DE2613790A1 - LAUNDRY DETERGENT - Google Patents

Description

DR ^CH JUR. DIFL-CHEM. WALTER BE * 3 fl

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Our No. 20 426 D / mii

Your Procter & Gamble Company Cincinnati, Ohio, V.3t.A.

laundry detergent

The present invention relates to detergents that remove dirt Contain cellulose ethers. The invention Detergents consist of optimal combinations of anionic and non-ionic surface-active agents that

ο u ..., _- ». ·» -, ,, -,., -. ^,. , affect Dirt removal ability of the cellulose feathers is not significant / and effect superior fabric cleaning.

Intensive efforts have already been expended to various Finding compounds that improve the dirt release of fabrics when they are washed in household washing machines. Here different polymers were primarily used as V / ash-

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ORIGINAL INSPECTED,

Medium additives used with the aim of making this out of water To deposit detergent on fabrics made of cotton, polyester and polyester / cotton, which has the advantage of releasing dirt is reached during later ash processes.

The literature on soil release polymers shows that efforts to improve detergents containing such additives focus on the nature of the polymers self concentrated, and various such polymers have been made and tested.

The continued search for laundry detergents that are genuinely effective Containing soil release additives led to the finding that many of these materials fail in this regard are particularly effective except at high concentrations · The use of high concentrations of any additive in detergents is an economic loss if au.6h smaller amounts would suffice. .Furthermore, these Addi = tive preferably broken down before they are discharged into the sewer system. Numerous previously known dirt-removing Materials are entirely satisfactory from a toxicological standpoint; their presence in wastewater in however, high concentrations lead to an increased biological oxygen demand, which reduces the water quality will. It would therefore be beneficial to have laundry detergents that contain small but effective amounts of soil release agents Contains additives.

The most interesting soil-releasing polymers are those based on cellulose as a starting material. A group such polymers are the cellulose ethers. The cellulose ethers are easy to manufacture, biodegradable and Acceptable from a toxicological point of view. Many substances of this type are known as food additives.

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Various soil release polymers are ceilulose ethers known, and many of them have been used both for detergents in combination with surfactants and for rinsing baths proposed in the absence of surfactants. In terms of ease of use, it is cheaper if the soil-releasing polymers are applied to the textile material in connection with the washing process.

The DAS (us "registration from the same day, us .Nr" 204-39) discloses that, contrary to the teaching of the prior art, the selection of the surface active agents that are to be used together with Cellulose ethers uses a significant and previously neglected influence on their dirt removal behavior Has. Numerous detergent-active surfactants have an effect together with the cellulose derivatives and significantly reduce their effectiveness as dirt removers. In the formulation Y / ash agents containing such materials either properties below the optimum had to be accepted, or one had to be inappropriately Use high concentrations of the cellulose ether polymers in the detergent to ensure good soil removal properties achieve.

As in the aforementioned DAS are surface-active alkyl sulfates, with certain Chain length ^ and alkylbenzenesulfonates ^ especially useful for the manufacture of "ash compositions, which fabrics in Present only smaller / ueXxujLoseäther improved as dirt remover Give dirt releasing capacity. Unfortunately, the ones that are most compatible with the dirt-releasing cellulose ethers Alkyl sulfates and alkyl benzene sulfonates are relatively short alkyl chains. These surface active agents are

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point of compatibility optimal, they behave as Detergent, however, is not the best.

it has now been found that certain non-ionic surfactants in combination with longer-chain, stronger detergent-effective anionic surfactants such as alkyl sulfates and alkyl benzene sulfonates can be used, and that these combinations of surfactants are compatible with soil-releasing cellulose ethers. The application of the invention therefore allows both the advantages the detergent active surface active like the gel = lulose ether to enjoy.

It was also found that certain textile equipment, in particular on polyester / Baumwoil-G-eweben, an essential one Influence on the ability of Öelluloseäthem to achieve Exercise optimal Sehmutz detachment. Those in combination with the presently preferred mixtures of surfactants Soil-releasing ether used can be used when washing unfinished polyester / cotton fabric from a large group of cellulose derivatives. However, if you want non-iron finished polyester or mixed goods wash, preference is given to certain cellulose derivatives, which are both treated and unfinished in the case of polyester Behave well with polyester / cotton mixtures. The basics of choosing these favorite dirt shedding pads Ethers are revealed below »

The aim of the invention is to provide a detergent of optimal reconciliation effect, with minimal concentrations optimal for dirt-releasing cellulose ether additives has a dirt-loosening effect.

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From the following patents and references is It can be seen that numerous cellulose derivatives and their mixtures have already been proposed for use in cosmetics became. The importance of the variety of surfactants in this case, it has apparently not yet been recognized.

Use of methyl and ethyl cellulose ethers in detergents is known from US Pat. No. 2,373,863. Numerous cellulose derivatives for use in ash detergents are out US Pat. No. 2,994,665, see also US Pat. No. 3,523,088. DAS 1,054,638 describes C 1-4 alkylbenzene sulfide fonates in combination with carboxylated cellulose derivatives. From GB-PS 1 084 061 it is known that small amounts of CeIIu = Use loose derivatives as stabilizers for liquid detergents. Also from GB-PSS 927 542, 765 811 and 340 232 cellulose derivatives are known in detergents. the ZA-PS 71/5129 discloses detergents which are hydroxyalkyl-alkyl cellulose derivatives contain; see also "Synthetic Deter = gents", McCutcheon (1950) pp. 230 and 248.

Different cellulose ethers can be used in distilled water be dissolved and applied to tissue, especially polyester, whereby one essential dirt repellency for oily Dirt achieved. In most cases the dirt-removing effect of these ethers decreases noticeably when you put them in Detergents are formulated containing surfactants, builders and the like. It has now been found that the problem of reducing an inherently good release effect of the cellulose ethers on oily dirt can be solved can without sacrificing the entire cleaning behavior to other types of dirt.

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(a) about 5 to about 65 GeWo5 & a surface-active component, which is a water soluble anionic surfactant Agents or mixtures thereof and a water-soluble non-ionic surfactant or mixtures thereof in an anionic to nonionic weight ratio of about 15: 1 to about 1: 1 (particularly preferred contains about 3: 1),

(b) about 0.1 to about 3 wt. ^ a & s = schmutsabiösenden alkyl cellulose ether, or Hydroxyalkylcelluloseäthers Hy = d roxyalkyl-alkyleellulo s eäthe rs,

(c) from about 0 to about 70% by weight of a builder component and

(d) the remainder are detergent auxiliaries and carriers.

