially soiled fabrics and practical tests of detergents for laundry. By comparing the ES values of any two compositions, one can evaluate the relative overall cleaning power (IES) of the two compositions.

15 Example 1

The following compositions were prepared: • i.

20 25 30 1 35 y '37 I I II I cm

OJ ^ Π ^ <N -S

S -1 ** n 2 λ 2 ^ u c

------—--- H

<o ^ 2 Z · '' '?.' * 2

+ ° - [J

4D

W

ps. 3

_ _ O r <1) -O

° H N N ·· - 's <r Ό c

~ ~ "n £ vO S 5H

: + "O O

---------- - VS

Ό O

^ ^ ^ "* 2

** * "^ ^ ~ s s h i <S

PH + 1-1 cm ο P

E <<ü ---------- p P * (1) θ '

n _ CM αΟ Ό * H

. - ^ s -s U -O

cOîsü “· '^ l-s Λ" CM u-i (1) “O

Ν * s °° π σ>> EW

i— (* I n (0 3 (0

* H U

---------- w c -P

. n O '<U

n CO ΓΜ U · E -P.

. s Λ s I · E

r ^ rjooi ICOVOrl CM (0 0)

ri η σ \ H I -P

I I ri U - H d

>. E

----------- c £ Λ

û) -PC

PO m '4) n ri (A * lO -s 0) E Ü

Ό £ · “5 £ I _ - CO -H U

™ w 5 "O n -P P 3 m T CM (0 -P w

Sj E · I O

--------.—------ „1 in m 0) p ΙΛ -H n - <com ^ a -P 3 3 'σ- ^ s" U w w

H Z «i · _ MJ w 3 I

_ + | 0 id Ό 0) ri 5 T CM P Ο Ό> s <σι ii υ ω,. ---—---—-— ο. <u seen S ri P Ό 3 <3 · CM ^ ΟΠ3Ι0

<ri -1 1 ö <H 11 4J

^ sr es, <<r ·· <r ^ ο υ Ο Ο υ 1-1 r * ri ri ri no + cm (d η £ l η υ 2 ----------- flj l _ £ “r ui ® W nn,„, ”ή '3 (U> w cm 1 ^ 1 co ^ σ <DP £

+ ^ -1 · Η Ό -H -P

CM C 10 '(U

_____ O p- 'C> s

• ri W MX

_ Λ _ - O 0) O

n laughed. C P · -P Λ

ri i i i O - rd U

CM ^ J-crt · ® * 2 £ C 3 (0 n CM CO 4) σ υ lin ιρ c n η -O E Ό

-------- -P n 3 I

U> t n cm _ ld £ c CM 00 ip -P O n n | | . . - .Γ P VU In cm 1 1 1 1 co ^ 3 - El

_ 'g V) V <Z

(OO IH lÿ. .S Z 4) “<i) H ^ i> V. ^ m en> z> ° cm n • -ces ci S 1 j - _ _ I -P -P ** -PH J3 * 7 2 2

Ci O O (0 CO-ή 10 10 £, · “? S

l in 2 .3 p "Pw -s S J2 ci w ΙΛ IW ο 10, ¾ IÖW η Φ CM El CMH Q? QU fd £ • P -PE * E" -P cm η Έ ï η Ό 4) P θ '- * On 0 5 * £

Oi0; 3 O UlO υ -: -P ram 2. 2

= Ό 3 (0 · Q, Μ σ O CFC

ο σ c d a n-P io-p Ξ Si H 2 <u P I O (0 (d CdC UC w H 2 <Σ 2 <| 2Μ · κηο) ηο) ω 1 E -EJ-1 i 38

With respect to the above table, it should be noted that Test # 11 is a repetition of Test # 1, using a composition freshly prepared as a sample.

5 From the results indicated in Table 1, the following conclusions can be drawn and the following observations made: The addition of the quaternary compound alone (Tests n ° 2 to 7) to the nonionic active surf (Test n ° 1) has a very negative effect on the cleaning action.

The addition of succinamate alone (Tests 3 and 6) greatly improves the cleaning power but, naturally, does not provide the advantage of the softening conferred by the quaternary compound.

The addition of quaternary compound and succinamate at a ratio of 1.7: 1 (Trial # 8) offers a significant improvement over the quaternary compound alone (Experiments # 2 and 7) but is still significantly less than the witness (Test No. 1).

