DE2333974A1 - LIQUID DETERGENT - Google Patents

Description

The invention relates to clear liquid heavy duty detergents which are easily dispersible in water, and in particular clear, easily dispersible liquid heavy duty detergents which are practical are neutral and easily biodegradable.

Lately the concern about the effects has been various Substances on groundwater, streams, rivers and lakes among governments and populations have increased sharply. Particularly undesirable is the high output of permanent compounds, which severely impair the quality of our water. Because of this widespread concern, manufacturers are making efforts to make synthetic non-biodegradable ones

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organic detergents, i.e. branched chain alkylbenzenesulfonates, to keep these substances out of standard household laundry as an organic surface-active substance. In connection with the exclusion of these non-biodegradable synthetic organic detergents also have the possible adverse effects of the polyphosphates and nitrilotriacetic acid builders which lead to Use with these and other synthetic detergents developed led to the endeavor to use these as well Avoid substances in detergents.

The polyphosphates as well as the nitrilotriacetic acid and its salts have been found in the known detergents and cleaning agents has a very beneficial building, sequestering and soil dispersing function, and it has proven to be very difficult have been shown to develop agents without phosphates or nitrogenous builders which give equally good results. Self " IOO9S will not develop active synthetic organic surfactants the effect produced by combinations of these compounds with the above builders.

Also, it was not previously thought possible to use the higher alkyl polyethene oxysulfates, which, although as additional Surfactants for combination with various other anionic and nonionic synthetic organic surfactants are known to be used as the main or sole surface-active substance in liquid heavy-duty detergents.

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The present invention is based on this state of the art and proposes new liquid heavy duty detergents which, as the main surface-active substance, are an anionic surfactant of the general formula RO (C ₂ H ₄ O) _n S (KM, where R is a fatty alkyl group with 10 "to 20 carbon atoms, η a number of 2 Ms 6 and preferably 1/5 "to 1/3 of the number of carbon atoms in R and M a salt-forming ion, generally an alkali, ammonium, lower alkylamino or lower alkanolamino ion, These heavy duty detergents can also contain a small amount of an additional synthetic surfactant, a foam control agent, perfumes, dyes and fluorescent brighteners.

The liquid heavy-duty detergents according to the invention are essentially free of phosphates and nitrogen-containing builders, have a low viscosity and consist essentially of 30 to 70% by weight of anionic surfactant of the general formula RO (CgH ^ O) SO ..M, where R is an alkyl group 10 to 20 carbon atoms, η a number from 2 to 6 "and preferably 1 / $ to 1/3 of the number of carbon atoms in R and M a salt-forming ion, generally an alkali, ammonium, lower alkyldmino or lower alkanolamino ion, is 0 to 25% by weight of an additional surfactant compatible with this anionic surfactant, preferably a nonionic surfactant of the general formula RO (CpH ₄ O) H, where R is an alkyl group with 10 to 20 carbon atoms and η

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a number from 5 to 14, but 2/5 to 1 times the number the carbon atoms in R is 7 Ms 25 wt. # of a lower one monohydric alcohol and 5 Ms 50 wt. # water.

In the anionic surfactants of the general formula RO (CgH ^ O) S (KM, which can be used in the agents according to the invention, the alkyl group R is preferably a straight-chain alkyl group with 10 Ms 20 carbon atoms, η a number of 2 Ms 6 and preferably i / 5 Ms i / 3 of the average number of carbon atoms in R, and M is a cation selected from the alkali metals such as sodium, potassium, etc., ammonium, lower alkylamines and lower alkanolamines group comprising. This anionic surfactant may be 30 ms 70 wt. i constitute ° of the total detergent, however, it is preferably in quantities of 35 ms 60 wt. $ and used, in particular of 50 Gew.5 ^.

So that the anion-active surfactant used in the agents according to the invention is easily biodegradable and has a higher Shows the washing effect, the fatty alkyl group is preferably a straight-chain pettalkyl which is terminated with the polyethenoxy chain is connected, which in turn is necessarily terminally connected to the sulfur in the sulfate group. Although a little branching of the higher alkyl group to less than 10% of the carbon content of the alkyl group This slight deviation from the linear structure can generally be tolerated

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_ 5 -

avoid. Likewise is a central bond of the alkyl group to avoid the polyethenoxy chain, although this "is tolerated to a small extent, i.e. less than $ 10 can; however, even such bonds should preferably be concentrated at sites near the end of the alkyl chain. Within of the range of alkyl groups with 10 "to 20 carbon atoms, those with 12 to 15 carbon atoms are preferred, of which, in turn, mixed alkyls with 12, 13, 14 and 15 carbon atoms in the chain are particularly suitable. In Each chain length is preferably at least $ 10 and at most $ 50 in such a mixture.

