DE2355983A1 - GRANULATED SPRAY-DRIED DETERGENTS AND DETERGENTS - Google Patents

Description

F8 Ai-J X FU KT AM MAi H - HÖCHST. 8 NOV. 1973

Our number "18 981 Ka / tk

The Procter & Gamble Company Cincinnati, Ohio, V.St.A.

Granulated spray-dried detergents and cleaning agents

The invention relates to granulated detergents and cleaning agents that contain a certain mixture of anionic surface-active substances, certain amounts of certain organic and / or inorganic salts and moisture contain. Such agents are formulated to be both low foaming and effective Have detergency as well as product stability. she can be made using conventional detergents Spray drying devices.

For years, commercial, synthetic detergents and cleaning agents contained substantial amounts of inorganic Phosphate salts used as builders. Such phosphate builders are used to build mineral ions that normally contained in household tap water, complex to bind to prevent such ions the behavior of synthetic surface-active substances Interfere with substances in such agents. Phosphate builders are also responsible for the physical stability of

409821/1046

granulated detergent products.

However, recent studies have shown that the phosphate "builders" can pose environmental problems because they serve as nutrients that promote algae growth and thereby biological aging (eutrophication) accelerate from natural waters. As a result of these possible harmful effects in constant use the phosphate framework in essentials struggled one is looking to find ways of reducing the need for phosphate salts in commercial detergents and cleaning agents can be reduced or eliminated.

A method, the absence of mineral complexing agents Phosphate builder salts in detergent and cleaning agent formulations To compensate, consisted in synthesizing agents that made the systems more surface-active Contained substances that were particularly insensitive to the mineral hardness of washing solutions. Such systems Surface-active substances, for example, contained surface-active substances that were relatively insensitive to minerals or mixtures of anionic surface-active substances (see US-PSs 2,086,215, 2,09 ** 451, 3,223,645, 3,322,876, 3 332 880, 3 513 099 and 3 658 727, BE-PS 65O 323 and

German patent application P ..... (our no. 18 98O)).

A mineral insensitive anionic surfactant Mixture, which is highly preferred due to the commercial availability of its components, contains one Combination of conventional, relatively mineral-sensitive alkylbenzenesulfonates with a relatively high foaming power and usual, relatively mineral-insensitive fatty alcohol ether sulfates with a relatively medium foaming power, which is usually known as alkyl ether sulfates.

409821/1046

Attempts to produce low-phosphate or phosphate-free granulated, Alkyl benzene sulfonate-alkyl ether sulfate detergents and cleaning agents with low foaming power (and the resulting economic advantages of granulated Products) by conventional spray-drying processes, however, were not entirely successful. The addition of an alkyl ether sulfate as a surfactant to spray-dried or puffed alkylbenzenesulfonate., as a surfactant, containing granules Problems with regard to foam behavior, processability and granulate stability.

While the addition of alkyl ether sulfate as a surface-active substance to such granules makes the system of surface-active substances less sensitive to dissolved water hardness (i.e. Ca and Mg ions) and thus more suitable for detergent and cleaning agent formulations that have no or only a few builders , this addition leads from Alkyläthersulfat generally to surfactant systems which provide the average foam performance that is higher than the _s that is acceptable for conventional cooking with little detergent S.chaumvermögen. In addition, the incorporation of alkyl ether sulfates into spray-dried detergent granules causes difficulties in processing such granules. Finally, the incorporation makes use of alkyl ether sulfates in blown detergent granules (connected to the .Weglassung or reduction of hygroscopic phosphate salts) .in general, the granulated final products more susceptible to caking and throws Riesel · - Aptitude and Lagerfähigkeitsproblerne.

409821/10 * 6

It was therefore the object of the invention to provide low-phosphate or phosphate-free mixed alkylbenzenesulfonate / alkylether sulfate Spray-dried detergents and cleaning agents containing (as a surface-active substance) are available which are effective for washing in mineral-containing water, which have a foaming effect, which with those of conventional low-foaming detergents and Comparable to cleaning agents, in granulated form acceptable cake-forming properties for commercial products, Have flowability and storage stability and that with conventional spray drying devices and -Apparatus can be processed.

It has surprisingly been found that by combining alkylbenzenesulfonate with a certain mixture a surface-active system formulated from alkyl ether sulfates can be that when it is in combination with certain organic and / or inorganic salts and Moisture is combined in certain essential concentrations, detergents and cleaning agents are available, who fulfill the above-mentioned tasks and which similar, currently known agents in their performance, their physical properties and in their machinability are superior.

The low-phosphate of the invention and phosphate-free granular spray-dried detergent and cleaning agent consisting essentially of about 10 to about 30 wt -.% Of a Alkylbensolsulfonat / Alkyläthersulfat mixture as a system of surface-active agents, from about 10 to about 90 wt -.% Of certain organic and / or inorganic salts and about 1 to 8 wt. Water. The surfactant system contains an alkyl benzene sulfonate

409021/1046

and an alkyl ether sulfate mixture in a weight ratio of alkyl berizole sulfonate to alkyl ether sulfate of about 0.1: 1 to 6: 1. The alkylbenzenesulfonate used as the surfactant is either a sodium or potassium salt of an alkylbenzenesulfonic acid in which the alkyl group contains from about 9 to 16 carbon atoms, or a mixture of such surfactants. The combination of the surfactant alkyl ether sulfate in the mixed surfactant system is a mixture of alkyl ether sulfates, the mixture having an average alkyl chain length of about 16.01 to 19 carbon atoms and an average degree of ethoxylation of about 1 to 5 moles of ethylene oxide. Such a mixture should also from about 0.1 to 2 wt .-% (^, - compounds of 0.1 to 33 wt -% ^c ^ u ^ _i t.:. ~ ^ ~ ^He compounds, from about 25 to 55 wt -.% Cg ^^ - compounds, from about 30 to '70 wt .- # C ₁ O,' -. compounds of about 1 to 30 wt .->% of compounds having a degree of Äthoxylierungs · ^ 0 , from about 50 to 80% by weight of compounds having a Athoxylierungsgrad ^1-1 J, of about 3 to 30 wt -..% of compounds with a Athoxylierungsgrad of 4 to 8 and from about 0.1 to 10 wt .-% of compounds with a degree of ethoxylation of greater than 8. The organic and / or inorganic salt component can be an alkali metal carbonate, an alkali metal silicate, an electrolyte salt, such as, for example, water-soluble alkali metal or alkaline earth metal carboxylates, sulfates or chlorides, or a mixture of such organic and / or inorganic Be salts.

As already stated above, the washing and detergents consisting essentially of three essential components, i.e. a particular surfactant

409821/1046

System of alkyl benzene sulfonates and alkyl ether sulfates, certain organic and / or inorganic salts and moisture. Each of these components are discussed below explained in more detail:

Surfactant system

About 10 to about 30% by weight, preferably about 17 to 25% by weight, of the detergents and cleaning agents according to the invention comprise a specific system of surface-active substances which contains a combination of alkylbenzenesulfonates and a specific mixture of alkyl ether sulfate as surface-active substances. If the total content of surface-active substances in the agents according to the invention is more than about 30% , processing problems occur when these agents are spray-dried. With a total content of surface-active substances * below about 10 % in the agents according to the invention, agents with poorer performance are obtained.

