DE2203004A1 - Liquid heavy duty detergent - Google Patents

Description

The invention relates to liquid heavy duty detergents.

For some time the public has become aware of the importance of keeping the environment clean and the effects of interfering with the environment, and therefore the problems of waste disposal have been re-examined. Numerous studies of lakes, rivers, streams and the groundwater have shown that some common household detergents, especially those containing poorly degradable synthetic organic detergents and phosphate builder salts, are harmful
Have an influence on waters. Surface active compounds that
can not be quickly dismantled after draining from pits, Yv'ash kettles or washing machines, can in streams, rivers, streams and
Getting in lakes.

The detergent manufacturers have therefore tried hard degradable organic Tenri.de such as the highly branched ones

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Alkyl-aryl-sulfonates by means of more easily degradable straight-chain alkylbenzenesulfonates or similar compounds that decompose in a short time.

Many attempts have been made to produce detergent mixtures which have excellent cleaning effects but do not contain phosphates. This is the problem difficult because of the polyphosphates, especially pentasodium tripolyphosphate, tetrasodium pyrophosphate and similar others Polyphosphates, particularly effective builders, peptizers, Have dirt-carrying and cleaning properties.

The invention is therefore based on the object of developing a coarse detergent that while maintaining excellent Washing properties do not have any phosphates or organic nitrogen compounds contains.

A liquid heavy duty detergent is used to solve the problem proposed, which is characterized by a content of about 8 to about 30 $ of a water-soluble anionic organic surfactant of the general formula RO (CpH <O) εΟ, Μ, in which R is a pettalkyl group with 10 to 20 carbon atoms, η an integer from 2 to corresponding to one fifth to one third of the number of carbon atoms in R, and M mean a salt-forming cation, about 10 $ bis about 30% of a citrate builder salt, about $ 0 to about $ 15 one hydrotropic compound, about $ 0 to $ 5 of a water-soluble soap,

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about $ 0 to about $ 10 of a water soluble silicate, about $ 0 to $ 10 of a water-soluble carbonate and about $ 15 to about 80 $ of an aqueous solvent.

The liquid detergents according to the invention have a simple, cheap and commercially available, biodegradable anionic surfactant. They contain almost no polyphosphates or other phosphate forming salts or significant amounts of nitrogen compounds as builders. Instead, sodium citrate or equivalent compounds are used used for this purpose. The Y / ash agents according to the invention preferably contain a hydrotropic compound. The various constituents of the detergents according to the invention are relevant to their compatibility, solubility and cleaning effect and builder effect are interdependent. When using suitable compounds in suitable amounts within The specified limits can be used to produce liquid coarse detergents, the effect of which the effectiveness of mit'Buildersalzen commercial detergents produced during washing tests

or/

with dirty laundry, either in the laboi / in household washing machines, is equivalent to. When using the liquid coarse detergents according to the invention, the washing water can, however, in the usual way Wise dispensed without thereby the ecological problems of the previous detergents provided with builder salts result.

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The inventions ε according to en liquid coarse detergents contain about 8 $ to 30 $ of an anionic organic surfactant of the general formula RO (C ₂ H ₄ O) SO ^ M, in which R is a fatty alkyl group with 10 bic 20 carbon atoms, η an integer from 2 to 6, corresponding to a fifth to a third of the number of carbon atoms in R and M, an alkali-forming cation, usually an alkali metal, ammonia, lower alkylamines or lower alkanolamines, mean 10 $ to 30 $ citrates and optionally $ 1 to $ 15 of a hydrotropic compound, usually a salt of cumene sulfonates, benzenesulfonates, toluenesulfonates or xylene sulfonates. The detergents also contain water and customary amounts ($ 0.001 to $ 10) of optical brighteners, dyes, perfumes or other auxiliaries. The detergents according to the invention are clear, single-phase, stable liquids which only need to be used in small quantities for washing a washing machine load »

The formula RO ^ H.O ^ f.O ^ M, in which R is a fatty alkyl group with 10 to 20 carbon atoms, η an integer from 2 to 6 corresponding to a fifth to a third of the number of C atoms in R and M are a salt-forming cation such as an alkali metal, ammonia, lower alkylamines or lower alkanolamines mean, correspond to sulfated, epoxylated higher fatty alcohol parts. In order to ensure the best possible washing power and biodegradability, the fatty alkyl group is the solution terminal with the polyoxyethylene chain and this in turn

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be terminally linked to the sulfur to form a sulfate group. A certain branching of the higher alkyl chains up to 10% of the carbon content of the alkyl chains can be tolerated, but this slight deviation from the general linear structure should also be avoided. The central linkage of the alkyl chain on the polyethyleneoxy chain should also only be present to a small extent, generally less than 10 $, and such a non-terminal linkage should preferably be present near the end of the chain. Within the range of 0 ^ ₀ to Cp ^ -alkyl groups, alkyl groups with 12 to 15 carbon atoms are preferred, mixed alkyl groups with 12, 13, H and 15 carbon atoms being particularly preferred. This mixture should preferably contain at least $ 10 · of each chain length and no more than $ 50 of any given chain length.

