CH668982A5 - DETERGENT COMPOSITION. - Google Patents

Description

DESCRIPTION

The present invention relates to a detergent composition which can be used for cleaning and simultaneously softening textiles in the washing process of a washing program. The essential constituents of the detergent composition according to the invention include a nonionic surfactant, a quaternary mono (higher) alkylammonium compound as a fabric softening, antistatic agent and a sulfosuccinamate surfactant compound.

Useful compositions for treating textiles to improve their softness and tactility are known.

When washing in the home, the fabric softeners are usually added to the rinse water during the rinse cycle, which only lasts about 2 to 5 minutes. The consumer is therefore forced to monitor the washing program or take other precautions to ensure that the fabric softener is added at the right time. This makes it necessary for the consumer to go to the washing machine either shortly before or at the start of the washing program, which is undoubtedly annoying. In addition, special precautionary measures must be observed in order to use a suitable amount of the textile softener and to avoid overdosing, which could make the textiles water-repellent by depositing a greasy film on the textile surface and also cause them to yellow to a certain extent.

To overcome these problems, it has been proposed to use textile softeners which are compatible with conventional detergents, so that they can be combined with the detergents in just one package and used in the wash program. Examples of such in

Fabric softening compositions added to the wash cycle are described in U.S. Patent Nos. 3,351,438, 3,660,286, 3,703,480 and many others. These fabric softening compositions to be added in the wash contain a cationic quaternary ammonium compound as fabric softener and additional components which make the softening compounds compatible with the usual detergents.

However, it is also known that the cationic softening compounds added to the wash cycle either as a constituent in a wash-softening composition or as wash-cycle softeners in the wash cycle deteriorate the whitening effect and the cleaning action of the detergent. As a result, attempts have been made to compensate for this deterioration in the washing and softening compositions to a certain extent by using nonionic surfactants, higher concentrations of brighteners, car-boxymethyl cellulose, yellowing-preventing compounds, bluing agents, etc. However, there is little improvement in laundry softening compositions using a variety of surfactants, most of which are anionic.

There have been numerous recommendations for detergent compositions that contain cationic plasticizers including the quaternary ammonium compounds as plasticizers and nonionic surfactants. Representative of this prior art are US Pat. Nos. 4,264,457.4,239,659, 4,259,217, 4,222,905, 3,951,879, 3,360,470, 3,351,483, 3,644,203, etc. In addition, in U.S. Pat. Nos. 3,537,993,

3,583,912, 3,983,079, 4,203,872 and 4,264,479, in particular combinations of nonionic surfactant, cationic fabric softener and other ionic surfactant or modifiers such as zwitterionic surfactants, amphoteric surfactants and the like.

Although many of these known compositions enable adequate cleaning and / or softening under many different conditions, they nevertheless have the disadvantage that they do not ensure adequate softening, which is comparable, for example, to that of plasticizers added in the rinse cycle.

U.S. Patent 3,920,565 proposes a rinse liquid fabric softening composition comprising 2 to 15% of a cationic fabric softener and 0.5 to 4.0% of an alkali metal salt of a fatty acid having 16 to 22 carbon atoms (soap) and optionally bis contains 2% of a nonionic emulsifier and water as the remainder. The di (higher) alkyl-dimethylammonium chlorides are the preferred cationic compounds, although mono (higher) alkyl quaternary compounds are also mentioned.

It is also generally believed that the quaternary mono (higher) alkylammonium compounds, such as steaiyltrimethylammonium chloride, which are relatively water-soluble, are less effective as plasticizers than the cationic quaternary di (higher) alkyl compounds (see, e.g., U.S. Patent 4,326,965), which is why their use in conjunction with, for example, anionic surfactants such as fatty acid soaps, with which they can form softening complexes, has been proposed as a rinse cycle textile softener.

In US Pat. No. 3,997,453, resistant textile-softening compositions with improved dispersibility in cold water when used in the rinse cycle have already been proposed, which comprise a cationic quaternary ammonium compound as the only plasticizer and an anionic sulfonate in a weight ratio of cationic to anionic compound of about 80: 1 to 3: 1. According to this patent, both cationic and quaternary alkyl compounds and also alkylbenzenesulfonate are provided as anionic compounds as cationic quaternary plasticizers. According to this patent, the addition of smaller amounts of the anionic sulfonate in

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aqueous dispersions of excess amounts of quaternary plasticizer, the viscosity of the dispersion and creates a homogeneous liquid that is easily dispersible in cold water (e.g. the rinse cycle of an automatic washing machine).

However, as mentioned earlier, one day it was found that it would be much more convenient to apply the fabric softening formulation with the detergent in the washing machine wash cycle.

U.S. Patent 4,222,905 lists detergent compositions which may be in liquid form and made from certain nonionic surfactants and certain cationic surfactants including quaternary mono (higher) alkylammonium compounds such as tallow alkyl trimethylammonium halide in a weight ratio of nonionic cationic surfactant from 5: 1 to about Are formulated 1: 1. This patent teaches that the amount of anion-generating substances should be kept as low as possible and preferably avoided entirely, but that in any case anionic materials with a dissociation constant smaller than 1 x 10 ~ 5 such as sodium Cllj8 (linear) alkylbenzenesulfonate should only be contained in amounts of up to 10% by weight of the cationic surfactant.

U.S. Patent 4,239,659 describes detergent compositions based on a mixture of nonionic and cationic surfactant with a weight ratio of nonionic: cationic of about 1: 1 to 40: 1, the nonionic surfactant of the class having a hydrophilic-lipophilic balance (HLB ) from about 5 to 17 and the cationic surfactant belongs to the class of the quaternary mono (higher) alkylammonium compounds in which the higher alkyl has about 20 to about 30 carbon atoms. This patent contains a general indication that other additional components can be incorporated in their usual concentrations, which are stated to be about 0 to 40%. A long list of auxiliary ingredients is listed including semi-polar, nonionic, anionic, zwitterionic and ampholytic cosurfactants, builders, dyes, fillers, enzymes, bleaches and many others. There are no examples using and no indication of anionic surfactants, however, it is exempted that the cosurfactants must be compatible with the nonionic and the cationic surfactant and can be any of the anionic surfactants from U.S. Patent 4,259,217.

This latter patent describes surfactant mixtures of nonionic surfactants with an HLB of about 5 to about 17 with a cationic surfactant including quaternary mono (higher) alkylammonium compounds in a weight ratio of nonionic: cationic from 5.1: 1 to about 100: 1. According to this patent, the detergent compositions can contain up to about 50%, preferably about 1 to about 15%, anionic surfactants and / or zwitterionic surfactants. The anionic surfactants include linear alkyl benzene sulfonates and alkyl ether sulfates, among others. Example XV in column 40 of this patent describes a liquid heavy-duty detergent composition with the following approach:

Component weight%

Sodium sulfate with 3 moles of EO

5.0

C12_i5 ethoxylated alcohol

With an average of 6.5 moles of EO

20.0

ethoxylated Cn-o alcohol

Coconut alkyl trimethyl ammonium chloride

3.5

Glycine

8.0

Sodium toluenesulfonate

10.0

Water and minor components

Rest to 100

The following liquid heavy-duty detergent composition is given in Example XVII (column 41):

Component weight%

Condensation product of a CI4_15 fatty alcohol 28.5 with an average of 7 moles of EO triethanolamine salt of linear 20.0

Alkylbenzenesulfonic acid in which the alkyl chain has an average of 11.9 carbon atoms. C8_i8-alkyldihydroxyethylmethylammonium 1.5 chloride

Ethanol 10.0

Diethylenetriaminepentamethylphosphonic acid 0.3

Citric acid 0.2

9.1 Mixture of dimethylpolysiloxane and 0.3 acrogel silica emulsified in strongly ethoxylated fatty acid (commercially available from Dow Corning as DB31)

Saturated fatty acid with 16 to 22 0.75

Carbon atoms in the alkyl chain Proteolytic enzyme 0.4

Minor auxiliaries and water rest up to 100

U.S. Patent 4,264,457 describes a liquid washing and softening composition comprising about 3 to 35 percent by weight nonionic surfactant, about 3 to 30 percent by weight quaternary mono (higher) alkylammonium compound as a cationic surfactant and a Mixture of anionic surfactants including (a) Ci-Cio alcohol sulfates and (b) Ci2-C22 alcohol (ethoxylated) contains ether sulfates or carboxylates. The molar ratio of the total cationic surfactants to the total anionic surfactants can vary from 0.8: 1 to 10: 1. In this patent specification it is stated that the selection of and the proportions of the two special anionic surfactants, with the exclusion of the other known anionic surfactants, is essential in order to achieve the maximum effectiveness with regard to detergency, softening and antistatic properties.