At a total addition of quaternary compound and succinamate of 8 percent by weight, a quaternary compound / succinamate ratio of 1: 1.7 (Trial 9) offers the best cleaning action and is slightly better than a ratio 1 : 1 (Trial 4), while a ratio of 25 1: 3 (Trial 12) offers roughly the same cleaning action as succinamate alone (Trials # 3 and 6) at rates of 4% and 8% . In fact, the ratio of 1: 3 at the rate of 8% by weight (Test No. 12) is less than the ratio of 1: 1 (Test 10) at the total rate of 4% by weight.

Therefore, under the conditions of this test, the preferred ratios of quaternary compound to succinamate are between about 1: 1 and about 1: 2, ratios of from 1: 2 to about 1: 3, however, still providing improvements in cleaning action 35 (for example bleaching) as well as a better softening / anti-static action 39.

Example 2

Tests 1 to 12 of Example 1 were each repeated, but adding an anionic surfactant: 5 a (linear dodecyl) benzene sulfonate (Na salt) (DLBS)? in the amounts shown in Table 1. The results are also shown in Table 2. For ease of comparison, the values of ES (Total) and IES compared to Test No. 1 of Example 1 are also shown in Table 2.

IES compared to

Test% in wt% in wt ES (total) test n ° l n ° DLBS of SNO with without with without

DLBS DLBS DLBS DLBS

I 4 - 207.3 204.8 15 2 41 - 213.3 185.7 +6.0 -19.1 3 44 212.8 213.3 +5.5 +8.5 * - 4 41 4 219, 2,219.2 +11.9 +14.4. * 5 (29% nonionic surfactant 20 8 - 211.4 206.5 +4.2 +1.8 6 88 214.4 213.4 +7.1 +8.8 7 81 - 208.7 191.7 +1.3 -13.1 8 51 3,220.5 195.8 +13.1 -8.9 9 31 5,218.7 221.3 +11, 4 +16.6 25 10 21 2,218.2 214.7 +10.9 +9.9 II 4,210.7 208.0 +3.4 +3.2 12 21 6,218.1 213.2 +10 , 8 +8.4 ^ 1: 1 quaternary compound / DLBS weight ratio.

The following observations can be made and conclusions drawn from the results shown in Table 2.

Test No 2 and Test No 7 correspond to the compositions which are the subject of French patent application '35 15 15278, that is to say mixtures of non-ionic surfactant i * 40 with 1: 1 mixtures of cationic fabric softener and anionic surfactant (without sulfosuccinamate).

Tests No. 3,4,6,8,9,10 and 12 are in accordance with the present invention. As can be seen, over the range of quaternary compound / succinamate ratios of 1.7: 1 (Test # 8) to 1: 3 (Test # 12), a much better cleaning action is obtained compared to quaternary compound alone (Tests n ° 2 and 7) or succina-10 mate alone (Tests n ° 3 and 6).

In addition, the presence of the anionic surfactant in these formulations adds the additional advantage of improving the antistatic and softening action of the compound of mono (higher alkyl) quaternary ammonium, and in the preferred compositions containing an optical brightening agent, the anionic surfactant also serves to deposit the brightening agent more efficiently. At the same time, it is also evident that in some formulations, the combination of the succinamate type surfactant and the anionic surfactant strongly enhances the overall cleaning action (for example by comparing total ES for Test No. 8 of the Example 2 with that of Test n ° 8 of Example 1).

In Examples 1 and 2, it should be noted that at a utilization rate of 1/2 cup, 21% and 29% of

Neodol 25-7 corresponds to 25 grams per wash and 35 grams per wash respectively; 4% and 8% of Arquad T-50 correspond to 5g per wash and 10g per wash, respectively; 4% and 8% of Monawet SNO correspond to 30 to 5g per wash and 10g per wash, respectively.

Example 3

If Example 1 or Example 2 is repeated using an equal amount of Neodol 23-6.5 (R0 (C2H40) 6f5H where R = mixed primary alcohol of 12 and 13 carbon atoms) or Tergitol 15- S-7 or Tergitol 15-S- ν '41 9 (both of which are linear, secondary ethoxylated C1-C15 alcohols, marketed products of Union Garbide Corporation, the former with 7 moles of ethylene oxide and the second with 9 moles of ethylene oxide) 5 or with any one of a nonylphenol condensed with 5 5, 7 or 9 moles of ethylene oxide, of an isooctylphenol condensed with 9, 10, 11 or 12 moles of ethylene oxide, etc. ... in place of Neodol 25-7, similar results are obtained.

10 If in Example 1 or Example 2, Monawet SNO-35 is replaced by an equal amount of Astromid 18, Astromid 22, Alkasurf SS-OA or Alkasurf SS-ΤΑ we get similar results.