The ethylene oxide content of the anionic surfactant is so high that η is a number from 2 to 6, preferably 2 to 4 and on average generally about 3, especially when R is a mixture of C ^ "" ¹³ ^ s C \ j- -Alkyl groups. In order to maintain the desired balance between hydrophilic and lipophilic properties with a carbon content of the alkyl chain in the lower range of 10 to 20 carbon atoms, the ethylene oxide content can be reduced so that η is about 2, while for alkyl groups with 16 to 18 Carbon atoms η can be a number from 4 to 6.

The salt-forming cation can be any solubilizing metal or radical, but is usually an alkali metal, like sodium or potassium, or ammonium. If the cation is a

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is lower alkylamine or lower alkanolamine ion, the alkyl or alkano! groups therein generally contain 1 to 4 carbon atoms, with the amines and alkanolamines can be mono-, di- or tri-substituted.

The importance of using the anionic surfactants mentioned in the agents according to the invention is shown by the fact that the corresponding alcohol sulfates fail in the same liquid detergents. The corresponding alcohol sulfates do not wash nearly as well as the alcohol polyethene oxysulfates. For example, "a higher alcohol sulfate in which the alcohol is a mixture of C ₁ P" to C ₁ C-Alcohol in detergent compositions which correspond to those of the invention shows a significantly poorer detergency than the corresponding ethoxylated sulfates with otherwise the same composition . also within the preferred range of Alkoholpolyäthenoxysulfate is a better washing effect for products with a mixed C ^ - "to C .. (- Alkoholpolyäthenoxy sulphate over other higher Alkoholpolyäthenoxysulfaten such as a mixed C ₁ - to C ₁ ^ compound found The surfactant preferred for the compositions according to the invention is available from Shell Chemical Company under the designation "Neodol 25-3S, sodium salt ¹¹ , which is normally traded with a content of 60 $ active ingredient and 40 $ aqueous solvent system including a small amount of ethanol. As was said above, is

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the "preferred material" is the sodium salt, but can also other soluble salts can be used in place of the sodium salt.

Higher alcohol polyethene oxysulfates, which can be used as an anion-active surfactant in the liquid detergents according to the invention or as a partial replacement for the preferred anion-active surfactants described above, are, for example: normal primary mixed C ^ p ^ -jc-alkyltriäthenoxysulfat, sodium salt, Myristyltriäthenyltriäthenyldiätjänjulat, dietary ; Lauryl diethenoxy sulfate, ammonium salt} palmityl tetraetheneoxy sulfate, sodium saltj _{normal primary mixed C 1,.} amine salt; normal primary mixed C ₁ q -g alkyl triethenoxy sulfate, potassium salt. Small amounts of the corresponding branched-chain and intermediate alkoxylated surfactants, ie the above corresponding surfactants with ethoxylations on central carbon atoms, for example on one. A carbon atoms removed from the end of the chain. Carbon atom, are also used, but the carbon content: ^ of the higher alkyl group is the same. The bond of a normal alkyl can also be one or two carbon atoms away from the chain end on a secondary carbon. In any case, however, only the small amounts mentioned above may be present.

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In addition to the anion-active sulfated surfactant, the Agents according to the invention still have a small amount, i.e. from 0 "to 25% by weight and preferably 0 Ms 15% by weight, non-ionic Tens id contain, which consists of a condensation product of higher alcohol and ethylene oxide. Although these non-ionogenic Surfactants are occasionally detrimental to the viscosity and gel properties of the anion-active sulfated When surfactants have an effect, they can generally be incorporated into the detergents according to the invention in small amounts without increasing the viscosity of the concentrate obtained. the dispersibility of the agent in water increases Reduce. Preferred nonionic higher alkyl polyetheneoxy surfactants are compounds of the general formula RO (CpH.0) H, where η is a number from 5 to 14 and R is an alkyl group with 10 to 20 carbon atoms, where η is, however, the 2 / 5- to 1 times the number of carbon atoms in R. In general are mixed alkyls due to the manufacturing process used, the Ä'thylenoxidketten in the range of 5 to 14 ethylene oxide units can be of different lengths.