The applicant has also already found (US Serial No. 661 775) that the softening and antistatic effect of a detergent and a cationic quaternary mono- (higher) alkyl compound as a fabric softener is significantly improved when the cationic softener is considered to be about 1: 1 -Complex used with an anionic surfactant, which is a linear alkyl aromatic sulfonate. In addition, this increase in softening / antistatic effect was made possible without loss in and in certain cases even with significantly improved whitening and cleaning action.

Although the liquid nonionic detergent compositions based on the complex of cationic fabric softener and linear alkylbenzenesulfonate are greatly improved in terms of softening and antistatic action, further improvements in the overall cleaning action are nevertheless desirable. It is also desirable to be able to form the fabric softening quaternary mono (higher) alkyl compound with a broader range of commercially available anionic surfactants than only the linear alkyl aromatic anionic sulfonate surfactants.

It has now been found that both of these goals can be easily achieved by adding an additional surfactant compound to the composition, which is a sulfosucci namate compound. The incorporation of the sulfosuccinamate compound significantly increases the detergency of the nonionic / cationic mixture with or without further support from other anionic surfactants such as linear alkyl benzene sulfonate.

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It is therefore the object of the invention to improve the softening, whitening and antistatic action of detergent compositions which contain quaternary ammonium compounds and nonionic surfactant compounds as softening agents, while at the same time significantly improving the overall cleaning action.

It is also an object of the invention to formulate stable liquid detergent compositions using quaternary mono (higher) alkylammonium compounds as cationic plasticizers with nonionic and sulfosuccinate surfactants as the main and essential surfactant components which are compatible with fluorescent brighteners, enzymes, dirt-releasing substances and other detergent additives .

Another object of the invention is to provide a detergent softening composition that effectively cleans a wide range of soils including clays, oils, grease, etc., and gives softness to both natural and synthetic fibers and fabrics.

The detergent composition according to the invention, which can be used for washing soiled textiles in an aqueous washing liquid, preferably contains, in addition to the nonionic surfactant and a sulfosuccinamate surfactant, as essential surfactants and a quaternary mono (higher) alkyl-ammonium compound as a cationic fabric softener, an anionic surfactant. In the preferred embodiment, the detergent composition is in the form of an aqueous liquid and can contain at least one coloring and / or whitening substance, in particular dyes, bluing agents, optical brighteners and mixtures thereof and other optional detergent additives, in particular enzymes and dirt-removing substances.

In other possible forms of training, the composition can be formulated with only or predominantly non-aqueous liquid carrier or a mixture of water and organic solvent. In a further embodiment, the composition can be pasty or a highly viscous liquid.

The nonionic surfactants in question can generally be any nonionic surfactants known to be suitable for cleaning soiled textiles.

Suitable nonionic surfactants are commercially available and are formed by the condensation of alkylene oxide or an equivalent reaction partner with a reactive hydrogen-containing hydrophobic compound. The organic hydrophobic compounds can be aliphatic, aromatic or heterocyclic, although the first two classes are preferred. The preferred types of hydrophobic compounds are higher aliphatic alcohols and alkylphenols, although others are also applicable, such as carboxylic acids, carboxamides, mercaptans, sulphonamides, etc. The ethylene oxide condensation products with higher alkylphenols or higher fatty alcohols are preferred classes of nonionic compounds. In general, the hydrophobic part should be at least 6 , preferably at least 8 and may even have up to 50 carbon atoms or more, a preferred range being 8 to 22, especially 10 to 18 carbon atoms for the aliphatic alcohols and 10 to 20 for the higher alkylphenols. The amount of alkylene oxide varies considerably depending on the hydrophobic part. As a general guideline and rule, at least 3 moles of alkylene oxide per mole of hydrophobic part up to 200 moles, preferably 3 to 50 moles, particularly preferably 5 to 20 moles of alkylene oxide per mole of hydrophobic part, provide the required cleaning action and compatibility with the other components.

Preferred classes of nonionic surfactants are given by the formulas

R0 (ch2ch20) "H (I),

wherein R is a primary or secondary alkyl chain having about 8 to 22 carbon atoms and n is an average number of 5 to 50, preferably 5 to 20, especially 6 to 13;

and

Rl_0-O- (CH2CH2O) mH (II),

wherein R1 is a primary or secondary alkyl chain with 4 to 12 carbon atoms and m is an average number from 5 to 50, preferably 5 to 20, especially 6 to 13.

The preferred alcohols from which the compounds of formula I can be prepared include lauryl, myristyl, cefyl, steaiyl and oleyl alcohol and mixtures thereof. Particularly preferred meanings of R are Cio to Ci8, the Ci2-Ci5-alkyls and mixtures thereof being particularly preferred.

The preferred meanings of R1 in formula II are Có to Ci2, with Cs and Ca including octyl, isooctyl and nonyl being particularly preferred.

Typical examples of a nonionic compound of the formula I are lauiyl alcohol condensed with 5 or 7 or 11 moles of ethylene oxide. Typical examples of a nonionic compound of formula II are isooctylphenol or nonylphenol condensed with 3 to 8 moles of ethylene oxide.

Other applicable nonionic surfactants include the poly-oxyalkylene esters of organic acids such as higher fatty acids, resin acids, tall oil acids, acids from crude oil oxidation products, etc. These esters usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 3 to about 30 moles of ethylene oxide or its equivalent.

Further preferred nonionic surfactants are the alkylene oxide condensation products with the higher fatty acid amides and amines. The fatty acid group generally contains 8 to 22 carbon atoms and can be condensed with 3 to 30 moles of ethylene oxide (preferred). The corresponding carboxamides and sulfonamides can be taken as real equivalents.

Although ethylene oxide has been exemplified as the alkylene oxide group present in the nonionic surfactants,

it also falls within the scope of the invention to use nonionic surfactants which have been prepared with propylene oxide, preferably a mixture of ethylene oxide and propylene oxide. For example, the non-ionic surfactants of the known Plurafac series, such as Plurafac B-26, the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, have a mixed chain of ethylene oxide and propylene oxide with a terminal hydroxyl group.

In the preferred poly (lower) alkoxy (higher) alkanols, the number of lower alkoxy groups, particularly for achieving the best balance of the hydrophilic and lipophilic portions, makes up about 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic surfactant usually contains at least 50% of this preferred poly (lower) alkoxy (higher) alkanol. Higher molecular weight alkanols and various other normally solid nonionic surfactants and surfactants can contribute to the gelation of the liquid detergent formulations, which is why they are preferably omitted or their amount limited in the liquid detergent compositions of the invention, although small amounts thereof can be used because of their cleaning properties, etc. and may be desirable in the more viscous or pasty formulations. In both the preferred and the less preferred nonionic surfactants, it is particularly preferred that the alkyl groups present therein are linear,

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although a low degree of branching can be tolerated, such as on the carbon adjacent to the carbon atom or two distant from the straight chain terminal carbon atom and distant from the ethoxy chain, if such an alkyl branch is no longer than 3 carbon atoms. Typically, the amount of carbon atoms in such a branched configuration is less and rarely exceeds 20% of the total carbon atom content of the alkyl. Similarly, although linear alkyls that are terminally attached to the ethylene oxide chains are particularly preferred and are believed to provide the best combination of detergency, biodegradability, and freedom from gelling, it can be in the chain to medium and secondary linkage with the ethylene oxide come. This is usually only the case for a smaller proportion of these alkyls, generally less than 50%, but can make more of a difference, as for example in the case of tergitols. When propylene is present in the lower alkylene oxide chain, it is usually less than 20% of the same, and preferably less than 10% of the same, although higher percentages can also be used, as in some Plura facet surfactants.