Surprisingly, only certain surface-active Alkyl benzene sulphonates and alkyl ether sulphates are combined in certain amounts to form a system of surface-active substances Means to realize the required mineral insensitivity when used in the present means of surfactants, low foaming power and processability of the agent.

Alkyl benzene sulfonate

The alkylbenzenesulfonate component of the surfactant system Substances of the present compositions can be any of the various specific relatively mineral-sensitive, alkylbenzenesulfonates used as surfactants be with a relatively high foaming power. to

409821/1046

such surfactants include the sodium and potassium salts of alkylbenzenesulfonic acids, in which the alkyl group contains from about 9 to 20 carbon atoms, holds.

Such sodium and potassium salts of alkylbenzenesulfonic acids, multiply the alkyl group containing from about 9 to 20 carbon atoms, can be straight or branched chain and are described in U.S. Patents 2,220,099 and 2,477,383. Examples of suitable compounds of this type are Natriumdecylbenzolsulfonat, Natriumundecylbenzolsulfonat, sodium dodecylbenzenesulfonate, Natriumtridecylbenzolsulfonat, Natriumtetradecylbenzolsulfonat, Natriumtetrapropylenbenzolsulfonät, "Kaliumdecylbenzolsulfonat, Kaliumundecylbenzolsulfonat, Kaliumtridecylbenzolsulfonat, Kaliumtetradecylbenzolsulfonat.-Kaliumtetrapropylenbenzolsulfonät and mixtures thereof. Particularly preferred for use in the inventive compositions are the sodium and potassium salts of straight chain alkyl benzene sulphonic acids in which the alkyl group has about 11 to about I ¹ J C-atoms. A particularly preferred surfactant of this strain is sodium linear alkyl benzene sulfonate, wherein the alky! chain averaging about 12 carbon atoms.

Alkyl ether sulfate mixture

The second component of the system of surface-active substances of the inventive compositions is a particular mixture of Alkalimetallsälzen of sulfated Fettalkoholäthoxylaten ", commonly referred to as alkyl ether sulfates ,, Any surfactant in'einem such sulfated Alkoholäthöxylat mixture has the general '' ■ - common formula

RO (C ₀ H ₁₁ O) S0, M

c η η j

4QS821 / 104S

where R is an alkyl chain: ^ that of a higher fatty alcohol is derived, η is the number of moles of ethylene oxide within the compound, i.e. the degree of ethoxylation, -and M mean an alkali metal, surprisingly only a very specific mixture of such compounds provides acceptable mineral insensitivity, • Washing performance, low foaming power and processability of the surface-active system when it is in the surface-active system System of means according to the invention incorporated will.

Alkyl ether sulfate mixtures according to the invention have an average carbon chain length (arithmetic mean) in the range from about 16.01 to 19 carbon atoms, preferably from about 16.5 to 18 carbon atoms and an average degree of ethoxylation (arithmetic mean) of about 1 to 5 mol of ethylene oxide , preferably from about 2 to ¹ J moles of ethylene oxide.

Furthermore, the alkyl ether sulfate mixtures, which have the above-mentioned average carbon chain length and the average degree of ethoxylation, essentially have a certain distribution of the carbon chain lengths and the degrees of ethoxylation. Such mixtures comprise from about 0.1 to 2 wt -..% Of the mixture of C ₁₂ _, - compounds of about 0.1 to 33 wt .- # of the mixture of C. ^ _lt - ~ i- ^{verb ndun} g i ^s from about 25 to 55 wt .-% of the mixture of (^ - ^ - compounds, and from about 30 to 70 wt -.% of the mixture of _o C., "- connects

lö-iy

fertilize. In addition, such Alkyläthersulfat mixtures contain from about 1 -to 30 weight ■ -.% Of the mixture of compounds having a Athoxylierungsgrad of 0, from about 50 to 80 wt -.% Of the mixture of compounds having a

409821 / $ 104

Degree of ethoxylation of 0, from about 50 to 80% by weight? of the mixture of compounds with a degree of ethoxylation of 1 to 4, from about 3 to 30 .Gew.-? of the mixture of compounds with a degree of atoxylation of 5 to 8 and from about 0.1 to 10 wt. of the mixture of compounds with a degree of atoxylation greater than 8.

Such mixtures preferably contain from about 0.1 to 1.75 wt. of the mixture of C ^ p. ., - connections, from about 1 to 20 wt. of the mixture of C j,, .- compounds, from about 28 to 40 wt. of the mixture of ^c -i6_-t7 compounds and from about 40 to 60 wt. of the mixture of C ₁ o_ _iq compounds. In addition, such preferred alkyl ether sulfate mixtures contain from about 10 to 25% by weight? of the mixture of compounds with a degree of ethoxylation of 0, from about 51 to 70 wt. of the mixture of compounds with a degree of ethoxylation of 1 to M _t of about 10 to 28 wt. of the mixture of compounds with a degree of ethoxylation of 5 to 8 and of about 1 to 8 wt. of the mixture of compounds with a degree of ethoxylation greater than 8.

Particularly preferred alkyl ether sulfate mixtures contain from about 0.1 to 1.5 wt. of the mixture of ^c ip_i3 "compounds, from about 10 to 15% by weight of the mixture of C ₁ I, ..j- ¹ compounds, from about 30 to 33% by weight of the mixture of Cg" compounds and in addition, contain 50 to 55 wt? of the mixture of C. '. _q compounds. such a particularly preferred Alkyläthersulfat mixtures of about 15 to 20 weight? of the mixture of compounds having a Athoxylierungsgrad of 0, from about 52 to 57% by weight of the mixture of compounds with a degree of atoxylation of 1 to 4, from about 20 to 25% by weight

409821/1046

Mixture of compounds with a degree of ethoxylation of 5 to 8 and from about 3 to 7 wt .- /? of the mixture of compounds with a degree of ethoxylation greater than 8.

Alkyl ether sulfate mixtures according to the invention can be a wide variety of alkyl ether sulfates with shorter or longer chain length than that specified above ' and degrees of ethoxylation higher than those specified above, provided the mixture contains the required concentrations of the essential alkyl ether sulfates described above.

Examples of alkyl ether sulfate mixtures falling within this range are shown in Table I.

409821/1046

Table I.