The ethylene oxide content of these surfactants can be between 2 to 6 and preferably 2 to 4, generally around 3 mol, especially when R is a mixture of alkyl chains with 12 to 15 carbon atoms. To achieve the desired hydrophilic-lipophilic balance can be maintained when the carbon content of the alkyl chain is in the lower range of the specified limit the ethylene oxide content can be reduced to η = 2; on the other hand, when R has 16 to 18 carbon atoms, η may be 4 to 6. as salt-forming cations are usually alkali metals or ammonia. When using alkylamines or lower alkanolamines the alkyl or alkanol groups usually contain 1 to 4

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C atoms, these amines and alkanolamines being mono-, di- or Can be trisubstituted, such as, for example, monoethanolamine, diisopropanolamine or trimethylamine.

The importance of the use of the suitable anionic surfactant in the detergents according to the invention arises, for example from the fact that alcohol sulfates in corresponding liquid detergent preparations do not have the same high detergency as have the higher alcohol polyethenoxysulfates described. Higher alcohol sulfates with, for example, 12 to 15 carbon atoms in the alcohol group show a much weaker detergency than the athoxylated sulfates used according to the invention. Even an increase in detergency can be determined within the specified limits of alcohol polyethene oxysulphates, if mixed alcohol polyethenoxy sulfates with 12 to 15 carbon atoms compared to other alkyl ethene oxysulphates with mixed Alkyl groups with H to 15 C atoms and the same ethenoxy chain length are present. Preferably used as an anionic Surfactant is called "Neodol 25-3S" as the sodium salt from Shell Chemical Company; the connection is in solution with $ 60 active connection and about 40 $ aqueous solvent with a minor Amount of ethanol before. "Neodol 25-3S" is the sodium salt, in part or entirely instead of the sodium salt, the potassium salt can also be used or other suitable soluble salts can be used.

In addition to or instead of the specified connection

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this compound can be used, for example: sodium salts of the mixed ^ λο ~ ^ λ ^ normal primary alkyltriethenoxy sulfate, potassium myristyl triethenoxy sulfate, diethanolammoniura-n-decyl diethenoxy sulfate, ammonium lauryl diethenoxy sulfate, sodium palmityl tetraethene oxy-sulfate sulphate, sodium salts of the mixed C 1 to C 1 normal primary alkyl tri and tetraethenoxy sulphates, trimethylammonium stearyl penteethoxy sulphate or potassium salts of the mixed C 1 to C ₈ normal primary alkyl triethenoxy sulphates, where appropriate, smaller proportions can also be used the corresponding branched-chain or moderately alkoxylated surfactants are used; these compounds correspond to those described above, except that the ethoxylation has occurred on a central carbon atom such as, for example, on carbon atom 4, calculated from the end of the chain? however, the total carbon content of the alkyl chain must be the same. Smaller amounts of almost terminally linked compounds in which ethoxylation has occurred on a secondary, last or penultimate carbon atom, calculated from the end of the chain, can also be used.

The citrate builder of the heavy duty detergents according to the invention can be used as urodium citrate or in the form of another water-soluble Citrates such as potassium, lithium, ammonium, amine, alkylolamine salt or the like. Salts used will. When using the detergents according to the invention

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Citric acid can also be added in the acidic pH range. The citrates can be in the form of hydrates or in anhydrous form Form to be added.

The hydrotropic salts improve the solubility of the anionic surfactants and thus enable the production of a concentrated liquid heavy duty detergent. They also help hydrotropic compounds that keep the builder in solution in high concentrations and thus prevent phase separation or the formation of insoluble precipitates. In addition, the hydrotropic compounds improve the solubility of various auxiliaries with relatively low solubility such as optical brighteners and lower the viscosity of the Mixtures; this is particularly desirable at high concentrations.

As' hydrotropes are preferably salts of aryl sulfonic acids, in particular '. . . . Benzenesulfonic acids with unsubstituted or pheny ring substituted with short-chain alkyl groups. The short-chain alkyl groups contain 1 to 4 C atoms and are preferably methyl, ethyl or isopropyl groups. The phenyl ring can have up to three such pubes Carry out, compounds are preferred which have no, one or two Eubstituenten. The preferred hydrotrope Compound jet a water-soluble, for example sodium salt of cumene sulfate. Other similarly substituted aryl

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sulfonates and compounds with others, related to the Cations described in surfactants can be used. Preferably alkali salts, lower alkylamine, lower alkanolamine or ammonium salts are added; if appropriate, the free acids can also be used, especially when the mixtures or the ash water contains sufficient alkali to convert it to the soluble salt form.