The amount of nonionic surfactant is generally the minimum amount that allows an adequate cleaning effect when added to the wash water. In general, amounts in the range from 1 to 50%, preferably 10 to 40 and particularly preferably 12 to 35% by weight, based on the composition, can be present.

A second essential component in the compositions according to the invention is the cationic fabric softener. Softening substances are used to soften fabrics or textiles, and the terms "softening" and "softening agent" refer to handling, hand, touch or feel; this is the tactile impression that the fabrics or textiles convey to the hand or body. It is of aesthetic and economic importance. The cationic fabric softeners contained in the composition according to the invention are the quaternary mono (higher) alkylammonium compounds and preferably have the following formula

R2. R3 1

x "(iii)

R3 R3

's'

wherein R2 is a long chain aliphatic group having 10 to 22 carbon atoms and the three R3 are independently lower alkyl or hydroxyalkyl groups, X represents a water soluble salt forming anion such as halide e.g. Chloride, bromide, iodide; Sulfate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or similar inorganic or organic solubilizing residues. The carbon chain of the aliphatic radical, which contains 10 to 22, preferably 12 to 20, particularly 12 to 18 and especially 16 to 18 carbon atoms, can be straight-chain or branched, saturated or unsaturated. The lower alkyl radicals usually have 1 to 4, preferably 1 or 2, carbon atoms, methyl being particularly preferred, and can contain a hydroxyl radical. The long chains are preferably obtained from long-chain fatty acids derived from tallow or soybean oil. The terms "soybean" and "tallow" etc. refer to the starting substance from which the long fatty alkyl chains are derived. Mixtures of the fabric softening quaternary ammonium compounds can be used. The preferred ammonium salt is a mono (higher) alkyl trimethyl ammonium chloride in which the alkyl group is derived from tallow, hydrogenated tallow or stearic acid. Specific examples of plasticizing quaternary ammonium compounds of Formula III that are particularly suitable for use in the compositions of the invention include the following:

methyl ammonium chloride, hydrogenated Talgtrimethylammonium chloride, Trimethylsteaiylammoniumchlorid, Triethylsteaiylammo-niumchlorid, trimethylcetylammonium chloride, Sojatrimethyl ammonium chloride, Stearyldimethylethylammoniumchlorid, tallow diisopropylmethylammoniumchlorid, the corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide salts thereof, etc.

Another preferably applicable class of commercially available textile-softening quaternary ammonium compounds are the ethoxylated compounds of the formula IV

R3 +

r2-N- (CH2CH20) xH x- (iv) ^

(ch2ch20) yh where X, R2 and R3 are as defined in formula III, x and y are each positive numbers of at least 1 and the sum of x + y is 2 to 15.

A particularly preferred compound of formula IV is sold by Armak under the trade name Ethoquad 18/12 (R3 = CH3-, R2 = cis-alkyl, x + y = 12).

The amount of the fabric softening cationic quaternary monoalkyl compound can generally make up 1 to 20, preferably 4 to 16, particularly preferably 5 to 10% by weight of the composition.

The weight ratio of nonionic surfactant to cationic fabric softener can be in the range from 1: 1 to 15: 1, preferably 1.5: 1 to 10: 1, particularly preferably 2: 1 to 8: 1.

The sulfosuccinamate surfactant is the third essential active component of the compositions according to the invention. These compounds are primarily characterized by the fact that they have an open-chain Cio-C22 hydrocarbon substituent which is bonded to the nitrogen atom of the carbonamide - (- CONc) group, which is located on a terminal carboxylic acid group of the succinamate part, and by the sulfonyl- (-S03-) Group which is bonded to one of the carbon atoms in the a or β position with respect to the carbonamide group.

Examples of the sulfosuccinamate compound include disodium n-octadecyl sulfosuccinamate (available as Alkasurf SS-TA from Alkaril Chemicals, or as Astromid 18 from Alco Chemical Corp.), disodium N-oleylsulfosuccinamate (available from Alkaril Chemicals as Alkasurf SS-OA) ; Tetrasodium N- (1,2-dicarboxy-ethyl) N-octadecylsulfosuccinamate (available as Astromid 22 from Alco Chemical Corp., or as Monawet SNO-35 from Mona Industrie, Inc.).

More generally, however, suitable sulfosuccinamate compounds can be represented by the following general formula V

0 R4 ÇH2-C-N <(V)

Z-O3-S-CH-COOZ

where Z is a monovalent salt-forming cation such as alkali metal, ammonium and amine, R4 is hydrogen, lower alkyl, carboxy (lower) alkyl or 1,2-dicarboxy (lower) alkyl, and R5 is an open chain hydrocarbon with 10 is up to 22 carbon atoms.

Sodium, potassium or lithium are preferred as the alkali metal, and sodium is particularly preferred.

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

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The “lower alkyl” group can contain 1 to 5, preferably 1 to 3, particularly preferably 1 to 2 carbon atoms.

The open-chain hydrocarbon for R5 can be saturated or unsaturated, straight-chain or branched and is preferably an alkyl or alkenyl group with 14 to 18, preferably 16 to 18 carbon atoms such as e.g. Tallow, hydrogenated tallow, fractionated tallow, oleyl, octadecyl, steaiyl, etc.

When R4 is carboxy (lower) alkyl or 1,2-dicarxyl- (lower) alkyl such as carboxyethyl, carboxypropyl, carboxy-2-methylethyl, 1,2-dicarboxyethyl etc., the carboxyl group (s) in the Form -COOY are present, where Y is the group Z or lower alkyl; preferably YZ is particularly preferably sodium.

The amount of SulFosuccinamate must be carefully selected depending on factors such as the type and amount of the nonionic surfactant and the cationic fabric softener, the special SulFosuccinamate and the intended washing conditions including the type of textiles, soiling, washing temperature, water hardness etc. In general, however, the best cleaning effect is achieved if the amounts of sulfosuccinamate surfactant, nonionic surfactant and textile softening cationic mono (higher) alkyl compound are in parts by weight, based on the total composition, in the following ranges:

Full

Preferred a) nonionic surfactant

10-50

12-35

b) Quaternary monoalkyl compound

1-10

2-6

c) SulFosuccinamate surfactant

1-10

2-6

Within 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. In most cases, however, the ratios of a: b and a: c are in the range from 15: 1 to 1: 1, preferably 10: 1 to 1.5: 1, particularly preferably 8: 1 to 2: 1. The weight ratio of b: c should generally be in the range from 3: 1 to 1: 3, preferably 2: 1 to 1: 2, particularly preferably 1.3: 1 to 1: 2. Furthermore, the weight ratio of a: b + c is in particular 10: 1 to 1: 1, preferably 6: 1 to 1.5: 1.

For example, in a preferred embodiment of the invention in which the nonionic surfactant is a Cn-iî alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of alcohol (such as Neodol 25-7 from Shell Oil Co.) in an amount of 15 to 25% by weight of the total composition, the fabric softening quaternary monoalkyl compound is tallow trimethylammonium chloride and the sulfosuccinamate tetranetrium-N- (1,2-dicarboxyethyl) -N-octadecylsulfosuccinamate (e.g. Monawet SNO-35) is the preferred ratio of nonionic surfactant quaternary compound or quaternary compound to sulfosuccinamate in the range from 12: 1 to 4: 1 or 1: 1 to 1: 2, which is typical washing conditions, ie 48.9 ° C, 0.2% product concentration, 100 ppm hardness ions and applies to a wide range of textiles and soiling.

An optional but preferred additional component of the detergent composition according to the invention is an anionic surfactant. Therefore, as in the aforementioned US Ser. No. 661 775 the softening and the antistatic effect of the mixture of nonionic surfactant and textile softening quaternary higher alkylammonium compound was significantly increased by using a linear alkyl aromatic SulFoantten-sids, preferably as a molar 1: 1 complex with the quaternary textile softener.

Examples of suitable anionic surfactants include the water soluble salts, e.g. the sodium, potassium, ammonium alky

lolammonium salts of higher linear alkyl aromatic sulfonates with about 8 to 26, preferably 10 to 22 carbon atoms in the alkyl radical. (The term alkyl includes the alkyl portion of the higher acyl residues.)