Mixture characteristic ' Alkyl ether sulfate mixture no. 2.. . . 3 16, l ' 5 Average
Carbon chain length
(Number of carbon atoms). . , ' 1 17.3 . 16.9 1 % 17.1 12-13 carbon atoms (weight-50 16.6 1 % . 0.1 % 29 % 0.1% 14-15 carbon atoms (wt %) 1 % 3 % 1.9 % 36 Si A Of
J. / J 16-17 carbon atoms (wt 13 % 28 % 49 Si. 34 % 44% 18-19 carbon atoms (wt .-? 0 31 % 67 % 49 % 2.25 54 Si ' Average
Degree of ethoxylation
(Number of moles ÄO) · ■. . . 54 % 3.0 2.0 19% 2.75 O moles of ethylene oxide (wt. %) ■ 3.0 18 % 22 55 70 % • 4 si 1-4 moles of ethylene oxide (wt 18 % 55 % .71 % 9 # 76 % ' 5-8 moles of ethylene oxide (weight SO 5.5 % 22 % 6% 2% 18 si 9 ⁺ moles of ethylene oxide (wt ^ - / 0 22 % 5 *. 1 / a K salt 5% N / A N / A .' K Well. ■.

ro co cn

Alkyl ether sulfate mixtures, such as those described above, can by conventional oil or fat reduction, ethoxylation, sulfation and neutralization processes (see, e.g., U.S. Patents 3,309,392, 3,598 7 ^ 7 and 3 660 313). For the production of mixtures, the components of the required specified Contain carbon chain lengths and degrees of ethoxylation, can use conventional distillation and stripping processes can be applied.

Formulation of the surfactant system

That in the detergents and cleaning agents according to the invention as surface-active. System used alkyl benzene sulfonate / Alky läthersulfat mixture contains the above-described alkylbenzenesulfonate and alkylether sulfate mixture in a weight ratio of alkyl benzene sulfonate to alkyl ether sulfate surface-active mixture from about 0.1: 1 to 6: 1, preferably from about 0.5Jl to 1: 1. Ratios of the alkyl benzene sulfonates and alkyl ether sulfates used as surfactants within systems of surface-active substances that are sufficiently insensitive to minerals in this area provide in low-phosphate and phosphate-free detergent formulations to be used that have a foam behavior that is comparable to that with conventional low-foaming Detergent mixtures is achievable and also little during the usual surfactant manufacturing process and spray drying Cause processing difficulties. Ratios of alkyl benzene sulfonate to alkyl ether sulfate, the above those described above, provide surface-active systems which, when used in phosphate

ORiGiNALSNSPECTED

poor and phosphate-free formulations too sensitive to minerals are, while ratios of alkylbenzenesulfonate to alkylether sulfate ,. those under the above above, provide resources that are difficult to process.

• Essential organic and / or inorganic salts

About 10 to about 90 wt. % Of the agents according to the invention, preferably about UO to about 75 wt., - / S, are composed of certain organic and / or inorganic salts that serve to improve the performance of the agents and that Process ^ u facilitate. Organic and / or inorganic salts suitable according to the invention are alkali metal carbonates, alkali metal silicates, electrolyte salts, such as water-soluble alkali metal or alkaline earth metal allcarb oxy late, sulfates and chlorides, and mixtures of such organic and / or inorganic salts.

Examples of suitable alkali metal carbonates include sodium carbonate, potassium carbonate, lithium carbonate, Sodium sesquicarbonate, potassium sesquicarbonate and lithium sesquicarbonate. Most preferred is sodium carbonate.

Alkali metal silicates are generally silicon-containing compounds that are generally commercially available in many different physical and chemical forms. Water-soluble alkali metal silicates can be crystalline or amorphous, hydrated or anhydrous and can have different ratios of alkali metal _{oxide (M 2} O) to silicon dioxide (SiO ₂ ) within their structures. Generally these ratios will range from about 1: 0.5 to Is5.0 on a weight basis.

409821/1046

Examples of alkali metal silicates suitable according to the invention are sodium metasilicate, potassium metasilicate, sodium sesquisilicate, potassium sesquisilicate, sodium orthosilicate and potassium orthosilicate. According to the invention most preferred compounds are the sodium silicates, which have a sodium oxide to silicon dioxide ratio of about 1: 2.4.

Other suitable organic and / or inorganic salts are electrolyte salts, such as the water-soluble alkali metal and alkaline earth metal carboxylates, sulfates and chlorides. Examples of this type of salt are sodium- acetate, potassium acetate, sodium citrate, sodium propionate, Matrxumnitrilotriacetate, sodium oleate, sodium stearate, Sodium salt of coconut fatty acid, sodium salt of tallow fatty acid, potassium chloride, sodium chloride, magnesium sulfate and trisodium sulfosuccinate (described in U.S. Patents 3,328,314, 3,424,600 and 3,533,944).

Preferred electrolyte salts are sodium acetate, potassium acetate, Trisodium sulfosuccinate and magnesium sulfate.

In the most preferred phosphate-free embodiments of the detergents according to the invention, mixtures of all three of the organic and / or inorganic salts described above are used. In general such mixtures (a) contain from about 40 to about 65 wt -.% Of the mixture of organic and / or inorganic salts of alkali metal carbonates, (b) from about 35 to about 60 wt -.% Of the mixture of organic and / or inorganic salts of alkali metal silicates, and (c) from about 1 to about 10 wt -.% of the mixture of organic and / or inorganic salts of sodium acetate,

409821/1046

Potassium acetate, alkali metal sulfosuccinate, or magnesium sulfate. In particular, such a mixture of organic and / or inorganic salts contains (a) from about 45 to about 60% by weight of the mixture of the organic and / or inorganic salts of sodium carbonate, (b) from about ¹ JO to about. 50 wt -% of the mixture of organic and / or inorganic salts of sodium silicate having a weight ratio of sodium oxide to silicon dioxide of about 1:. 2.4 and (c) from about 2 to about 7 wt .-% of the mixture of organic and / or inorganic salts of trisodium sulfosuccinate.

In the low-phosphate embodiments of the agents according to the invention (described in more detail below), a preferred organic and / or inorganic salt comprises a mixture of alkali metal silicates and an alkali metal sulfosuccinate. In general, such salt mixtures contain from about 65 to 96% by weight of the salt mixture at one Alkali metal silicate or mixtures of such silicates with a weight ratio of MpO / SiCL of about 1: 2.0. to 1:. 2.4 and of about k to 35 wt -% of the salt mixture on a Alkalimetallsulfosuccinatο particular contain such salt mixtures of about 70 to .90 wt .-% of the salt mixture of a sodium silicate or a mixture of sodium silicates having a weight ratio of NaPO / SiO from about 1: 2.0 to 1: 2,. *! and from about 10 to 30 percent by weight of the salt mixture of trisodium sulfosuccinate.

The main radio-ti on j, which is caused by the above-described organic and / or inorganic salts or salt mixtures ₅ is to make compositions of the invention under conventional spray drying conditions for granular detergent spray drying capable »detergent formulations _s' that described above

contained organic and / or inorganic salts in the specified concentrations are easier to be processed in soap mixers and spray drying towers.

The alkali metal carbonates and silicates not only serve as essential machining or processing aids when spray drying the washing machine according to the invention and cleaning agents, but also the adjustment of the pH of the aqueous washing solutions of the present Average to values between about 9.5 and 10.5, at which the performance of the surface-active substances peaks achieved. Some of these salts described above, such as sodium carbonate, sodium nitriloacetate and sodium citrate also serve as detergent builders.

water

The third essential component of the spray-dried washing and cleaning agents according to the invention is water or moisture. It has been found that detergent granules which contain the above-described particular surfactant system of alkylbenzenesulfonate and alkyl ether sulfate and the particular? '? organic and / or inorganic salts, may not contain more than about 8 wt .- & moisture, if free-flowing, non-caking detergent granules are desired. Accordingly, spray-dried agents according to the invention during normal spray drying to a moisture content of about 1 to 8 wt -.% Dried. Preferably, detergent granules according to the invention contain from about 3 to about 5% by weight of water.

