CH643881A5 - DETERGENT COMPOSITIONS. - Google Patents

Abstract

Built laundry detergent compositions containing specific mixtures of selected anionic, nonionic and water-soluble cationic surfactants. The compositions are especially effective in removing greasy soil from fabrics.

Description

The invention relates to detergent compositions which have improved greasy dirt removal capabilities. More specifically, the detergent compositions according to the invention provide an unexpectedly good washing power behavior against greasy and oily soiling with a pronounced content of particulate dirt.

Cationic surfactants have often been incorporated into detergent compositions of various types. However, the influence of such cationic surfactants generally serves the purpose of providing an additional fabric care benefit and not the purpose of cleaning. For example, certain cationic surfactants have been included in detergent compositions for the purpose of conferring a germicidal or harmless effect on laundered surfaces, as disclosed in U.S. Patent 2,742,434, issued April 17, 1956 to Kopp , U.S. Patent 3,539,520, issued November 10, 1970 to Cantor et al, and U.S. Patent 3,965,026, issued June 22, 1976 to Lancz. Other cationic surfactants, such as ditallow dimethyl ammonium chloride, have been included in detergent compositions for the purpose of providing a fabric softening effect, as in U.S. Patent 3,607,763, issued September 21, 1971 to Salmon et al, and U.S. Patent 3 644 203, issued February 22, 1972 to Laberti et al. U.S. Patent 3,951,879, issued April 20, 1976 to Wixon, and U.S. Patent 3,959,157, issued May 25, 1976 to Inamo-rato also disclose that such components are in detergent compositions for the purpose included to combat static electricity and to soften washed textiles.

Compositions are also known in the art which have mixtures of anionic, cationic and nonionic surface-active agents. So in the bri5

lü

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table patent 873 214 describes compositions which thus give textiles washed an improved antistatic character, while compositions having improved germicidal and washing power behavior are disclosed in British patent 641,297.

Surprisingly, however, it has now been found that builder-containing detergent compositions, which have water-soluble or dispersible mixtures of specific anionic, cationic and nonionic surface-active agents in critical relative amounts, provide an unexpectedly improved cleaning action on greasy and oily soils, even if they do have a high content of particulate material. Furthermore, this excellent effect is observed at both high and low washing temperatures and over a range of realistic types of soils and washing conditions. Furthermore, the improved effect of removing greasy stains is achieved without damaging the detergency against conventional types of dirt and stains and, most surprisingly, without damaging the dirt suspending or fabric whitening properties of the compositions.

According to the present invention, a solid, particle-shaped detergent composition is provided,

a) 2 to 60% by weight of a surface-active system which essentially consists of a water-soluble or water-dispersible combination of anionic, alkoxylated nonionic and water-soluble, cationic quaternary ammonium surface-active agents, the anionic weight ratio being: cationic surfactant is not greater than 5: 1 and the weight ratio is nonionic: cationic surfactant is at least 2: 3 and wherein the surfactant system contains anionic and cationic surfactants in an equivalent ratio of at least 1: 1, and b) at least 10 % By weight of a detergency builder.

Detergent compositions according to the invention contain, as an essential component, an active three-component system which has anionic, alkoxylated nonionic and water-soluble cationic surface-active agents. This active system makes up 2 to 60% by weight of the compositions. In granular laundry detergent applications, the active system is generally present in the range from about 4% to about 30%, preferably from about 6% to about 15% by weight of the compositions.

The compositions according to the invention are preferably formulated in such a way that they have a pH of at least about 6 in the washing solution at conventional use concentrations (about 1% by weight) in order to optimize the cleaning effect. More preferably they are alkaline in nature when placed in the wash solution and have a pH greater than about 7, especially greater than about 8. At the higher pH values, the surface activity of the compositions according to the invention is improved and in some cases quite pronounced improved.

In the preferred system, the anionic and cationic surfactants combined have a total of no more than 34 carbon atoms, counted in hydrophobic groups with at least four successive carbon atoms (e.g. alkyl, alkaryl, aryl, aralkyl groups, etc.). In more preferred systems, the total number of such carbon atoms of hydrophobic groups is about 18 to 33, especially about 26 to 32, the anionic surfactant providing at least 12 of the carbon atoms. It has been found that these hydrophobic

Restrictions on the quality optimize the interaction of the ternary active system with greasy and oily stains on textiles and correspond to compositions with the maximum fat-washing effectiveness.

An essential feature of the present compositions is that the surface-active system in surface-active anions and cations must be essentially neutral or else have an ionic excess of surface-active anions over surface-active cations. This is important not only in terms of optimizing fat removal, but also to ensure a good suspension of dirt in the detergent wash liquor (ie to prevent redeposition of dirt) and also to ensure that water-insoluble agents with an anionic effect, such as anionic fluorescent compounds , keep their effectiveness in composition. It is of course well known that the effectiveness of anionic fluorescent compounds is quenched or inhibited in the presence of cationic surfactants. Surprisingly, the fat and oil detergency benefits of the present invention are assured without suppressing the activity of fluorescent compounds. It is therefore extremely important that the total equivalent ratio of anionic: cationic surfactant in the present compositions is at least 1: 1 within the error limits of production.

For typical compositions, the production error in the anionic and cationic surfactant components is up to about 5% by weight for each component.

Subject to the above conditions, the weight ratio of anionic: cationic surfactant can range from about 5: 1 to about 1: 3, especially from about 2: 1 to 1: 2, the weight ratio of nonionic: cationic from about 300: 1 to about 2: 3, in particular from about 20: 1 to about 1: 1, and the weight ratio anionic: nonionic from about 7: 1 to about 1:20, in particular from about 2: 1 to about 1:10, vary. Expressed as amounts of surfactant, the surfactant system preferably has at least about 5% by weight of the water-soluble cationic surfactant and a total of at least about 60% by weight of the anionic and nonionic surfactants. In a preferred embodiment, the surface-active system each has at least 15% by weight of the anionic and cationic surface-active agents and 15 to 60% by weight / b of the nonionic surface-active agent. In another preferred embodiment, the surfactant system each has at least 5% by weight of the anionic and cationic surfactants and at least 60% by weight of the nonionic surfactant.