According to the invention, for example, sodium cumene sulfonate, potassium cumene sulfonate, Ammonium cumene sulfonate, ammonium benzenesulfonate, sodium toluenesulfonate, Potassium xylene sulfonate, triethanolamine benzenesulfonate or diethanolamine cumene sulfonate can be used. For the respective Ingredients and their amounts, the most effective hydrotropic compound must be selected; for most of the invention Laundry detergent is the most effective compound. If appropriate, mixtures of the hydrotropic compounds can also be added, or in some cases also the -acid form of the compounds are used? the acid form becomes but mostly neutralized beforehand or converted into a soluble form in another way.

AIc solvent of the liquid Grobwaschmitfcel according to the invention is water, optionally with additives of other solvents, used for certain components, AndereLößungsmittel may generally be up to 30 ° /> and preferably up

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less than 10 $ of the total water content must be present. Such additional solvents are either lower alkanols or lower diols or polyols such as, for example, ethanol, isopropanol, ethylene glycol, propylene glycol or glycerine. Possibly can also ether polyols such as diethylene glycol or Cellusolve can be added.

The water is preferably used in deionized form in order to prevent the formation of insoluble precipitates or colored particles with components of the liquid detergent due to ions that may be present in the water. The content of metal ions in deionized water is generally below 10 ppm, calculated as calcium carbonate. Although the use of deionized water is preferred, normal tap water can also be used if necessary, provided that the hardness of the water is sufficiently low and that no ions are contained that can react with the constituents of the PlÜBsig detergent. If desired, small amounts of an equestant (0.01 to 2%) can be added to prevent possible impairments due to water hardness or heavy metal ions. For example, sodium nitrilotriacetate, sodium EDTA, gluconates, lactates, inorganic phosphates and similar salts can be added as sequestering agents.

Most household washing machines are top-closed and have a drum capacity of 56.8 to 68.1 1

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Water. Due to the drum movements and the fact that the drums are open at the top, the foam formed during Y / ashening drifts upwards and therefore does not interfere with the washing process of the laundry. However, this can occur in washing machines to be loaded from the front , which generally have a lower water capacity of 26.5 to 34.1 liters , whereby the same washing effect can be achieved with less detergent in these machines, provided that the foam does not leads to a reduction in the contact between the detergent solution and the laundry. Most of the time, the foam helps wash away the dirt particles in top-loaded Y / ash machines, and housewives used to equate good foam properties with good Y / ash power, but in recent years it has been shown that it is desirable to reduce the amount of foam produced to limit.

Therefore, the liquid coarse detergent according to the invention, both for use in from above as well as for washing machines to be loaded from the side, preferably mixed with a foam-inhibiting agent. Such Anti-foaming agents must be used with the other components of the Detergents must be compatible and the Y / nschkraft as such do not affect negatively. With clear, single-phase, stable, heavy-duty liquid detergents that often form part of the bentand parts contained dissolved up to the vicinity of the solubility limit exists there is always the risk that by adding large amounts of hi Impairment of the preparation occurs.

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The liquid heavy duty detergents according to the invention can as an anti-foaming agent or as an anti-foaming agent while maintaining a high detergency with a water-soluble soap of higher fatty acids or with a mixture of such Soaps are added. The higher fatty acid soaps are mostly in the form of alkali salts, for example as sodium or potassium salts, higher mixed fatty acids, for example as mixtures of natural animal or vegetable fats or oil. These soaps usually contain a larger proportion of saturated fatty acid soaps with one chain length from 10 to 18 carbon atoms. Mixtures of tallow and coconut oil fatty acids or soaps of mixtures are particularly preferred from sebum and coconut oil. The soaps to be used according to the invention usually contain more than 50 $ and preferably 80 $ to 100% sebum, with the rest consists of coconut oil or another oil. In addition to the alkali metals, ammonia, triethanolamine, Trimethylamine, other lower amines or alkanolamines as well as the synthetic surfactants are present.

It is known that the higher fatty acid soaps, in addition to their foam-inhibiting properties, also have excellent washing properties so that their use as anti-foaming agents does not result in any impairment of detergency. As the soaps a particularly good cleaning effect on certain types of dirt the ash effect is even improved as a result.

