DE2411466A1 - LOW PHOSPHATE OR PHOSPHATE-FREE DETERGENT AND METHOD OF USING IT - Google Patents

Description

Low-phosphate or phosphate-free detergent and method for its use "

As is known, contain detergents and detergents to be used in the household Cleaning agents often contain larger amounts of condensed phosphates, especially triphosphates. These should be the Binding hardness components of tap water complex and the cleaning power of the capillary-active washing active substances increase. However, the public is aware of the phosphates that enter rivers and lakes via sewage considerable influence on the eutrophication of the waters, which leads to an increase in the growth of algae and of oxygen consumption. The aim is therefore to eliminate the phosphate from the detergents or at least to significantly reduce its proportion.

The substitutes proposed so far, such as strong alkalis, nitrogen-containing sequestering agents such as nitrilotriacetate and ethylene diamino tetraacetate or polyanionic ones Polymers, e.g. water-soluble \ polyacrylates and salts of Copolymers of unsaturated polybasic carboxylic acids and vinyl compounds, for their part, have numerous disadvantages on, be it that they wash insufficiently, change the pH value of the sewage, are not biodegraded or for their part, eutrophicate the waters or prevent the flocculation of suspended matter in the sewage treatment plants. The possibility, Tap water intended for washing uses ion exchangers to soften it, as in commercial ones Laundries happen a lot, but in private households they usually fail because of the cost issue. Since also

409840/0933

2A1U66

Henkel & de GmbH μ «, qr _w mx,» «! ^ D 4631/4715/4770

When the exchanger is regenerated, considerable amounts of salt get into the wastewater, such a solution appears problematic.

In DOS 1 617 058 the proposal was already made to use flat structures made of phosphorylated cotton to soften the water during the washing process. However, this does not represent a solution to the problem, since the phosphoric ester groups are relatively easily hydrolyzed and thus phosphate ions can get into the wastewater. The capacity of the exchanger is also relatively low, which is why considerable amounts of it, for example 25 % based on the laundry to be cleaned, are required in hard water. The other cellulose derivatives mentioned in the same proposal, namely sulfethoxy cellulose, carboxymethyl cellulose and the succinic acid half-ester of cellulose, have an even lower calcium binding capacity and should therefore not be considered for practical use.

In DOS 2,055,423, water-insoluble cation-exchanging polymers, specifically crosslinked copolymers of polyacrylic acid with divinyl compounds, for example divinylbenzene and deiren sulfonation products, are proposed for the same purpose. They are used in powdery to granular form (grain size 0.02 - 1.2 mm), namely they are added directly to the washing powders or filled into water-permeable containers or bags beforehand and then added to the washing liquor in this form. However Bs can be demonstrated experimentally that dia though, albeit slowing in containers packed ion exchanger, which engage in the hardness of the wash liquor to tie assets in these Fora no washing effect even not if the exchanger container will provide for effective flooding. A sufficient effect to remove cords

409840/0933

HENKEL & CLE GMBH SU 3? «R foLnfonm.ld ™ ,, D 46J 1 4715/4770

can only be seen if the exchanger particles can come into direct contact with the textile fiber during the washing process, ie if the powdery to granular exchanger material is added directly to the detergent or the washing liquor. However, when the exchange resins specified in DOS 2,055,423 are used, this procedure has a number of serious disadvantages. Exchanger particles that get caught in the textile are no longer completely flushed out during the subsequent rinsing process. Rather, they adhere to the textile material as an impurity and are only grounded in a later heat treatment, a, B. in hot drying, 'Ie5ii ~ - mangling or ironing, inseparably cemented with the paser. In addition, when used in drum washing machines, the exchanger particles partially settle on the bottom of the fixed outer drum. The heating elements are usually also arranged in this area. The exchanger resins can fuse with the heated hot rods when they come into contact with them and damage them due to the deteriorated heat transfer. The resins can also settle in pumps, filters and sewage pipes, especially in areas of low flow intensity, for example in inspection shafts and lead to blockages. .

The present invention is based on the object of finding an environmentally friendly detergent and washing process, which does not have the deficiencies described and in particular the wastewater does not or only to a small extent polluted with phosphate or additional amounts of other inorganic salts and organic material.

409840/0933

HENKEL & CIE GMBH $ .n. JfvntaivaoumMmev 46351/4715/4770

The invention relates to phosphate-free or low-phosphate detergents and cleaning agents containing water-insoluble, granular cation exchangers made from spatially crosslinked copolymers of olefinically unsaturated, mono- and polyvalent carboxylic acids, characterized in that the cation exchanger has a predominantly open-cell sponge structure and an exchanger cap has a capacity of at least 4 mVal / g and a water absorption capacity of more than 500 % t, each based on the anhydrous exchanger.

Another object of the invention is a washing method, in which little or no phosphate is present and that in the absence of a water-insoluble one in the wash liquor dispersed ion exchanger is carried out, this cation exchanger having the properties defined above.

The sponge, foam or cell structure of the cation exchanger should predominantly be open-pored, ie the proportion of open cells should be on average at least 70 %, preferably more than 90 % . The cell structure can be arbitrary, ie honeycomb, polyhedral, irregular or also fibrous.

The cation exchangers to be used according to the invention with foam structure are specifically light and can therefore be advantageously sprayed with conventional and therefore specific light up washing powders combine. The liter weight the cation exchanger is "" in the order of magnitude of the liter weight of spray-dried detergents and amounts to 100 to 800 g, preferably 200 to 600 g. The liter weight of granular or powdery exchange resins without varnish or The foam structure is much higher, usually above 1000 g.

409840/0933 _ ₅

241H66

HENKEL & C! E GMBH su j / ' "rrc" nion _T ..id _un3 d 4651/4715/4770

The water absorption or swelling capacity of the foamed cation exchangers, based on the dry substance, is more than 500 %, preferably 600 to 3000 %, while it is usually 150 to 500 % for the granular exchange resins. It can be determined by allowing a weighed amount of ion exchanger to swell to saturation in distilled water, whereupon the material is filtered off using a paper filter. The ion exchanger remains on the filter until no more water drains off. The ion exchanger is then weighed back again. The percentage weight increase based on anhydrous material then gives the water absorption capacity.

The water absorption of the cation exchangers according to the invention runs extremely quickly, i.e. the final state of swelling is complete after an average of 10 to 60 seconds. In the case of granular exchange resins, the swelling is usually considerably slower. As the total exchange capacity is only available after complete absorption of water, the effect of the cation exchangers according to the invention continues Compared to the usual exchange resins, it is applied much earlier, i.e. at the beginning of the washing process. Even the exchange processes run comparatively faster in the case of the ion exchangers according to the invention. These properties are particularly important for the use of the means in programmed automatic ash machines, as these there is only a limited time available for the individual work cycles.

The grain size of the cation exchanger in the dry state is expediently 0.01 mm to 2.0 mm, with at most 3 Cew .-? O a grain size of more than 1.6 mm, at most 10 wt , 8 mm and at most 10% by weight, in particular at most 5 %, should have a grain size of less than 0.02 mm on iron. The average grain size is preferably between 0.05 and,

^α > 5 ω *. 409840/0933

241H66

Henkel & CIe GmbH μλ ^ i.rrct.nfo.m.wu «g d ^ 631/471 5 / 477Ο

The cation exchangers according to the invention with a foam structure have the essential advantage that they are in water or can be suspended very evenly in washing liquors and that the suspension is much more stable than that of powdery exchange resins. Because of this good suspension capacity, the particles do not settle on the Textile fibers or stuck in the fabric and easily and completely removed when rinsing. The sedimentation speed the suspension is correspondingly low, so that there is no residue on the bottom of the tub or in drains and put down sewer pipes.