Also, in Examples 1 and 2, similar results can be obtained by using: hydrogenated tallow chloride-trimethyl ammonium stearyl trimethyl ammonium chloride stearyl chloride triethyl ammonium chloride stearyl-dimethylethyl ammonium 20 tallow-diisopropylmethyl ammonium chloride and the corresponding sulfates, methosulfates, ethosulfates, bromides and hydroxides, in place of Arquad T-50. Arquad T-50 can be replaced in whole or in part, for example by Ethoquad 18/12, or other similar ethoxylated mono (higher alkyl) quaternary compound.

In Example 2, instead of the anionic active surfactant, the (linear dodecyl) benzene sulfonate, generally similar results are obtained by using, for example, Neodol 25-3S (from Shell Oil 30 Products, formula R0 (C2H40) 3S03Na, R = mixed primary fatty alcohol, in C12 to C15). The anionic surfactant DLBS can also be replaced in whole or in part, for example by a sodium alpha-olefin sulfonate of 14 to 18 carbon atoms or a sodium paraffin sulfonate> 35 of 13 to 17 carbon atoms, or the corresponding potassium salts 42 of either of these compounds.

Example 4

The following compositions were tested (indicated in Table 3, in the same manner as in Example 5 1, and the ES Total results) being also indicated in Table 3.

10 15 20 25 30 '35' ùr 43 ’LT) Ο M <rH - O 00

COCMIOM <IM <M <I1M <IH CM

m ο ο Η * · ο en [-cmiom <im <m <ii [m <h cm in o sx>

Hl- o in

Ο CM Ο M <I M <M <I M <I I H CM

r- m oo o r ~ -

H - - - O CM

inCMHOM <M <IM <OM <l IH CM

r "m o m

H - - O CM

m <cmhom <m <im <iiim <h cm - in fi fl> <

H

he m <

Eh

p- m o r ~ - H - - o en

00 CM H Ο M <I 1 M <I I Μ * 1 H CM

Γ "in o oo H * - o in

CMCMHOM <IIM <IIIM <H CM

η m ο o H - - O M <

HCMHOM <IIM <IM <IIH CM

S

fl

(L) 03 -H

fl S Ό m fl • H 0 co fl 'β <! d) in i 0 P- (β P-l Ά CO O CM 00 Qj + J i h a h ί α »a CM H v flin0fl) r-Hinrö in

d) CM fl M <d) CM H Ά Ά in H

• H (d H in Q) Φ -P -H H · fô

T3H, fl (öfl H + JueußSO1 + J

'(D 0 + -> 0 * d) - 0 03 0 | S 0 0 0 M'öajotncn'öfl.fldiflfl · «eh inoHflomo-p-pfl + J-flfl fld3M-H <flifld) -Hû) ocnenoi en 44

Example 5

In each of the compositions of Example 4, a portion of Neodol 25-7 is replaced by Ethomeen T-25, an ethoxylated amine of formula:

5 (CH2CH20) XH

suet-N (x + y = 15)

! \. (CH2CH20) yH

available from Armak, in an amount capable of providing about 3 to 8% of the ethoxylated amine, and, correspondingly, about 18 to 13% of the nonionic surfactant. Improvements in cleaning, softening and anti-static effect can be observed. Formulations containing 15% by weight of nonionic surfactant and 6% by weight of the ethoxylated amine give particularly good results.

EXAMPLE 6 In each of the compositions of Examples 9 4 and 5, the incorporation of an enzyme, for example a protease type enzyme, in a proportion reaching approximately 1%, in particular approximately 0.5% by weight of the composition, improves the cleaning action on certain soils; for example the protease acts on protein deposits, amylase on starch deposits, etc. The enzymes are stable in the compositions and it is possible to use mixtures of different enzymes. Example 7

Very stable aqueous, transparent, homogeneous compositions are prepared having actions

cleaning agents based on the following ingredients: 30 A B

Neodol 25-7 21 16

Neodol 25-3S 4

Sodium dodecylbenzene sulfonate - 4 "35 Monawet SNO-35 4 3 r 45

Arquad T-5Ο 43

Sodium citrate 4

Sodium xylene sulfonate 4 3

Optical brightener 0.5 0.5 5 Enzyme 0.5 0.5 ^ Water, q.s. per 100 100

Example 8

This example highlights the effect of the washing temperature on the cleaning action and also shows that the combination of quaternary cationic compound and succinamate in the preferred proportions is effective at both low and high temperatures. . As described in Example 1, the following liquid compositions shown in Table 4 were prepared and evaluated under the conditions described in Example 1 at a water temperature wash at 49 ° C or 21 ° C. The results (IES values relative to the nonionic surfactant alone (21% - Test No. 1) as a control) are shown in Table 4.