Preferred agents according to the invention are by, a 3 weight ratio between anionic surfactant and dirt-dissolving ether from about 5? 1 to about 100: 1 and especially preferably characterized from about 10: 1 to 30: 1.

The detergents according to the invention contain two essential components, namely the mixture of anionic and nonionic surfactants} and the dirt-releasing cellulose ether.

The anionic surfactants used here are water-soluble sulfates or sulfonates of the general formula RX ^- M ⁺ , where R is an alkyl radical (including unsaturated alkyl radicals), alkylbenzene or ethoxylated alkyl, X is the sulfate or sulfonate and M is a counterion such as H ⁺ or a such cation; that the anionic surfactant is water soluble _? represent, for example, an alkali metal, ammonium, alkanolaminonium ion, or the like. The anionic surfactants used herein

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The present invention is based on the discovery that anionic surfactants such as the long chain alkyl = sulfates and long-chain alkylbenzenesulfonates can be combined with certain non-ionic surface active agents can produce highly detergent mixtures that have a significantly lower inhibiting effect on the Soil release behavior of the cellulose ethers exert than the long-chain anionic surface-active agents used alone. It is therefore now through a suitable choice of the mixture of anionic and non-ionic surface-active agents possible to provide detergents that both clean the fabric excellently and remove dirt in the wash cycle grant, whereby you need much smaller amounts of dirt-releasing cellulose derivative than previously imagined.

It has also been found that the finishing agents commonly used on polyester / cotton fabrics improve soil release properties the cellulose ether can significantly impair. When formulating optimal inventive Detergents are therefore preferred, both a preferred mixture of anionic and nonionic surface-active agents as well as using a preferred cellulose derivative in the manner described below.

Finally, it was found that the removal of Elektro = lytes (e.g. water-soluble builders) that Increase soil release capacity of the agents according to the invention can. The following are the highly preferred detergents with zeolite builders, those of water-soluble builders are essentially free.

The invention relates to detergents characterized by

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are thus the typical alkylbenzene sulfates and sulfonates, ülkylsulfate and -sulfonate and ethoxylated alkyl ethers = sulphates and sulphonates, ■ 'ie known in the ash detergent industry are. These anionic surfactants are after various known technical processes can be easily produced.

The anionic surfactants used herein are water-soluble detergents of the type described above. Mixtures of these anionic surfactants can also be used. Preferred anionic surfactants include the C, _O-G., G-alkylbenzene sulfate =, Q ₁ QG.g-Aikylbenzolsulfonate, Cjq-C jg alkyl sulfates, O. _t Q-ö. ^ - alkyl sulfonates, the ethoxylated G ^ -G ^ -alkyl = ether sulfates and the ethoxylated CQCg-alkyl ether sulfo = aafce.

. Gp ^ .g-alkyl benzene, the G, are especially preferred due to their superior Heiü2igungswirkung - G _i g alkyl sulfates and G. ₂ -G ^ g ethoxylated alkyl ether sulfates =.

The anioniseiien. Surface active agents can be used in the free acid hair dryer. Since the protective effect in. Aqueous oil ^? lotte used to be at basich.en yyh-nerten. is much higher, but are these surface active agents generally found in I ^? In the form of their water-soluble salts , as already mentioned, any gene ion that supplies a water-soluble salt of the anionic surface active is suitable; . Usually and preferably, however, the surface active ^{agents are used in J 1} OrE of the sodium salts for reasons of cost.

The following is a non-limiting list of anionic

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more surface-active, which are useful for the invention Surfactants are representative. As surface-active alkylbenzene sulfates and sulfonates are suitable for Example sodium dodecylbenzene sulfate, potassium dodecylbenzene = sulfonate, sodium tetradecylbenzenesulfate, triethanolammonium = tetradecylbenzenesulfonate, ammonium hexadecylbenzenesulfate, Ammonium hexadecylbenzenesulfonate, diethanolammonium octadecyl = benzenesulfonate and monoethanolammonium octadecylbenzenesulfo = nat. In the anionic surfactants based on alkylbenzene, the alkyl radical can either be straight-chain or branched be. The straight-chain radicals are preferred as the corresponding Compounds are biodegradable.

On an industrial scale, the alkylbenzene sulfates and sulfonates are easily produced from petroleum fractions which contain alkylbenzene mixtures with different chain lengths of the alkyl = substituents. Alkylbenzene sulfates and sulfonates obtainable from these mixtures are entirely suitable for the present purposes and are preferred for reasons of cost. The particularly preferred mixtures are those with a major proportion of derivatives with "heavy" or long-chain alkyl radicals. A particularly preferred anionic mixture consists of alkylbenzenesulfonates with an average of about 11.8 carbon atoms in the linear alkyl radical (abbreviation C _{11 Q} LAS).

The presently usable surface-active alkyl sulfates are available from petrochemical feeds and alcohol-based feeds. Specific examples of suitable Alkyl sulfates and sulfonates are decyl sulfate, Decyl sulfonate, dodecyl sulfate, dodecyl sulfonate, ietradecyl sulfate fat, tetradecyl sulfonate, hexadecyl sulfate, hexadecyl sulfonate, Octadecyl sulfate and octadecyl sulfonate. The particularly preferred

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Added alkyl sulfates and alkyl sulfonates are those whose Alkyl chain length is about 14 to 13 carbon atoms.

as in JT'all of the anionic surfactants on the base of Alk ^ -lbenzenes also the alkyl sulfates and -sulfonates usually used in -ö'orm water-soluble salts, with the sodium salt being most preferred. Specific examples of preferred alkyl sulfates and sulfonates are the sodium tetradecyl sulfate, ammonium tetradecyl sulfate, Sodium hexadecyl sulfate, triethanolammonium hexadecyl sulfonate, Monoethanolammonium octadecyl sulfate, triethanolammonium = octadecyl sulfate and sodium octadecyl sulfate.

As in the pail of anionic surfactants based on alkylbenzene Mixtures of alkyl sulfates and sulfonates can also be used here. Again, it is preferred that these mixtures have a major proportion with long-chain, that is to say C * 4 and longer, alkyl substituents, since these compounds are better detergents than the shorter chain ones Homologues.

For reasons of cost, preference is given to alkyl sulfate mixtures, in particular those obtained from alcohol mixtures such as coconut fatty alcohols and tallow fatty alcohols. A special one preferred alkyl sulfate mixture contains the so-called Tallow alkyl sulfates, and these contain larger amounts of longer-chain alkyl compounds than coconut alkyl = sulfates.