0 9 8 2 1/10 46

Preferred optional ingredients phosphate salts

The present detergents and cleaning agents may optionally legally in a low-phosphate embodiment about 1 to about 35 wt .- $, preferably about 20 to 27 wt -.% (Compared with a phosphate content of about 50 wt .-% in total builder-containing washing and cleaning agents ) contain certain water-soluble, polyvalent, inorganic phosphate salts. Such water-soluble phosphate salts are alkali metal pyrophosphates, alkali metal polyphosphates or alkali metal tripolyphosphates. Examples of such phosphate compounds are sodium tripolyphosphate, potassium tripolyphosphate, sodium orthophosphate, lithium orthophosphate, potassium hexametaphosphate, tetrapotassium pyrophosphate and sodium pyrophosphate. The most preferred salt is sodium tripolyphosphate.

Fatty acids

A second highly preferred optional component in the low sudsing compositions of the invention is a fatty acid component such as fatty acids containing from about 8 to about 24 carbon atoms, or mixtures such fatty acids. Such fatty acids serve to increase the foaming power and foaming of the inventive To further suppress detergent mixtures in washing solutions.

Suitable fatty acids can be obtained from natural sources such as vegetable or animal esters (e.g. palm oil, coconut oil, babassu oil, soybean oil, saffron flower oil, tallow oil, gold lacquer oil, castor oil, tallow, whale and fish oils, fat, lard and their Mixtures). Fatty acids are also not synthetic manufacture (e.g. by oxidation of petroleum or by

409821/1046

Hydrogenation of carbon monoxide according to the Fischer-Tropsch process). Examples of fatty acids which can be used according to the invention are caproic acid, lauric acid, myristic acid, Palmitic acid, stearic acid and palmitoleic acid. Examples for commercially available fatty acids for use as anti-foaming agents in the mixtures according to the invention include C-105, C-108, C-IlO, T-IO, T-II and OL-910 (The Procter & Gamble Company) and Hyfac, one hydrogenated fish oil fatty acid (Emery Industries, Inc.). The preferred fatty acids include (1) mixtures of fatty acids derived from coconut oil and sebum, i.e. coconut fatty acid and tallow fatty acid, (2) hydrogenated fish oil fatty acid containing from about 17 to 18.5 carbon atoms and (3) mixtures of these day fatty acids and hydrogenated fish oil fatty acids.

The fatty acid component of the present compositions is about 0.5 to 3% by weight, based on the total agent. Preferably the fatty acid component is from about 1 to about 2% by weight of the agent.

Other optional components

The detergents and cleaning agents according to the invention contain in addition to the essential components described above, a large number of non-interfering components optional ingredients. These optional ingredients can include, for example: brighteners, hydrotropes and processing aids such as alkali metal toluene sulfonates, perfumes, bleaches such as sodium perborate solids or potassium monopersulfate, soil removal improver, such as polyethylene glycol, enzymes, corrosion inhibitors, anti-graying agents, calcium precipitation inhibitors and / or dyes. Such optional materials can contain up to about 50 wt. of the present detergent turn off.

40982 1/1046

Manufacture and use of the agent

The low-phosphate and phosphate-free granulated detergents and cleaning agents according to the invention are produced by spray-drying an aqueous suspension of the detergent components described above. Conventional detergent spray drying equipment can be used in this preparation. An aqueous slurry to be spray dried is prepared by mixing the above-described surfactants, organic and / or inorganic salt components and optional components in a soap mixer with sufficient water to produce a slurry containing about 64 to ^ 5% by weight. % Solids, preferably about 68% solids by weight. The mixer temperature is generally maintained between about 71 and 90.5 degrees Celsius, preferably about 82 degrees Celsius. Such a slurry is pumped into a conventional spray-drying tower, wherein the material to granules is spray dried to the required 1 to 8 wt -% contain moisture.. Preferred methods and apparatus for spray-drying the present compositions are described in XJS-PSs 3,629,951 and 3,629,955.

The present agents are used by dissolving them in aqueous washing solutions, the amount of which is from about 0.01 % to about 2% by weight. These agents are preferably used in water in an amount of about 0.06% up to about 0.18% by weight used »This preferred concentration is approximately achieved when about 0.5 to 1.5 cups of the present detergent 64, H to 87.1 1 of water, the general capacity of commercially available washing machines, can be added. The pH of such

403 8 21/1046

Wash solutions is generally between 9 _S 5 and 10.5. Dirty substances or other objects are added to the wash liquor and cleaned in the usual way.

The following examples serve for further explanation the invention.

example 1

A spray-dried detergent and cleaning agent with the following composition was produced:

Components . Weight %

System of surface-active substances 22 %

Sodium dodecylbenzene- -v. sulfonate. 15 %

Alkyl ether sulfate

Weight ratio

^{Tabel Σ} 7 Ty _{Mixture 2jli}: 1}

Sodium carbonate 74 %

Water ' ■ k%

Such a composition is excellent Washing performance on textiles when they are washed under normal home washing conditions in a washing liquid with a Water hardness of 4.8 and a concentration of about 0.12% by weight is used. Holds under these conditions the foaming behavior of the agent of Example 1 compares favorably with that of conventional low-foaming detergent formulations. One such Medium is pourable and is produced with the help of conventional spray drying equipment.

409821/1046

Agents with essentially the same washing performance, physical properties and processability were found prepared when in Example 1 described above sodium dodecylbenzenesulfonate by an equivalent Amount of one of the following compounds has been replaced: sodium decylbenzenesulfonate, sodium undecylbenzenesulfonate, Sodium tridecylbenzenesulfonate, sodium tetradecylbenzener sulfonate, sodium tetrapropylene benzene sulfonate, potassium decylbenzenesulfonate, Potassium undecylbenzenesulfonate, calcium tridecylbenzenesulfonate, Potassium tetradecylbenzenesulfonate or potassium tetrapropylenebenzenesulfonate.

Agents with essentially the same washing quality, Physical properties and processability were established following the example given above 1 the alkyl ether sulfate mixture No. 1 with an equivalent amount of an alkyl ether sulfate mixture No. 2, 3, * J or replaced 5 from Table I above.

Agents with essentially the same washing performance, physical properties and processability were established when in Example 1 above the sodium carbonate with an equivalent amount of sodium metasilicate, Potassium metasilicate, sodium sesquisilicate, Potassium sesquisilicate, sodium orthosilicate, potassium orthosilicate, Sodium sesquicarbonate, sodium acetate, potassium acetate , Sodium nitrile triacetate, trisodium sulfosuccinate, Magnesium sulfate, sodium citrate, sodium salt of tallow fatty acid, sodium chloride or mixtures of sodium silicate (V = 1: 2.4), sodium carbonate and trisodium sulfosuccinate replaced.