Preferred examples of the linear alkyl aromatic sulfonates are those which have 10 to 16 carbon atoms in the linear alkyl group, e.g. the sodium, potassium and ammonium salts of the higher linear alkylbenzenesulfonates, higher linear alkyltoluenesulfonates, higher linear alkylphenolsulfonates and higher linear alkylnaphthalenesulfonates. The linear higher alkylbenzenesulfonates such as the C10_i6 alkyl, especially C10_i4 alkyl, e.g. Ci2 (n-dodecyl) alkylbenzenesulfonates are particularly preferred anionic surfactants.

In addition to the linear alkylaromatic sulfonates, another preferred class of anionic surfactants, which can increase the overall action, in particular the antistatic and softening action of the detergents according to the invention, comprises the alkyl ether sulfates of the formula

R60 (CH2CH20) p-S03M,

wherein R6 is higher alkyl with 8 to 20, especially 10 to 18 carbon atoms, M is a solubilizing salt-forming cation such as an alkali metal ion, alkaline earth metal ion, ammonium ion, ammonium ion substituted with 1 to 3 lower alkylene or mono-, di- and trialkanolamine with 2 to 3 carbon atoms in the alkanol group or groups, and p is a number from 2 to 8, preferably 2 to 6 (especially Vs to Vi or Vi the number of carbon atoms in R6). A preferred polyethoxylated alcohol sulfate surfactant is available from Shell Chemical Company as 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, the potassium salt and other suitable soluble salts of triethenoxy (higher) alcohol (12 to 15 carbon atoms) sulFate and other such compounds described herein and those previously mentioned and those described below be used instead of or partially in place of the sodium salts. As with the various substances of the compositions according to the invention, mixtures can be used.

Examples of the higher alcohol polyethene oxysulfates which can be used as an anionic surfactant component of the composition according to the invention or as a partial replacement, include: mixed CI2_i5 normal or primary alkyltri-ethenoxysulfate, sodium salt; Myristyl triethenoxy sulfate, potassium salt; n-decyl diethenoxy sulfate, diethanolamine salt; Lauiyldiethe-noxysulfate, ammonium salt; Palmityltetraethene oxysulfate, sodium salt; mixed Ci4_i5 normal primary alkyl (mixed) tri- and tetraethene oxysulfate, sodium salt; StearylpentaethenoxysulFat, trimethylamine salt and mixed Cio-18 normal primary alkyltriethenoxysulFat, potassium salt. Small amounts of the corresponding branched and mid-alkoxylated surfactants, for example those described above, but which are modified to be ethoxylated on a medium carbon atom, e.g. at a four carbon atoms distant from the chain end can be used, the carbon atom content of the higher alkyl being the same. Similarly, the linkage to normal alkyl can take place on a secondary carbon atom or on two carbon atoms removed from the chain end. In any case, as stated above, only small amounts, usually 10 or 20%, should be present.

The poly (lower) alkoxy (higher) alkanol sulfates, like the preferred nonionic surfactants, are readily biodegradable and have a better detergency if the fatty alkyl is terminally linked to the poly (lower) oxyalkylene chain which is terminally bound to the sulfate. Again are like in the case

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The non-ionic surfactants tolerate small amounts, for example not more than 10%, of branching and linking. In general, it is preferred that the alkyl in the anionic alkoxylate surfactant, like the nonionic surfactant, is a mixture of different chain lengths, for example 11,12,13,14 and 15 carbon atoms or 12 and 13 carbon atom chains, rather than all having a chain length. Nevertheless, the invention is applicable to liquid detergents which contain pure nonionic and anionic components.

Of course, ethylene oxide is the preferred lower alkylene oxide of the anionic alkoxylate surfactant such as the nonionic surfactant. Its proportion in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethylene oxide groups per mole of anionic surfactant, particularly preferably 2 to 4 moles and most preferably 3 moles, especially if the higher alkanol has 12 to 13 or 11 or 12 to 15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic balance, if the carbon atom content of the alkyl chain is in the lower part of the Cio_i8 range, the ethylene oxide content of the surfactant can be reduced to 2 moles per mole, whereas in the higher part if the higher alkanol 16 has up to 18 carbon atoms, the number of ethylene oxide groups can be increased to 4 or 5 and in some cases even to 8 or 9. Similarly, the salt forming cation can be changed for best solubility. It can be any suitable solubilizing metal or residue, but is most commonly alkali metal, e.g. Natirum or ammonium. When lower alkyl amine or alkanol amine groups are used, the alkyls and alkanols generally contain 1 to 4 carbon atoms and the amines and alkane oil amines can be mono-, di- and trisubstituted as with monoethanolamine, diisopropanolamine and trimethylamine.

The poly (lower) alkoxy (higher) alkanol sulfates and the linear alkyl aromatic sulfonates are the most preferred supplemental side in the compositions of the invention, but other anionic surfactants can be used with them or in their place. Above all, alpha olefin sulfonates, paraffin sulfonates and higher alcohol sulfates can be used. The olefin sulfonate salts generally contain long chain alkenyl sulfonates or long chain hydroxyalkanesulfonates (with the OH on the carbon atom that is not directly linked to the carbon atom bearing the SO3H group). The olefin sulfonate surfactant generally contains a mixture of such compound lyses in varying amounts, often together with long chain disulfonates or sulfate sulfonates. These olefin sulfonates are described in many patents, for example in U.S. Patent 2,061,618,3,409,637, 3,332,880,3 420,875, 3,428,654, 3,506,580 and in the UK Patent

1,129,158. The number of carbon atoms in the olefin sulfonate is usually in the range of 10 to 25, more often 10 to 20 or 12 to 18, for example a mixture of mainly Ci2, Cm and Ci6 with an average of about 14 carbon atoms or one Mixture mainly of Ci4, Ci6 and Cis with an average of about 16 carbon atoms.

Another class of anionic surfactants that can be used is that of the higher paraffin sulfonates. These can be primary or secondary paraffin sulfonates from the reaction of long chain alpha olefins and bisulfites, e.g. Sodium bisulfite, or paraffin sulfonates in which the sulfonate groups are distributed along the paraffin chain, as in products from the reaction of a long-chain paraffin with sulfur dioxide and oxygen under ultraviolet light and then neutralization with sodium hydroxide or another suitable base (as in US Pat. No. 2,503,280 ,

2 507 088, 3 260 741, 3 372 188 and DE-PS 735 096). The paraffin sulfonates preferably contain 13 to 17 carbon atoms and are normally present as monosulfonates, but can optionally be di-, tri- or higher sulfonates. The Di and

PolysulFonate are mostly used in a mixture with a corresponding MonosulFonate, for example as a mixture of Mono- and DisulFonate with a content of up to about 30% DisulFonat. The hydrocarbon substituent thereof is preferably linear, but branched parafinsulfonates can be used if necessary, although their biodegradability is not so good. The paraffin sulfonate can be terminally sulfonated, or the sulfonate substituent can be linked to the carbon in the 2-position or another carbon of the chain io; Similarly, any di- or higher sulfonates used can have the sulfonate groups distributed on the various carbon atoms of the hydrocarbon chain.

The paraffin sulfonates and olefin sulfonates are preferably in the form of their alkali metal, e.g. Sodium and potassium, ammonium, or mono-, di- and tri (lower) alkanolamine salts or mixtures thereof. Triethanolamine is the preferred alkanolamine salt forming cation. The linear alkyl benzenesulfonates and alkyl ether sulfates are particularly preferred as anionic surfactant 20.

These anionic surfactants can not only react with the quaternary mono (higher) alkyl compound to improve the softening and antistatic effect, but can also cause various additional optional surfactant auxiliaries, as described in detail below, in particular optical brighteners, to be more effective deposit on the washed textiles.

While no specific rules can be given for all combinations of ingredients and washing conditions, it has been observed as a general rule that, of the two preferred classes of anionic surfactants, the linear alkyl benzene sulfonates are slightly more effective than the alkyl ether sulfonates in terms of softening are somewhat less effective in terms of cleaning - although adding any anionic surfactant often provides little improvement in cleaning performance compared to the same composition without an anionic surfactant. Mixtures of two or more anionic surfactants can of course be used.