A third class of anionic surfactants useful for the purposes of the present invention comprises the ethoxylated alkyl ether sulfates and sulfonates. These

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* -11-

typically contain a C ..QC..g-alkyl radical which is ethoxylated with about 1 to about 20 and preferably 3 to about 10 ethoxy groups, which are in the terminal position of the molecule
are then sulfated or sulfonated. As with the alkyl sulfates, these ethoxylated compounds can be mixtures obtained from loading mixtures such as coconut alcohols or saline alcohols.

The ethoxylated alkyl ethers are typically used as salts, the sodium salt being preferred for reasons of cost will.

Examples of suitable ethoxylated alkyl ethers are listed below. (As usual, the degree of ethoxylation (EO) is indicated by a subscript. The degree of ethoxylation is usually given as the mean value for a given ethoxylated mixture): Sodium dodecyl (EO) sulfate, Potassium hexadecyl (EO), sulfate, iriethanolammonium octadecyl (EO) “sulfate, sodium _{decyl (E0) 5} sulfonate and diethanolammonium octadecyl (EOJ-ps ^ i ^ on ³ ^ ·

Mixtures of ethoxylated alkyl sulfates such as sodium coconut alkyl (EO) ₆ sulfate and sodium tallow alkyl (EO) g sulfate are particularly useful because they are commercially available and _{contain substantial amounts of the higher (C 14} and more), optimally detergent-effective alkyl ether sulfates .

The detergents according to the invention use a non-ionic = s surface-active agent, which serves to ensure compatibility between anionic surface-active and soil-dissolving To manufacture cellulose ethers. The non-ionic Surfactants are present in a weight ratio Anionics: Nonionics from about 15: 1 to about 1: 1 and preferably

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wise from about 4: 1 to about 1.5: 1 used to this compatibility effect exercise. It is believed that the mixed anionic / non-ionic surface-active Micellar structures formed in aqueous washing liquid do not interfere with the oils in an undesirable manner Loose ethers react in the same way as the "free" anionic surface-active conomers do.

The non-ionic surfactants used here are condensation products of relatively long-chain Ethylene oxide and primary alcohols, secondary alcohols or alkylphenols. Such non-ionic surfactants are well known. An important feature of the invention is that the nonionics mentioned are based on ethylene oxide base, those of shorter-chain ethylene oxide condensates and free alcohols, which are usually free in commercial mixtures of such materials serve to make the anionic surfactant compatible with the cellulose ether.

The compatibilizing surfactants used herein are nonionic surface active agents of the formula E "(EO), where E" is a straight-chain or branched one Hydrocarbyl radical from a primary or secondary alcohol with about 8 to about 20 and preferably about 10 to about 18 Carbon atoms or an alkylphenol radical whose Al = kylgruppe is straight-chain or branched and about. Has 6 to about 12 carbon atoms, EO is the abbreviation for ethylene = oxide group and χ represent the degree of polymerization of the ethylene oxide component, where χ is an integer of at least about 9 and preferably denotes the ratio of χ to Number of carbon atoms in the hydrocarbyl radical, that is

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the EO to hydrocarbon ratio is about 0.6: 1 to about 3s1.

It has been found that the more easily water-soluble nonionics, especially the Cj ^ -CLg (E0) "- bis (EO) ^ - compounds are particularly suitable for making the anionic surfactants compatible so that they can be used in combination with the cellulose ethers." Ethoxylated nonionic surface-active compounds of the formula £ "(OCH) ₂ CH ₂ ^ ₁ OCH ₂ CH ₂ OH, where E" is an alkyl = radical (including unsaturated alkyl) or alkylbenzene = radical and χ is an integer according to the above, are particularly suitable Representing importance as compatibilizing surfactants. Specific examples of such surface active agents are the compounds nC ₁₀ (EO) _g , nC ₁₂ (EO) ₁₂ , HC ₁₄ (EO) _15j, nC ₁₀ (E0) ₁₅ , ^ C ₁₂ (EO) ₂₀ , nC ₁₂ (EO) ₅₀ , sec -C ₁₀ (SO) ₉ , sec-C, _g (EO) ₁₂ , sec-) sec-ö _i0 (EO) ₅₀ , decylbenzene- (EO) ₁₂ , dodecylbenzene-

₁₅ , '. Cetradecylbenzene (EO) ₅₀ and the like.

Both the above pure nonionics and mixtures thereof are useful. The pure compounds are relatively expensive to produce, since the pure alcohol or the pure alkylphenol must be produced, followed ^by thoxylation and a second separation process to produce the pure compounds; therefore, mixtures of these compounds are preferred for reasons of cost which are suitable for the present purposes, for example, when essentially all of the lower ethoxylates and unreacted alcohol or unreacted alkylphenol, which are usually present in such mixtures, have been stripped off. For example, alcohol mixtures such as fallow alcohols or coconut alcohols can be used ätfaoxylieren an average degree of ethoxylation of about 9 to 12. The resulting product

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ORIGINAL INSPECTED

holds certain amounts of the shorter-chain ethoxylates such as the Example the triethoxylate, hexaethoxylate and the like as well as some unreacted alcohol-these short-chain Compounds are more volatile than the desired longer-chain ethoxylates and can be removed by distillation or other known! separation processes largely from the reaction mixture removed. The resulting stripped mixture is then of the desired longer chain alcohols enriched and is preferred for present purposes.

Numerous ethoxylated materials, even those with degrees of ethoxylation of up to 30 and more, can be used as compatibilizing honionics according to the present invention. It is desirable that all of the surface-active components in the finished detergent formulation contribute to its cleaning ability. It is known that certain ethoxylated nonionics are particularly useful for removing oily soil from synthetic fabrics such as polyester, while other nonionics do not have this property. For this reason, preference is given to choosing non-ionic surface-active agents which not only make the anionic surface-active agents compatible with the dirt-dissolving ether, but which also make a noticeable contribution to the overall cleaning capacity of the finished detergent. In general, the ^c -jq ~ " ^c -i5 (EO) _0. To (EO). ^" Ethoxylates are preferred, since they are both useful for making the substance compatible and are detergent-active surfactants.

Among the preferred detergent-effective and compatible ones Surfactants include the condensation products that contain about 9 to about 12 ethylene oxide units and primary or

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secondary C ₁₀ to C ₁ alcohols and alkylphenols whose alkyl substituent has about 6 to about 9 carbon atoms. The alcohol ethoxylates are preferred to the alkylphenol ethoxylates for reasons of cost and because of their biodegradability.

Specific examples of these preferred nonionics are: nCQ (£ O) _g ; Cg ^ Q "stripped" alcohol (S0) _Q such as Dobanol 91-3 (Shell) _; Dobanol 91-12 and Neodol 01 E ₁₂ (C _10-1 ^ alcohol, average 12 EO groups, Shell).