409821/1046

Example 2

A phosphate-free, spray-dried washing powder was and cleaning agents with the following composition:

Components

System of surface-active substances

Sodium linear alkyl benzene sulfonate, wherein the alkyl group has an average of about 11.8 carbon atoms

Alkyl ether sulfate mixture No. 1 from Table I.

9.9 11.0

Weight

20.0 %

Weight ratio of alkyl benzene sulfonate / alkyl ether sulfate mixture =
0.82: 1

Sodium silicate (Na ₂ 0 / Si0 ₂ weight ratio = 1: 2.4)

sodium

Trisodium sulfosuccinate

Sodium sulfate
Sodium toluenesulfonate tallow fatty acid

Hydrogenated fish oil fatty acid, which is about Contains 18 carbon atoms

water

Small amounts of other substances

19.58 %

19.58 % 2.0 %

28.70 % 1.0 %

1.05 %

0.35 * 3.96 % remainder

The essential organic and / or inorganic salt component of Example 2 described above is a mixture of sodium silicate, sodium carbonate and trisodium sulfosuccinate with the following composition: Sodium Silicate - 47.6% by weight of the organic and / or inorganic salt mixture; Sodium carbonate - ^ 7.6 % By weight of the organic and / or inorganic salt mixture; Trisodium sulfosuccinate - 4.8 wt .- / l of the organic and / or inorganic salt mixture.

409821/1046

Although sodium sulfate is an electrolyte salt as stated above, it is used as an essential component of the agent according to the invention is not preferred and is generally only as a by-product of the manufacture of the surfactants. The preferred one Mixture of essential organic and / or inorganic Salts of example 2 consists. Therefore of only one Carbonate-silicate-sulfosuccinate mixture.

Such a composition exhibits excellent detergency performance on textiles when there under normal home washing conditions in a wash liquor a water hardness of 6.7 in a concentration of 0.12 weight - is applied.%. Under these conditions, the foam behavior of the agent of Example 2 withstands a favorable comparison with that of conventional low-foam detergent formulations. Such an agent is easy to pour and has a long shelf life and is produced in conventional spray-drying apparatus.

Means with in general. the same washing characteristics, physical properties and processability were prepared as the sodium linear-alkyIbenzοIsulfonat was replaced by an equivalent amount of the following compounds in the above-described Example 2: Natriumdecylbenzolsulfonat, Natriumundecylbenzolsulfonat ₃ sodium dodecylbenzenesulfonate, Natriumtridecylbenzolsulfonat, Natriumtetradecylbenzolsulfonat, Natriumtetrapropylenbenzolsulfonat, Kaliumdecylbenzolsulfonat, Kaliumundecylbenzolsulfonat, Kaliumtridecylbenzolsulfonat _s Kaliumtetradecylbenzolsulfonat , Potassium tetrapropylenebenzene; sulfonate or mixtures of these surfactants.

Agents with essentially the same washing performance, physical Properties and processability were

489821/1048

- 2h -

produced when in Example 2 described above, the alkyl ether sulfate mixture No. 1 was replaced by an equivalent amount of alkyl ether sulfate mixtures of No. 2, 3, O or 5 from Table I listed above.

A means having substantially the same wash performance, physical properties and workability was manufactured, when about 10 percent in the above described Example 2 -.% Natriumperboratfeststoffe have been incorporated, with all other components were present in the same relative weight proportions.

Example 3

A low-phosphate, spray-dried detergent and cleaning agent with the following composition was produced:

Components by weight %

Surfactant system 10.80 %

Sodium linear alkylbenzenesulfonate, in which the alkyl group
average about 11.8
C-Atce has 4.9 *,

Alkyl ether sulfate mixture ffonate / alkyl ether sulfate no. 1 from Table I 5.9 % ^} fat mixture = 0.83: 1

Sodium silicate ^ p

Weight ratio = 1: 2.4) 13.60 %

Sodium carbonate 18.30 %

Trisodium sulfosuccinate 2.0 %

Hydrogenated fish oil fatty acid, the

contains about 18 carbon atoms 2.0 * 1 %

409821/1046

17th , 65 32 , 0 2 ,8th rest

Components . Weight-i

⁺⁺ sodium sulfate

⁺⁺ mixed sodium sulfate water

minor additions

The essential organic and / or inorganic salt component of the example described above is a mixture of sodium silicate, sodium carbonate and trisodium sulfosuccinate, of the following composition: sodium silicate - 40% by weight of the organic and / or inorganic salt mixture; . Sodium carbonate - ^ 5 wt -% of the organic and / or inorganic salt mixture; Trisodium sulfosuccinate - 6% by weight of the organic and / or inorganic salt mixture.

Although sodium sulfate is an electrolyte salt as stated above, it is used as an essential component of the Agent according to the invention is not preferred and is generally mainly only as a by-product of the production ■ of the surface-active substances. The preferred mixture of the essential organic and / or inorganic salts of Example 3 therefore consists only of the silicate-carbonate-sulfosuccinate mixture.

Such an agent exhibits excellent laundry performance on fabrics when used under normal home washing conditions in a wash liquor with a water hardness of 6.7 in a concentration of about 0.12% by weight - applied will.

Under these conditions, the foam behavior of the Example 3 provides a favorable comparison with that of conventional low-foaming detergent formulations the end. Such agents are easy to pour and have a long shelf life and can be removed using conventional spray-drying apparatus produce.

409821/1046

Agents with essentially the same washing performance, physical properties and processability were found produced when in Example 3 described above, the sodium linear alkylbenzenesulfonate by replaced an equivalent amount of the following compounds: sodium decylbenzenesulfonate, sodium undecylbenzenesulfonate, Sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate , Sodium tetradecylbenzenesulfonate, sodium tetrapro-.pylenebenzenesulfonate, Potassium decylbenzenesulfonate, potassium undecylbenzenesulfonate, Potassium tridecylbenzenesulfonate, potassium tetradecylbenzenesulfonate, Potassium tetrapropylene benzene sulfonate or mixtures of these surfactants.

Means having substantially the same wash performance, physical properties and processability were produced when the Alkyläthersulfat mixture listed in the above-described Example 3 Mr. 1 by an equivalent amount of Alkyläthersulfat mixtures of Nos. 2, 3 »4 and 5 of the above- Table I was replaced.

.Example ¹ I.

A low-phosphate, spray-dried laundry detergent was and cleaning agents of the following composition represents:

Components wt .- / S

Surfactant system 18.0 %

Sodium linear alkyl benzene sulfonate, wherein the alkyl group

r ^ ™? ¹ ! ^; ^ ^{About 11> 8} R 1 t \ weight ratio

C atoms grow o, l> J .- ,,,, * ■ -. *.

' (from Alkylbenzenesulfone

Alkyl ether sulphate mixture - (alkyl ether sulphate

No. 1 from Table I 9.9 % J mix = 0.82: 1

409821/1046

Components wt. -%

Sodium silicate ₃₂

Weight ratio - 1: 2, * 0 5 _S 95 %

⁺ Sodium silicate (Na ₃ OZSiO ₂ .