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The liquid heavy duty detergents according to the invention can contain numerous other auxiliaries, such as, for example Soil-carrying substances such as polyvinyl alcohol, sodium carboxymethyl cellulose, Hydroxypropyl-methyl-cellulose, optical brightener such as cotton, polyamide and polyester brighteners, other organic surfactants such as sodium lauryl sulfate, Myristyl-polyoxyethylene-ethanol with 10 moles of polyethylene oxide, linear tridecyl benzenesulfonates, pH regulators such as sodium hydroxide, triethanolamine, f-sulfuric acid, Buffers such as sodium borate, sodium bisulfate, inorganic builder salts such as borax, sodium carbonate and silicates, enzymes such as proteases or amylases, thickeners such as guinmen, alginates or agar-agar, foam improvers such as La urinsäure-myri st insäur e-d in ethanol amide, lauryl-dimethy1-aminoxide, Foam inhibitors such as silicone; bactericides such as tetrachlorosalicylanilide or hexachlorophene, Fungicides, dyes, water-dispersible pigments, preservatives, UV-Xichtabsorbentien, fabric softener mitfcel, Mlttol, die a pearl screen, opacifiers such as Behenic acid, polystyrene suspensions or hydrogenated castor oil (castor wax), or perfumes. Important tools for the erfindungsgorn availability Liquid heavy-duty detergents are the optical brighteners, as it is expected of a washed laundry today, that it is not only clean and white, but also luminous. The optical brighteners are noun in relation to the weight

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beautiful textiles, this substantivity is sometimes selective, and in general the brighteners are relatively poorly soluble. It is therefore important that they are in the Plüssigwaschinmittel be kept in solution and that they distribute evenly and instantly in the wash water, otherwise they become shiny Stains can form on the laundry instead of an evenly shiny appearance. Just need it proportionately to be used small amounts of the brightener so that their solubility limits are not exceeded. From the known some optical brighteners are particularly suitable because of their good solubility; to these favorite brighteners include both cotton brighteners and polyamide-polyester brighteners.

The coarse detergents according to the invention can be admixed with a single brightener, but in general a mixture of brighteners will be used in order to achieve good brightening effects for cotton, nylon, polyester and mixed fabrics and a good brightening effect even in the presence of chlorine bleaches. An excellent description of the different types of brighteners is in "Optical Brighteners and Their Evaluation" by Per £. Stensby, in "Soap and Chemical Specialties" April, May, July, August and September 1967, ΐ respectively. 3-5, given.

as

The cotton brighteners are often referred to as ^ CC / DAS brighteners, since they are reaction products of cyanuric chloride and the disodium salt of diamino-stilbene-disulfonic acid, the compounds

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fertilizers differ in the substituents on the triazine and aromatic rings. Chlorine bleach stable brighteners Bind mostly Benz ¹ dinsulfon-disulfonic, Naphthotriazolylstilben-sulfonic acids or Benzimidazolinderivate. The polyamide brighteners are either aminocoumarins or diphenylpyrazoline derivatives and polyester brighteners, which are also suitable for polyamides, are mostly naphtho-triazolyl-stilbenes. The brighteners are mostly in the form of salts, but they can also be added as free acids. Mostly the cotton whiteners do. . aun the greater portion of the mixture; the smaller part consists of polyamide polyester heaters. Preferably used brighteners are, for example: Calcofluor White ALF (American Cyanamid), ALF-N (American Cyanamid), EOF A-2001 (CIBA), CWD (Hilton-Davis), Phorwhite RKH (Verona), CCL, Fäurepulver (American Cyanamid) , CEL, liquid, moncethanolamine salt (American Cyanamid), FB 766 (Verona), Blancophor PD (GAF), UNPA (Geigy), Tinopal RBS (Geigy) and RBC 200 (Geigy.

Anionic surfactants are preferred as additional surfactants , Surfactants are used because they are best compatible with the main component of the heavy duty detergents. Preference is given to using it higher straight chain alkyl benzenesulfonates and 12 bis 16 carbon atoms in the alkyl chain, higher Fettalfcoholiuilfate, higher Olefineulfonatc, higher fatty acid ripening at the same time as Foam-inhibiting agents work, and higher alkyl-tolnolsulfonate. The higher / illiyl groups contain 10 bir; 18 and vorrvugrweiije 12 to 16 C-Atüiue. Preferably used njeblioujsehe surfactants

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are the polyätlioxylierte higher alcohols, the middle or higher alkyl-phenol-polyethyleneethanols, the block copolymers from ethylene oxide and propylene oxide ("Pluronics") and the mixed polymers of ethylene oxide and propylene oxide, which are either terminally esterified or free hydroxyl groups contain. The imidazolines, pyrazolines, imides or “Mannheimer” amphoters can be used as amphoteric surfactants. Cationic Surfactants are generally not used because they react with the anionic surfactants and thus the detergency "weaken both connections.

As additional inorganic builder salts Various compounds are used such as borax, sodium carbonate, anhydrous sodium carbonate or the Silicates. In addition, fillers such as sodium sulfate or sodium disulfate can be added. It must be noted, however, that the inorganic compounds do not react with the other components of the detergent or in the liquid detergent are insoluble.