The dirt-releasing component consists of etherified Cellulose. The basic structure of the cellulose ethers provided according to the invention corresponds to the following formula:

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where η is an integer from about 100 to about 10,000 and R ^{1 is} an alkyl, hydroxyalkyl or mixed alkyl and hydroxyalkyl radical of the type described below. Suitable alkyl radicals are the methyl, ethyl, propyl, butyl, pentyl, isobutyl, hexyl, nonyl radical and the like. Preferred alkyl radicals are the methyl, ethyl, propyl and butyl radical, with the methyl radical being most preferred for reasons of cost because of its ease of manufacture and behavior. Preferred hydroxyalkyl radicals are the hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutyl radical, of which the hydroxybutyl radical is most preferred. In particularly preferred, commercially available products, R ¹ consists of mixtures of methyl and hydroxybutyl.

Processes for the production of the cellulose ethers are known and do not form part of the invention. In the preparation of of the soil-releasing alkyl cellulose ethers according to the present invention, the hydroxyl groups of the anhydro = glucose units of cellulose with an alkylating agent implemented, the hydrogen of the hydroxyl groups being replaced by alkyl substituents. The number of substitutes Alkyl groups can be given in percent by weight or as the mean value of the alkyl (i.e. alkoxy) groups per anhydroglucose units, i.e. by the Degree of substitution (DS-alkyl). All three are available substituted positions on each ArLhydroglucose unit, the DS-alkyl is designated by (3); are If 2 hydroxyl groups are substituted on average, the DS-alkyl is indicated by (2), etc. A similar nomenclature is used to define the hydroxyalkyl and hydroxy = alkylalkyl cellulose ethers. When describing hydroxy = alkylalkyl cellulose derivatives is the degree of substitution

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given for both types of substituents.

In the technical process for the production of alkyl = cellulose ethers, for example, is simply the respective alkyl halide, for example methyl chloride, with a GeIIu = loose raw material of the type defined below brought into contact with alkaline conditions. (Of course, those used to make the cellulose ethers can be used Alkyl halides minor amounts of others, of the selected one Alkyl halide. contain various alkyl halides. The resulting cellulose ethers can be smaller Amounts of mixed alkyl groups exhibited what for the purpose of the invention is not important). This gives a DS-alkyl below 2 and generally from about 1.5

Cellulose ethers with higher DS-alkyl can be obtained by exhaustive Alkylation of cellulose with an alkyl halide such as methyl chloride and alkali, preferably sodium hydroxide, in a pressure vessel in a manner analogous to that of the cellulose derivatives with lower DS-alkyl. You can Simply repeat the alkylation and continue until the product with a higher DS- is obtained. In any case, the The progress of the alkylation reaction is monitored periodically by taking samples of the reaction product and the AIk = degree of oxylation determined in a known manner.

The exhaustive alkylation results in the formation of cellulose ethers with a DS-alkyl in the range of about 1.7 to about 3.0 (theoretical maximum). A group of highly preferred alkyl cellulose ethers has ^{the methyl radical as substituent E 1} and is characterized by a DS-methyl in the range from about 2.0 to about 2.7.

Also the production of hydroxyalkyl-alkyl-cellulose ethers

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takes place according to known methods. In a typical procedure becomes a cellulose starting material with sodium hydro = xide solution swollen, whereby one obtains alkali cellulose, which then with an alkyl halide (preferably methyl chloride) and an alkylene oxide (preferably butylene oxide). The DS-alkyl and DS-hydroxyalkyl of the resulting Gelulose ethers can be determined via the reaction stoichiometry, reaction time and reaction temperature controlled in a known manner will"

Hydroxyalkyl cellulose ethers can be prepared by the cellulose starting material with an alkylene oxide and alkali treated in a manner known per se, usually at elevated temperatures and pressures.

The cellulose starting materials used for the production of the soil-releasing ether can be made from cellulose, for example or cotton linters. Under the strict alkaline conditions of the etherification reaction, the Degree of polymerisation (the whole number η in the above formula) usually reduced to 100 to 2000. This is of no essential importance for the purposes of the present invention.

Examples of soil-dissolving cellulose ethers suitable according to the invention are: methyl cellulose, DS-methyl 1.5; Ethyl = cellulose, DS-ethyl 1,2; Methyl ethyl cellulose, DS-methyl 1.0 * DS ethyl 0.7; Hydroxyethyl cellulose, DS-hydroxyethyl 1,2} Hydroxypropyl cellulose, DS-hydroxypropyl 1.5 »methyl-hydro = xyethyl cellulose, DS-Iäethyl 1.5, DS-hydroxyethyl 0.1; Uethylhydroxyethyl cellulose, DS-methyl 1.5, DS-hydroxyethyl 0.5; and butyl cellulose, DS-butyl 1.5.

The cellulose ethers used here are water-soluble and have a negative temperature coefficient of

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Marked solubility. Because of their polymeric state and the ability to intermolecular linkage via the side chain substituents increase cellulose ether the viscosity of aqueous solutions, especially in concentrations of about 2? £. The solution viscosity of CeI = Lulose ether is not important in the manufacture of granular detergents, because the ethers are present in the later washing solution in very small concentrations. In making more fluid In detergent according to the present invention, the concentration of the ether in the solution can be high enough so that this viscosity creates difficulties. Liquid detergents that are easy to pour and easy to use are desirable. to measure and which do not have a gelatinous or syrupy consistency. For the manufacture of these liquid detergents a cellulose ether of the type described above with a solution viscosity below about is preferred 250 cP. The solution viscosity of the cellulose ether used in liquid detergents is preferably in the range from about 20 to about 200 cP (measured on a 2 percent by weight aqueous solution at 32 ° C).

By selecting the surfactants from a narrow fraction as described, the dirt dissolving power of the Detergents which contain essentially any soil-releasing ether of the type described above, generally improved. Bas means that the selected surfactants, which are used according to the invention, which Dirt removal properties of cellulose ethers (measured by the deposition on fabrics made from pure distilled water) significantly less hindering than other members of the general class of these surfactants outside of the specified range. That is not to say, however

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become that all dirt-dissolving ethers with regard to their Behavior on fabrics are equivalent, especially not with polyester and polyester / cotton mixtures. .Certain üellulose ethers give less dirt like others, even when you get them from distilled water in the absence of interfering surfactants Applied textiles. For example, certain hydroxypropyl cellulose ethers are inherently inferior with regard to this their ability to dissolve dirt, even when applied to the fabric from an aqueous medium in the absence of surface active agents ^ compared to methyl hydroxybutyl cellulose ethers with analogous application. This difference carries over of course to the above-mentioned surfactants Mixtures. In order to achieve optimum soil release properties, certain of the above are preferably selected disclosed soil release ethers for use in combination with the surfactants of those disclosed above selected group.