The sedimentation rate can be determined in a simple manner by adding approx. 1 to 3 g of the cation exchanger? (based on anhydrous substance) in a graduated, 100 ml standing cylinder, filled with water up to the top mark. After thorough mixing, the layer height of the cation exchanger that settles on the bottom of the vessel is read off as a function of time. The volume of the water column that is above the settling layer is a measure of how many % of the original suspension have separated or how many % of the exchanger are sedimented. Powdery to granular exchange resins, which do not have a foam structure, set within 30 seconds. 90 to 95 % and within 1 min. 95 to 100 % on the bottom of the measuring vessel. The inventive foamed cation of the sedimented portion is after 30 see less than 30% and after 1 min. V ^r ess than 50%. In most cases, the sedimented portion is still considerably lower and amounts to 0 to 20 % after 1 minute and only reaches a level of 10 to 50 % after 10 minutes.

409840/0933

241U66

Henkel & Cie GmbH · uxJ ^ »r rotMionm«! * · »· Ο 46j51 / 47T 5/4770

The cation exchangers according to the invention should be per unit weight have the greatest possible number of carboxyl groups capable of salt formation. The capacity should at least 4 mVal / g, preferably 5 Ms 13 inVal / g. The capacity of the exchanger can be determined in such a way that a weighed sample with 0.1 η Treated with HCl, washed acid-free with distilled water and treated with 0.1 η NaOH against pheno3.phthalein as an indicator titrated.

The cation exchangers are produced in a manner known per se by polymerizing monolefinically unsaturated ones Carboxylic acids in the presence of polyolefinically unsaturated copolymerizable compounds in the presence a space-forming matrix or an inflation agent.

Suitable unsaturated polymerizable carboxylic acids bind for example acrylic acid, methacrylic acid, maleic acid, fumaric acid, - itaconic acid, hesaconic acid, citraconic acid, aco ~ nitic acid, 1-butene-2, 3,4-tricarboxylic acid and mixtures thereof. " If necessary, copolymerizable, simply olefinically unsaturated compounds may be present which contain no free carboxyl groups, however can be converted into carboxylic acids after the polymerization. These include the esters, amides and nitriles of the aforementioned monounsaturated carboxylic acids, and also mono-olefinically unsaturated aldehydes, such as acrolein or crotonaldehyde. By saponifying the copolymers containing ester, amide and nitrile groups or by rearrangement of the copolymer Suitable ion exchangers are also obtained in aldehydes according to Cannizzaro in the presence of strong alkalis.

Usable polyolefinically unsaturated compounds which copolymerize with the aforementioned unsaturated carboxylic acids with crosslinking are aliphatic, cyclo «aliphatic and aromatic diolefins, for example butadiene or divinic benzene, and also polyunsaturated ethers and esters, for example divinyl ethers, diallyl ethers of glycols, esters of Acrylic acid and methacrylic acid rtvit two " ^Ulld polyhydric alcohols,

409840/0933

Henkel & Cie GmbH sh " W ", PounianmtWuns d '+631 / 4715/4770

such as glycol diacrylate, those made from vinyl or allyl alcohol and polybasic carboxylic acids, such as divinyloxalate and Divinyl maleate, as well as those made from unsaturated alcohols mit.unsaturated acids such as vinyl acrylate or allyl methacrylate. Diamides are also possible, e.g. those from Acrylic or methacrylic acid and diamines such as ethylene bisacrylamide. Also polymers with at least 2 polymerizable Double bonds, e.g., unsaturated polyesters made from maleic acid and diols, are useful. In general, the proportion is of the polyolefinically unsaturated compounds 1 to 20, in particular 2 to 10 percent.

To modify the properties of the ion exchangers Further copolymerizable compounds can be added to the starting material, e.g. ethers and esters of vinyl alcohols or allyl alcohol · ^,. wie Vinylmethylätbsr or vinyl acetate, vinyl pyrrolidone, monounsaturated Hydrocarbons, such as styrene or vinyl toluene, also preformed polymers and copolymers, e.g. polyacrylic acid or copolymers of acrylic acid with one or more of the aforementioned vinyl or divinyl compounds, e.g. from acrylic acid, styrene and butyl acrylate or butylene glycol diacrylate.

Before or during the polymerization, the starting material is converted into the foam state. The foaming takes place in a known manner, in which, for example, volatile propellants such as air, steam, low-boiling agents Solvents or gases evolving reagents are used and the mass is by heating, relaxing or Triggering the gas formation causes it to inflate. Usual auxiliaries which promote foam formation, such as surface-active agents Substances or viscosity-increasing agents can be present. The Z-foaming is conducted co that im essential open-cell foams arise.

409840/0933

24.1H66

Henkel & Cfo GmbH su Ϋ _"r rai.nicnm.M. _ne ο 4631/4715/4770

The copolymerization is preferably carried out in the presence of crystallizing liquids, which by Solidify a solid of randomly arranged or oriented crystals before or during the polymerization form the existing matrix. Suitable crystallizing liquids are e.g. water, glacial acetic acid, trioxane, molten urea or salts melted in their water of crystallization, such as sodium sulfate decahydrate or dinatriutahyrcrogen phosphate dodecahydrate. The one consisting of crystallizing liquid and monomeric starting materials Solution or dispersion, which may also contain emulsifying agents came \, we el before the polymerization to temperatures below the solidification point cooled. Directional crystal growth can be achieved by applying the dispersion or Solution cuf a chilled "area" causing foams with an iaser-like cell structure. Such a thing Method is for example in British Patent 1,235 described. The finished polymer is heated and the molten liquid is squeezed off or spun off or washing away.

The polymerization is usually initiated by free radicals. The radicals can be generated by exposure to high-energy radiation, for example by β- or ^ -ray, x-rays and neutron rays or ultraviolet or visible light, optionally in the presence of photosensitizers, for example benzil, bezoin, acyloin ethers, benzophenone or benzaldehyde. Suitable radical formers are also ions of the transition metals, v / ie Fe, Co, Cr, Mn, V, U and Cu, and also oxidizing agents, for example periodates, peroxides and peroxide hydrates, such as H ₂ O ₂ , H ₂ S ₂ O ₃ and benzoyl peroxide ,; as well as Οί ', οη and certain azo compounds. In the case of polymerization in the presence of a crystalline matrix, initiation is expediently carried out by exposure to high-energy light radiation.

409840/0933

-10--

Henkel & Cie GmbH - s.; .. jjff "rr ^ i" ..! "", D I ₁ 6J1 / 47T5 / 477O

The copolymers obtained become flakes or powders comminuted according to the grain size specified above. Dusty fractions can be sieved out and, if necessary, be added to a monomeric starting mixture.

The cation exchangers can either be in the acid form or as sodium or potassium salts. they are however, they can also be used in the form of ammonium salts, for which purpose also the salts of organic ATCmonium bases. count, for example Mono-, di- or triethanolamine, .. Korpholin. or K-methylmorpholine. Unless the? ICation exchangers in the sow reform are used, it is recommended that the detergent or washing liquor be sufficient for neutralization Add amount of alkalis.

The cation exchangers can use conventional detergents !! added or processed together with these or packaged separately from them and only in the washing process the suds can be added «. You can also without using additional detergents or auxiliary washing agents, for example can be used in the pre-wash cycle. With some In washing machines, the program initially sees loosely adhering dirt being rinsed out of the laundry without prior notice Adding detergent before. Already unfold at this stage, i.e. before the addition of other detergents and auxiliary agents the cation exchangers their advantageous properties.

The amount necessary to get a good ws. of cation exchangers depends on the one hand on the number of active ones per unit weight of the exchange material Carboxylate groups, for the amount and degree of soiling of the laundry to be washed and for the Hardness uid the amount of water used. When using hard water, it is advisable to adjust the amount of cation exchanger to be dimensioned so that the residual hardness of the water

409840/0933

HENKEL & CIE GMBH "* τί -νημ">. Μ. ". Ο 4631/4715/4770

no more than 5 ° dH (corresponding to 50.mg CaO / l), preferably 0.5 to 2 ° .dH (5 to 20 mg CaO / l). To achieve For an optimal washing result, it is advisable to use a certain amount, especially for heavily soiled laundry To use excess of cation exchanger in order to wholly or completely remove the hardness builders contained in the detached dirt partially to tie.