The pH of the liquid detergents according to the invention can vary between pH 2 and pH 12, particularly favorable washing properties result in a pH range of 7 to 9 · A slightly higher alkalinity can be achieved by the presence due to auxiliary materials that have a very high pH value to achieve solubility, such as the poorly soluble ones Brighteners, need.

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The concentrations of the constituents of the liquid floor detergents according to the invention are for manufacture a uniform product with good Y / ash force is important. In the absence of phosphate builder salts, the Detergents contain a large amount of fatty alcohol ethylene oxide sulfate and citrate. To make the clear homogeneous and easily pourable liquid detergents are 8 up to 30, usually 10 to 20 and preferably about 15% of the anionic Surfactants of the formula RO (CpH.0) SO, M are required. These amounts together with the citrate used, produce the desired properties. The amounts of additional surfactants will be limited to about $ 30 of the main surfactant; aside from that These auxiliary surfactants must not lead to incompatibilities or phase separations in the detergent.

The citrate builder salt makes, calculated as sodium citrate dihydrate as the preferred citrate, $ 10 to $ 30, mostly $ 15 to $ 25 and preferably $ 20 of the total product. A Part of the citrate, preferably only a small part, can be replaced by other builder salts within the specified limits. The upper limit of the addition of citrate often results from the solubility of the citrate within the specified limits,

The addition of a hydrotropic compound is desirable in order to improve the compatibility of the individual constituents; this connection is available in amounts ranging from $ 1 to $ 15, usually $ 5 bit 10 $ and preferably 8 $ to 9 $ »based on the total

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- ΐθ -

mixture, used. Larger concentrations are not necessary and can even affect the phase stability, while smaller amounts are not sufficiently hydrotropic Have an effect and thus lead to a lower shelf life. In most cases, sodium cuinolsulfonate can be used in smaller amounts than other hydrotropic compounds such as potassium xylene sulfonate with the same solubilizing properties Effect can be used.

The solvent is preferably water, the smaller one Amounts such as up to $ 30 may contain mono-, di- and polyalcohols and similar solvents. The total amount of solvent is at least $ 15 to $ 30, usually $ 40 to $ 60, and preferably about $ 50 of the total mixture. Often will already introduced $ 10 to $ 60 of the total water to be added by the other components, so that only the remaining Water in the form of deionized water needs to be set during the mixing process. The proportion of aqueous solvents can vary within wide limits, but care must be taken to ensure that there is sufficient water for the solution of the various constituents must be present in the presence of the hydrotropic compound and that, on the other hand, too dilute Solutions are not sufficiently effective.

The anti-foam inhibition and because of the additional Detergency soap is available in amounts from $ 0.5 to $ 5, and preferably $ 1 to $ 2. The brightener mixture

holds 51 ^C £ to 90 $ of a cotton whitening agent and further polyamide whitening agents, polyester brightening agents and chlorine bleaching stable brightening agents. The total content of brighteners in the confectionery detergent according to the invention is $ 0.2 to $ 2, usually $ 0.4 to $ 1, and preferably about $ 0.7. Such amounts are soluble in the liquid heavy duty detergents according to the invention and have a good brightening effect on the washed laundry.

The amount of other auxiliary compounds should generally not be more than 20% of the detergents according to the invention lind will usually be less than $ 15 and preferably less than $ 10. The individual ingredients should not exceed $ 10, usually no more than $ 5 and preferably less than $ 3 of the total mixture turn off. If larger amounts are used, the properties of the raw detergents according to the invention can be considerably increased change, and therefore the addition of larger amounts should be avoided.

The use of the clear liquid heavy duty detergents is simple and effective. It will only be relatively small Quantities of the liquid washing agent for from above or from the side loading washing machines required. When using a liquid detergent according to the invention with a content of $ 50 Solids and $ 50 water only need about a third of a cup of detergent for a full load of an automatic Washing machine with a water volume of 56.0 to 68.1 1 used to ground. The weight was about 50 g

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for one to be loaded from the side and about 100 g for one Top loading washing machine. The amounts used correspond to approximately 0.1 to 0.3 g / l higher fatty alcohol polyethenoxy sulfate., 0.1 to 0.5 g / l citrate, 0.07 to 0.2 g / l hydrotrope, 0.01 to 0.1 g / l soap, 0.01 to 0.02 g / l optical brighteners and 0.01 to 0.1 g / l other excipients. These amounts of active ingredients can also be achieved with more dilute or concentrated liquid detergents, however, various problems arise here, such as, for example, the transport of the unnecessary in the case of more dilute detergents Water and the larger volume and with more concentrated solutions it often turns out that they are too thick or some Components become insoluble during storage.