For the lengths of the fatty alkyl and ethylene oxide chains there are within the above ranges, however, a critical level in order to simultaneously achieve good washing properties and the desired Solubility and compatibility with the biodegradable sulfated anionic main surfactant of the invention To obtain funds. The alkyl group should generally contain 10 to 16 carbon atoms, and the average

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liehe carbon content of the preferred compounds hot 11 or 14 to 15. Consist in the most preferred nonionic surfactants of the class described above the alkyl groups generally up to over $ 80 from chains with a length of 14 to 15 carbon atoms »The ethylene. oxide chains preferably consist of 5 to 6 or 10 to ethylene oxide units and a particularly preferred one non-ionic compound is the number of ethylene oxide units per chain essentially 11. An example of such a preferred nonionic surfactant is the commercial product "Neodol 45-11" (R = mixed CL * - and C., - alkyl groups, η = average 11), which der.Shell Chemical Company is manufactured. The desired balance between hydrophilic and lipophilic properties is adhered to by adding n, i.e. the number of ethylene oxide units per alkyl radical, to 2/5 to 1 times Value of the number of carbon atoms in R holds.

In addition to maintaining the appropriate chain lengths in the hydrophilic and lipophilic part of the surfactant, it is also important that the nonionic surfactants have a certain structure to achieve the best washing effect and biodegradability to have. · As with the sulfated anionic surfactants, the ethylene oxide chain is necessarily linear, and they should preferably be attached to the end of a linear alkyl group. Although little branching to an or two carbon atoms from the end of the chain

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Carbon atoms can be tolerated, should be such Branching should be kept as low as possible and below $ 20 and preferably below $ 10 of the total alkyl content of the non-ionic surfactant.

Although these nonionic surfactants are preferred, they can also be wholly or partially replaced by other surfactants that contain the sulfated anionic surfactant are compatible, be replaced. These interchangeably usable other surfactants include although also some cationic and amphoteric or ampholytic surfactants, but one preferably uses other anionic or nonionic surfactants j and if one If the preferred nonionic surfactants are replaced by these other secondary surfactants, the amount of these secondary surfactants is kept Surfactants preferably less than 10% by weight of the total product. Mixtures of such surfactants can of course also be used, as long as the total content of secondary surfactant is below $ 25 is kept and the surfactants used with each other and are compatible with the anion-active sulfated surfactant. Such optionally additionally usable surfactants are, for example, higher fatty acid esters of polyethylene glycols, Block copolymers of ethylene oxide and propylene oxide (Pluronics), Alkyl (higher molecular weight) dialkyl (lower molecular weight) amine oxides, the sodium salts of sulfuric acid derivatives of denaturation products higher fatty alcohols with ethylene oxide, triethanolamine lauryl sulfate, straight-chain alkyl sulfonates, sodium lauroyl sarcoside, Cetyltrimethylammonium bromide, benzethonium chloride,

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Dimethyldibenzylammonium chloride, N-alkyl (higher molecular weight) - NjN-dialkylCniedermolekularJ-aminopropanaulfonate, Amidosulfobetaine, Betaines and amido betaines. Such in addition Usable surfactants are, for example, in the book "Synthetic Detergents" by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers, New York, in particular on pages 25 to 143 ». It should be noted that such surfactants in general only for special Purposes and compared to the main surfactant, i.e. the anion-active sulfated polyetheneoxy compound, only in small amounts are used and are generally only used if certain washing properties of the same for a particular one Area of application are desired.

Furthermore, the detergents according to the invention contain, as has already been said above, 7 to 25 wt. ^ And preferably 7 to 15 wt. # Lower monohydric alcohol with 2 to 4 carbon atoms, such as ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, tert-butanol, etc. Although any of these alcohols can be used, isopropanol is preferred. The lower monohydric alcohol is an essential component of the agents according to the invention, since it reduces the viscosity of the concentrated liquid obtained Coarse detergent reduces and at the same time a fast Promotes dissolution of the various components including surfactants in the wash water. Besides this acceleration the addition of one prevents dissolution in the wash water

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lower monohydric alcohol formation of a gel, though the anion-active product is added to warm water. Although initially formed gels can be easily stirred solve again, it is preferred for both practical and aesthetic reasons that the invention Quickly distribute liquid detergent immediately after pouring it into the washing water. Since gel formation and Insufficient dispersion in the wash water resulting in local overconcentrations of teriside and other components of the Detergents according to the invention would result in letting out the lower monohydric alcohol from the invention Means a considerable degree of staining to occur. Although the lower monohydric alcohols mentioned all can be used, the others seem to reduce the viscosity of the liquid detergents according to the invention and not being as effective in accelerating their dissolution in the wash water as isopropanol, which is preferred. Likewise, other compounds such as polyhydric alcohols, e.g., propylene glycol, ethylene glycol and the like, are also suitable for the Products according to the invention are unsuitable because they do not reduce the viscosity or prevent gel formation.