If you work in the absence of phosphates, the concentration increases on ion exchangers' appropriately dimensioned in such a way that that with an average water hardness of 10 to 20 dH ° per liter of wash liquor an exchange capacity of 5 to 70 n> Val is available. With a capacity of 8 to 11 mVel / g, ■ how they prefer the exchanger material to be used network? Has polyacrylic acid, this corresponds to an application concentrate ion from about 0.5 to 7 g / l »preferably from 1 to 4 g / l washing liquor. With significantly higher water hardness must accordingly more, with lower water hardness or when using pre-softened water can accordingly are used less. In the majority of cases, a content of 1.5 to 3.5 g / l is sufficient. If phosphate, especially sodium tripolyphosphate is used, its amount, which is usually 1.5 to 3.5 g / l, e.uf less than 1.5 g / l, for example 0.1 to 1 g / l, can be reduced.

Particularly cheap. Results are achieved when at a total concentration of 1.5 to 3 g / l of softening agent 50 to 70% by weight thereof from tripolyphosphate and 30 to 50% by weight thereof from the cation exchanger according to the invention consists. Appropriately composed means contain, for example 15 to 25 wt .- # of phosphate and 5 to 20 wt .- # on cation exchangers. Such agents or washing liquids can be comparable products that only contain phosphate contained as a softening agent, not only outperform in terms of their washing power, but also prevent them fiber incrustation "to a much greater extent.

The cation exchangers are preferably used together with conventional Woschroiltelbt & l & vvaUtiie * used, for which purpose in particular

409840/0133

HANDLE. & CIE GMBH se ^ T * »» rf. ».» Nm.i <i, _n , d A6J1 / 4715/4770

Surfactants, inorganic salts and sequestering agents, also dirt carriers, bleaching agents, optical brighteners and Count enzymes.

Suitable surfactants are those from the sulfonate or Type of sulfate, for example alkylbenzene sulfonate, in particular h-dodecylbenzenesulfonate, olefin sulfonates,. Primary alkyl sulfonates and sulfo fatty acid esters and secondary alkyl sulfates as well as the sulfates of ethoxylated or pr.opoxylated higher molecular weight alcohols. The sulfated partial ethers can also be used and partial esters of polyhydric alcohols such as the alkali salts of the monoalkyl ethers or the monofenic acid esters of glycerol monosulfuric acid ester or 1,2 «dioxypropanesulfonic acid. Farner come sulfates of ethoxylated or propoxylated fatty acid amides .and alkylphenols so / ie fatty acid tauri & s and fatty acid isäthionate in question.

Alkali soaps are further suitable anionic detergent raw materials of fatty acids of natural or synthetic origin, e.g. the sodium soaps from coconut, palin kernel or tallow fatty acids. As zwitterionic Ifaschrohstoff e Alky! betaines and especially alkylsulfobetaines come possible, e.g. 3- (N, N-dimethyl-N-.alk.ylamnonium) - propan-1-sulfonate and 3- (N, N-dimethyl-N-alkylammoniuDi) -2 » hydroxypropane-1-sulfonate. ■

The anionic Viasch raw materials can be in the form of sodium, Potassium and ammonium salts as well as salts of organic bases, such as mono-, di- or triethanolamine, are present. Provided said anionic and zwitterionic compounds have an aliphatic hydrocarbon radical, this should preferably be straight-chain and 0 to 22 carbon atoms In the compounds with an araliphatic carbon grate, they preferably contain Unbranched 'alkyl chains on average 6 to 16 Carbon atom ?. 409840/0933 ..

241H66

Hang! & Cie GmbH

Patent department

/ 3

In a preferred embodiment, the agent contains at least one compound of the following formula as active washing substance;

R - (OCH ₂ CH ₂ J _n -OSO ₃ Me

in which R stands for an alkyl or alkenyl radical with 10 to 22 carbon atoms, Me for Na, K, KH. or an organic one Ammoniuingruppe and η stands for a number from 0 to 4, the weight ratio of washing active substance according to the above Formula for cation exchanger is 1:20 to 5: 1.

The alkyl or alkenyl sulfates or ether sulfates mentioned can differ from secondary, but preferably primary n-alcohols derive with 10 to 22 carbon atoms. These include Decanol, lauryl, myristyl, cetyl, stearyl, arachyl and Oleyl alcohol as well as from natural ones. Mixtures of fatty substances obtained by isolation or conversion, also synthetic ones Alcohols such as those obtainable from oxo synthesis, paraffin oxidation or ethylene polymerization. Mixtures too the aforementioned alcohols can be used as starting materials. Examples of such mixtures are odor coconut fatty alcohol Tallow fatty alcohol, which can be obtained from the corresponding fatty acids or fatty acid derivatives by reduction.

The alkyl or alkenyl sulfates or -ätiiersulfate can in Fonr the sodium, potassium and ammonium salts and as salts of organic bases, such as mono-, di- or triethanolamine, are present. The sodium salts are of particular practical interest.

Ether sulfates are preferably used which have an average of 1 to 3 ethylene glycol ether groups (AO). Examples for this, the sulfuric acid esters of coconut fat ~ alcohol-2-ÄO, tallow fatty alcohol-3-ÄO, oleyl alcohol-2-ÄO and Palm kernel fatty alcohol-2-ÄO.

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409840/0933

241K68

Hang! £ Cie GmbH

Patent department

Another object of the invention, containing such agents which in addition, at least one-v / urther anionic, nonionic or zwitterionic detergent active Substanze. The mixing ratio of the ether sulfates to the other active substance is 10: 1 to 1: 5, preferably 4: 1 to 1: 2. The cleaning effect of the agents is particularly good in this area. .

Polyglycol ether derivatives of alcohols are primarily used as non-ionic surface-active detergent substances, Fatty acids and alkylphenols in question, the 3 to 30 glycol ether groups and contain 8 to 20 carbon atoms in the hydrocarbon residue. Polyglycol ether derivatives are particularly suitable, in which the number of ethylene glycol ether groups is 5 to 15 and their hydrocarbon radicals are straight-chain, primary alcohols containing 12 to 18 carbon atoms or from alkylphenols with a straight chain, 6 to 14 carbon Atoms containing alkyl chain derive * By addition ■ of 3 to 15 mol of propylene oxide to the latter polyethylene glycol ethers or by transferring into the jicetals, detergents become obtained, which is characterized by a particularly low foaming power distinguish.

Other suitable, non-ionic washing raw materials are the water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts of polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the Alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Also non-ionic compounds of the amine oxide and sulfoxide type, which can optionally also be ethoxylated can be used.

Another preferred embodiment relates to an agent which acts as a washing active substance

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409840/0933

Henkel & Cie GmbH

Patent department

Mixture of at least 2 polyglycol ether derivatives containing aliphatic or alkyl aromatic hydrocarbon radicals having 10 to 22 carbon atoms and wherein at least one of the polyglycol ether derivatives 3 to 6 ethylene glycol ether groups on average and at least one of the polyglycol ether derivatives 10 to 18 on average Ethylene glycol ether groups on v / ei st.

The polyglycol ether derivatives can be derived from secondary, but preferably primary alcohols having 10 to 22 carbon atoms derive. These include decanol, LauryX, myristyl, cetyl, stearyl, arcyl and oil alcohol as / ie Mixtures obtained from natural fatty substances by isolation or conversion, also synthetic alcohols, v / how they can be obtained from oxo synthesis, paraffin oxidation or ethylene polymerization. examples for such mixtures are coconut fatty alcohol or tallow fatty alcohol. The polyglycol ethers can also be derived from alkylphenols with preferably unbranched alkyl chain with Derive 7 to 14 carbon atoms. Instead of these polyglycol ether derivatives, which are preferably to be used, these can also be used are used, which differ from primary or secondary alkylamines, mercaptans, fatty acids, fatty acid amides and Derive 1,2-diols, these being one of the abovementioned feed alcohols have the appropriate structure and composition. Mixtures of the aforementioned polyglycol ether derivatives can also be used be used.