The wash water is preferably of low or medium hardness and is used at elevated temperatures. However, washing can also be done in hard water and at low temperatures. The water hardnesses can be between 0 and over 300 ppm, calculated as calcium carbonate, and the water temperatures between 10 ^° C. and 90 ^° C. The washing process is preferably carried out at temperatures of 20 C to 70 C in an automatic washing machine, in which, after the washing process, a rinsing process and a spinning process or other drying or centrifuging actions take place · Of course, the liquid coarse detergents according to the invention can also be used for hand washing; in these cases they can be partially undiluted for removal

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certain stains from the ashes or for soaking the Wash in a more concentrated solution can be used. The washing process generally takes 3 minutes to 1 hour depending on the fabric to be washed and the degree of soiling. After finishing the Y / ashing and hurling the laundry is preferably dried in an automatic tumble dryer. Between Y / ash process and Drying process, a rinsing process with the addition of a fabric softener is preferably switched on.

The liquid rough detergents according to the invention dissolve very quickly in cold or warm Y / ash water and have an excellent cleaning effect on all types of Y / ash. It can be used in Y / ash machines that are loaded from above or from the side, whereby the foam development can be adjusted. The detergents according to the invention are clear, stable liquids which retain their effectiveness without phase separation on prolonged storage. Comparative tests with commercially available coarse detergents provided with builder salts show that the detergents according to the invention are judged very favorably, especially in view of the fact that the washing liquor does not require any special treatment before it is poured away or discharged into drains or sinks. The Y / ash properties are excellent, the application ii.t convenient, εο that with comparable Y / ash properties with known detergents] η the overriding advantage of the inventors; in other words, wherever there is no washing

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server pollution from phosphates.

The following examples are intended to explain the invention in more detail. Unless otherwise stated, all refer to Partial information on the weight.

EXAMPLE 1

R0 (C ₉ H ₁ O), SO, Na ("Neodol 25-3 £", 60% aqueous 25.0 * ■ * '* solution containing 14 $ ethanol, 1 $ non-sulfated alcohol, R = mixed primary alkyl groups with 12, 13, 14 and 15 carbon atoms

Sodium Citrate Dihydrate 20.0

Sodium cumene sulfonate, 43 $ aqueous solution 20.0

(with V / o sodium sulfate)

Deionized water 35.0

100.0

By adding the sodium cumene sulfonate, des Citrates and Neodol to the specified amount of water at room temperature of 25 C became a clear liquid rough detergent obtain. The order of addition and the temperatures can be changed on request clear plus detergent that also works for longer times are stable in storage. The pH of the product is 8.5.

The washing power of the detergent according to the invention " compared to commercially available detergents, it was

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Turn of tap water from New Brunswick, New Jersey, containing 100 ppm for calcium carbonate, magnesium and calcium hardness compared. In one series of experiments, cotton laundry items were repeatedly soiled by periodically rubbing them against human skin during one day so that they contained dirt, grease, flakes of skin and sebum secretions. This wash was equally ^v e * shares and hydrotropes in a laboratory washing machine "Terg-o-tometer" in a solution of detergent invention or a Kontrollwaschmittels.ohne Verbindungen.gewaschen. The washed laundry was examined with a reflectometer and the removal of real dirt was determined. A statistical analysis of the results was then carried out to determine whether or not there was a difference in the detergency of the detergents tested. The statistical analysis showed that the liquid coarse detergents according to the invention without a content of polyphosphates as builder salts have just as good detergency as the commercially available detergents with a content of 35% polyphosphates. The same results were obtained when the tests were repeated using the same, re-soiled and rewashed laundry. In experiments with the detergent according to the invention and a commercially available detergent in the so-called "bundle test", in which a large number of soiled items of laundry made of cotton, cotton-polyester fabric, rayon and nylon are used in a commercially available automatic washing machine, the Erßehiiivne with the "Terc-o -toracter "confirmed. Similar results were obtained

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also get if instead of the "Neodol 25-32" other higher ones Fatty alcohol polyethenoxy sulfates with, for example, mixed higher pettalkyl groups with 12 to 13 or 14 to 15 carbon atoms were used, but the mixtures with 12 to 15 carbon atoms appeared to develop a somewhat better Y / ash force than the fractions with 14 to 15 carbon atoms. With regard to the ethoxylation, comparable results were obtained when the higher fatty alcohol was ethoxylated two to four times, provided that the hydrophilic-lipophilic balance was that of the des "Neodol 25-3S" is similar. When using alkyl groups with a higher content of carbon atoms should therefore be the Äthoxylierungsgrad higher, for example 4 or 5, while on the other hand with a lower content of carbon atoms in the alkyl groups, the degree of ethoxylation 2 to 4 should be. Excellent washing effects were also found when using the fatty alcohol polyethenoxy sulfates described potassium, ammonia, lower alkylamines or lower alkanolamines were present as cations.