40 Since the anionic surfactant presumably forms a complex with the cationic plasticizer, which leads to the improved plasticizing / antistatic effect, the cleaning action of the nonionic surfactant or brightener not being disturbed or slightly improved, the ratio of 45 cationic to anionic compound is in The detergent formulation is particularly critical since large excesses of each ingredient can affect the overall effect. Thus, ratios of cationic to anionic substance of above all 1.3: 1 to 1: 1.5, preferably 1.2: 1 to 1: 1.2, particularly preferably from 1.1: 1 to 1: 1, 1 and most preferably from about 1: 1 improved softening and antistatic effect as well as improved whitening and possibly cleaning.

The total amount of the cationic / anionic softening mixture in the composition is generally in the range from 2 to 20, preferably 5 to 15,% by weight, based on the total composition. Furthermore, the total amount of cationic plasticizer and anionic surfactant should generally be in the range from 20 to 100, preferably 30 to 80,% by weight, based on the nonionic surfactant. In addition, the cationic / anionic softening mixture is compatible with the nonionic surfactant, sulfosuccinamate and optical brightener etc. within the above amounts and ratios.

The liquid carrier for the liquid detergent composition according to the invention is preferably an aqueous one, can be exclusively water or essentially water with additional solvents for dissolving special constituents in a manner known per se. Because of the availability of water and

9

668 982

its minimal cost, it is preferred to use it as the main solvent. However, other solvents, generally up to 20% and preferably at most 15% of the total, can be used. Generally such a supplemental solvent is either a lower alkanol or a lower diol or polyol, e.g. Ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin or the like. Etheric polyols such as diethylene glycol and those known as cellosolves can also be used.

In addition to the supplemental solvent, it is also generally preferred to incorporate a hydrotropic material into the formulation to maximize the compatibility of all active ingredients and to make the liquid formulation more homogeneous and stable. Examples of suitable hydrotropes include the alkali metal layl sulfonates such as sodium benzene sulfonate, sodium toluenesulfonate, sodium xylene sulfonate and the corresponding potassium salts. The hydrotrope can be used in amounts of up to 15, preferably up to 10% by weight of the total composition, for example from 1 to 8 or 2 to 6 percent. Although aqueous carriers are preferred, non-aqueous liquid carriers such as the above-mentioned organic cosolvents can be used as the sole or main liquid carrier, i.e. the non-aqueous liquid carriers can make up 50 to 100% by weight of the liquid carrier, the remainder optionally being composed of water and / or hydrotropic material. Mixtures of two or more organic solvents can also be used.

In addition, it is possible to formulate the detergent compositions, which contain the three essential components nonionic surfactant, quaternary mono (higher) alkylammonium compound and sulfosuccinamate surfactant plus optional anionic surfactant and any detergent adjuvants, in the form of highly viscous compositions such as gels, pastes, etc., for example by known ones and conventional thickeners can be used with the liquid carrier. Examples of suitable thickeners include e.g. the cellulose ethers such as hydroxyethyl cellulose, hydroxymethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose etc., xanthan gum, clay minerals etc. Alternatively, the compositions can also be prepared directly as pastes or highly viscous liquids by simply using the various components in the absence of a liquid carrier or in the presence of only small amounts, for example up to 20% by weight of the liquid carrier, preferably water or a mixture of water and organic solvent.

The water for formulating the liquid or pasty detergents according to the invention can originate from the starting materials themselves, for example the solutions or suspensions of the various surfactant salts, or it can be added. If it is added, demineralized water or water of low hardness is preferably used, for example below 50 ppm hardness salts as calcium carbonate, preferably below 10 ppm CaCo3. However, hard water can be used, even if it is undesirable, and satisfactory hard water products of around 200 ppm are obtained, but the use of such water is usually avoided if possible.

Various selected compatible auxiliaries for achieving desired functional or aesthetic properties can also be present in the detergent composition. This is how you can incorporate into the formulation: enzymes e.g. Proteases, amylases, lipases, etc. and mixtures thereof; Bleach; Bleach activators and stabilizers; substances that carry dirt or prevent refilling, e.g. Polyvinyl alcohol, sodium carboxymethyl cellulose, hydroxypropyl cellulose; dirt-removing substances, e.g. Alkaril Chemical's Polymères QCJ for engine oil detachment, etc .; Dyes, bluing agents, pigments, optical brighteners, e.g. Cotton, amide and polyester brighteners; Bactericides, e.g. Hexachlo-

rophen; Protective substances e.g. Methyl parasept or sodium benzoate; Ultraviolet absorber; pH-modifying substances, e.g. Amines, pH buffers; Opacifiers, e.g. Behenic acid, polystyrene suspensions, etc .; and perfumes. The auxiliaries and additives 5 are of course chosen so that they are compatible with the main components of the detergent formulation.

Of the adjuvants mentioned, the optical brighteners may be the most important in terms of their functional effect, since the modern housewife expects that washed clothes are no longer just clean and white, but also shine in bright colors. The optical brighteners are sub-substantive to the washed textiles (this substantivity can be selective) and sometimes have comparatively low solubilities. It is therefore important that they are kept in solution in the liquid detergent composition. Even more importantly, they must be immediately dispersed in the wash water to prevent the laundry obtained from showing noticeable lightened spots instead of a uniform, luminous appearance. The choice of the brightener to achieve the best results is a matter for the skilled person. It has been found that relatively small amounts of brighteners should be used in order not to exceed the solubility limits. Within the class of these materials, certain brighteners have proven to be particularly easily soluble and 25 are therefore suitable for incorporation into these products. Fortunately, these preferred brighteners include both cotton and amide polyester brighteners, making them suitable for laundry made from a variety of materials, including synthetic ones. Commercial brighteners used in the system of the invention include Tinopal UNPC, Tinopal CBS (Ciba-Geigy), Arctic White CC (Hilton Davis) and the following Phorwhites from Verona: BKL, BBC, BBC solution , BRV solution, DCR liquid, DCBVF, EV liquid, DBS liquids and ANR.

35 Other types of optical brighteners that produce superior whitening effects are those components without sulfonate parts. The preferred brightener class for use in the composition according to the invention comprises 2- (4-styrylphenyl) -2H-naphthol [1,2-d] triazoles, 4,4'-bis (1,2,3-triazol-2-yl) stilbene, 40 4,4'-bis (styiyl) bisphenyls and the y-aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylamino-coumarin, 1,2-bis (benzimidazol-2-yl) ethylene and 1,3-diphenylpyrazolines and 2,5-bis (benzoxazol-2-yl) thiophene, 2-styiyl-napth [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naphthol [1,2-d] tria-45 zol.

The optical brightener content of the liquid composition is normally 0.2 to 3.0, preferably 0.25 to 2.7%. Such concentrations are soluble in the liquid detergents described and bring about a remarkable improvement in washed clothes. As mentioned above, the presence of the anionic surfactant can improve the uniform deposition of the optical brightener.

Another class of auxiliary agents that may be present are the organic builders, other than the Nitrilotri-55 acetate, and sequestering agents. Representative of the class of builders and sequestrants or chelating agents are sodium citrate, potassium gluconate, polyacrylic acids, ethylenediamine tetraacetic acid and the alkali metal, alkaline earth metal, amine, alkanolamine and ammonium salts thereof, etc. In general, it is preferred and often necessary to completely avoid the inorganic builders, especially the phosphate builders. However, small amounts of inorganic phosphate builders can be incorporated into the compositions in locations where environmental conditions do not prohibit them.

The content of the other auxiliaries is preferably kept below 5, particularly preferably below 3% by weight of the product. The use of larger amounts than these described

668 982

10th

Bindings can often significantly change properties such as the stability of the liquid detergent and should therefore be avoided.

Although the liquid detergent composition of the invention is a stable, clear, single-phase solution, a compatible opacifier can be added to give the formulation a creamy appearance.