As mentioned above, the cationic surface-active component of the composition according to the invention is characterized as being water-soluble. In this context, we refer to "water solubility" to the solubility of the cationic surfactant in monomeric form, the solubility limit being determined by the start of micellization and measured in the form of the critical micelle concentration (C.M.C.). The cationic surfactant should thus have a C.M.C. for the neat material, greater than about 200 ppm, and preferably greater than about 500 ppm, determined at 30 ° C and in distilled water. If possible, literature values are taken, in particular surface tension or conductometric values - see Criticai Micelle Concentrations of Aqueous Surfactant Systems, P. Mukerjee and K.J. Mysels, NSRDS-NBS 36 (1971).

Another important characteristic is that the ternary

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active system itself in combination with the rest of the detergent composition must be dispersible in water or soluble in water. This implies that in an aqueous equilibrium mixture of the detergent composition (containing about 1000 ppm surfactant) the ternary active system exists in one or more liquid (as opposed to solid) surfactant / water phases. In other words, the surfactant system should have a Krafft point of no more than about 25 ° C.

Another essential component of the present compositions are at least 10% by weight, preferably about 20% to about 70% by weight, of a detergency builder, e.g. a water-soluble inorganic or organic electrolyte. Suitable electrolytes have an equivalent weight of less than 210, especially less than 100, and include the usual alkaline multivalent calcium ion sequestering agents. However, water-insoluble calcium ion exchange materials can also be used to advantage. Surprisingly, it is found that the degreasing effect of the present compositions is sensitive to the ionic strength and the amount of free hardness ions in the detergent liquor, and these parameters must be carefully controlled for optimal effect. Thus, if the compositions are used in about 1% solution, the weight ratio of builder-surfactant is preferably greater than about 1: 3, more preferably greater than about 4: 1, and in particular greater than about 8: 1. On the other hand, the weight ratio of calcium ion sequestering or exchange agent: surface-active agent is preferably greater than about 1: 1 and in particular greater than about 3: 1, while the weight ratio of electrolyte: surface-active agent is preferably greater than about 3: 1, in particular greater than about 6: 1.

Optimal detergency for fat and particulate also depends sensitively on the choice of nonionic surfactant, and from the point of view of fat detergency, biodegradable nonionic surfactants with a lower critical solution temperature are in the range of about 25 to about 65 ° C, preferably about 30 to about 50 ° C, particularly desirable. Extremely suitable nonionic surfactants of this type have the general formula R0 (CH2CH20) nH, where R is primary or secondary branched or unbranched C9.15-alkyl or alkenyl and n (the average degree of ethoxylation) is 2 to 9, in particular 3 to 8, is. However, more hydrophilic nonionic detergents can be used to provide detergency for particulate and anti-graying, e.g. nonionic detergents of the general formula given above, wherein R is primary or secondary, branched or unbranched C8.24 alkyl or alkenyl and n is 10 to 40. Combinations of the two classes of nonionic surfactants can of course also be used to advantage.

The individual components of the composition according to the invention will now be described in detail.

The cationic surfactant

The preferred cationic surfactant is a water-soluble quaternary ammonium compound with a critical micelle concentration of at least 200 ppm at 30 ° C. Structurally speaking, the preferred cationic surfactant has 1 to about 4 quaternary ammonium groups, only one of which has the general formula:

R'mT2xN +

15

in which each R1 is a hydrophobic alkyl or alkenyl group which is optionally substituted or interrupted by phenyl, ether, ester or amide groups, which has a total of 8 to 20 carbon atoms and which can additionally contain up to 20 ethoxy groups, m a Number is 1 to 4 and no more than one R1 can have more than 16 carbon atoms when m is 2 and cannot have more than 12 carbon atoms when m is 3, each R2 is an alkyl group that has 1 to 4 carbon atoms contains, or is a benzyl group, where no more than one R2 in one molecule is benzyl, and x is 0 to 3.

An extremely preferred group of cationic surfactants of this type has the general formula:

R'n.RVmN + Z

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wherein R1 is selected from Ca to C2o alkyl, alkenyl and aryl groups, R2 is selected from Ci_4 alkyl and benzyl groups, Z is an anion in a number that gives electrical neutrality and m is 1.2 or 3 is provided that when m is 2, R1 has less than 15 carbon atoms and when m is 3, R1 has less than 9 carbon atoms.

25 When m is 1, it is preferred that R2 is a methyl group. Preferred compositions of this type with a long chain include those wherein R1 is a Cio to Ci6 alkyl group. Particularly preferred compositions of this class contain Cn-alkyl-trimethylammonium-30 halide and Ci4-alkyl-trimethylammonium-halide.

When m is 2, the R 'chains should have less than 14 carbon atoms. Thus, ditallow dimethyl ammonium chloride and distearyl dimethyl ammonium chloride, which are conventionally used in detergent compositions as textile softeners and anti-static agents, cannot be used as cationic components in the surface-active mixtures according to the invention. Particularly preferred cationic materials of this class include di-Cs-alkyldimethylammo-40 nium halide and di-Cio-alkyldimethylammonium halo-genide materials.

When m is 3, the R 'chains should be less than 9 carbon atoms in length. An example is trioctylmethylammonium chloride. The reason for this limitation in chain length, as in the case of the cationic compounds with two long chains described above, is the relative insolubility of these materials with 3 and 2 long chains.

Another group of useful cationic compounds are the polyammonium salts of the general formula:

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r.

-N

r,

- (CVrf r

i:

-n i

r

-r

4 '

-TO

wherein R3 is selected from Cs to C2o alkyl, alkenyl and alkaryl groups, each R- is Ci to C4 alkyl, n is I to 6 and m is 1 to 3.

A specific example of a material in this group is:

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ch,

(1) tallow-n + - (ch „), - n +

I 3

ch,

(ch3) 3, (ch co2 ~);

Another preferred type of cationic component has the formula:

r1

2- (z1) a- (r3) n-z2- (oh2) m-n + -rl x r1

wherein R1 is Ci to C4 alkyl, R2 is unbranched or branched chain Cs to C ^ o alkyl or alkenyl, alkylbenzene or r

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R1- ^

il

■ (ch2) s-

is

wherein s is 0 to 5, R3 is Ci to C2o alkyl or alkenyl, a is 0 or 1, n is 0 or 1, m is 1 to 5 20, Z1 and Z2 are each selected from the group are that out

? 0 0 OH HO OH HO

1! ii ii iii iii ii i i ii

-c-0-, -0-c-, -0-, -o-c-o-, -c-n-, -n-c3 -o-c-n, -n-c-0-,

and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide, and X is an anion that renders the compound water-soluble, preferably selected from the group consisting of halide , Methyl sulfate, hydroxide and nitrate, preferably chloride, bromide or iodine.