Examples of such polyglycol ether derivatives which have an average of 3 to 6 ethylene glycol ether groups (JiO) are coconut fatty alcohol-4-EO, tallow fatty alcohol ~ 5-EO, oleyl alcohol-5-EO and nonylphenol-5-EO. Examples of polyglycol ether derivatives with an average of 10 to 18 EO groups are Laurylalköhol AEO-12, tallow-14-AEO alcohol, cetyl alcohol, oleyl alcohol-15 æŒ _r-13 EO and nonylphenol-14 EO.

409840/0933

Hang! & Cie GmbH

Petentübfeilcnq

-40

The mixing ratio of the two active substances with low and high glycol ether content is expediently 2: 1 to 1: 5> preferably 1: 1 to 1: 3. The cleaning effect of the agents is optimal in this area .

In addition to the polyglycol ether derivatives mentioned, those according to the above structure can also be present which have 7 to 10 ethylene glycol ether groups in the middle.

To improve the protective wear capacity, the agents can contain graying inhibitors or dirt dispersants · - γαη. These include water-soluble polyanionic polymers, for example the "alkali metal salts of carboxymethyl cellulose, polyacrylic acid and their copolymers, as well as polyesters and polyamides, which are obtainable from tri or tetracarboxylic acids and diols, dialaines or N-alkyldialkanolamines and contain free carboxyl groups capable of salt formation the alkali metal salts of polymeric sulfonic acids, for example of polyvinyloulfonic acids, polyesters and polyamides dor suIίο-succinic acid, sulfonated phenol-formaldehyde condensates, or of polyesters made from dicarboxylic acids and N-alkyldialkanolaminone which have been made water-soluble by reaction with sultones or haloalkanesulfonic acids.

- 17th

4G984Ö / 0933

Hang! & Cie GmbH

Patent department

Furthermore, nonionic dirt dispersants are used water-soluble or water-dispersible polymers such as methyl cellulose, hydroxyethyl cellulose, ethoxylated Starch, polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinylpyrrolidone, polyglycol, polyacrylamide and Polyethyleneimine as well as partial alkylation or with under- ' Polyäthylenimme reacted stoichiometric amounts of dicarboxylic acids. Copolymers of the aforementioned vinyl compounds with one another or with ethylene, styrene or Vinyl ethers have been suggested. Monomers are also emulsifying active compounds suitable as Schimrfczdispergatoren, e.g. water-insoluble, 1 to 4 glycol ether groups containing- polyglycol ether derivatives of fatty alcohols, fatty amines and fatty acids with 12 to 20 carbon atoms ■ or of dialkylphenols with 6 to 16 carbon atoms in the alkyl chains. Also mixtures of different dirt dispersers are usable.

Oxygen-releasing bleaching agents, such as alkali metal perborates, alkali percarbonates, perpyrophosphates and persilicates, and urea perhydrate can also be used as a further constituent of the mixture. Sodium perborate tetrahydrate is preferably used. In order to stabilize the per compounds, the agents can contain magnesium silicate, for example in amounts of 5 to 20% by weight, based on the amount of perborate. For washing textiles at temperatures below 7O ⁰ C agents to be applied, so-called cold detergent bleach activators, particularly tetraacetyl or tetraacetylethylenediamine as Pulverbestandteil.enthalten. The powder particles consisting of the bleach activator or the per compound can be coated with coating substances such as water-soluble polymers or fatty acids in order to avoid an interaction between the per compound and the activator during storage. "..

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409840/0933

Henkel & Cie GmbH

Patent department

The agents can also contain enzymes from the dox class of proteases, lipases and amylases or mixtures thereof. The enzymes can be of animal or vegetable origin, for example from digestive ferments. or yeast. Preferably, from bacterial strains or fungi, v / ie Bacillus subtilis and Streptomyces griseus. obtained enzymatic V / irkstoffe used which are relatively resistant to alkali compounds and anionic detergent active substances and are not significantly inactivated at temperatures between 50 ° and 7O ⁰ C.

The detergents can also contain optical brighteners, in particular derivatives of dianiinostilbene disulfonic acid or alkali metal salts. Suitable salts are, for example, salts of the ■■ 4 _f 4 ^t -bis (-2 ^u -anilino - ^ "-) dorpholino-1,3, .5-trizinyl-6" -aiiiino) stilbene - ^^ '- disulfonic acid or similarly structured compounds which, instead of the morpholino group, a diethanoid

- amino groups a methylamino group or a ß-methoxy-

• carry an ethylamino group. Other possible brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (~ p-sulfonamidophenyl) -5 ~ (p-chloro-'phenyl) -Δ -pyrazoline and similarly structured compounds, which instead of the sulfonamido group is a carboxymethyl or carry acetylamino group. Substituted amino coumarins, e.g. the 4-methyl-7-diB] ethylamino- or 4-methyl-7-diethylamine coumarin. Furthermore are as polyamide brighteners the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-; 5-phenyl-7-diethylamino-carbostyril useful. As brighteners / for polyester and polyamide fibers, the compounds are 2, iJ-bi- (2-benzoxazolyl) -thiophene, 2- (2-bensoxazolyl) -naphtho- [2,3-b ] thiophene and 1,2-di (5-methyl «2« benzoxazolyl) ethylene suitable i Furthermore, brighteners of the substituted Dlphenylstyrile be close. Also mixtures of the aforementioned brighteners can be used.

409840/0933 - 19 -

Henkel & CIe GmbH

Patent department

As inorganic Gerüs.tsubstanzen primarily come into question washing alkalis such as alkali metal silicates, particularly Natr.iuiasilikat, in which the ratio of Na ^ O: SiO ₂ ---- 1: 3.5 to 2: 1, and also carbonates, bicarbonates and borates of sodium or potassium. As long as a certain phosphate content does not interfere, condensed alkali metal phosphates, in particular pentanatric triphosphate and mixtures thereof with di- and tetraphosphates, can also be present. Furthermore, for the purpose of stabilizing oxidation-sensitive ingredients e _f, such as optical brighteners and fragrances, known sequestering agents, the detergents can contain.

These include the Alkali ™ or ammonium salts of nitrilotriacetic acid, Ethylenediarainotetraacetic acid, diethylenetriaminopentaacetic acid and the higher homologues of the aminopolycarboxylic acid mentioned. Suitable homologs can for example by polymerization of an ester, amide or nitrile of N-acetic acid aziridine and then Saponification to carboxylic acid salts or by reaction of polyamines with a molecular weight of 500 to 100,000 with chlorosetic acid or bromoacetic acid salts in alkaline Environment established. Y / citere suitable aminopolycarboxylic acids are polymeric N-succinic acid «, N-tricarb illylic acid and N-butane tricarboxylic acid ethylene imines, which are available analogously to N acetic acid & erivaton. Usable phosphorus-containing ^ Sequestrie- · " Rüngsmittil are the alkali and ammonium salts of aminopolyphosphonic acids, in particular Aiainotri- (methylenephosphonic acid), Ethylenediaiainotetra- (methylenephosphonic acid), 1-hydroxyethane-i, 1-diphosphonic acid, methylenediphosphonic acid, Ethylenediphosphonic acid and the higher homologues of the polyphosphonic acids mentioned .. Also Mixtures of the aforementioned sequestering agents can be used. . / ·

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409840/0933

Henkel & Cie GmbH

Patent department

30 241U66

In addition, nitrogen- and phosphorus-free, with Calcium ion complexing "polycarboxylic acids" as sequestering agents to be present. Citric acid, V7eic acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid are suitable. Polycarboxylic acids containing carboxymethyl ether groups can also be used, such as 2,2'-oxosuccinic acid and with Glycolic acid partially or completely etherified polyhydric alcohols or hydroxycarboxylic acids, for example triscarboxymethylglycerol, Bis-carboxymethylglycerijic acid and carboxymethylated bzv7. oxidized polysaccharides.