1 2345678

Neodol 25-7 21 21 21 21 21 21 21 21

Neodol 25-3S - 4444444

Adogen 471 ^ · - - 444-44 25 Monawet-SNO-35 - - 4 4 4 8 -

Sodium citrate - --- 44-8

Water - the rest IES comparatively - +4 +3 +14 +13 +9 +10 +7

in Test n ° l 49 ° C

30 IES compared - +1 -4 +10 +10 +5 0 +4

at Test n ° l 21 ° C

tallow-trimethylammonium ichloride, from Sherex.

- 35

Claims (21)

46 1. Detergent composition, characterized in that it comprises a nonionic detergent, a fabric softening and antistatic agent of the type 5 of mono (higher alkyl) quaternary ammonium, and a * detergent compound of the sulfosuccinamate type. 2. A detergent composition according to claim 1, characterized in that it further comprises an anionic surfactant chosen from an aromatic (linear higher alkyl) sulfonate, a (higher alkanol) -poly-lower alkoxy) -sulfate, an olefin- sulfonate and a paraffin sulfonate. 3. Detergent composition according to claim 1, characterized in that the detergent compound of the sulfosuccinamate type is a compound of formula (V): 0 .R4 Ä ch2-cn ^ (V) / ZO3-S-CH-COOZ in which Z is a monovalent salt-forming cation, 20 r4 is a hydrogen atom, lower alkyl, carboxy (lower alkyl) or 1,2-dicarboxy (lower alkyl), and R5 is an open-chain hydrocarbon residue of 10 to 22 carbon atoms. 4. Detergent composition according to claim 25 3, characterized in that in formula (V), Z is an alkali metal, ammonium or an amine, R4 is a hydrogen atom, a methyl, ethyl, carboxymethyl group. , carboxyethyl, carboxypropyl, 2-carboxy, 2-methylethyl, or 1,2-dicarboxyethyl, and R ^ is a straight or branched chain alkyl or alkenyl group having about 14 to 18 carbon atoms. 5. Detergent composition according to claim 1, characterized in that the sulfosuccinamate type detergent compound is disodium N-octadecylsulfosuccinamate, disodium N-oleyl-sulfosuccinamate or 47 N- (1,2-dicarboxyethyl) -N-octadecyl -tetrasodium sulfosuccinamate. 6. A detergent composition according to claim 1, characterized in that it comprises about 10 to 50% of the nonionic active surfactant, about 1 to 10% of the quaternary monoalkyl compound / and about 1 to 10% of the sulfosuccinate. 7. A detergent composition according to claim 6, characterized in that it comprises approximately 12 to 35% of non-ionic surfactant, approximately 2 to 6% of quaternary monoalkyl compound and approximately 2 to 6% of sulfosuccinamate. 8. Detergent composition according to claim 6, characterized in that it additionally contains an anionic surfactant chosen from a (linear higher alkyl) - aromatic sulfonate, a (higher alacanol) -poly (lower - alkoxy) -sulfate, a an olefin sulfonate and a paraffin sulfonate in an amount sufficient to provide an IA ratio of the quaternary monoalkyl compound to the anionic surfactant from about 1.3: 1 to 1: 1.5. 9. A detergent composition according to claim 8, characterized in that the weight ratio of the nonionic surfactant to the quaternary monoalkyl compound is between about 15: 1 and 2: 1, and the ratio of the quaternary monoalkyl compound to sulfosuccinamate is included between about 3: 1 and 1: 3. 10. Liquid aqueous detergent composition intended for cleaning and softening soiled fabrics and which can be added to the washing cycle of an automatic washing machine, characterized in that it comprises: (A) approximately 10 to 50% a nonionic liquid detergent chosen from the compounds of formulas (17 and (II): RO (CH2CH20) nH (I) 35 in which R is a primary or secondary alkyl chain of approximately 8 to 22 carbon atoms , and n is on average equal to about 5 to 20, and Rl-0 ”°" (CH2CH20) mH (11) in which r! is a primary or secondary alkyl chain of 4 to 12 carbon atoms, and m is on average? equal to about 5 to 20; (B) about 1 to 10% by weight of a mono {higher alkyl) compound quaternary ammonium of formula (III) or (IV): 10 r3 + X "(III) _R3 --- * ^^ R3 R2 ___ (CH2CH2O) X1 + X “(IV) 11. Composition according to claim 10, characterized in that the anionic detergent (D) is present at a ratio (C) :( D) of approximately 1.3: 1 to approximately S 1: 1.5. (St 12. Composition according to claim 10, characterized in that it comprises: approximately 12 to 35% of (A) approximately 2 to 6% of (B) approximately 2 to 6% of (C) a sufficient quantity of (D ) to provide a ratio (C) :( D) of about 1.2: 1 to 1: 1.2 0.2 to 2% by weight of (E) to about 10% of (F) up to about 3% of (G) up to about 2% of (H) up to about 2% of (I) and the remainder consisting of (J). 