Yet another optional but highly preferred ingredient in the detergent compositions of the invention is an ethoxylated fatty amine such as the Ethomeen series of compounds from the Armak Company and the Varonic series from Ashland Chemicals. These compounds can be represented by the general formula

^ ^ (CH2CH20) xH R7 -N

(CH2CH20) yH

in which R7 is a fatty alkyl group having 10 to 22, preferably 12 to 18 carbon atoms and the sum of x + y is about 2 to about 15. The R7 group can be saturated or unsaturated and can be derived, for example, 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 static properties. Usual amounts of ethoxylated amine up to 15, preferably up to 10, for example 1 to 10 or 1 to 8, in particular 2 to 8% by weight of the total liquid composition are sufficient.

To support the solubilization of the surfactants and optical brighteners that may be present in the liquid detergents, a small amount of alkaline material or a mixture of such materials is often incorporated into the formulations according to the invention. Suitable alkaline materials include mono-, di- and trialkanolamines, alkylamines, ammonium hydroxide and alkali metal hydroxides. Of these, the alkanolamines are preferred, especially the trialkanolamines and, above all, triethanolamine. The pH of the finished liquid detergent containing such a basic material is usually neutral or weakly basic. Satisfactory pH ranges are 7 to 10, preferably 7.5 to 9.5, but since a pH reading on the liquid detergent using a glass electrode and a reference calomel electrode may be inaccurate, since the detergent system is often substantially non-aqueous, A better determination can be obtained if the pH of a 1% solution of the liquid detergent in water is measured. Such pH is also normally in the range of 7 to 10, preferably 7.5 to 9.5. The pH in the wash water is usually in this range or may be slightly more acidic, for example around 0.5 to 1 pH unit, due to the level of soiled organic acid laundry. According to the measurements carried out with a Brookfield viscometer at room temperature using a spindle number 1 to 12 rpm, the viscosity of the liquid formulations at 25 ° C. is 40 to 120, preferably 40 to 100, particularly preferably 70 to 100 and am most preferably 80 to 95 10 -3 Pas.

The liquid composition is usually added to the washing water in a top or front loading type automatic washing machine so that the concentration thereof in the washing water is in the range of about 0.05 to 1.5, usually 0.1 to 1.2%. Depending on the type of machine and the degree of filling with soiled textiles, the amount of liquid formulation to be added is generally in the range from about 1 A to about PA measuring cups, the typical amount being about Vi measuring cups (120 ml).

The wash water used can be quite soft

Water or water of moderate hardness and is generally used preferably at elevated temperature, especially at about 37.8 ° C or higher, for example at 48.9 ° C to 82.2 ° C or higher. The composition of the invention is also suitable for washing textiles in very hard water and at lower temperatures. For example, the water hardness can range from 0 to over 300 ppm, calculated as calcium carbonate, and the washing temperatures can range from 4.44 to 48.9 ° C or higher. Washing is usually carried out in an automatic washing machine, which is followed by rinsing, spinning or other draining or wringing processes. Of course, the detergent composition can also be used for hand washing. In this case, it can sometimes be applied in full strength to certain stains on the laundry, or the laundry can be soaked in a more concentrated detergent solution before washing.

The washing process generally takes 3 minutes to 1 hour, depending on the textiles to be washed and the degree of soiling found. After washing, spinning, draining or wringing, it is preferable to dry the laundry in an automatic dryer shortly afterwards, but you can also dry on a line.

The detergent composition according to the invention dissolves very easily in warm and cold water and effectively makes clothes clean, soft and prevents electrostatic charging of the textiles without making their surface water-repellent. It can be used in top loading or front loading machines and is set to the correct foam size as required. The product is an attractive, product-resistant liquid that maintains its activity and uniformity over a long period of storage. In tests in which the effects of the detergents according to the invention were compared with those of commercially available detergents, they performed very favorably.

This product can be easily prepared by mixing the various ingredients at room temperature with stirring to ensure their solubilization in the aqueous medium. The order of addition of ingredients and the mixing temperature can be varied without affecting the formation of the single-phase, clear, liquid product of the invention. In the same way, more viscous formulations or pastes can be prepared by known methods.

The detergent composition of the invention exhibits desirable behavior in terms of both physical properties and effectiveness when used. As far as the physical properties are concerned, the liquid compositions are edible and free-flowing from the container both after manufacture and after aging. They show a high degree of stability when stored at room temperature of around 210 C for many months without any significant precipitation. As a result, they can be used by the consumer in the usual way by adding very small amounts to a washing bath, detergents and plasticizers being present in a constant composition in each part. Although compatible adjuvants can be added to make the final product translucent or opaque as desired, the condition of a single phase solution of the main ingredients ensures effective washing and softening power with each portion and favors the stability and homogeneity of the product. The composition can be packaged in any suitable container or in packaging material such as metal, plastic or glass.

The following specific examples illustrate various forms of the invention.

In order to test the cleaning effect of the detergent compositions, various formulations were produced and in standardized test procedures with numerous types of dirt

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

11

668 982

and tested on different substances with different concentrations and amounts of active ingredients. All cleaning tests were carried out under the same conditions (unless stated otherwise) in identical washing machines (Terg-O-Tometer): 48.9 ° C, 100 ppm Ca ++, 64.4 liters of washing water, 0.2% product concentration (V2 measuring cup ). The fabrics include nylon, cotton and a polyester (Dacron) / cotton blend (65/35). The test soil comprised mixed dirt (TF) from Test Fabrics Co., Piscataway clay (PC) and oily dirt (on cotton) (EMPA) from Test Fabrics Co. The cleaning effect was determined by measuring the

example 1

The following compositions were made:

NEN reflectance (Rd) determined as a measure of the white content. These readings were correlated to give a total dirt removal (SR) score by multiplying the Rd values of the various contaminants by a coefficient determined for each artificially contaminated material to determine the relationship between cleaning performance reproduce on the artificially soiled fabrics with practical washing tests. The relative total cleaning effect (SRI) of the two compositions can be determined by comparing the SR values of any two compositions.

Table 1

1

2nd

3rd

4th

5

6

7

8th

9

10th

11

12

Neodol 25-7 1

21st

21st

21st

21st

29

21st

21st

21st

21st

21st

21st

21st

Arquad T-50 2

-

4th

-

4th

-

-

8th

5

3rd

2nd

-

2nd

Monawet SNO-35

-

-

4th

4th

-

8th

-

3rd

5

2nd

-

6

water

rest

Ratio Quat./SNO

-

-

-

1: 1

-

-

-

1.7: 1

1: 1.7

1: 1

-

1: 3

SRI vs.Ans.No. 1

-

-19.1

+ 8.5

+ 14.4

+1.8

+ 8.8

-13.1

-8.9

+ 16.6

+ 9.9

+ 3.3

+ 8.4

SRI vs.Ans.No. 11

-3.2

-22.3

5.3

11.2

-1.5

5.5

-16.3

-12.2

13.3

6.7

-

5.2

SR (total)

204.8

185.7

213.3

219.2

206.5

213.5

191.7

195.8

221.3

214.7

208.0

213.2

Part of Neodol 25-7

1 Nonionic surfactant: primary C12-i5 fatty alcohol with 7 moles of ethylene oxide (7 EO), from Shell Oil Products Arquad T-50

2 Quaternary ammonium: tallow trimethyl ammonium chloride, from Armak Monawet SNO

3 tetrasodium N- (1,2-dicarboxyethyl) N-octadecylsulfosuccinamate, from Mono Industries, Inc.

In the table above, approach (Ans.) No. 11 a repetition of Ans. No. 1 using a freshly prepared sample composition.

The following can be seen and concluded from the results shown in Table 1:

The addition of a quaternary ammonium compound alone (batches 2 and 7) to the nonionic surfactant (batch No. 1) has a very considerable negative effect on the cleaning power.

The addition of the succinate surfactant alone (batches 3 and 6) significantly improves the cleaning effect, but of course does not impart any softening which is a contribution of the quaternary compound.

The addition of quaternary compound and succinamate in a ratio of 1.7: 1 (batch 8) brings a significant improvement over the quaternary compound alone (batches 2 and 7), but is still considerably inferior to the comparison batch (batch No. 1).

With a total addition of quaternary compound and succinamate of 8% by weight, a ratio of quaternary compound: succinamate of 1: 1.7 (batch 9) gives the best cleaning action and is slightly better than a 1: 1 ratio

(Approach 4), whereas a ratio of 1: 3 (approach 12) gives approximately the same cleaning effect as succinamate alone (approaches 3 and 6) both at concentrations of 4 and 8%. In fact, the 1: 3 ratio at a content of 8% by weight (batch No. 12) is inferior to the 1: 1 ratio (batch 10) at a total content of 4% by weight.