In order to improve skin tolerance and foam formation, fatty ^{acid alkylolaiides, in particular C} - | 2 ~ ^C 18 ~ fatty acid aono- and diethanolamides, can be used. Agents that are intended for use in drum washing machines instead contain known foam-suppressing agents, such as saturated fatty acids or their AlValise soaps with 20 to 24 carbon atoms or triazine derivatives, e.g. Tr i- 'alkylmelaiaine or propoxylated or butoxylated melamines and paraffins and higher moiecular fatty acid esters or triglycerides.

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Henkel & Cio GmbH s.itijgf _M rPot.nion «.«! Dgn _e d 4631/471 5/4770

Other constituents that can be contained in the agents according to the invention are skin protectants, conditioning agents active agents, bacteriostatic substances such as halogenated phenol ethers and thioethers, halogenated carbanilides and Salicylanilides and halogenated diphenylmethanes, as well Dyes and fragrances.

The cation exchangers can with the aforementioned, As powder, hollow ball powder or granules, V / ash agent constituents are mixed or also directly added to the liquid or paste-like detergent formulations intended for conversion into powder form and with dry or spray these together. A special one One advantage is the high absorbency of the foamed To see cation exchangers, which may be a Drying process, especially energy-saving hot spray drying, unnecessary. So can a water-containing detergent slurry by intimate mixing with the powdery exchanger directly into a pourable and free-flowing powder ■ be convicted. If necessary, during the noise or subsequent drying by means of heated air.

Another advantage of the foamed ion exchanger is the possibility of powdery, non-adhesive Detergents with a high content of non-ionic washing active substances, especially ethoxylated alcohols, to manufacture. The non-ionic washing active substances possess a particularly high cleaning power, especially against greasy soiling, and act on top of that due to their dirt-dispersing properties as anti-graying agents when washing textiles

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Henkel & CFe GmbH su J ^ "" ^ot " ^lonm " ^Wu "e t> 4631/4715/4770

Synthetic fibers and finished cotton. In usual Powdery or spray-dried detergents, however, can only be incorporated into relatively small proportions of nonionic surfactants, since it is precisely the most effective ones Representatives of this class of compounds are liquid and lead to sticky powders if the dosage is too high. In phosphate-free Laundry detergents that contain only a small proportion of porous, contain absorbent powder components, the maximum acceptable amount of non-ionic compounds is still considerably lower. It has now been shown that the genchäuiaten ion exchangers to be used in den.Vasohmittel e: .n have high absorption capacity for nonionic surfactants and that ion exchangers charged with such surfactants with usual Wasclimlttol constituents' au non-sticky, can be mixed up with storage-stable powders. Up to 300 g can be added to 100 g of ion exchanger non-ionic washing active substances are applied, without sticking or clumping.

The calcium binding capacity of the cation exchanger is less the washing process, especially if a low residual hardness of the washing liquor was sought, not yet exhausted. she are therefore able to at least partially soften the final rinse water and thus prevent hardness builders from depositing to counteract the so-called fiber incrustation on the washed textile goods. This is as an additional To see the advantage of the invention.

The used ion exchangers can be transferred to a downstream Filter collected and discharged. Because of their porous, spongy character, they are easy to filter and do not clog or set the filter

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Henkel & Cie GmbH since. $ 3 _τυ , ί _α , <, _ηΙαηπ , _Μυη * t> 4631/471 5/4770

there is no significant resistance to the flowing liquid. But they are also harmless in wastewater, because they are retained by conventional filter systems or grease wipers or are located in clarifiers completely settle and can therefore be easily discharged.

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409840/0933

241H66

HENKEL & CIE GMBH * · »'3Τ« r Pal.nton _MI l <tun _a υ 4631/4715/4770

Examples

A) Examples of recipes

The quantitative composition of detergents which can be used according to the invention is shown in the following scheme (Figures in% by weight):

- 80 %, preferably 5-40%, of cation exchanger, preferably in the form of the sodium salt

.1 - 50 %, preferably 2-30 % of at least one compound from the class of nonionic, anionic and pjwitterionic washing active substances,

also at least one of the following substances, in the minimum amount specified as preferred:

- 60 %, preferably 1-30 % of at least one washing alkali compound from the class of carbonates, bicarbonates, silicates, borates and sulfates of sodium and potassium,

- 25 %, in particular not more than 20 % , of phosphorus • containing compounds from the class of tripolyphosphates, pyrophosphates, metaphosphates and organically bound phosphonates in the form of sodium and potassium salts,

- 10 %, preferably 0.1-5 ^ at least one chelating agent from the class of aminopolycarboxylic acids and their sodium and potassium salts,

- 40 %, preferably 10-30 % bleaching agents, in particular per compounds and their mixtures with bleach activators or stabilizers,

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Henkel & CIe GmbH s.ite «Λ ^ t r <a» ni _a «mMma ο 4631/4715/4770

O -. 1.5 ^, preferably 0.1 - 1? 6 optical brighteners,

0 - 5 ^, preferably 0.1 - 3% foam suppressants, especially saturated fatty acids and their alkali salts,

0.1 - 20 % t, preferably 0.5-10 % other detergent ingredients, such as graying inhibitors, skin protection substances, organic silk, enzymes, avi vier end ν; Active agents, solution mediators as well as dyes and fragrances.

The Wasohaktivsubstanzen can preferably _t 5 to 70% of compounds of the sulfonate and or or sulfate type, up to 100 *? $, Preferably 5 to 80% of non-ionic compounds from Polyglykoläthertyp and up to 100%, preferably 10 to au 100% to 50 % soap. The washing alkali metal compounds, up to 100%, preferably from 0 preferably from 10 to 50% consist of soda, up to 100%, preferably 10 to 50% of sodium silicate, and up to 100%, and 80 ^c from a sodium sulfate. The phosphorus-containing compounds that may be present can be composed of up to 100 % of pentasodium triphosphate and up to 50 % of aminotrialkylidene phosphonates, alkylene phosphonates and hydroxyalkylene phosphonates in the form of the sodium or potassium salts. Sodium perborate is primarily used as a bleaching agent; if bleach activators are present, their proportion is expediently 10 to 100 %, based on the amount of perborate. However, the invention is not restricted to the composition given above and can differ more or less therefrom.

G. the cation exchangers

Χ.) In 50 parts by weight of water, 2.6 parts by weight of acrylic acid and after adding 0.14 parts by weight. ^r iclrbsteilen an AO weight percent aqueous solution of sulfonated

A09840 / 0933 " ²⁶ "

241H66

Henkel & CIO GmbH - l \ ,. Q $ _ilk rdenlMnWMung D 4631/4715/4770

Rieinus oil, 0.6 part of ethylene glycol diacrylate, 0.035 part of benzoin methyl ether and 1 part of a 40% emulsion of a copolymer of 50 % butyl acrylate, 45 % styrene and 5 % acrylic acid emulsified. The dispersion is poured in an approx. 5 mm thick layer onto a metal surface cooled to -15 ° C., * which has previously been coated with a 0.3 mm thick solidified aqueous solution of 5% ethoxylated castor oil (40 mol of ethylene oxide) had been. After cooling and solidification, it was irradiated for 10 minutes with a UV light source (Philips black light lamp TL 40 W / 0.8) at a distance of 25 cm. The solidified structure is thawed, neutralized with 0.1 η KaOH, washed with deionized water and dried at 60 ° -80 ° in flowing air. The material is then pre-shredded in a shredder and ground in a colloid mill to an average grain size of 0.1. The fractions with a particle size of more than 0.8 ram and less than 0.01 mm were each below 0.1% _t The weight per liter was 455 g, the water absorption capacity 820%, and the capacity determined by titration / g 8.5 Myal. An aqueous suspension still showed no measurable segregation after 2 minutes. After a resting time of 5 minutes, about 20 %, after 15 minutes about 50 % of the ion exchanger had settled. The supernatant liquid was very cloudy after 1 hour due to finely dispersed fractions, after 5 hours the exchanger had completely settled.