In addition to the advantages of the others, disclosed herein- 35

Cationic surfactants, this particular cationic component is desirable in terms of environmental protection because it is biodegradable, both in terms of its long alkyl chain and in terms of its nitrogen-containing segment.

Particularly preferred cationic surfactants of this type are the choline ester derivatives of the following formula:

ch5

r2 — c — 0 — ch2ch2 — n + —- ch, x "

ch.

as well as those in which the ester bond in the above formula is replaced by a reverse ester, amide or reverse amide bond.

Particularly preferred examples of this type of cationic surfactant include quaternary ammonium halides of caproylcholine ester (R2 = Cs alkyl), quaternary ammonium halides of palmitoyl choline ester (R2 = Ci5 alkyl), quaternary ammonium halogen

45 nides of myristoylcholinester R2 = Cn-alkyl), ammonium halides of lauroylcholinester (R2 = Cn-alkyl) and quaternary ammonium halides of capryloylcholinester (R2 = C7-alkyl).

Additional preferred cationic components of the choline ester variety are represented by the structural formulas below, in which p can be 0 to 20.

0 0 ch,

, ii ii l + 3 -

r -0-c- (ch2) pc-0-ch2ch2-n -c ^ x

CH,

ch.

0

0

ÇH3. +

x ch3- n-ch2ch2-0-c- (ch2) p-c-0-ch2-ch2-n -ch3 x ch ch,

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The preferred cationic choline derivative substances discussed above can be prepared by direct esterification of the fatty acid of the desired chain length with dimethylaminoethanol in the presence of an acidic catalyst. The reaction product is then quaternized with a methyl halide to form the desired cationic material. The cationic materials derived from choline can also be made by direct

Esterification of a long-chain fatty acid of the desired chain length together with 2-halogenoethanol in the presence of an acidic catalyst material. The reaction product is then used to quaternize triethanolamine to form the desired cationic component.

Another type of new, particularly preferred cationic material has the formula:

R

R

r3-0 [(ch) 0] - (z1) n y <

In the above formula, each R1 is a Ci to C4 alkyl group, preferably a methyl group. Each R2 is either hydrogen or Ci to C3 alkyl, preferably hydrogen. R3 is a straight or branched chain C4-Cso-alkyl, -alkenyl or -alkylbenzyl group, preferably a Cs to Ci8-alkyl group, most preferably one

(r \ -z2- (ch2) m-n + -r1 x "

R

Cn alkyl group. R4 is a Ci to Cio alkylene or alkenylene group. n is 2 to 4, preferably 2, y is 1 to 20, preferably about 1 to 10, most preferably about 7, a can be 0 or 1, t can be 0 or 1, and m is 1 to 5, preferably 2. Z1 and Z2 are each selected from the group consisting of

0 0 0 oh ho ohho

Xo-, -I-, -0-, -o-c-o-, -c-n-, -n-c-, -0-c-n-, -n-c-o-

and in which at least one of the groups mentioned is selected from the group consisting of ester, reverse ester, amide and reverse amide. X is an anion that makes the compound water-soluble and is selected from the group consisting of halides, methyl sulfate, hydroxide and nitrate, especially chloride, bromide and iodide.

If these surface-active agents are used in the compositions according to the invention, they result in an excellent removal of particulate dirt, body dirt and grease and oil dirt. In addition, the detergent compositions combat static electricity, soften the textiles washed with them and inhibit the transfer of dyes in the washing solution. Furthermore, these new cationic surfactants are desirable from an environmental standpoint because their long chain alkyl segments as well as their nitrogen segments are biodegradable.

Preferred embodiments of this type of cationic component are the choline esters (R1 is a methyl group and Z2 is an ester or reverse ester group), 40 of which special formulas are given below, in which t is 0 or 1 and y is 1 to 20 is.

0 oh3

R3-0 (CH2CH20) y- (CH2) fc-C-0-CH2-CH2-n -ch3 x

CH,

0 ch3. +

r3-0 (ch2ch20) y-c-ch2-n -chy x ch3

f5 î ï! 3 -

R3-0 (CHCH20) y-C-CH2-N -CH3 x ch,

ph o ch,

i 3 ii "u3

R -0 (CHCH20) - (CH2) t-C-0-CH2-CH2-N -ch3 x ch3

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0

ch: I -

r3-0 (ch2ch20) y-c- (ch2) t-c-0-ch2ch2-n -ch3 x ch.

0

ch.

+

r3-0 (ch2ch2ch2ch20) y-c-ch2-n -ch3 x ch,

1 +

r3-0 (ch2ch2ch2ch20) y- (ch2) fc-c-0-ch2ch2-n -ch3 x ch.

The preferred choline derivatives described above can be prepared by reacting a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate having an alkyl chain of the desired length with oxalyl chloride to form the corresponding acid chloride. The acid chloride is then reacted with dimethylaminoethanol to form the corresponding amine ester, which is then quaternized with a methyl halide to form the desired chlorine ester compound. Another route for the preparation of this compound is by direct esterification of the corresponding long chain ethoxylated carboxylic acid together with 2-halogenoethanol or dimethylaminoethanol in the presence of heat and an acidic catalyst. The reaction product formed is then quaternized with methyl halide or used to quaternize.

The anionic and nonionic surfactant

A typical list of anionic and nonionic surfactants useful herein appears in U.S. Patent 3,925,678, which is incorporated herein by reference. The following list of detergent compounds that can be used in the present compositions are representative of such materials.

Water soluble salts of higher fatty acids, i.e. "Soaps" are useful as the anionic detergent component of the present compositions. This class of detergents includes common alkali metal soaps, such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids, which contain from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and oils or by neutralizing free fatty acids.

The sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow are particularly useful, i.e. Sodium or potassium tallow and coconut nut soap.

An extremely preferred class of anionic detergents includes water-soluble salts, especially the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric acid reaction products which have in their molecular structure an alkyl group containing about 8 to about 22, especially about 10 to about 20 carbon atoms, and have a sulfonic acid or sulfuric acid ester group. (In the expression «alkyl» is the alkyl portion of acyl groups

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). Examples of the detergent compositions according to the invention are the sodium and potassium alkyl sulfates, in particular those obtained by sulfating the higher alcohols Cs to Cis carbon atoms) which are produced by reducing the glycerides of tallow or coconut oil, and sodium and Potassium alkylbenzenesulfonates, wherein the alkyl group contains from about 9 to about 15 carbon atoms in unbranched or branched chain configuration, e.g. that of the type described in U.S. Patent 2,220,099 and 2,477,383. Linear unbranched alkylbenzenesulfonates, in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as Cn, g LAS, are particularly valuable.

A preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, the mixture having an average (arithmetic mean) carbon chain length in the range of about 12 to 16 carbon atoms, preferably about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation about 1 to 4 moles of ethylene oxide.

Other anionic detergent compounds useful herein include sodium alkyl glyceryl ether sulfonates, particularly those higher alcohol ethers derived from tallow and coconut oil, sodium coconut oil fatty acid monoglyceride sulfonates and sulfates, and sodium or potassium salts of alkylphenol ethylene oxide ether bisphenate 10, which Contains ethylene oxide unit per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms.

Other anionic detergent compounds useful herein include the water-soluble salts of esters of a-sulfonated fatty acids containing about 6 to 20 carbon atoms in the fatty acid group and about 1 to 10 carbon atoms in the ester group, water-soluble salts of 2-acyloxyalkane-1-sulfonic acids, which contain about 2 to 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane radical, alkyl ether sulfates which contain about 10 to about 20 carbon atoms in the alkyl group and about 1 to 30 moles of ethylene oxide, water-soluble salts of olefin sulfonates which contain about 12 to Containing 24 carbon atoms, water-soluble salts of paraffin sulfonates which contain about 8 to 24, in particular 14 to 18, carbon atoms, and β-alkyloxyalkanesulfonates which contain about 1 to 3 carbon atoms in the alkyl group and about 8 to 20 carbon atoms in the alkane radical.

Mixtures of anionic surfactants

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can also be used e.g. 5: 1 to 1: 5 mixtures of an alkylbenzenesulfonate with 9 to 15 carbon atoms in the alkyl radical and mixtures thereof, the cation being an alkali metal, preferably sodium, and about 2% to about 15% by weight of an alkyl ethoxy sulfate with 10 to 20 carbon atoms in the alkyl radical and 1 to 30 ethoxy groups and mixtures thereof which have an alkali metal cation, preferably sodium. The nonionic detergent materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (of a hydrophilic nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group that is condensed with any particular hydrophobic group can be easily adjusted to give a water-soluble compound with the desired degree of balance between hydrophilic and hydrophobic elements.

Examples of suitable nonionic detergents include:

1. The polyethylene oxide condensates of alkylphenol, e.g. the condensation products of alkylphenols having an alkyl group containing 6 to 12 carbon atoms in either a straight or branched chain configuration with ethylene oxide, the ethylene oxide being present in amounts equal to 1 to 40 moles, preferably 2 to 9 moles, of ethylene oxide per mole of alkylphenol. The alkyl substituent in such compounds can e.g. be derived from polymerized propylene, diisobutylene, octene or nonene. Other examples include dodecylphenol fused with 12 moles of ethylene oxide per mole of phenol, dinonylphenol fused with 5 moles of ethylene oxide per mole of phenol, nonylphenol fused with 9 moles of ethylene oxide per mole of nonylphenol, and diisooctylphenol fused with 5 moles of ethylene oxide.

2. The condensation product of primary or secondary aliphatic alcohols having 8 to 24 carbon atoms in either unbranched or branched chain configuration with 1 to about 40 moles of alkylene oxide per mole of alcohol. The aliphatic alcohol preferably has between 9 and 15 carbon atoms and is ethoxylated with between 2 and 9, expediently between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol. Such nonionic surfactants are preferred from the standpoint of providing good to excellent detergency on greasy and greasy soils, as well as in the presence of hardness sensitive anionic surfactants such as alkylbenzenesulfonates. The preferred surfactants are made from primary alcohols that are either linear (like those that are derived) from natural fats from the Ziegler process of ethylene, e.g. Myri-styl, cetyl, stearyl alcohol) or partially branched, such as the dobanols and neodols, which have about 25% 2-methyl branching (Dobanol and Neodol are trade names of Shell) or Synperonics, which are believed to be about 50% 2-methyl branch (Synperionic is a trademark of ICI) or the primary alcohols with more than 50% branched chain structure sold by Liquichimica under the trade name Liai. Specific examples of nonionic surfactants that fall within the scope of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-11, Dobanol 91-3, Dobanol 91-6, Dobanol 91-8, Synperonic6, Synperonic 14 , the condensation products of coconut alcohols with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion has essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present compositions, in particular those tergitol series ethoxylates with about 9 to 16 carbon atoms in the alkyl group and up to about 11, in particular about 3 to 9, ethoxy radicals per molecule.

3. The compounds formed by the condensation of ethylene oxide with a hydrophobic base substance formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800. Such synthetic nonionic detergents are available on the market under the brand name "Pluronic" and are supplied by Wyandotte Chemicals Corporation.

An extremely preferred mixture of surface-active agents is a mixture of a Cs to C22 alkylbenzenesulfonate and a Cs to Ci5 alkanol, which is ethoxylated with 3 to 8 moles of ethylene oxide per mole of alkanol. Extremely preferred mixtures include Cn-alkylbenzenesulfonate and C14- to Ci5-alcohol- (7) -ethoxylate in ratios of 2: 1 to 1:10, preferably 1: 1 to 1: 8. In even more preferred compositions, Cs to C24 alkanoethoxylate with 10 to 40 moles of ethylene oxide per mole of alkanol is added to the mixture described above, preferably in an amount of 1% to 5%.