Weight ratio = 1: 2.0) 5.95%

+ Trisodium sulfosuccinate 3.0 %

Sodium tripolyphosphate 2M, 0.5S

"^ Sodium Sulphate 26.58 %

Netrium perborate solids 5 »3 %

Sodium toluenesulfonate 0.72 %

Hydrogenated fish oil fatty acid, the

contains about 18 carbon atoms 1.1 %

Water 8.0 %

minor additions rest

The essential organic undZoder inorganic salt component of Example ¹ I described above is a mixture of sodium silicate and trisodium sulfosuccinate of the following composition: Sodium silicate 80.0 wt -% of the mixture of the organic undZoder inorganic salts;. Trx sodium sulfosuccinate - 20% by weight of the mixture of organic and / or inorganic salts.

Although sodium sulfate, as stated above, a Is electrolyte salt, it is not preferred as an essential component of the agent according to the invention and is generally only as a by-product of the manufacture of the surfactants. The preferred one The mixture of the essential organic and Z or inorganic salts of Example 4 therefore consists only of the silicate-sulfosuccinate mixture »

Such a composition exhibits excellent wash performance on fabrics when it under normal home washing conditions in a wash liquor a Viasserhärte of 6.7 ° in a concentration of about 12 wt 0 _s - is applied.%. Under these conditions, the foam behavior holds

409821/1046

The means of Example 4 is a favorable comparison with that of conventional, moderately low-foaming detergent formulations the end. Such a means is easy to pour and storage stable and can be in the usual Manufacture spray drying equipment.

Agents with essentially the same washing performance, physical Properties and processability were established when in Example 4 above the sodium linear alkylbenzenesulfonate is replaced by an equivalent amount of the following compounds became: sodium decylbenzenesulfonate, sodium undecylbenzenesulf onate, sodium dodecylbenzenesulfonate, sodium tridecylbenzenesulfonate, Sodium tetradecylbenzenesulfonate, sodium tetrapropylenebenzenesulfonate, Potassium decylbenzenesulfonate, Potassium undecylbenzenesulfonate, potassium tridecylbenzenesulfonate, Potassium tetradecylbenzenesulfonate, potassium tetrapropylenebenzenesulfonate or mixtures of these surfactants.

Agents with essentially the same washing performance, physical properties and processability were produced, when in the above-described Example 4, the alkyl ether sulfate mixture No. 1 by an equivalent Amount of alkyl ether sulfate mixtures of No. 2, 3 »4 or 5 from Table I listed above has been replaced.

Agents with essentially the same washing performance, physical properties and processability were found prepared when in Example 4 described above, the sodium tripolyphosphate by an equivalent amount Sodium orthophosphate, potassium tripolyphosphate, lithium orthophosphate, Potassium hexametaphosphate, tetrapotassium pyrophosphate, or sodium pyrophosphate has been replaced.

409821/1046

■ - afr- -

An agent with essentially the same washing performance, Physical properties and processability were established when in the example described above 4 the sodium perborate pests have been removed, whereby all other components were in the same relative weight ratios.

Wash and Wear Test

The detergency of agents according to the invention was with that of a commercially available builder-containing, granulated laundry detergent in a wash and wear test tested. The test was carried out as follows: Light colored shirts, cotton t-shirts, and other textiles, such as pillow cases, were given to different people distributed. Every shirt and t-shirt became a normal one Worn under uniform conditions for a working day, and the other items became common to them usual purposes. The soiled clothes and textiles were then in an automatic Agitator washing machine washed with detergent solutions at 37> 8 C for 10 minutes. The detergents used were those of Examples 2, 3 and 4 at a concentration of about 250 cm (0.9 cup) per 87jl 1 Water and Tide, a commercially available, built-up, granulated detergent that, at different concentrations was used. Washing water with a water hardness of 1.9 °, 6.7 ° and 11.5 ° was used. To After washing, the garments were rinsed (6 spray rinses and 1 immersion rinse) and then dried.

A panel of rent examiners made direct visual comparisons between 1 pair of shirts and textiles, which have been worn and soiled by the same person

409821/1046

10

viaren, at. The shirts, t-shirts and other textiles used were achieved on the degree of whiteness and. Degree of cleaning assessed, with the latter property in the collars and cuffs of the shirts and in the pillowcases being given special attention. As used herein the term "cleaning" or "purity" of the measure of the ability of the .Waschmittels actually means water marks and debris to be removed, such as penetrating deeply as fat margins on collars and cuffs and pillows where the dirt has the opportunity. Whiteness on the other hand is a more general concept and is the measure of the ability of the washing and cleaning agent sectors to make know the dirty weak or mediocre. The relative cleaning effectiveness of each detergent in each area is measured visually on a scale divided into 9 lines under artificial lipids, the highest value being assigned to the relatively best performance achieved.

Based on these comparisons, it was found that the compositions of Examples 2, 3 and ¹ I of the invention have cleaning and whitening performance of the commercial detergent Tide-equal amounts are comparable to that.

Foaming behavior test

The extraordinary foam consistency of the present detergents and cleaning agents is demonstrated with the aid of the foam height evaluation test. The compositions of Examples 2, 3 and ¹ I and a commercial, low-sudsing laundry detergent, Dash described above were / aschmittelkonzentration at different wash water temperature, water hardness, V and pollution in a

409821/1046

₉ General Electric top-loading automatic washing machine tested in a standard wash cycle. After 2, 3, 5, 8 and 10 minutes, the foam heights for each wash solution to be tested were measured in cm and an average for at least 2k washes under each set of conditions was calculated. The product concentration varied between 125 and 375 cm (1/2 to 1 1/2 cups) of the Viaschmitteis per 87.1 l of wash water; the water hardness fluctuated between 0.48 ° and about 13 ^; the pollution ranged from medium to very severe and the washing water temperature fluctuated between about 21 and about 60 ° C.

Over this wide range of washing conditions, that holds up Foaming behavior of the agents of Examples 2, 3 and 4 a favorable comparison with that of the commercial laundry detergent Dash.aus

Storage stability test

The storage stability of the agents according to the invention was determined with the aid of a storage stability test. The granulated agents to be tested were packed in externally waxed, laminated and poly-laminated cardboard boxes, which had various types of closures, and stored for different times in chambers with constant temperature and humidity. These chambers were generally maintained under conditions varying between ambient temperature and humidity and the rather severe temperature / humidity conditions of 26.7 ° C and 80 % relative humidity. At certain time intervals, the agents to be tested were taken from the temperature / humidity constant environment

409821/1046

removed and tested for caking and pourability properties to be determined after this storage.

Although this test demonstrates that the invention Agents have a somewhat poorer storage stability than the commercially available, fully framework-containing, phosphate-containing surfactants, the storage stability of the present agents is for commercially available Purposes and still acceptable for sale.