II.) 0.14 parts by weight of sulfurized castor oil, dissolved in 0.16 parts by weight of water, and 1.2 parts by weight of polyacrylic acid were dissolved in 30 parts by weight of water. After adding 0.6 parts by weight of 1,4-butanediol diacrylate, 0.035 parts by weight of benzoin isopropyl ether and 2.3 parts by weight of acrylic acid, the dispersion was placed in a tub which was cooled to -15 ° C. from below. Polymerization was then carried out as described above, and the polymer was washed, dried and comminuted. The mean grain size was 0.15 mm. 50 wt -.% Of the ion exchanger

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Henkel & Cie GmbH see Q, ■ », Pa! .Monn -., Idation d 4631/47 1 5/4770

had a grain size of 0.1 to 0.2 mm. Parts longer than 0.8 min and less than 0.01 mm were not present. The liter weight was 270 g, the water absorption capacity 980 % and the capacity determined by titration 10.8 meq / g. Within 2 minutes, no measurable proportions had settled from an aqueous suspension of the ion exchanger, after 1 hour 99 % of the exchanger had sedimented, after 4 hours the supernatant solution was clear.

ISU ^cne .

§.§Ί.2Ρ.ΐ £.! -.uL.JL Al olJi

In a laboratory washing machine (Launder-o ~ meter, loaded with 10 metal balls), textile samples made of cotton which had been soiled with dust and sebum were washed. The washing temperature was 95 ° C., the washing time 30 minutes, the capacity 8.4 g of textile material, the floct ratio (textile weight to weight of the "wash liquor) 1:12 and the hardness of the tap water 16 ° dll (corresponding to 286 ppm CaCO.,"). This was followed by rinsing 5 times for 15 seconds each time.

The composition of the detergent was (in percent by weight)

40.0 % structural substance 9.5 % washing active substance

2.5 % soap (sodium salt of tallow fatty acid and behenic acid in a ratio of 1: 1). .

3.5 % ratriura silicate (Na ₂ O: SiO ₃ = 1: 3.3) 24.0 % sodium perborate tetrahydrate 11.0 % sodium sulfate

1.2 % Na carboxymethyl cellulose -

0.2 % Ila-Ä-ttiylondiaminotetraace-tat (EDTA) 8.1 % water

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Henkel & Cie GmbH s <, dd. £ $ " _r ρ"). _Π ι ₃ »γ .. ^ π ₈ ο 4631/4715/4770

The active washing substance used was (V 1) 7.0 % n-dodecylbene sulfonate (Na-SaIa)

2.5 % tallow alcohol (JZ 45) ethoxylated 10 times

(W 2) 9.5 # tallow fatty alcohol (JZ 45) ethoxylated 10 times

The. according to Yersuch B / l and B / lI produced ion exchangers as well as a comparison of sodium ·· tripolyphosphate and sodium sulfate.

The composition of the structural substance, the concentration of the detergent and the photometrically determined reflectance values are listed in Table 1. The examples are irdt numbers, the associated comparison tests with Marked with letters. For Ka-tripolypbosphate was the abbreviation TPP is used.

The residual hardness of the washing liquor when using the ion exchanger with a detergent use of 5 g / l was 2.5 ° dll, with 7.5 g / l 1.7 ° dH and with 10 g / l 1.5 ° dH.

The results show that with a practical detergent concentration of 7.5 g / l, as is usually the case with the correct dosage in the main wash cycle of an automatic Household washing machine is present, the washing power of tripolyphosphate is achieved. Left on the textile samples no exchanger residues are found even on microscopic examination.

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241H66

4631/4715/4770

example Washing active Framework % Remission for a detergent 7.5 g / l IO g / l substaaz .substance concentration of 83 83 5 g / l ' 83 83 1 W 1 Exchanger I. 81 84 84 2 Exchanger II 82 - 70 7O a TPP 84 84 84 b Well SO
2 4 65 84 84 3 W 2 Exchanger I. 82 84 83 . 4th Exchanger II 83 74 73 C. TPP 84 d Na ₂ SO ₄ 76

Table 1

£ Regular games

In a Ilaushaltswaschiffaschine (Miele Automatic 421) v / ere 4 kg cotton textiles gov, ash ^r consisting of 2,4 leg white, unstained towels, 2.4 kg Light blue, dark red, dark green colored towels (Frotteeware) and 0.2 kg artificially soiled samples made of standardized cotton fabric. The water temperature was S5 ° C., the liquor ratio 1: 5, the detergent concentration 7.5 g / l and the water hardness 16 dH. The washing time (including the heating-up period) was 30 minutes, then the washing liquor was diluted with tap water and pumped off, then rinsed 4 times and spun.

The detergents had the following composition (in percent by weight):

40.0 % structural substance

10.0 % tallow alcohol 10 times ethoxylated 5.0 % sodium silicate (Na ₂ O:. SiO ₂ = '1:' 3.3) 0.3 % EDTA (Na-Salz)

1.0 % Na-carboxmethyl cellulose

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2.0 ^c / o Mg silicate

30.0 % sodium perborate tetrahydrate 4.0 % sodium sulfate
7.7 % water

The structural substance used was the ion exchanger I and its equipment with sodium tripolyphosphate and sodium sulfate used. For comparison, pure sodium tripolyphosphate was used used. Table 2 shows the composition of the builder substance.

The degree of whiteness of the standard textile samples was plicto metrically determined (maximum remission 84 %) . Furthermore vur ö.en the attached colored and white towels beiaugte with no deposits were observed tilgut of ion exchangers in the Southwestern. The remission values (mean values from 5 measurements) are listed in Table 2. They show that a complete or partial replacement of the phosphate is possible without the favorable ash result noticeably changing.

example 40 Framework Substance % 'Remission 5 20th % Ion exchanger I. 79 6th 20th ^ Ion exchanger I. 81 30th % Na tripolyphosphate 7th 10 % Ion exchanger I. 80 20th % Na tripolyphosphate 8th 20th % Ion exchanger I. 78 40 % Sodium sulfate comparison % Na tripolyphosphate 80

Table 2

409340/0933

Henkel & CIe GmbH * .n. JFT, "r * .-." ™. ",, * ,, ο ^4631/471 5/4770

Examples 9 and 10

A detergent of the following composition was used

(in percent by weight):

40.0 % structural substance

7.0 % n-dodecylbenzenesulfonate (Na-Salz) 3.9 % tallow alcohol - 10 times ethoxylated 3.2 % soap (tallow fatty acid / behenic acid 1: 1) 3.5 % sodium silicate (Na ₂ O: SiO ₂ - 1: 3.3) 1.4 % Na-carboxyniethyl cellulose 2.0 % Mg-silicate

28.5 % Na perborate

. 0.3 % EDTA. .

10.2 % water

The following mixtures were used as structural substances:

(G 1) 10 % ion exchanger I 10? Έ sodium sulfate 20 % pentasodium triphosphate

(G 2) 5 % ion exchanger I 15 % sodium sulfate 20 % pentasodium triphosphate

(G 3) 10 % sodium sulfate

20 % pentasodium triphosphate

(G 4) 40 % Na tripolyphosphate

Fabric strips with the dimensions 40 χ 50 cm made of cotton (EW), finished cotton (ABW) and blended fabrics made of polyester fiber and cotton (ΡΕ / BW) and polyester fiber and finished cotton (ΡΕ / ΛΕΝ), as described in Examples 5 to 8, washed repeatedly in a household washing machine, in each case 3.5 kg of clean Bauia wool laundry (towels) and 150 g with Cotton soiled by skin fat and dust were also placed in the washing drum. The dirt load corresponded that of very heavily soiled laundry.