It has also been found that the dirt-releasing properties of all cellulose ethers are better when they are used in combination with the preferred surfactants disclosed above, compared to use in combination with surface active agents outside of this Great, but that this property through textile finishing agents is adversely affected. It has now been found that certain cellulose ethers work well, even when treated Polyester / cotton fabrics. There are therefore particularly preferred versatile cellulose ethers for use in combination with the selected group of surfactants are suitable for both polyester and finished and unfinished blended fabrics have the property =. to issue the dirt repellent »

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According to the invention preferred alkyl cellulose ethers are Cj to C, alkyl ethers, in particular Metb.ylatb.er, with a DS-alkyl from about 1.2 to about 2.9 alkyl ethers with a ' DS-alkyl from about 1.3 to about 2.0 are commercially available and are particularly useful members of this class dirt-repellent ether.

Hydroxyalkyl cellulose ethers preferred according to the invention are hydroxyethyl, hydroxypropyl and hydroxybutyl cellulose loose ether with a DS hydroxyalkyl of about 1.2 to about 2.9 and preferably about 1.5 to about 1.7. Considered as a total group, the hydroxyalkyl cellulose ethers have a slightly lower dirt dissolving power than the alkyl or mixed hydroxyalkyl-alkyl cellulose ethers. Nevertheless they are suitable for the purposes of the invention and. offer the advantage of a slightly higher solubility in water the other cellulose ethers, which have corresponding advantages in liquid formulations.

The hydroxyalkyl-alkyl-gelulose ethers, especially those with a DS hydroxyalkyl of at least about 0.01 and a DS-alkyl of at least about 1.0, preferably with a DS-alkyl of about 1.3 to about 2.5 »represent one particularly preferred class of ethers that can be used according to the invention, since they have particularly good dirt-dissolving properties own. Many such products are commercially available.

Preferred hydroxyalkyl-alkyl cellulose ethers are those their DS-hydroxyalkyl at least about 0.05 and. whose DS-alkyl is at least about 1.0, and whose total degree of substitution DS- (alkyl + hydroxyalkyl) is at least about 1.05, and preferably at least about 1.5. Particularly Hydroxyalkyl-alkyl-cellulose ethers are preferred

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with alkyl radicals with 1 to 4 carbon atoms and in particular the methyl radical in which the hydroxyalkyl radicals consist of hydroxyethyl, hydroxypropyl or hydroxybutyl.

In making more versatile laundry detergents that can do both For finished and non-finished fabrics, especially polyester / cotton knit, the one should choose Cellulose ethers preferably from the class of the alkyl or hydroxyalkyl-alkyl compounds. They are the most versatile Alkyl cellulose ethers with relatively high DS-alkyl in the range from about 1.7 to about 2.7 · These high DS-alkyl cellulose ethers can be readily prepared according to the above exhaustive alkylation procedures are presented. Characterized by a DS methyl in the range from about 1.8 to 2.2 Ethyl cellulose ethers are easily available and are particularly preferred according to the invention.

Also with the hydroxyalkyl-alkyl-cellulose ethers are higher substituted representatives of the class, in particular with higher DS-alkyl, the versatile derivatives. Preferably those ethers with a DS-alkyl in the range are grounded from about 1.7 to 2.7 and in particular from 1.8 to 2.2, the methyl radical being the preferred alkyl substituent. Within of this preferred class of cellulose ethers, DS-hydroxyalkyl is less critical than DS-alkyl, and it falls in a range from about 0.01 to 1.0 and especially preferably from about 0.06 to 1.0. The most preferred hydroxyalkyl substituent is the hydroxybutyl radical.

Methyl-hydroxy = is particularly preferred according to the invention butyl cellulose with an average DS-methyl of 1.8 to 2.2 and an average DS-hydroxybutyl of 0.08, the un- · The trade name "Methocel HB" is available.

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Other preferred ethers are ethyl-hydroxyäthylcellu = loose, OS-ethyl 1.7, DS-Hj-hydroxyethyl 0.9; and a methyl = hydroxyethylellulose, BS-Ujethyl 1.7, D3-hydroxyethyl 0.09.

As already mentioned, the solution viscosity of the cellulose ethers is not critical for their behavior. However, this parameter is useful in combination with DS-alkyl and DS-hydroxyalkyl for determining the versatile cellulose ethers which are particularly preferred according to the invention. The solution viscosity (in 2-form aqueous solution) of this cellulose = loose ether is in the broad range from about 100 to 25,000 cP and in particular from 400 to 15,000 cP.

Of course, the usual, anionic substi = fall Cellulose ethers such as carboxymethyl cellulose are not included in the cellulose ethers intended according to the invention; These According to the invention, anionic cellulose derivatives are not intended as soil-dissolving ether components, but they can they are used in detergents in smaller quantities because of their well-known properties as visual suspension agents, Carriers, thickeners and the like.

The detergents according to the invention can optionally contain any detergent builders which are usually provided for detergents. The detergents according to the invention can contain from about 1 to about 70% and preferably from about 25 to about 65% by weight of builder. To. Suitable for the present purposes builders include all conventional ^a BTganischen and organic water-soluble builder salts as well as various water-insoluble builders (so-called "seeded" builders).

To. suitable inorganic builders belong to the

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Example water-soluble phosphates, pyrophosphates, Ortho = phosphates, polyphosphates, phosphonates, carbonates, poly = hydroxysulfonates, silicates, polyacetates, carboxylates, poly = carboxylates and succinates. Special examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, phosphate and hexametaphosphate. The polyphosphonates include especially the sodium and potassium salts of ethylene = diphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Examples of those containing phosphorus Builders can be found in US-PSS 3,159,581, 3,213,030-, 3,422,021, 3,422,137, 3,400,176 and 3,400,148. Sodium tripolyphosphate is a particularly preferred water soluble one inorganic builder.

Phosphorus-free chelating agents can also be used as builders will.

Specific examples of phosphorus-free inorganic builders are the water-soluble inorganic carbonate, bicarbonate and silicate salts. They are especially useful Alkali metal, for example sodium and potassium carbonates and bicarbonates.

Water-soluble organic builders can also be used. For example, the alkali metal, ammonium and substituted ammonium polyacetates, -carboxylates, -polycarboxylates and -polyhydroxysulfonates for the inventive Purposes as builders useful. Specific examples of polyacetate and polycarboxylate framework salts are the sodium, potassium, lithium, ammonium and substituted Ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid,

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Benzene polycarboxylic acids, and citric acid.