409821/1046

Claims (19)

Claims (l) Granulated, spray-dried detergent and cleaning agent, consisting essentially of: A. From about 10 to 30% by weight of a system more surfactant Substances consisting essentially of, (i) an alkylbenzenesulfonate such as (a) the sodium or potassium salts of alkylbenzenesulfonic acids, in which the Alkyl radical from 9 to 20 carbon atoms contains, or (b) mixtures thereof, and (ii) an alkyl ether sulfate mixture of compounds of the general formula RO (C ₂ H ₁₁ O) _n SO ₃ M where R is an alkyl radical, η is an integer representing the degree of ethoxylation, and M is sodium or potassium, the average number of carbon atoms in the radical R within the alkyl ether sulfate mixture between 16.01 and 19 and the average degree of ethoxylation of the mixture between 1 and 5 Moles of ethylene oxide varies, the mixture from about 0.1 to 2 % by weight of the alkyl ether sulfate mixture of compounds containing 12 or 13 carbon atoms, from about 0.1 to 33% by weight of the alkyl ether sulfate mixture of compounds which I ¹ J or 15 carbon atoms contain from about 25 to 55 wt .- $ 5 of the alkyl ether sulfate mixture of compounds containing 16 or carbon atoms from about 30 to 40952 '70 wt .-% contain the Alkyläthersulfat mixture of compounds containing 18 or 19 carbon atoms, from about 1 to 30 wt -.% Of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 0, from about 50 to 80 wt -.% Alkyläthersulfat of the mixture of compounds having a degree of ethoxylation of 1 to 4, from about 3 to 30 wt -.% of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 5 to 8 and from about 0.1 to 10 parts by weight of the JS Alkyläthersulfat -Mixture of compounds with a degree of ethoxylation greater than 8, the weight ratio of the alkylbenzenesulfonate to the alkylether sulfate, ^ - mixture within the surface-active system varies between 0.1: 1 and 6: 1, (B) from about 10 to 90 wt. an organic and / or inorganic salts such as alkali metal silicates, alkali metal carbonates, electrolyte salts such as water-soluble alkali metal or alkaline earth metal carboxylates, sulfates or -Chlorides, or mixtures of these organic and / or inorganic salts and (C) from about 1 to 8 weight percent water. 2. Means according to claim 1, characterized in that (A) the surfactant system in one Amount of about 17 to 25 wt .- /? (B) the organic and / or inorganic salt in an amount of about ^ iO to 75 wt -.%, And (C) water in an amount of from about 3 to about wt -.% Are present. 409821/1046 3. Composition according to claim 2, characterized in that the organic and / or inorganic salt sodium carbonate, sodium metasilicate, sodium sesquisilicate,
Potassium metasilicate, potassium sesquisilicate, sodium orthosilicate, potassium orthosilicate, sodium sesquicarbonate, sodium acetate, potassium acetate, sodium nitrilotriacetate, trisodium sulfosuccinate, magnesium sulfate, sodium salt of
Tallow fatty acid, sodium citrate, sodium chloride, mixtures
of (a) alkali metal silicates, (b) alkali metal carbonates and (c) alkali metal sulfosuccinates or mixtures of
(a) alkali metal silicates and (b) alkali metal sulfosuccinates. k. Agent according to claim 3, characterized in that the weight ratio of alkylbenzenesulfonate to
Alky lather sulfate-Gemis is from about 0.5: 1 to 1: 1 '. 5. Composition according to claim 4, characterized in that the alkylbenzenesulfonate is the sodium or potassium salts of straight-chain alkylbenzenesulfonic acids
which the alkyl radical contains from 11 to about Ik .Kohlenstoffatome, or mixtures thereof. 6. Means according to claim 5 * characterized in that that the alkylbenzenesulfonate is sodium linear, alkylbenzenesulfonate wherein the alkyl chain contains an average of about 12 carbon atoms. 7. Composition according to claim 4, characterized in that the alkyJLäthersulfat mixture an average
Has a carbon chain length of about 16.5 to 18 carbon atoms and an average degree of ethoxylation between about 2 and 4 moles of ethylene oxide, 409821/1046 wherein the alkyl ether sulfate mixture from about 0.1 to 1.75 wt .- / £ of the alkyl ether sulfate mixture of compounds with 12 or 13 carbon atoms, from about 1 to 20 wt 15 carbon atoms, from about 28 to 40 Ge \ -i .-% of Alkyläthersulfat mixture of compounds having 16 or 17 carbon atoms, from about 40 to 60 wt -.% of Alkyläthersulfat mixture of compounds having 18 or 19 carbon atoms ^ of about 10 to 25% by weight of the Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 0, from about 51 to 70% by weight of the Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 1 to 4, from about 10 to 28 wt. - % of the alkyl ether sulfate mixture of compounds with a degree of ethoxylation of 5 to 8 and from about 1 to 8 % by weight of the alkyl ether sulfate mixture of compounds with a degree of ethoxylation greater than 8. 8. Composition according to claim 7, characterized in that the alkylbenzenesulfonate is the sodium or potassium salts of straight-chain alkylbenzenesulfonic acids, in '. -the alkyl radical range from 11 to about 14 carbon atoms contains, or means mixtures thereof. 9. Composition according to claim 8, characterized in that the alkylbenzenesulfonate sodium linear alkylbenzenesulfonate, where the alkyl chain averages about Comprises 12 carbon atoms. 10. The phosphate-free detergents -Ind detergent according to claim 4, characterized in that the organic and / or inorganic salt is a mixture of salts comprising from about 40 to 65 wt - \ mixture allcarbonaten% of Sal Alkalimet, from about 35 to. 60 Ge \ .- # des SaIz- 409821/1046 mixture of alkali metal silicates and of about 1 to wt -.% of the salt mixture of electrolyte salt such as Natriumacetät, potassium acetate, or magnesium sulfate Alkalimetallsulfosuccinaten contains. 11. Means according to claim 10, characterized in that that (A) the alkylbenzenesulfonate the sodium or potassium salts of straight-chain alkylbenzene. sulfonic acids in which the alkyl radical contains from -11 to about 14 carbon atoms, or Mixtures of these is and (B) varies the average number of carbon atoms in the group R within the Alkyläthersulfat mixture from 16.5 to 18 and the average "degree of ethoxylation of the mixture is between 2 and 4 and the mixture of about 0.1 to 1.75 percent. ~ % of the alkyl ether sulfate mixture of compounds with 12 or 13 carbon atoms, from about 1 to 20 wt -.% of Alkyläthersulfatgemisches of compounds having 14 or 15 carbon atoms, from about 28 to 40 wt -.% of Alkyläthersulfat mixture of compounds having 16 or 17 carbon atoms, from about 40 to 60 percent by weight of the alkyl ether sulfate mixture to compounds with 18 or 19 carbon atoms, from about 10 to 25 parts by weight of the alkyl ether sulfate mixture on compounds with a degree of ethoxylation of 0, from about 51 to 70 weight percent of the alkyl ether sulfate mixture on compounds with a degree of ethoxylation of 1 to 4, 409821/1046 from about 10 to 28 wt -.