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HENKEL & CIE GMBH s »n.3Äi.« ^{R tot} "" ^orin * ^lllun e ^{D 4631/4715/4770}

After 25 wash treatments, the graying was on photometric Paths determined. The incrustation of the textile samples was determined by first taking the samples boiled with an EDTA solution to elute the thermally fissile calcium and magnesium salts, whereupon the Textile sample are incinerated .. The incrustation then results from the additional weight of the eluted components the additional weight of ash compared to a comparative sample treated in the same way. Furthermore, the "Hand" (softness) of the towels after 7, 14 and 2? Laundry cycles rated (grade 1, highest rating, grade 6 \ m Evaluation) c The "results are listed in Table J5. The values for graying and fiber incrustation are given in Mean values from 5 individual determinations, the mean values for the handle mean 10 individual determinations.

A comparison of those with the structural substances G 1 and G 2 The results obtained ei it the results of the 1st comparative experiment (framework substance G 3) shows that already relatively Small amounts of ion exchanger in a detergent with reduced phosphate content are sufficient to reduce the Significantly reduce graying and incrustation of the textile fiber. Also compared to a high-performance detergent with a high proportion of phosphate (structural substance G 4) still exists a definite advantage. The grip of the fabric is not adversely affected by the use of ion exchangers, this confirms that no polymer is deposited in microscopic form on the textile fiber became. Likewise, there were no coarser exchange residues that could be seen with a magnifying glass or the unarmed eye can be determined on the textile samples. There was no residue in the lint filter of the washing machine of deposited exchangers and the heating elements showed no limescale.

409840/0933

.Textile - BV / ' 2411 466 G 2 G 3 G 4 material ,. ««. Ο 4631/4715 / 47.70 83 82 83 Framework • 79 78 81 Henkel & CIe GmbH s * ft * 3y * »treima ·» BW Example comparison 80 76 79 ABV / G 1 75 67 77 ΡΕ / BW 84 4.5 7.8 4.7 PE / ABW 81 Graying BW 79 (° / o Reniission) 75 2.9 2.6 2.6 2.6 3.1 3.1 3.0 Incrustation 3.7 4.0 3.8 (in % dos Tex by weight) 2.7 Reach for 3.0 7 cycles 3.9 14 cyclone Table 3 25 cycles Example 11

In a further series of experiments, a stirring paddle washing machine was used which was equipped with a lye pump and with which the washing lye could be pumped around in the circuit. The machine was charged with 3.8 kg of clean and 0.2 kg of soiled (sebum, dust) cotton textiles, the latter being attached to the agitator blades for better circulation. The water hardness was 16 ° dH, after heating was 30 minutes at 9O ⁰ C and washed equilateral circulated the wash liquor. The following were used as "detergents":

^a ) 3 g / l ion exchanger I as an additive to the washing liquid,

b) the same amount as under a), but the exchanger was not in the detergent solution, but in an externally arranged one equipped with a filter Container -given that of the urag-pumped detergent solution was flowed through,

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A631 / 471 5 / 477O

c) 3 g / l of a commercially available resin exchanger (Pernrutit C 67) as an additive to the washing liquor

d) the same amount of resin exchanger according to c) in the Arrangement b),

e) the same amount of resin exchanger according to c), sewn into a water-permeable bag and into the wash liquor given,

f) distilled water.

No other additives (chemical active substances, etc.) are used. After the laundry treatment, 3 sharks were flushed and the degree of whiteness (remission) was photorsotrically D3-stiiiirvit. The results (average from 10 determinations) can be found in Table A ¹ .. The residual hardness of the washing liquor after the end of the V-washing test is also given.

arrangement % Remission Residual hardness in ° dll a 62 0 b 48 0.5 C. 51 0 d 47. 0.3 e- 46 '1.5 £ 46 0

Table 4

The series of tests first shows that the erfindungsge-Biäßes Ion exchanger even in the absence of washing active substances have a cleaning effect (experiment a). It also emerges that with an experimental set-up, at which the ion exchanger cannot come into direct contact with the textile fiber (experiments b, d and o), no riennensv: «rte Improvement over washing with distilled water (Attempt f) is obtained.

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HENKiEL & ClE GMBH s.iit jjf "^ ⁰¹ · ¹ " ⁰¹ "" · ¹ ' ¹ '" ¹ » ^D 4631/4715/4770

The test result is also unsatisfactory. C. At this Arrangement resulting from DOS 2 055 423 set After a very short time, a large part of the resin exchanger is on the bottom of the liquor container or in the Redirection from. Adhered after rinsing three times there were still individual exchanger particles on the laundry, while the laundry treated according to experiment a) had no deposits exhibited.

At st> i el 12-14

In the Launder-o-raeter, as stated in Example 1 to 4, Soiled textile samples can be washed with a detergent after the composition (weight, »$

30io % 0ctedccyl ~ bis- (2,3-dihydroxyprop3'2) "ammonium" pr op anus sul f ob e tain

3.0 % soap (as in example 1 to 4) 20.0 $ o framework substance

5.0 yo sodium sulfate
10.0 % sodium silicate (Ha ₂ O: SiO ₂ = 1: 3.3)

1.2 % ! ^ - carboxymethyl cellulose

0.2 % EDTA
24.0 % sodium perborate

6.6 % v / water.

The? Type of textile material used, the temperature, the liquor ratio and the concentration of the wash liquor and the composition of the builder substance are shown in the table 5 listed. The examples according to the invention are indicated by numbers, the comparative searches by letters marked. The results show the superiority of the agents according to the invention over those with low Phosphate content or those with a content of known phosphate substitutes.

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example Textile material temperature
O
C. Flute ratio concentration
g / l Framework Remission 12th cotton O
90 1:12 10 Exchanger II 81.0 a Na tripolyphosphate 70.5 b Na-Süikat 73.2 C. Na citrate 76.9 13th
I. cotton
Refined 0
60 1 ; 30th 5 Exchanger II 60.5 a Na tripolyphosphate 60.5 b 55.5 Na citrate 56.3 14th
a Polyester with
high parents
cotton 60 ° 1:30 5 Exchanger II
Na tripolyphosphate 55.3
53.0 b Na-Süikat 52.0 C. Na citrate 52.0

T a b e 1 1 e

—J

HENKEL & CIE GMBH

Sello ^ Jt ί "'Polenl jmnnWuno D Example 15

Detergents with the following composition were used

used (iodine number of tallow fatty alcohol = 45, ÄO = ethylene glycol groups, EDTA = Na salt of ethylenediaminotetraacetic acid, CMC = Na salt of carboxymethyl cellulose, quantities in percent by weight). ¹

Tallow alcohol-14 ÄO
Tallow alcohol-5 ÄO
Na ₂ O.3.3 SiO ₂

Mg SiO ₅

♦ 4 H ₂ O

9.5 %

4.6 % 5.0 % 2.5 %

l> 0.0% 0.3 % 1.8 %

D, J? / 0

The structural substance was composed as follows:

A. B. C. comparison
D. Exchanger I. 15 % 15 % 15 % Na ₂ SO ₄ 25 % 15 % 5% 10 % Na ₅ P ₅ O ₁₀ - 10 % 10 % ■ 30 % Na ₂ CO ₅ - - 10 % -

A household washing machine (type "Miele de Luxe 421 S") was carried out with 3.8 kg of clean cotton textiles and 0.2 kg of standard test cloths containing skin oil and pigments had been artificially soiled, loaded. The test rags consisted of cotton, refined cotton and