If much larger amounts of the abovementioned active ingredients are used, solubility problems arise, so that the liquid detergent is often not clear or forms two phases. This can also occur if more than 5 / »" Neodol 4511 "is added to the mixture instead of the corresponding amount of water. "Neodol 4511" is a higher (C-. To C ₁ , -) alkyl-polyethenoxy (11 mol ethylene oxide) alcohol. Even if the alcohol polyethene oxy sulfate is replaced by higher alcohol sulfates, the stability and Fh: »Gonunft fe & tßcc toJ Ί t are deteriorated.

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Instead of the sodium citrate dihydrate, citric acid or mixed citrates such as potassium, ammonium or lower alkanolamine salts can be used with the same effectiveness.

Even if the sodium cumene sulfonate is replaced by potassium xylene sulfonate or ammonium benzenesulfonate, clear and stable liquid detergents are obtained. The proportion of the hydrotropic compound was varied within the specified limits, as was the amounts of the citrates. In each case, clear, stable Plüssig detergents with excellent detergency were obtained.

More Plüssigwaschmittel were produced, the optical brightener, cotton and polyester and nylon brightening agents contained. These detergents are single-phase detergent with good detergency, which also lighten the washed laundry.

The Plüssig detergents according to the invention were used in amounts corresponding to one third of measuring beakers for washing machines to be loaded from above in the experiments indicated, but this amount can be reduced to half for washing machines to be loaded from the side. Excellent washing properties are found in both cases. When used for washing soiled laundry, the concentration of PlÜBsig detergent can be 1 to 2.5 g / l depending

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In general, 1 to 2 g / l will be sufficient for a normal wash. The washing time varies depending on the laundry to be washed and the degree of soiling. In general, washing times between 3 minutes to 1 hour are observed, 45 minutes being usual . in hot water better cleaning effect is found, but the detergent can also be used in cold water because it dissolves quickly and completely, "the water temperatures used in the experiments were 65 ⁰ C. Under these conditions, the pH is the Washing water about 7 to 9; in most experiments the pH value at the beginning of the washing process was about 8.5 and was lowered by about one unit as the washing process progressed, depending on the type of laundry and its acid or buffer compound content washing is rinsed with water, sometimes three times, and the remaining water by spinning, Wringing, applying a vacuum, etc. removed and the laundry preferably dried in an automatic tumble dryer «

EXAMPLE 2

Example 1 was repeated with the exception that the sodium nitrate was replaced by 20% citric acid. The pH value of the finished liquid detergent is 1.3. The detergency is somewhat lower than that of the detergent from Example 1.

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EXAMPLE- 5

Example 1 was repeated except that no sodium cumene sulfate was added and the water content was increased $ 55 was increased. The detergent is more viscous than the one off Example 1, the detergency is comparable.

EXAMPLE 4

Example 1 was repeated, except that instead of 20% cumene sulfonate, 10% sodium xylene sulfonate in 40% strength aqueous solution and 10% water were used.

Example 5

The following Plüssig detergents were produced:

% Components

ABC DE

"Neodol 25-3S" 25.0 25.0 29.5 20.0 25.0

Sodium citrate '2HgO 20.0 20.0 23.5 20.0 20.0

Sodium cumene sulfonate (43%) 20.0 20.0 Sodium xylene sulfonate (40%) 5.0 12.0

with 11 MoI
Ethylene Oxide ("Neodol 4511") 3.0 3.0

Isopropyl alcohol 1.0

Water 50.0 54.0 35.0 37.0 32.0

209833/1 UI

EXAMPLE 6

A liquid detergent made from the following ingredients was produced:

"Neodol 25-3S" 25

Sodium citrate · 2H ₂ O 10

Sodium cumene sulfonate ($ 43) 20

Sodium carbonate 10

Sodium silicate 10

Water 25

EXAMPLE 7

Example 6 was repeated, with $ 10 citrate (so a total of $ 20) being added instead of the sodium carbonate became.

EXAMPLE 8

Example 1 was repeated, the content of "Heodol 25-3S" being changed with a corresponding change in the water content was changed as follows:

A. 8 $ alcohol polyethenoxy sulfate ("Neodol 25-3S")

B. 15 $ alcohol polyethenoxy sulfate ("Neodol 25-3S")

C. 50 $ alcohol polyethenoxy sulfate ("Neodol 25-3S")

D. 20 $ sodium n-deoxyJ diethenoxy sulfate

E. 25 $ ammonium lauryl diethenoxy gulfat

P. 15 $ diethanolamine-stearyl-pentaüthenoxy-sulfate G. ??. ','< Potassium myr: ' ιΛνΙ -triätlienoxy-rnlfat

209833/1141

In rille cases, wurcu-n aur.ftozeichneiv i'i'rrlmirre erlu; ttoi !.