The builder

The detergent composition according to the invention also contains at least about 10% of a detergency builder, in particular a water-soluble inorganic or organic electrolyte. Suitable electrolytes have an equivalent weight of less than 210, especially less than 100, and include the usual alkaline polyvalent calcium ion sequestering agents. However, the builder can also contain water-insoluble calcium ion exchange materials. Nonlimiting examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates, sulfates and chlorides. Specific examples of such salts include sodium and potassium tetra borates, perborates, bicarbonates, carbonates, tripoly phosphates, orthophosphates, pyrophosphates, hexameta phosphates and sulfates.

Examples of suitable organic alkaline detergency builders include: (1) water soluble aminocarboxylates and aminopolyacetates, e.g. Sodium and potassium glycinates, ethylenediaminetetraacetates, nitrilotriacetates and N- (2-hydroxyethyl) nitrilodiacetates and diethylenetriamine pentaacetates; (2) water soluble salts of phytic acid, e.g. Sodium and potassium phytates; (3) water-soluble poly-phosphonates, including sodium, potassium and lithium salts of l-hydroxyethane-l, l-diphosphonic acid; the sodium, potassium and lithium salts of ethylenedi-phosphonic acid; and the like, (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid,

or carboxymethyloxy succinic acid, 2-oxa-l, 1,3-pro-pantricarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, cyclopentane-cis, ice, cis-tetracarboxylic acid, mellitic acid and pyromellitic acid; (5) water-soluble organic amines and amine salts such as monoethanolamine, diethanolamine and triethanolamine and the salts thereof.

Mixtures of organic and / or inorganic builders can be used herein. Such a builder mixture is disclosed in Canadian Patent No. 755 038

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e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium 1-hydroxyethane-1,1-diphosphonate.

Another type of detergency builder material useful in the present compositions and methods comprises a water-soluble material that is capable of forming a water-insoluble reaction product with water hardness cations, preferably in combination with a seed that can provide growth sites for the reaction product . Such "vaccinated builder" compositions are fully disclosed in British Patent No. 1,424,406.

Another class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent No. 814,874, issued November 12, 1974, which is incorporated herein by reference. This patent discloses and claims detergent compositions containing sodium aluminosilicates of the formula:

Naz (A102) z (Si02) yXH20

where z and y are integers equal to at least 6, the molar ratio of z to y is in the range of 1.0: 1 to about 0.5: 1 and X is an integer from about 15 to about 264, the Alumosilicates have a calcium ion exchange capacity of at least 200 milligram equivalent / gram and a calcium ion exchange rate of at least 130 mg calcium carbonate per minute and gram. A preferred material is

Nai2 (Si02A102) i227H20

Additional ingredients

The compositions according to the invention can be supplemented by all types of detergent components, either by including such components in the aqueous slurry that is to be dried or by mixing such components with the compositions according to the invention after the drying step. Soil suspending agents at about 0.1% to 10% by weight, such as water-soluble salts or carboxymethyl cellulose, carboxyhydroxymethyl cellulose and polyethylene glycols with a molecular weight of about 400 to 10,000, are common components of the present invention. Dyes, pigment optical brighteners and perfumes can be added in varying amounts as desired.

Other materials such as fluorescent compounds, minor amounts of enzymes, anti-caking agents such as sodium sulfosuccinate, and sodium benzoate can also be added. Enzymes suitable for use herein include those discussed in U.S. Patents 3,519,570 and 3,533,139, which issued on July 7,

July 1979 and January 5, 1971 to McCarty and McCarty et al. were granted.

Anionic fluorescent whitening agents are well known materials, examples of which are dinitrium-4,4'-bis (2-diethanolamino-4-anilino-s-triazin-6-yl-amino) -stilbene-2,2'-disulfonate , Disodium 4,4'-bis- (2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2,2'-disulfonate, disodium 4,4'-bis- (2, 4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate, disodium 4,4'-bis (2-anilino-4- (N-methyl-N-2-hydroxyethylamino)) s-triazin-6-ylamino) -stilbene-2,2'-disulfonate, disodium-4,4'-bis- (4-phenyl-2, l, 3-triazol-2-yl) -stilbene-2 , 2'-disulfonate, disodium 4,4'-bis- (2-anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazin-6-ylamino) -stil-ben-2,2'- disulfonate and sodium 2- (stilbyl-4 "- (naphtho-1 ', 2': 4.5) -1,2,3-triazole-2" sulfonate.

An alkali metal or alkaline earth metal silicate can also be present. The alkali metal silicate is preferably used in an amount of 0.5% to 10%, preferably 3% to 8%. Suitable silicate solids have a SiCh / alkali metal HO molar ratio in the range from about 0.5 to about 4.0, but more preferably from 1.0 to 1.8, especially about 1.6. The alkali metal silicates suitable herein can be commercially available preparations of the combination of silicon dioxide and alkali metal oxide, melted together in various ratios.

The compositions according to the invention may require the presence of a foam control or braking agent.

Foam control components are normally used in an amount from about 0.001% to about 5%, preferably from about 0.05% to about 3%, and especially from about 0.10% to about 1%. The anti-foam (regulating) agents, which are known to be useful as detergent foam inhibitors, can be used in the present compositions. These include the silicone foam retardants, particularly the mixtures of silicones and silica, described in U.S. Patent No. 3,933,672, the disclosure of which is incorporated herein by reference. A particularly preferred anti-foaming agent is the material known as "HYFAC", the sodium salt of a long-chain (Cao-C24) fatty acid.

Microcrystalline waxes with a melting point in the range from 35 to 115 ° C. and a saponification number of less than 100 represent an additional example of a preferred foam-regulating component for use in the present compositions. The microcrystalline waxes are essentially water-insoluble, but in the presence of organic ones surfactants dispersible in water. Preferred microcrystalline waxes have a melting point of about 65 to 100 ° C, a molecular weight in the range of 400 to 1000 and a penetration value of at least 6, determined at 77 ° C according to ASTM-D1321. Suitable examples of the above waxes include microcrystalline and oxidized microcrystalline petroleum waxes, Fischer-Tropsch and oxidized Fischer-Tropsch waxes, ozokerite, ceresin, montan wax, beeswax, candelilla wax and carnauba wax.