13. Composition according to claim 12, characterized in that (A) is a compound of formula (I) in which R is a C 2 -C 15 alkyl group or a mixture of such alkyl groups and n is a number 4β 50 of about 6 to 13; (B) is tallow-trimethyl-ammonium chloride, (C) is disodium N-octadecyl-sulfosuccinamate, disodium N-oleyl-sulfosuccinamate, or r · ^ 5 N- (1,2-dicarboxy-ethyl) -N-octadecyl-sulfosuccinamate tetrasodium, and (D) is a (linear dodecyl) benzene-sulfonate or a (C1-C12 alkanol] _5) -triethenoxy-sulfate. 14. Composition according to claim 10, 10 characterized in that it comprises (A) about 15 to 25% by weight of a compound of formula (I) in which R is a primary or secondary alkyl group C ^ o to Cyg et na has a value of about 6 to 13; (B) about 2 to 6% of a compound of formula (III) in which R2 is an aliphatic radical of ^ 12 to 18 carbon atoms and each R 3 is a group j. methyl; ; (C) about 2 to 6% of the sulfosuccinamate of formula 20 (v) in which R ^ has about 14 to 18 carbon atoms and R4 is hydrogen or a 1,2-dicarboxyethyl radical, and an aqueous liquid vehicle. 15. Composition according to Claim 14, characterized in that the ratio (B) :( C) is between approximately 1: 1 and approximately 1: 2. 15 R3 "" ^^ ^^ (CH2CH20) y where R2 is a long chain aliphatic radical of about - 10 to 22 carbon atoms, ^ each of the symbols R3 in formula (III) ^ and R3 in formula ( IV) are independently lower alkyl or hydroxy (lower alkyl), X is an anion forming a water soluble salt, and x and y are each a positive number of at least 1 and the sum x + y is 2- 15; (C) about 1 to 10% by weight of a detergent compound of the sulfosuccinamate type of formula: O R4 * X H2c - C - N ^ I '"' '' 'R5 ZO3-S-CHCOOZ wherein Z is a monovalent salt forming cation, R4 is a hydrogen atom, lower alkyl, carboxy (lower alkyl) or 1,2-dicarboxy (lower alkyl), and î- 35 r5 is an open chain hydrocarbon of 10 to 22 c Λ 49 carbon atoms; (D) up to about 10% by weight of an anionic surfactant chosen from aromatic (linear higher alkyl) sulfonates, (higher alkanol) -poly (lower alkoxy) -suifates, olefin sulfonates and? paraffin sulfonates; La (E) up to about 3% of an optical brightening agent; (F) up to about 15% of an ethoxylated amine; (G) up to about 5% of an alkaline substance; (H) up to about 3% of enzymes; (I) up to about 3% of soil release agent, and (J) an aqueous solvent vehicle. 16. Composition according to claim 14, characterized in that it further comprises (D) a (linear higher alkyl) -benzene-sulfonate or a (higher alkanol) -polyethoxy-sulfate in an amount capable of providing a ratio ( C) :( D) from about 1.1: 1 to about 1: 1.1. 17. Composition according to claim 16, characterized in that the ratio (B) :( C) is between approximately 1.5: 1 and approximately 3: 1. * 25 18. Method for cleaning and softening 51; ... λ v * * soiled fabrics, characterized in that it consists in bringing the soiled fabrics in an aqueous washing bath in contact with the detergent composition according to claim 1. r A 5 19. The method of claim 18, characterized in that the contacting is carried out in an automatic washing machine comprising a washing cycle and a rinsing cycle, and in that the detergent composition is added during the cycle of washing. 20. The process as claimed in claim 19, characterized in that the temperature of the aqueous washing bath, at least during the washing cycle, is at least approximately 21 ° C. , <· *