_ 29 -

EXAMPLE 9

Examples 8 A to 8 G were repeated, the citrate content being varied as follows with a corresponding change in the water content:

A. 1Ο5έ sodium citrate. 2 H ₂ O

B. 30% Sodium Citrate Anhydrous

C. IO96 Citric Acid

D. 20% Potassium Citrate Anhydrous

E. 15% ammonium citrate

P. 25% diethanolammonium citrate G. 1556 trimethylammonium citrate Each of these detergents showed excellent properties.

EXAMPLE 10

All previous examples have been added with the following compounds :

A. 0.05% sodium EDTA

B. 1.0% sodium nitrilotriacetate

C. 1.0 % sodium tripolyphosphate D · 0.08% tetrapotassium pyrophosphate The mixtures were comparable to the detergents from Examples 1 to 3.

EXAMPLE 11

r,

Examples 1 to 3 were repeated, with a corresponding reduction in det. \ iia -.r-received. one

209833/1 UI

Sodium tallow coconut oil fatty acid soap (80:20) was added:

A. $ 1.0>

B. 2.0%

C. 3.0 ° />

EXAMPLE 12

Examples 1, 3, 8C and 8D were repeated repeated, whereby the following additional surfactants were added while reducing the water content:

A. 3.5 fo sodium lauryl sulfate

B. 3.0 #. Sodium n-tridecyl benzenesulfonate

C. 4.0 % myristyl nonethenoxy ethanol

EXAMPLE 13

Examples 8C and 8E were repeated, with how

in example 12 separately $ 7.5 sodium lauryl sulfate, at 8D

7.5 ° ß> sodium dodecyl-'ibenzenesulfonate and at 8E 7.5 % dodecanol with 15 mol of ethylene oxide were added,

209833/1 U1

Claims (7)

PATENT CLAIMS 1. Liquid heavy-duty detergents not containing phosphates or nitrogen-containing builder salts, characterized by a content of about 8 io to about 30 $ of a water soluble anioniEchen organic surfactant of the general formula RO (C ₂ Hi0) _n f0, M, in the Ii a fatty alkyl group with 10 up to 20 carbon atoms, η is an integer from 2 to 6, corresponding to a fifth to a third of the number of carbon atoms in R and M are an alkali-forming cation, about 10 to about 30 io of a citrate builder salt, about 0 ^C / O to about 15 Ψ 'of a hydrotropic compound, about 0 i> to 5% of a water-soluble feife, about 0 ^ to about 10 ^c / o of a waeserlös] cozy filicates, about i 0 $ to 10 io a water-soluble carbonate and about 15 » to about 80% of an aqueous solvent. 2. Liquid coarse detergent according to claim 1, characterized in that it 8 / »to 30 io of a water-soluble anionic surfactant, in the general formula M is an alkali metal, ammonium, lower alkylamines or lower alkanolamines, 10 $ to 30 io of a citrate builder salt, 5 io io to 15 of a hydrotrope such as cumene sulfonates, benzenesulfonates, toluenesulfonates or xylene sulfonates and 15 ^c /> contains 80 io of an aqueous solvent. 2 0 9 8 3 3/1 U 1 3. Liquid coarse detergent according to claim 2, characterized in that it contains 10 fo to 20% RO (C ₉ H. 0) £ 0, M <~ H- ϊϊ ί ι where R is a straight-chain alkyl chain with 12 to 15 carbon atoms, η is an integer from 2 to 4 and M is an alkali metal, 15 fo to 25 $> of an alkali citrate, 5% to 10 "/> of an alkali metal of a hydrotropic compound and 40 fo contains up to 60 % of an aqueous solvent. 4. Liquid coarse detergent according to claim 3, characterized in that it is 10 to 20 i » RO (C ₂ H ₄ O) SO ₅ M, where R is a mixture of straight-chain alkyl chains with 12 to 15 carbon atoms, which are terminated with the oxygen the Polyäthenoxykette are connected η = 3 and M is sodium mean 15% to 25% sodium citrate, 5 # bit 10% sodium cumene sulfonate and contains 40% to 60 io water. 5. Liquid coarse detergent according to claim 4, characterized in that it 15 ^ RO (C ₂ H ₄ O) ₅ SO ₅ Na, 20 # sodium citrate, 8.5% sodium cumoleulfonate and in addition small amounts of optical brighteners, dyes, perfumes and contains other excipients in a clear, stable, single-phase solution. 6. Liquid coarse detergent according to claim 2, characterized in that it contains 0.5 $> to 5 # of a water-soluble alkali soap as a foam-inhibiting agent. 209S33 / 1U1 7. Liquid coarse detergent according to claim 3, characterized in that it contains 0.4 % to 1 $ of a mixture of optical brighteners in which the greater part is cotton brightener and the smaller part is polyester-polyamide brightener, in a clear single-phase solution. 209i * 3 / mi .. * In·