The present granular detergent compositions can advantageously also contain a peroxygen bleaching component in an amount of about 3% to about 40% by weight, preferably about 8% to about 33% by weight. Examples of suitable peroxygen bleaching components for the present use include perborates, persulfates, persilicates, perphosphates, phercarbonates, and more generally all inorganic and organic peroxygen bleaches known to be suitable for use in the present compositions. The composition may also advantageously contain a bleach activator, which is normally an organic compound containing an N-acyl or a 0-acyl (preferably acetyl) group. Preferred materials are N, N, N ', N' -Tetraacetyläthy-lendiamin and N, N, N'N'-tetraacetylglycouril.

Another preferred ingredient of the present compositions is from about 0.01 to about 4%, especially from about 0.5 to about 2.2% by weight, of a polyphosphonic acid or salt thereof, which has been found to have washing power benefits provides bleachable stains.

Particularly preferred polyphosphates have the formula:

\

n- (ch -ch -n) -r y 2 d j n

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

643 881

10th

wherein each R is CH2PO3H2 or a water-soluble salt thereof and n is 0 to 2. Examples of compounds within this class are aminotri- (methylenephosphonic acid), aminotri- (ethylidenephosphonic acid), ethylenediaminetetra- (methylenephosphonic acid) and diethylenediamine-penta- (methylenephosphonic acid). Of these, ethylenediaminetetra (methylenephosphonic acid) is particularly preferred.

Another optional, although preferred, component is about 0.1% to about 3%, especially about 0.25% to about 1.5%, of a polymeric material that has a molecular weight of 2,000 to 2,000,000 and that is a copolymer of Maleic acid or anhydride and a polymerizable monomer which is composed of compounds of the formula:

(i) 0R1

I 1

hc = ch2

wherein Ri is CHj or a C2 to Ci2 alkyl group,

h2c = c

COOR,

D

where R2 is H or CH3 and R3 is H or a Ci to C10 alkyl group,

(Üi) Rn Rq

| 4 | 5

hc = ch in which R4 and Rs each represent H or an alkyl group, so that R4 and Rs together have 0 to 10 carbon atoms,

(iv) .co; ch2

n

^ ch2 — ch2 hc = ch2

hc = ch and (vi) mixtures of any two or more of them is chosen, copolymers optionally being completely or partially neutralized on the carboxyl groups by sodium or potassium.

Extremely preferred examples of such carboxylates are 1: 1-styrene / maleic acid copolymers, diisobutylene / maleic acid copolymers and methyl vinyl ether / maleic acid copolymers.

Other suitable polycarboxylates are poly-a-hydroxy-acrylic acids of the general formula:

- [- CRiR2-C (OH) - (COOH) -] "-

wherein Ri and Ri each represent a hydrogen atom or an alkyl group containing 1, 2 or 3 carbon atoms, and wherein n represents an integer greater than 3. Such materials can be made as described in Belgian Patent 817,678. Also suitable are poly-lactones which are produced from the hydroxy acids as described in British Patent 1,425,307.

A method is suitable for producing the detergent composition according to the invention which comprises the steps of spray-drying a soap mixture which contains the anionic, cationic and builder components and then absorbing the nonionic surface-active agent in liquid or molten form into the spray-dried granules. This method is particularly valuable if the builder has an aluminosilicate exchange material.

In another process aspect that is particularly applicable to compositions containing aluminosilicate builders, the nonionic material is incorporated into the soap mixture for spray drying, but the components of the surfactants are premixed prior to the addition of the aluminosilicate.

Of course, other methods for producing the compositions according to the invention can be used. Thus, the anionic and nonionic surfactants and the builder and filler components can be spray dried in a conventional manner to form a base powder composition, and the cationic component can then be added to the base powder either as an approximately 1: 1 mixture with a portion of those retained for that purpose Builder or filler components or as an inclusion complex of, for example Urea can be added. Alternatively, the cationic surface-active agent can be sprayed onto the base powder or added as dry-mixed granules produced by spray drying, agglomerated with an inorganic or organic agglomeration aid, or spray-dried separately and added to the base powder as dry-mixed granules. Alternatively, the cationic surfactant and the base powder compositions can be individually spray dried in separate stages of a multi-stage spray drying tower.

The compositions according to the invention can also be provided in the form of two- or multi-component products, which are either mixed before use or added separately to a washing solution in order to achieve a concentration of the ternary surface-active system of from about 100 to about 3000 ppm, in particular about 500 to about 1500 ppm. Each product component contains one or more of the active ingredients of the ternary surfactant system, and a mixture of the products in prescribed amounts should have the required granular form. In a preferred embodiment, one product is formulated as a conventional anionic or nonionic detergent composition suitable for use in the main wash of an automatic washing machine, and the other is formulated as an additive or activator product containing a cationic substance for simultaneous use with the conventional detergent during the Formulated main wash. In addition to the cationic material, the additive product contains nonionic and / or anionic surfactant, so that the overall composition formed by mixing the product components in certain amounts has the required ternary active system.

The compositions according to the invention can also be used as

5

io

15

20th

25th

30th

35

40

45

50

55

60

65

11

643 881

special pre-wash composition can be formulated, which are intended to be used before the main wash of the conventional washing cycle. Such prewashing compositions normally consist of a single product component which contains the differentiated ternary active system.

In the following examples, the abbreviations used have the following meanings:

LAS: Linear Ci2-alkylbenzenesulfonate

TAS: tallow alkyl sulfate io

TAEn: tallow alcohol, ethoxylated with n moles of ethylene oxide per mole of alcohol

MTMAC: myristyltrimethylammonium chloride

LTM AC: lauryltrimethylammonium chloride

Dobanol 45-E-7: A Cm to Ci5 oxo alcohol with 7 mol 15

Ethylene oxide, marketed by Shell

Dobanol 45-E-3: A Ci4 to Cis oxo alcohol with 3 moles

Ethylene oxide, marketed by Shell

Silicate: sodium silicate with an SÌO2: Na2Û ratio of 1.6

Wax: microcrystalline wax - Witcodur 272 enamel - 20

point 87 ° C

Silicon: Comprises 0.14 parts by weight of a mixture of signed silicon dioxide and silicone in a weight ratio of 85:15, granulated with 1.3 parts of sodium tripolyphosphate and 0.56 parts of tallow alcohol, condensed with 25 molar equivalents of 25% ethylene oxide

Gantrez ANI 19: trade name for maleic anhydride /

Vinyl methyl ether copolymer, which is believed to have an average molecular weight of

240,000 has been marketed by GAF. This turned 30

pre-hydrolyzed with NaOH before addition.