Particularly preferred phosphorus-free builders (organic and inorganic) are sodium carbonate, sodium carbonate, Sodium silicate, sodium citrate, sodium oxydisuccinate, Ua = triummellitate, sodium nitrilotriacetate, sodium ethylenediamine = tetraacetate and mixtures thereof.

Further particularly preferred organic builders are the polycarboxylates of US Pat. No. 3,308,067. Examples thereof are the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaeonic acid, Mesaconic acid, fumaric acid, aconitic acid, citraconic acid and Methylenemalonic acid.

Further preferred builders include those which are water-soluble Salts, especially the sodium and potassium salts, of carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, cis -cyclohexane hexacarboxylic acid, cis — Cyclopentantetra = carboxylic acid and phloroglucinotrisulfonic acid.

A particularly preferred water-soluble organic builder is sodium nitrilotriacetate. ·

Further builders which can be used in the agents according to the invention are water-soluble compounds, which with the cations of the water hardness in combination with a crystallization- seed, which provides growth sites, form a water-insoluble reaction product. Sole marriage "germ-containing builders" (seeded builder) are known from BE-PS 798 856.

The germ-containing builders which can be used according to the invention contain a crystallization nucleus with a large part

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marriage dimension less than 20 microns and preferably having a particle diameter of from about 0.01 to about 5 microns, in combination with a material useful in forming a water-insoluble reaction product is capable of free metal ions.

Numerous sex builders, for example the water-soluble ones Carbonates, precipitate water hardness cations and thus exercise the structural function. Numerous precipitating builders, which are used in detergents, however, unfortunately reduce the content of free metal ions in the washing liquid not quickly, so that these builders only with the organic detergent and the dirt in terms of free Metal ions compete. As a result, some of the free metal ions are removed from the solution, others rea = however, yaw with the organic detergent and soil, so that the detergency is reduced. The usage of the crystallization nucleus increases the rate of precipitation of the metal hardness, so that the hardness ions are removed, before they can adversely affect washing behavior.

When using a material which is capable in combination with a crystallisation seed for forming a water-insoluble product with free Itetallionen, the concentration of free metal ions in an aqueous wash liquid within about 12ü3ek _e uf less than 0.4S ° dH be lowered · The preferred nucleating containing Builders even reduce the free hardness to less than 0.09 ° dH within about 30 seconds.

Preferred germ-containing builders consist of: A water-soluble material that is capable of having bivalent ones and polyvalent metal ions such as calcium, magnesium and iron ions. A reaction product having a solubility in Viasser of less than about 1.4 χ 10 "" wt. ^ (At 25 ° C)

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and a crystallization nucleus (0.001 to 20 microns Diameter), which consists of a material which does not completely dissolve within 120 seconds in water of 25 G solves.

Specific examples of compounds capable of forming the water-insoluble reaction products are the water-soluble ones Carbonates, bicarbonates, sesqui carbonates, silicates, aluminates and oxalates. For reasons of convenience and cost the alkali metal salts, especially the sodium salts, preferred.

The crystallization nucleus used in these nucleated builders consists preferably of calcium carbonate, calcium or magnesium oxalates, barium sulfate, calcium, Magnesium or aluminum silicates, calcium or magnesium = oxides, calcium or magnesium salts of fatty acids with 12 to 22 carbon atoms, calcium or magnesium hydro = xides, calcium fluoride or barium carbonate. Specific examples germ-containing builders are 3: 1 mixtures (weight) of sodium carbonate and calcium carbonate of 5 micron particle diameter, 2.7: 1 mixture of sodium sesqui carbonate and calcium carbonate with 0.5 * particle diameter, 20: 1 mixtures of sodium sesqui carbonate and calcium hydroxide with 0.01 micron particle diameter and 3: 3: 1 mixtures of sodium carbonate, Sodium aluminate and calcium oxide with 5 micron particle diameter.

A germ-containing builder made from a mixture of sodium carbonate and calcium carbonate is particularly preferred. A particularly preferred builder of this type consists of a 30: 1 to 5: 1 (parts by _{weight Na 2} CO _{5 : CaCO 5} ) mixture of sodium carbonate and calcium carbonate, in which the calcium carbonate has an average particle diameter of 0.01 to 5 microns.

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Other useful builders are the various im essential water-insoluble materials capable of reducing the hardness content of washing liquids are, for example, by ion exchange processes. Examples of these builders are the phosphorylated wipes according to U.S. Patent 3,424,545.

As already mentioned, avoiding Elek = achieves trolytes (e.g. water-soluble framework salts) have a further beneficial effect on dirt-dissolving power of the cellulose ethers / surface-active mixtures according to the invention. It is therefore particularly advantageous to provide agents which contain the preferred surface-active agent, CeIIu = contain loose ether and a builder, which is an important electrolyte (i.e. insoluble in water) is

The complex aluminosilicates, that is to say zeolite-like substances, are particularly suitable builders for the purposes of the invention, since they are insoluble in water and easily soften the water _, i.e. eliminate the C a hardness. Both naturally occurring and synthetic zeolites, in particular zeolite A and hydrated zeolite A, can be used as builders / plasticizers, and they do not hinder the cellulose ethers. Zeolite A and a process for its preparation is described in US Pat. No. 2,882,243 «

The detergents according to the invention can be any and detergents contain commonly used additives and carriers. For example, fragrances, optical Bleaches, fillers, anti-caking agents, fabric softeners, and the like can be added to the to bring about the benefits brought about by the use of these substances in detergents.

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Also, the perborate bleaching agents commonly used in European laundry detergents can be present in the detergents according to the invention. 3They are mixed in dry.

In addition, enzymes, especially those used in detergents, can be used stable proteolytic and lipolytic enzymes, dry admixed to the detergents according to the invention will.

As fillers, granular "detergent materials such as Sodium sulfate can be added. Water and water / alcohol— Mixtures (especially 20: 1 to 10: 1 mixtures of water and ethanol) are suitable carriers for liquid detergents according to the invention.

The soil release capacity of the detergents according to the invention is compared to a typical, difficult-to-remove greasy one Dirt, namely dirty engine oil, tested. This dirty engine oil test (DHO test) is as follows carried out: pieces of fabric (polyester or polyester / cotton) are washed in an aqueous bath, which is detergent Amounts (approx. 200 ppm) of the respective mixture of anionic and non-ionic surface-active agent in combination with a "typical" builder / elec = trolyte mixture (600 ppm sodium tripolyphosphate, 250 ppm sodium sulfate, 70 ppm sodium silicate) and a cellulose = contains ether in various concentrations. After washing / treatment with the dirt-releasing ether, the fabric samples are removed stained with known amounts of contaminated engine oil and repositioned in a commercially available detergent with phosphate = builders (bath concentration 0.12? ») and the dirt-releasing agent Ether (12 ppm in the bath) · As an alternative, the samples are again washed with the mixture of surfactants washed. The removal of dirt can be determined visually, but it is preferable to compare gravimetrically

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with comparison samples (no treatment with dirt-removing Polymer).