% of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 5 to 8 and from about 1 to 8% by weight of the alkyl ether sulfate mixture of compounds with a degree of ethoxylation greater than 8. 12. Composition according to claim 11, characterized in that it additionally contains from about 0.5 to 3 wt -%, or mixtures containing of the mixture of an antifoaming agent such as fatty acids, having from about to 24 carbon atoms, such fatty acids.. 13. Composition according to claim 12, characterized in that the organic and / or inorganic salt mixture of about 45 to 60 wt .-% of the salt mixture of sodium carbonate, from about 40 to 50 wt -.% Of the salt mixture over sodium silicate, wherein the weight ratio of sodium oxide to silicon dioxide is about 1: 2.4, and from about 2 to 7 weight -% by weight of the salt mixture in trisodium sulfosuccinate.. 14. Means according to claim 13, characterized in that (A) the alkylbenzenesulfonate sodium linear alkylbenzenesulfonate with the alkyl chain an average of about 12 carbon atoms includes, (B) the alkyl ether sulfate mixture of about 0.1 to 1.5 wt -.% Of Alkyläthersulfat- mixture of compounds having 12 or 13 carbon atoms, from about 10 to 15 wt -.% of fat Alkyläthersul = mixture of compounds having 14 or 15 carbon atoms, 409821/1048 from about 30 to 33% by weight of the alkyl ether sulfate mixture to compounds with 16 or 17 carbon atoms, From about 50 to 55% by weight of the alkyl ether sulfate mixture on compounds with 18 or 19 carbon atoms, from about 15 to 20 % by weight of the alkyl ether sulfate mixture of compounds with a degree of ethoxylation of 0, ■ from about 52 to 57 wt -.% of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 1 to 4, from about 20 to 25 wt -.% of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 5 to 8 and from about 3 to 7 wt -.% of Älkyläthersulfat-Gemis.ches of compounds having a degree of ethoxylation greater than 8 and containing (C ) the antifoam coconut fatty acid, tallow fatty acid, hydrogenated fish oil fatty acid having about 17 to 18.5 carbon atoms, or mixtures of tallow fatty acid / is hydrogenated fish oil fatty acid having about 17 to 18.5 carbon atoms, wherein the anti-foaming agent in an amount of about 1 to 2 wt -.% of Total mixture is present. 15 »Low-phosphate washing and cleaning agent according to claim H _9, characterized in that (A) the organic and / or inorganic salt a mixture of salts is that of about 65 to 96 wt -% of the salt mixture of alkali metal silicate or silicate mixture, wherein the silicate has a weight ratio of MPO / siop of about 1:. 2.4 includes 2.0 to 1 , and from 409821/1046 contains about h to 35 wt .- ^ of the salt mixture of alkali metal sulfosuccinate and (B) the agent additionally contains from about 1 to 35 % by weight of a water-soluble polyvalent inorganic phosphate salt such as alkali metal 1-pyrophosphates, alkali metal polyphosphates or alkali metal tripolyphosphates. 16. Means according to claim 15 _3, characterized in that (A) the alkylbenzenesulfonate the sodium and potassium salts of straight-chain alkylbenzenesulfonic acids, wherein the alkyl radical contains from 11 to about 14 carbon atoms, or mixtures thereof is, (B) the average number of carbon atoms in the radical R within the alkyl ether sulfate Geraisches between 16.5 and 18 and the average degree of ethoxylation of the mixture varies between 2 and ¹ J and the mixture from about 0.1 to 1.75 wt. -JS of the alkyl ether sulfate mixture of compounds with 12 or 13 carbon atoms, from about 1 to 20 wt -.% of Alkyläthersulfat mixture of compounds having Ik or 15 carbonic t offat omen, from about 28 to 40 wt. -JS of the alkyl ether sulfate mixture to compounds with 16 or 17 carbon atoms, of about kO to 60 wt -.% of Alkyläthersulfat mixture of compounds having 18 or 19 carbon atoms, from about 10 to 25 wt -.% of Alkyläthersulfat-Gemisohes of compounds having a Äthoxylierun ^ sgrad of 0, 409821/1046 • - ii4 - ■ ■ * from about 51 to 70 En \ -i .-% of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 1 to 4, from about 10 to 28 wt -.% of Alkyläthersulfat mixture of compounds having a degree of ethoxylation of 5 to 8 and contains% of Alkylathersulfat mixture of compounds having a degree of ethoxylation greater than 8, and (C) the water-soluble multivalent inorganic phosphate salt Natriumtrxpolyphosphat, potassium tripolyphosphate, sodium orthophosphate, lithium orthophosphate, potassium hexametaphosphate - - from about 1 to 8 wt. _s is tetrapotassium pyrophosphate or sodium pyrophosphate. 17 · Agent according to claim 16, characterized in that it additionally contains from about 0.5 to 3 % by weight of the mixture of an antifoam agent such as fatty acids containing from about 8 to 2k carbon atoms, or mixtures of such fatty acids. 18. Means according to claim 17, characterized in that (A) the organic and / or inorganic salt mixture from about 70 to 90 percent by weight of the mixture an. Sodium silicates with a weight ratio of NapO / SiOg of about 1: 2.0 to 1: 2.4 and from about 10 to 30 wt .- # of the mixture of trisodium sulfosuccinate ' contains and (B) the water-soluble polyvalent inorganic phosphate salt in an amount of about 20-27 Wt .- # of the mixture is present. 409821/1046 19. Means according to claim l8, characterized , that (A) the alkylbenzenesulfonate sodium linear alkyl benzenesulfonate, the alkyl radical being average has about 12 carbon atoms, is, (B) the alkyl ether sulfate mixture from about 0.1 to
1.5 wt .- / £ of the alkyl ether sulfate mixture
Compounds having 12 or 13 carbon atoms, from about 10 to 15 wt -.% Of Alkyläthersulfat mixture of compounds having 14 or 15 carbon atoms, from about 30 to 33 wt. of the alkyl ether sulfate mixture on compounds with 16 or 17 carbon atoms, from about 50 to 55 wt .- ^ of the alkyl ether sulfate Mixture of compounds with 18 or 19 carbon atoms, from about 15 to 20 Ge \ -j .-% of the alkyl ether sulfate mixture of compounds with a degree of ethoxylation of 0, from about 52 to 57 wt .- ^ of the alkyl ether sulfate mixture to compounds with "a degree of ethoxylation of 1 to 4, from about 20 to 25% by weight of the alkyl ether sulfate mixture of compounds with a degree of ethoxylation of 5 to 8 and from about 3 to 7 percent by weight of the alkyl ether sulfate mixture of compounds with a degree of sthoxylation greater than 8, (C) the water-soluble polyvalent inorganic phosphate salt is sodium tripolyphosphate and 4Q3821 / 1Ö48 (D) the antifoam agent coconut fatty acid _s Tallow fatty acid _s hydrogenated fish oil fatty acid _s
those from about 17 to 18 ₅ 5 carbon atoms
includes j, or mixtures of tallow and hydrogenated fish oil fatty acid containing _s IJ atoms of about up to 18.5 carbon, _s x-zobei the antifoam agent in an amount of about 1 to 2 wt ₀ - exists% of the total mixture. For: The Procter S) Gamble Company Cincinnati, / Ohio, V.St.A. Dr. H.! i J. Wolff Lawyer 409821/1046