Brightener: disodium-4,4'-bis- (2-morpholino-4-anilino-s-tria-

zin-6-ylamino) stilbene-2,2'-disulfonate

TAED: tetraacetylethylenediamine

Dequest 2060: trade name for diethylenetriaminepenta- 35 (methylenephosphonic acid), marketed by Monsanto

Dequest 2040: trade name for ethylenediaminetetra- (methylene-phosphonic acid), marketed by Monsanto.

The amount of zeolite A is given on an anhydrous basis; the material contains 21% crystal water.

The present invention is illustrated by the following non-limiting examples.

Examples 1 to 5 45

The following compositions were prepared by spray drying an aqueous slurry of the ingredients except for the Dobanol-derived nonionic surfactants sprayed on the spray dried granules and the sodium perborate and 50th

Enzyme that was dry mixed into the composition.

Examples

1

2nd

3rd

4th

5

%

° 'o

%

%

° / o

READ

7

8th

13

3rd

4th

MTMAC

2.25

5

4th

_

_

LTMAC

-

_

-

2nd

1.5

Dobanol 45-E-7

2.25

4th

3rd

_

2nd

Dobanol 45-E-4

-

-

-

_

2nd

TAEn

-

1

3.5

-

_

TAE25

-

_

-

3rd

-

Cj2 soap

-

4th

2nd

_

_

Pentasodium tripolyphosphate

4th

20th

0.5

18th

-

Disodium pyrophosphate

-

-

-

-

18th

Zeolite A

(Particle size 5 µm)

40

26

45

-

-

Gantrez ANI 19th

1.5

1

1.5

1.5

1

Dequest 2060

-

-

-

1

1

silicate

-

5

-

5

6

Protease enzyme

0.8

0.5

0.8

-

-

Sodium perborate

-

32

-

25th

20th

Silicone

-

-

-

2nd

2nd

wax

2.0

-

-

0.3

0.3

Brightener

0.15

0.15

0.15

0.15

0.15

Sodium sulfate, moisture up

and miscellaneous

100

These products provide an improved oil and grease stain removal effect with damage to the particulate clay soiling detergency, maintenance of the whiteness and fluorescent brightening properties on both natural and synthetic textiles both at high and at low washing temperatures.

Products with improved activity are also obtained if the sodium alkylbenzenesulfonate is replaced by molar equivalents of C10 to C22-01efinsulfonate, C10 to C2o paraffin sulfonates and C10 to C: o-alkyl ether sulfates.

The lauryl or myristyl trimethyl ammonium chloride in the above examples can be obtained by molar equivalents of lauryl or myristyl trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, coconut alkyl benzyl dimethyl ammonium chloride, Cu alkyl benzyl dimethyl ammonium chloride, or alkyl benzyl dimethyl ammonium chloride,

ch,

C12H25 ~ ° "(CH2) 3 ~ C00CH ^ CH ^ ~ ^ (+) ~ CH * s Cl (")

2 2

I.

ch.

CH,

i 3

C14H29 "0" CH2CH2OCOCH2-N (+) - CH3J Cl (-)

ch3

CH,

C. ,, - OCH ^ CH O-CO (CH0) COOCH ^ CH -N ^ + ^ - CH-, Br (_) 0.4 22 23 22 | 3rd

CH.

643 881

be replaced.

Examples 6 to 11

The following compositions were prepared similarly to Examples 1-5.

6

7

8th

9

10th

11

READ

1.2

2.2

5.0

2.2

2.0

MTMAC

1.0

1.8

2.8

2.0

1.8

1.6

TAS

-

-

3.0

-

-

-

Dobanol 45-E-7

8.0

6.6

-

1.5

6.6

3.0

TAEn

-

-

6.0

-

-

1.0

Dobanol 45-E-4

-

-

3.0

2.0

-

-

Ci2 soap

-

2.0

-

-

-

-

Cis soap

-

-.

0.75

-

-

-

Sodium tripolyphosphate 33.0

2.5

4.0

20.0

4.0

33.0

Zeolite A

-

-

20.0

-

-

-

Zeolite X

-

30.0

-

-

-

-

Gantrez ANI 19th

-

0.8

l ', 5

-

1.5

0.5

Dequest 2040

-

-

-

-

1.0

0.5

Dequest 2060

2.0

-

-

1.0

-

-

Protease enzyme

1.2

0.5

1.2

0.5

1.2

0.5

Sodium perborate

12.0

10.0

12.0

5.0

-

10.0

Sodium bicarbonate

-

-

-

-

10.0

-

Polyethylene eng. Col

(MG 6000)

-

1.0

1.5

-

1.0

-

Silicone

-

-

-

2.0

-

-

TAED

2.0

-

1.0

-

-

-

Brightener

0.15

0.15

0.15

0.15

0.15

Sodium silicate

(SiCh: Na2 = 2: l)

5.0

1

2.5

6.0

-

-

wax

0.3

-

-

0.3

-

0.3

Sodium silicate,

to

Moisture, miscellaneous

100

These products provide improved oil and grease stain removal effects without damaging the particulate clay stain detergency, maintaining whiteness and fluorescent whitening properties on both natural and synthetic textiles at both high and low wash temperatures.

12

Products with improved activity are also obtained if the Dobanol 45-E-7 is replaced by a C4-15 alcohol polyethoxylate, which contains an average of 6 mol of ethylene oxide, and a C | 2-15 alcohol polyethoxylate, which contains an average of 6.5 mol of 5 ethylene oxide, a C9_ir alcohol alcohol ethoxylate containing an average of 6 moles of ethylene oxide, a C! 2_i3 alcohol polyether ethoxylate containing an average of 5 moles of ethylene oxide and has been distilled to remove lower ethoxylate and non-ethoxylated fractions, a secondary 10 cis alcohol average 9 mole ethoxylate Ethylene oxide contains a Ci2 alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide, a Cio alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide, a Cio alcohol polyethoxylate, which contains an average of 6 moles of ethylene oxide, a Ci2 alcohol polyethoxylate, the average Contains 7 moles of ethylene oxide, and mixtures of these surfactants is replaced.