The IMO test performed in the presence of surfactant, builder and electrolyte is representative of the conditions under which fabrics heavily stained with greasy Sehmutz are treated in household washing machines. The H / tO test indicates that the agents which the invention intended mixtures of nonionics and anionics and cellulose ethers, the tissue one give a much better dirt-repellent finish than similar agents in which the non-ionic surface-active Funds are missing.

Granular detergents are conveniently made by removing all of the components apart from the cellulose ether and the non-ionic surfactants in an aqueous Slurry is combined and spray-dried in the usual manner to obtain homogeneous granules. Cellulose ether and nonionic are then added to these granules. Liquid laundry detergents are made by the components in a liquid carrier, typically water or water / alcohol (e.g. methanol, Ethanol, isopropanol) mixed. Preferred liquid carriers are water and 100: 1 to 10: 1 mixtures (weight) of Water and ethanol.

Granular detergents are typically used in amounts of 1 to 1 1/2 cups in 57 to 76 liters of water (concentration about $ 0.12). Liquid agents are typically employed in an amount of from 0.25 to 0.5 cups. Typical concentrations of surface active agents in the washing liquid are approx. 200 ppm (USA, to be loaded from above Machine), while the builder concentration is around 600 to 800 ppm and the concentration of the soil

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send ether amount to about 12 to 50 ppm. Larger or smaller amounts can be used, depending on the size of the consumer, the type of fabric and the degree of soiling. In general, the remedy is used in a weight ratio of surfactants to tissue weight of υ _? ϋ05: 1 to 0.01: 1 on.

From the above it follows that the invention envisaged mixtures from the visual ionic point of view. and anionic surfactants are formulated «that one -Sas intolerance problem overcomes that between Cellulose ethers and anionic surfactants occur. Although Honionie essentially eliminates this problem., It is preferable to use extremely high concentrations of anionic surfactants with extremely low concentrations of glulose ethers avoided. the Means are therefore preferably so forsrallertg that one Weight ratio between anionic surface-active and gelulose ethers in the range of about 5 x 1 to about 100: 1 and particularly preferably from about 10: 1 to about 30: 1, in order to avoid the non-ionic compatibilizing surfactants "suppressed" and the effect of the oleellulose ether is disturbed.

Example I.

Sin granular detergent with phosphate-G-erliststoff en consists Composition as follows

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Ingredient # (wt.)

C ₁₁ ο alkylbenzenesulfonate, sodium salt 15.0

5.0

läethocel HB 1500O ⁺ " ¹ " 1.0

Sodium tripolyphosphate 33.0

Sodium silicate (water soluble) 10.0

Sodium sulfate 25.0

minor additives (fragrance, opt.

Brightener, water and the like) rest

⁺ Mixed CQCg-alkylbenzenesulfonates, average alkyl = chain length 11.8

⁺⁺ methylhydroxybutyl cellulose, DS-methyl approx. 2, DS-hydroxy = butyl approx. 0.08; 2 ^L / o solution viscosity 15000 cP, manufacturer Dow Chemical.

The agent according to Example 1 is prepared by spray-drying an aqueous mixture which contains all of the constituents (with the exception of C ₁₀ (EO) ₉ and Methocel HB 15000) to form granules. These granules are then _{sprayed with the C 10} (EO) ₉ and the Methocel HB 15000 is added to the formulation as a dry ingredient.

The detergent according to * Example "= Ϊ is used in a concentration of 0.12% by weight in the aqueous extinguishing liquid for washing used by textiles. The agent has a good overall cleaning effect versus oily and particulate! Dirt, and the fabrics are covered with an oily dirt repellent Finish (DMO-Iest) provided.

Example II

A detergent with a high build-up and enzyme content,

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especially for European household washing machines are composed as follows:

component

C ... ο linear alkylbenzenesulfonate, sodium salt 20.0

Tallow alkyl sulfate, sodium saltζ 5.0

mixed tallow alcohol (SO) ₂ Q ethoxylate 5.0

Methocel HB 15000. 1.0

Sodium tripolyphosphate 65.0

Enzyme ⁺⁺ 0.5

minor additives (opt. brightener, water, fragrance and the like) rest

⁺ Tallow-based alcohol, ethoxylated to an average of ethylene oxide units and vacuum stripped to strip off essentially all of the shorter ethoxylates and unreacted alcohols.

⁺ Proteolytic enzyme from Thermoaetinomyces vulgaris ATCC 15734.

The granular 'detergent according to Example II is like the detergent of Example I, v / o in which the enzyme is admixed with the spray-dried granular material.

The detergent from Example II is used in a concentration of 0.24% by weight in an automatic washing machine with a front loading at an average water temperature of 90 ° C for washing a load from equipped and not Finished polyester and polyester / cotton fabrics are used. The fabrics are given a uniform dirt-repellent finish Equipment.

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In the detergent of Example II, the Methocel HB 15000 by an equivalent amount of methyl cellulose from the average DS-methyl 2.0, by methyl hydroxyethyl cellulose from average DS-methyl 2.0 and DS-hydroxyethyl 0.2 or replaced by methyl ethyl cellulose from DS ^ ü ^ ihd DS ethyl 0.5, excellent dirt-repellent finishes are also obtained.

Example III

A detergent with a phosphate-free builder is composed as follows:

component $> (Weight)

Setradecylbenzenesulfonate,

Sodium salt ^{10> 0}

Sulphated tallow alcohol (EO) ₆ 10.0

Methocel HB 15000 1.0

NeOdOL ₀₁ E ₁₂ ⁺ 5.0

Nitrilotriacetate, i-crin sodium salt 25.0

soluble sodium silicate 10.0

Sodium sulfate 35.0

minor additions rest

See definition above.

The granular detergent according to Example EL becomes like the detergent from Example I. When using in an amount of 1 1/2 cup in a usual, top down too Loading machine delivers the detergent from example III good cleaning properties, and it imparts to fabrics Made of a polyester / cotton blend with a dirt-repellent finish.

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ΐϋξΐη
If, in the detergent of Example III, the nitrilotriacetate is replaced by an equivalent amount of a builder made from hydrated zeolite particles (diameter about 1 micron), equivalent results are obtained.