40 Therefore, under the conditions of this test, the preferred ratios of quaternary compound to succinamate are in the range of about 1: 1 to about 1: 2, with ratios over about 1: 2 to 1: 3 still improving the cleaning effect (eg whitening) as well as improved softening / antistati-45 see effect.

Example 2

Batches 1 to 12 of Example 1 were each prepared again 5o, but with the addition of an anionic surfactant: linear dodecylbenzenesulfonate (sodium salt) (LDBS) in the amount shown in Table 2. The results are also shown in Table 2. For easier comparison, the values of SR (total) and SRI vs. Ans. No. 1 of Example 1 also shown in Table 55 2.

668 982 12

Table 2

Approach% by weight% by weight SR (total) SRI vs. Approach No. 1

No. LDBS SNO with LDBS without LDBS with LDBS without LDBS

1

4th

-

207.3

204.8

-

-

2nd

41

-

213.3

185.7

+ 6.0

-19.1

3rd

4th

4th

212.8

213.3

+ 5.5

+ 8.5

4th

41

4th

219.2

219.2

+ 11.9

+ 14.4

5 (29% not

ionic surfactant)

8th

-

211.4

206.5

+ 4.2

+ 1.8

6

8th

8th

214.4

213.4

+ 7.1

+ 8.8

7

81

-

208.7

191.7

+ 1.3

-13.1

8th

51

3rd

220.5

195.8

+ 13.1

- 8.9

9

31

5

218.7

221.3

+ 11.4

+16.6

10th

21st

2nd

218.2

214.7

+ 10.9

+ 9.9

11

4th

-

210.7

208.0

+ 3.4

+ 3.2

12

21st

6

218.1

213.2

+ 10.8

+ 8.4

1 weight ratio quaternary compound: LDBS = 1: 1

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

Batch 2 and Batch 7 correspond to the compositions that are the subject of US Serial No. 661 775 are the mixtures of nonionic surfactant with 1: 1 mixtures of cationic fabric softener and anionic surfactant (without sulfosuccinamate).

The approaches 3,4, 6, 8, 9, 10 and 12 correspond to the invention. As can be seen, in the range of quaternary compound / succinamate ratios of 1.7: 1 (batch 8) to 1: 3 (batch 12), a significantly better cleaning effect is obtained compared to both the quaternary compound alone (batches 2 and 7). or succinamate alone (approaches 3 and 6).

In addition, the presence of the anionic surfactant in these formulations brings additional advantages in that the antistatic and plasticizing effects of the quaternary mono (higher) alkylammonium compound are increased. In addition, the anionic surfactant in the preferred composition containing an optical brightener also causes the brightener to deposit more effectively. At the same time, it also becomes clear that in certain formulations the combination of the succinate surfactant with the anionic surfactant significantly increases the overall cleaning effect (compare e.g. SR total from approach 8 in example 2 with approach 8 in example 1).

It should be pointed out that in Examples 1 and 2 when using V2 measuring cups the content of 21% or 29% Neodol 25-7 corresponds to 25 g or 35 g / wash; 4% and 8% Arquad T-50 correspond to 5 g / wash and 10 g / wash; 4% or 8% Monawet SNO correspond to 5 g / wash or 10 g / wash.

Amount of astromide 18, astormid 22, Alkasurf SS-OA or Alkasurf 25 SS-TA replaced.

Similarly, leads to the Examples 1 and 2 to the same results if, instead of Arquad T-50 hydrogenated tallow trimethyl ammonium chloride, Steaiyltrimethylam-ammonium chloride, Steaiyltriethylammoniumchlorid, 30 Steaiyldimethylethylammoniumchlorid, Talgdiisopropylmethy-lammoniumchlorid and the corresponding sulfate, methosulfate, ethosulfate, Bromide and hydroxide salts are used. Arquad T-50 can also be replaced in part or in full by Ethoquad 18/12 or another similar quaternary ethoxylated 35 mono (higher) alkyl compound.

In Example 2, generally similar results are obtained if, for example, instead of the linear dodecyl-benzenesulfonate as the anionic surfactant Neodol 25-3S [from Shell Oil Products, formula R0 (C2H40) 3S03Na, R = mixed Ci2_i5 40 primary fatty alcohol] is used. The LDBS (anionic surfactant) can also be completely or partially replaced by, for example, sodium alpha olefin sulfonate with 14 to 18 carbon atoms or sodium umparafinsulfonate with 13 to 17 carbon atoms or the corresponding potassium salts.

45

Example 4

The following compositions shown in Table 3 were tested in the same manner as in Example 1 with the results (SR total) also given in Table 3.

Example 3 55

Similar results can be obtained by repeating Example 1 or Example 2 using an equal amount of Neodol 23-6.5 [R0 (C2H40) 5.5H, where R is a mixture of 12 and 13 carbon atom primary alcohols]

or Tergitol 15-S-7 or Tergitol 15-S-9 (both of which are linear secondary Cn_i5 alcohol ethoxylates from Union Carbide Corp., the former with 7 moles and the latter with 9 moles of ethylene oxide) or with one with 5 , 7 or 9 moles of ethylene oxide condensed nonylphenol or with an isooctylphenol condensed with 9, 10, 11 or 12 moles of ethylene oxide instead of 65 of neodol 25-7.

Similar results can be achieved if, in example 1 or example 2, the Monawet SNO-35 is replaced by an identical one

13 668 982

Table 3

Approach No. component 1 2

Neodol 25-7

21st

21st

21st

21st

21st

21st

21st

21st

Triethanolamine

1.7

1.7

1.7

1.7

1.7

-

-

-

Tinopal UNPA

0.5

0.5

0.5

0.5

0.5

0.5

0.5

0.5

Adogen 471

4th

4th

4th

4th

4th

4th

4th

4th

LDBS,

Sodium salt

-

-

-

4th

4th

-

-

-

Neodol 25-35

-

-

-

-

-

4th

4th

4th

Sodium citrate

4th

4th

4th

4th

4th

4th

4th

4th

Methocel

-

-

-

-

0.8

-

-

-

Monawet SNO-35

4th

-

-

-

4th

4th

-

-

Astromide 22

-

-

4th

-

-

-

-

4th

Astromide 18

-

4th

-

4th

-

-

4th

-

Water qs 100

qs 100

qs 100

qs 100

qs 100

qs 100

qs 100

qs 100

SR Total

240

238

237

225

227

236

230

234

Example 5

In each of the compositions of Example 4, a portion of Neodol 25-7 was replaced with Ethomeen T-25, which is an ethoxylated amine of the formula available from Armak

Tallow-N-

. (ch2ch20) xh (ch2ch20) yh

(x + y = 15)

in an amount that gives about 3 to 8% ethoxylated amine and, accordingly, about 18 to 13% nonionic surfactant. Improvements in cleaning, softening and static properties have been observed. The formulations containing 15% by weight of nonionic 35 surfactant and 6% by weight of ethoxylated amine give particularly good results.

Example 6

In each of the compositions of Examples 4 and 5, the incorporation of an enzyme, for example a protease enzyme, in an amount of up to about 1, in particular about 0.5% by weight, based on the composition, improved the cleaning action compared to certain Types of dirt, for example protease against protein deposits, amylase against starch deposits, etc. The enzymes are stable in the compositions. Mixtures of different enzymes can be used.

Example 7 50

The following ingredients were used to produce highly stable, homogeneous, clear, aqueous compositions with a comparable cleaning effect:

Example 8

This example demonstrates the effect of washing temperature on the cleaning effect and also shows that the combination of cationic quaternary compound and succinamate surfactant in the preferred ratios is effective at both low and high temperatures. In the same manner as described in Example 1, the following liquid compositions shown in Table 4 were prepared and tested under the conditions given in Example 1 at a washing temperature of 48.9 ° C or 21.1 ° C. The results (SRI values with nonionic surfactant alone [21% batch No. 1] as a comparison) are given in Table 4.