An improved effect is also obtained when the Gantrez ANI 19 is a copolymer of methyl meth-20 acrylate and maleic acid, the molar ratio of the monomers being about 1: 1, having a molecular weight of about 10,000, an ethylene-maleic acid copolymer with a Molecular weight of about 4000, a propylene-maleic acid copolymer with a molecular weight of about 30,000, 25 a 1-hexene-maleic acid copolymer with a molecular weight of about 30,000, a 1-hexene-maleic acid copolymer with a molecular weight of about 25,000, a vinylpyrrolidone-maleic acid copolymer having a molecular weight of about 26,000, a styrene-maleic acid 30 copolymer of acrylic acid and itaconic acid

1: 4 copolymer of 3-butenoic acid and methylene malonic acid, a 1: 1.9 copolymer of methacrylic acid and aconitic acid and a 1.2: 1 copolymer of 4-pentenoic acid and itaconic acid in the form of their sodium salts. 35 Products with an improved effect are also obtained if the sodium alkylbenzenesulfonate is replaced by molar equivalents of Ciò to C22-01efinsulfonaten, Cio to C2o paraffin sulfonates and Cio to C2o alkyl ether sulfates.

The myristyltrimethylammonium chloride in the above 40 examples can be obtained by molar equivalents of lauryl or myristyltrimethylammonium bromide, decyltrimethylammonium chloride, dioctyldimethylammonium bromide, coconut alkylbenzyldimethylammonium chloride, Ci2-alkylbenzyl-dimethylzyl-methylethylammonium-methylethylammonium-ammonium-methylethyl-ammonium-chloride-a-45-methylethyl-ammonium-tri-methyl-ammonium-chloride-45

fi

° 12h25 "°" (ch2) 3 "cooch2oh2" i <+> "ch3 'c1l_)

CH,

CH,

| 5

Cl4H29 ~ ° ~ CH2CH2OCOCH2 ~ | l (+) ~ ÓV Cl ("}

ch3

CH3 •

I (+ \ (-)

C 4-0CH2CH20-C0 (CH2) 3C00CH2CH2- ^; -CH3, Br ch3

be replaced.

G

Claims (12)

643 881 1. A solid particulate detergent composition which comprises a) 2 to 60% by weight of a surface-active system which has a water-soluble or water-dispersible combination of anionic, alkoxylated nonionic and water-soluble quaternary ammonium-cationic surface-active agents, in which the weight ratio anionic: cationic surfactant is not greater than 5: 1 and the weight ratio nonionic: cationic surfactant is at least 2: 3 and wherein the surfactant system contains anionic and cationic surfactants in an equivalent ratio of at least 1: 1, and b) at least 10 wt .-% has a detergency builder. 2. The composition of claim 1, wherein the cationic surfactant has 1 to 4 quaternary ammonium groups, only one of which has the general formula: R'mR2xN + where each R1 is a hydrophobic alkyl or alkenyl group which is optionally substituted or interrupted by phenyl, ether, ester or amide groups, has a total of 8 to 20 carbon atoms and which can additionally contain up to 20 ethoxy groups, m is a number is from 1 to 4 and cannot have more than one R1 more than 16 carbon atoms if m is 2 and not more than one R1 can have more than 12 carbon atoms if m is 3, each R2 is an alkyl group which is 1 contains up to 4 carbon atoms, or is a benzyl group, where no more than one R2 in one molecule is benzyl, and x is 0 to 3. 2nd PATENT CLAIMS 3. The composition of claim 2, wherein the cationic surfactant has the general formula: R'mRVmN + Z where R1 is selected from Ca to C2o alkyl, alkenyl and alkaryl groups, R2 is selected from CU4 alkyl and benzyl groups, Z is an anion in a number that gives electrical neutrality and m is the same 1, 2 or 3 is provided that when m is 2, R1 has less than 12 carbon atoms and when m is 3, R1 has less than 9 carbon atoms. 4. A composition according to any one of the preceding claims, wherein the cationic and anionic surfactant have a combined total of no more than 34 carbon atoms, only hydrophobic groups having at least 4 consecutive carbon atoms being counted. 5. A composition according to any one of the preceding claims, wherein the nonionic surfactant has the general formula R0 (CH2CH20) nH where R is branched or unbranched C9 to C15 alkyl or alkenyl and n is 2 to 9. 6. A composition according to any one of the preceding claims, wherein the weight ratio of nonionic: cationic surfactant is 20: 1 to 1: 1. 7. A composition according to any one of the preceding claims, wherein the weight ratio of anionic: cationic surfactant is 2: 1 to 1: 2. 8. A composition according to any one of the preceding claims, wherein the surfactant system comprises at least 5% by weight of the cationic surfactant and a total of at least 60% by weight of the anionic and nonionic surfactants. 9. A composition according to any one of the preceding claims, wherein the detergency builder comprises a water-soluble inorganic or organic electrolyte with an equivalent weight of not more than 210. 10. Composition according to one of the preceding claims, wherein the detergency builder comprises a water-soluble alkaline polyvalent inorganic 'or organic potassium ion sequestering agent. 11. A composition according to any one of the preceding claims, wherein the detergency builder is a water-insoluble alu-mosilicate ion exchange material of the general formula: Mz [(A1C> 2) z • (SÌO2X] x H2O where M is a calcium exchange cation, z and y are integers of at least 6, the molar ratio of AIO2 to SÌO2 is in the range of 1.05 to 0.5 and x is an integer of 15 to 264, the aluminosilicate Ion exchange material has a particle size diameter of 0.1 to 100 .mu.m, a calcium ion exchange capacity of at least 200 mg equivalent CaCCb / g and a calcium ion exchange rate of at least 130 mg calcium carbonate per minute and gram. 12. Composition according to one of the preceding claims, which additionally has 0.01 to 2% by weight of an anionic fluorescent substance.