If one also replaces the Ni = in the Viaschmittel of Example III trilotriacetate by an equivalent amount of a builder, that of a 15: 1 (weight) mixture of sodium = carbonate and calcium carbonate particles (mean particle size 1.0 micron), equally good results are obtained.

Befpiel IY

A liquid detergent, which contains the dirt-releasing cellulose ether, is made up as follows:

component $> (Weight)

C ₁₁ Q alkyl benzene sulfonate 10.0

Triethanolammonium salt

Methocel HB 15000 0.5

stripped C _1O (EO) "10.0

Diet hanolamine 3.0

Ethyl alcohol 10.0

Water - Eest

The detergent of Example IV is made by mixing the Get components. It is used in a cycle of 1/4 cup in a standard, top-loading washing machine. The detergent will have a good cleaning effect at the same time, polyester and non-iron polyester / cotton fabrics are given a dirt-repellent finish.

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Claims (26)

Claims Detergent, characterized by (a) about 5 to about 65 wt. ⁰ Jo a group consisting of a mixture of surface-active component which is a water-soluble anionic surfactant or mixtures thereof and a water-soluble nonionic surfactant or mixtures thereof in Gewicht3verhaitni8 of Anionic to Nonionic from about 15s1 to about 1 : 1 contains, (b) about 0.1 to about 3 wt. $> of a soil release Älkylcellul-oseäthers, Hydroxyalkylcelluloseäthers or hydroxyalkyl alkyl cellulose ether, (c) from about 0 to about 70 weight percent of a builder component and (d) the remainder detergent additives and carriers. 2. Detergent according to claim 1, characterized in that the weight ratio of anionic surfactant to soil release ether in the range of about 5: 1 to about 100: 1. 3. Detergent according to claim 2, characterized in that the non-ionic surface-active agent aua primary Gq- to Cp ^ -Alkoholäthoxylaten with 9 to 30 ethoxy groups, secondary Cg- to C ₂₀ -AIkOholäthoxylaten with 9 to 30 ethoxy groups or Cg- to C. ^ -Alkylphenoläthoxylaten with 9 to 30 ethoxy groups, the non-ionic surface-active agent is characterized by a ratio of ethylene oxide = units to hydrocarbon of about 0.6: 1 to about 3: 1. 4. Detergent according to claim 3 »characterized in that the anionic surface-active agent from ^G io" * ^ i8 "~ 609842/103 3 Alkylbenzenesulfates, C ₁ ACg-alkylbenzenesulfonates, CQ-C.jg-alkylsulfates, CQ-CLg-alkylsulfonates, ethoxy = lated C.-QC.g-alkyl ether sulfates or ethoxylated GQ-Cg-alkyl ether sulfonates or mixtures thereof. 5. A detergent composition according to claim 4> wherein the anionic surfactant is selected from the alkali metal, ammonium or alkanolammonium salts of C ₁ Q-to-linear Cjg-alkyl-benzene sulphonates or is mixtures thereof. 6. Y / ash means according to claim 4 »characterized in that the anionic surface-active agent from the alkali metal, ammonium or alkanolammonium salts of C.q-Cjg-alkyl sulfates or mixtures thereof. 7 · Detergent according to claim 4, characterized in that the anionic surface-active agent from the alkali = metal, ammonium or alkanolammonium salts of ethoxy = lated C-Q-C-g-alkyl ether sulfates or mixtures thereof .consists. 8. Detergent according to claim 2, characterized in that the soil-releasing ether is an AlkyleelIuIοseäther. 9. Detergent according to claim 3, characterized in that the alkyl cellulose ether consists of methyl, ethyl, propyl or butyl cellulose ether. 10. Detergent according to claim 9 »characterized in that the alkyl cellulose ether from a methyl cellulose ether with a DS methyl ranging from about 1.0 to about 3 feet consists. 609842/1033 11. Detergent according to claim 10, characterized in that . that the methyl cellulose ether has a DS-methyl of about 1.8 to about 2.2, 12. Detergent according to claim 2, characterized in that that the dirt-releasing iither consists of a hydroxyalkyl = cellulose ether. 13. Detergent according to claim 12, characterized in that that the hydroxyalkyl cellulose ether is made from hydroxymethyl, Hydroxyethyl, hydroxypropyl or hydroxybutyl cellulose = ether exists. 14 Ash detergent according to Claim 2, characterized in that that the soil-removing ether from a hydroxyalkylalkyl cellulose ether consists. 15 detergent according to claim 14, characterized in that that the hydroxyalkyl substituent in the hydroxyalkyl-alkyl cellulose ether is the hydroxymethyl, hydroxyethyl, hydroxypropyl or hydroxybutyl radical, while the The alkyl substituent is independently a methyl, ethyl, propyl or butyl radical. 16. Detergent according to claim 15, characterized in that that the hydroxyalkyl-alkyl-cellulose ether is made from methylhydroxybutyl cellulose consists of a DS methyl in the range from about 1.7 to about 2.7 and a DS-hydroxybutyl in the range of about 0.01 to about 1.0 is marked. 17 · Vüaschmittel according to claim 16, characterized in that that the DS-methyl of the gelulose ether is about 1.8 to is about 2.2. 609842/1033 18. VYaschnittel according to claim 17, characterized in that that the DS-hydroxybutyl of the cellulose ether is about 0.06 to about 1.0. 19 »Granular agent according to claim 2, characterized by about 15 to about 65 percent by weight of a water-soluble Detergent builder. 20. Detergent according to claim 19 »characterized by an inorganic detergent builder. ο Detergent according to Claim 20, characterized in that that the inorganic builder from sodium tripoly = phosphate. 22 "detergent according to claim 19" characterized by an organic ash builder. 23. A detergent composition according to claim 22, characterized in that _a ß d of the organic builder from Natriumnitrilo = consists triacetate. 24- detergent according to claim 2, characterized by about 15 to about 65 wt. £ of a germ-containing builder. 25 detergent according to claim 24, characterized in that that the germ-containing builder from a 30: 1 to 5ϊ1 (Weight) mixture of sodium carbonate and particulate matter Calcium carbonate with an average particle diameter from 0.01 to 5 microns. 609842/1 033 26. Detergent according to claim 2, characterized by about 15 to about 65 wt. ^ Of a substantially water-insoluble refractory. 27. Detergent according to claim 26, characterized in that it contains a zeolite-like material as a builder. For: The Procter & Gamble Company Cincinnati, Ohio, V.St.A. Dr H. Chr.Beil Lawyer 609842/1033 ^v COPY