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su 1 | d, », p _o <. _fl ia " _n .id» _ne d 4631/4715/4770

a 1: 1 blend of polyester fiber and refined cotton. The detergent concentration was 7.5 g / l liquor ratio 1 _f: 5, the water hardness 16 ° 'dH, the washing temperature 95 ° C and the wash time 30 minutes, 15 minute heat. The percent remission of the
Test swab was determined photometrically. The values given in the table below are mean values from 4 determinations in each case.

laundry detergent Trees of trees cotton Mixed fabrics refined A. 76 69 69 B. 79 71 T ⁷ y C. 78 70 71 D. 77 69 64

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1TW

Sponsor department

241U66

Example 16

With dust and sebum under standardized conditions. Soiled fabric samples made of cotton, refined cotton (wash-and-wear equipment) and a mixed fabric made of polyester fiber and refined cotton (50:50) were in a laboratory washing machine (Launder-ometer from ATLAS, USA) together with non-soiled FUIlgew.ebe (Cotton Renforce) and, according to the washing instructions, washed with the addition of 10 steel balls. The composition of the washing tool read (weight sprouted):

23.0 % tonsid

4.0 % soap (Na stearate Ka behenate 1: 1)

30.0 % exchanger Ϊ (according to main registration)

25.0 % sodium perborate

3.5 % water glass (Na ₂ O: SiO ₂ = I: 3.3)

0.5 % EDTA (Ha-SaIz)

2.0 5 ^ Na carboxymothyl cellulose

8.0 % water

4.0 % sodium sulfate

The surfactant used (all as Na salts):

A) Tallow alcohol * - 3AO-SuIfat and for comparison

B) n-dodecylbene sulfonate

C) οί-olefin sulfonate C-j ^ -Cjg

D) ο: - sulfofatty acid methyl ester (from hardened palm kernel oil

fatty acidsi)

E) alkyl ether carboxylic acid (from primary C ^^ - C., g-alcohol, 4.5 ÄO and monochloroacetic acid)

The detergent concentration was 2.5 g / l, the liquor ratio in the case of cotton wool, 1:12 in the case of the refined cotton, and the blended fabric .1: 30, the

409840/0933

Sheet 4 Our patent application D 4631/47 ^ 5 / 477O

νϊι. »Οι ti ^ 'Q VmA ..'. i patent department

2A1U66

Washing temperature for unrefined and refined cotton 90 ⁰ C, for the mixed fabric 60 ⁰ C and the hardness of the tap water 16 ° dH (160 mg CaO per liter). The washing time was 30 minutes in total (including heating) and 15 minutes at the specified temperature. It was then rinsed 3 times with clear water. The remission of the dried tissue samples was determined photometrically. The results are compiled in the following table. They show the comparatively good cleaning effect of the mixture A according to the invention.

Surfactant cotton cotton refined A. 63 54 B. 48 49 C. 51 53 D. 55 53 E. - "50 54

Mixed fabrics

55 48 51 52 54

Example 17

Under the same conditions as specified in Example 1, soiled fabric samples made of cotton and finished Cotton washed with detergents of the following composition (in percent by weight):

10.0 % surfactant

3.5 % soap (as in Example 1) 40.0 % cation exchanger I 5.0 % water glass 0.5 % EDTA

2.0 % Ra-carboxymethyl cellulose, remainder water

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Hang! & Cio GmbH

Patent department

The surfactant (Ma-SaIze) was composed as follows:

I) n-dodecylbenzenesulfonate

II) C - ^ - C ^ -alkyl- ^ AO-sulfate and n-dodecylbenzenesulfonate in a weight ratio of 1: 1

III) C ₁₂ -C ₁₄ alkyl 2Ä0 sulfate

% Remission Refined cotton Laundry detergent. cotton 45 I. 44 48 II 48 48 III 47

The partial replacement of the alkyl benzene sulfonate by the Ether sulfate increases the detergency.

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409840/0933

Claims (18)

Claims c h e Phosphate-free or low-phosphate detergents and cleaning agents with a content of water-insoluble, granular cation exchangers from spatially cross-linked copolymers olefinically unsaturated, mono- and polyvalent carboxylic acids, characterized in that the cation exchanger has a predominantly "of fine-pored sponge structure and an exchange capacity of at least 4 lnYal / g and a water absorption capacity of more than 500? · ', Each based on the anhydrous exchanger, owns. 2. Means according to claim 1, characterized in that the cation exchanger contained therein has a proportion of at least 70 %, preferably more than 90 % , of open cells. 3. smock according to claim 1 and 2, characterized in that that the liter weight of the cation exchanger contained therein is 100 to 800 g, preferably 200 to 600 g. 4. Composition according to claim 1 to 3, characterized in that the cation exchanger contained therein has a water absorption capacity of 600 to 3000 % . 5. Composition according to claim 1 to 4, characterized in that the cation exchanger contained therein a Has a grain size of 0.01 to 2 mm, v / ob ei at most 3 wt .- ^ a grain size of more than 1.6 mm, at most 10 wt. % A grain size of more than 0.8 mm and at most 10 wt. ~ $ I, in particular a maximum of 5 % a grain size of less than 0, 02 now have. - 43 - 409840/0933 Henkel & CIe GmbH Patent department 6. smock according to claim 1 to 5, characterized in that that the cations contained therein shear a capacity from 5 to 13 meq / g. 7 ". Means according to Claims 1 to 6, characterized in that that the cation exchanger contained therein consists of a crosslinked copolymer of acrylic acid. 8. Means according to claim 1 to 7 .. characterized in that • that the cation exchanger contained therein in the form des sodium odor KaliuuiS & lz ^f 2S is present. 9. Means according to claim 1-8, characterized in that the agent as a washing active substance at least one compound the following formula contains: R - in which R stands for an alkyl or alkenyl radical with 10 to 22 carbon atoms, Me for Na, K, NH ₄ or an organic ammonium group and η for a number from 0 to 4, the weight ratio of active washing substance according to the formula above Cation exchanger 1:20 to 5: 1. 10. Composition according to claim 9, characterized in that η in the formula is a number from 1 to 3 and R is a represents primary n ~ alkyl radical. 11. Means according to claim 9 and 10, characterized in that the means additionally have at least one more anionic, contain nonionic or zwitterionic washing active substance, the mixing ratio of ether sulfate according to the above formula for further washing active substances; 10: 1 to 1: 5. - 44 - 409840/0933 - ^D 4631/4715/4 770 patent department 12. Means according to claim 1 to 8, characterized in that the agent contains a mixture of at least 2 polyglycol ether derivatives as washing active substance, the aliphatic or alkyl aromatic hydrocarbon radicals with 10 to Have 22 carbon atoms, and at least one of the polyglycol ether derivatives on average 3 to 6 ethylene glycol ether groups and at least one of the polyglycol ethers ~ - derivatives on average 10 to 18 ethylene glycol ether groups having. 13. Composition according to claim 12, characterized in that the polyglycol ether derivatives differ from primary reid-chain Derive alcohols with 10 to 22 carbon atoms. 14. Means according to claim 12, characterized in that the da.ß Polyglycoiether derivatives are derived from alkylphenols ia.it straight-chain, Alkyl chain having 7 to 14 carbon atoms derive. 15. Means according to claim 12 to 14, characterized in that that the mixing ratio of the washing active substance with a lower number of glycol ether groups to that with a higher one The number of glycol ether groups is 2: 1 to 1: 5 and preferably 1: 1 to 1: 3. 16. Washing method using a cation exchanger finely divided in the wash liquor according to claim 1 to 15 _f, characterized in that the amount of the exchanger is measured so that the residual hardness of the washing liquid is not more than 5 ° dH, preferably 0.5 to 2 ° du. 17. The method according to claim 16, characterized in that one works in the absence of soluble phosphates. 18. The method according to claim 16, characterized in that one in the presence of less than 1.5 g / l, preferably 0.1 to 1 g / l, works on soluble phosphates. 409840/0933