Table 4

30th

l

2nd

3rd

4th

5

6

7

8th

Neodol 25-7

21st

21st

21st

21st

21st

21st

21st

21st

Neodol 25-3S

-

4th

4th

4th

4th

4th

4th

4th

Adogen 4711

-

-

4th

4th

4th

-

4th

4th

Monawet-SNO-35

-

-

-

4th

4th

4th

8th

-

Sodium citrate

-

-

-

-

4th

4th

-

8th

water

rest

SRI vs. Approach 1

48.9 ° C (120 ° F)

+ 4th

+ 3

+ 14

+ 13

+ 9

+ 10

+ 7

SRI vs. Approach 1

21.1 ° C (70 ° F)

-

+ 1

-4

+ 10

+ 10

+ 5

0

+ 4th

1 tallow trimethyl ammonium chloride from Sherex

B

Neodol 25-7

21st

16

Neodol 25-3S

4th

-

Sodium dodecylbenzenesulfonate

-

3rd

Monawet SNO-35

4th

3rd

Arquad T-50

4th

3rd

Sodium citrate

4th

-

Sodium oxyolsulfonate

4th

3rd

Optical brightener

0.5

0.5

enzyme

0.5

0.5

Water qs 100

qs 100

G

Claims (17)

668 982 2nd PATENT CLAIMS 1. Detergent composition, characterized by a content of a nonionic surfactant, a quaternary mono (higher) alkylammonium compound as a textile-softening, antistatic agent and a sulfosuccinamate surfactant compound. 2. Detergent composition according to claim 1, characterized in that it also contains an anionic surfactant from the group consisting of linear, higher alkyl aromatic sulfonate, poly (lower) alkoxy (higher) alkanol sulfate, olefin sulfonate and paraffin sulfonate. 3. Detergent composition according to claim 1, characterized in that the sulfosuccinamate surfactant compound is a compound of formula V. 0 ch2-c-n: z03-s-ch-c0ûz r4 R5 wherein R represents a primary or secondary alkyl chain of 8 to 22 carbon atoms and n is an average number of 5 to 20; and Rl-f3 "-0" (CH2CH20) mH (II)> wherein R1 represents a primary or secondary alkyl chain having 4 to 12 carbon atoms and m is an average number 10 of 5 to 20; (B) about 1 to 10% by weight of a quaternary mono (high ren) alkylammonium compound of formula III or IV / (V) R2 , R3 R3 x R3 (III) 20th where Z is a monovalent salt-forming cation, R is hydrogen, lower alkyl, carboxy (lower) alkyl or 1,2-dicar-boxyl (lower) alkyl and R5 is an open hydrocarbon chain with 10 to 22 carbon atoms. 4. Detergent composition according to claim 3, characterized in that in the formula VZ is an alkali metal, ammonium or an amine salt forming cation, R4 is hydrogen, methyl, ethyl, carboxymethyl, carboxyethyl, dicarboxymethyl or 1,2-dicarboxyethyl and Rs is a saturated or unsaturated, straight-chain or branched alkyl or alkenyl group having 14 to 18 carbon atoms. 5. Detergent composition according to claim 1, characterized in that the sulfosuccinamate surfactant compound is dinotronium-N-octadecylsulfosuccinamate, disodium N-oleylsulfosucci-namate or tetrasodium N- (1,2-dicarboxyethyl) N-octadecylsul-fosuccinamate. 6. Detergent composition according to claim 1, characterized in that it contains 10 to 50% of the nonionic surfactant, 1 to 10% of the quaternary monoalkyl compound and 1 to 10% of the sulfosuccinamate compound. 7. Detergent composition according to claim 6, characterized in that it contains 12 to 35% nonionic surfactant, 2 to 6% quaternary monoalkyl compound and 2 to 6% of the sulfosuccinamate compound. 8. Detergent composition according to claim 6, characterized in that it also contains an anionic surfactant from the group consisting of linear, higher alkyl aromatic sulfonate, poly (lower) alkoxy (higher) alkanol sulfate, olefin sulfonate and paraffin sulfonate in an amount which has a weight ratio of quaternary Monoalkyl compound to anionic surfactant from 1.3: 1 to 1: 1.5. 9. Detergent composition according to claim 8, characterized in that the weight ratio of nonionic surfactant to quaternary monoalkyl compound is in the range from 15: 1 to 2: 1 and the weight ratio of quaternary monoalkyl compound to sulfosuccinamate is in the range from 3: 1 to 1: 3 . 10. An aqueous liquid detergent composition according to claim 1 for cleaning and softening soiled textiles, which is suitable for addition to the washing cycle of an automatic washing machine, characterized by a content of the composition (A) 10 to 50% by weight of a liquid nonionic surfactant from the group consisting of compounds of the formulas I and II, namely r? r3 \ (CH2CH20) xH - (CH2CH20) yH / (IV) 25 wherein R2 is a long chain aliphatic radical having 10 to 22 carbon atoms, each of the R3 radicals in formula III and in formula IV independently denoting lower alkyl or hydroxy (lower-res) alkyl, X represents a water-soluble salt-forming anion and x and y in each case positive numbers of at least 1 are 30 and the sum of x + y is 2 to 15; (C) 1 to 10% by weight of a sulfosuccinamate surfactant compound of the formula 35 O CH2-C-N ' ZO3-s-ch-cooz R4 .RS (V) R0 (CH2CH20) nH (I), wherein Z is a monovalent salt-forming cation, R4 is hydrogen-4o, lower alkyl, carboxy (lower) alkyl or 1,2-dicarboxy (lower) alkyl and R5 is an open-chain hydrocarbon radical having 10 to 22 carbon atoms; (D) up to 10% by weight of an anionic surfactant from the group consisting of linear higher alkylaromatic sulfonates, poly (lower 45 ren) alkoxy (higher) alkanol sulfates, olefin sulfonates and paraffin sulfonates; (E) up to 3% of an optical brightener; (F) up to 15% of an ethoxylated amine; (G) up to about 5% of an alkaline substance; go (H) up to 3% enzymes; (I) up to 3% soil release agent and (J) aqueous solvent vehicle. 11. The composition according to claim 10, characterized in that the anionic surfactant D in a weight ratio 55 nis from C: D from 1.3: 1 to 1: 1.5 is present. 12. The composition according to claim 10, characterized in that it (A) 12 to 35%, (B) 2 to 6%, 60 (C) 2 to 6%, (D) in an amount that gives a weight ratio of C: D of 1.2: 1 to 1: 1.2, (E) 0.2 to 2% by weight, (F) up to 10%, 65 (G) up to 3%, (H) up to 2%, (I) up to 2%, (J) contains the rest. 3rd 668 982 13. The composition according to claim 12, characterized in that (A) is a compound of formula I, wherein R is a C12-C15 alkyl or mixture thereof and n is a number from 6 to 13; (B) means tallow trimethyl ammonium chloride; (C) is disodium N-octadecylsulfosuccinamate, disodium N-oleylsulfosuccinamate or tetrasodium N- (1,2-dicarboxyet-hyl-) N-octadecylsulfosuccinate and (D) means linear dodecylbenzenesulfonate or triethenoxy (Ci2-Ci5) alkanol sulfate. 14. The composition according to claim 10, characterized in that it (A) 15 to 25% of a compound of formula I, wherein R is a primary or secondary Cio-Cis-alkyl and n is 6 to 13; (B) 2 to 6% of a compound of formula III, wherein R2 is an aliphatic radical having 12 to 18 carbon atoms and each R3 is methyl; (C) 2 to 6% of the sulfosuccinamate compound of formula V, wherein R5 has 14 to 18 carbon atoms and R4 is hydrogen or 1,2-dicarboxyethyl, and contains an aqueous liquid carrier. 15. The composition according to claim 14, characterized in that the weight ratio of B: C is in the range from 1: 1 to 1: 2. 16. The composition according to claim 14, characterized in that it also contains (D) a linear higher alkylbenzenesulfonate or polyethoxy (higher) alkanol sulfate in an amount which has a weight ratio of C: D of 1.1: 1 to 1: 1 , 1 results. 17. The composition according to claim 16, characterized in that the weight ratio of B: C is in the range from 1.5: 1 to 3: 1.