The fluorescent or optical brighteners or whiteners used in the agents according to the invention are important Components of modern detergents, which give the washed fabric a shiny appearance, so that they do not are only clean but also appear clean. Because of

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the diversity of synthetic fibers in textiles, which make up laundry and clothing and others Textile processed, and the importance of Substantivity of the brightener connection to the fibers -man developed many different fluorescent brighteners, which, often mixed with one another, in the invention Detergents can be incorporated. They are of course also suitable for treating cotton Brighteners and brighteners which are resistant in the presence of oxidizing bleaches are important. So it is for those of the invention Laundry detergents are important in general, although they are of course only a single brightener for a particular one Intended use, a mixture of lighteners with good lightening effects for cotton, nylon, To use polyester and mixed fabrics made of these fibers, which are also resistant to bleaching agents. One a good description of these types of optical brighteners is in the work "Optical Brighteners and Their Evaluation" by Per S. Stensby, a reprint from in Soap and Chemical Specialties April, May, July, August, and September 1967 published articles, especially on pages 3-5.

The Baumwo11aufheller, which are often also called CC / DAS brighteners • are designated because they differ from the reaction product of cyanuric chloride with the disodium salt of diaminostilbene disulfonic acid in a molar ratio of 1: 2 are bistriazinyl derivatives

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of 4,4'-diaminostilbene-2,2'-disulfonic acid. In most Cases, CC / DAS is reacted with two moles of aniline or sulfanilic or metanilic acid and the product is also added to the Triazine rings substituted. Such connections have the

general formula

SO ₃ Na

wherein X is either hydrogen or SO ₃ Na and R is a radical derived from aniline, morpholine, N-methylethanolamine or diethanolamine. Since various laundry detergents are used in conjunction with bleaching agents, a bleach-resistant brightener is also used, generally a benzidinesulfondiaulfonic acid, a naphthotriazolylstilbene sulfonic acid or a benzimidazole derivative. These compounds correspond to the general formulas

SO ₃ Na

RNH-

SO ₃ Na

-NHH

, -CH = CH

SO ₃ Na

C-CH = CH-C

wherein R is hydrogen or a lower alkyl, lower alkanol, lower aminoalkanol, anilino or morpholino group or like is. The polyamide lightening which is particularly suitable for nylon they are generally either aminocoumarin or diphenylpyrazoline derivatives. Unfortunately, "both types are in the present not particularly stable from chlorine bleach. These compounds have the following general formulas, in which R and R 'correspond to the substituents mentioned for the optical brighteners described above, and X and Y also stand for such substituents or halogens or lower alkyl groups:

The polyester brighteners, which are gaining in importance as polyester is increasingly present in the Textiles used generally have one of the following general formulas, in which R, X and Y are the have the above meaning and Z can be one of the substituents mentioned for X and Y. These brighteners are generally used also for whitening polyamides:

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CH = CH

The brighteners are used in the form of their acids or their salts. They can be used as pesticides or as solutions used and can be blended with a carrier powder. Although the chemical and the physical Shape the whitening effect "can affect the compounds are used in soluble form, the whitening effects for the same compounds are based on the active Substance equivalent. The brighteners are used in the agents according to the invention and the washing solutions produced therewith kept sufficiently well in solution to be effective and evenly applied to the fabric to be washed Winding up textiles.

The brighteners, v / which in the agents according to the invention Can be used include the commercial products Calcofluor White ALF (American Cyanamid), ALF-N (American Cyanamid), SOF A-2001 (CIBA), CDW (Hilton-Davis), Phorwite REH (Verona), CSL powder, acid form (American Cyanamid),

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PB 766 (Verona), Blancophor PD (GAP), UIiPA (Seigy), Tinopal RBS (Geigy) and EBS 200 (Geigy). The acid forms or "nonionic" forms tend to be replaced by the in the Agents according to the invention used isopropanol to be made soluble, while the salts for water solubility tend. Thus, a combination of these solvents and the surfactant combination serve to make the fluorescent brighteners keep in solution.

Deionized water is preferably used as Y / ater in the agents according to the invention in order to avoid the presence of reactive ions which precipitate insoluble with other components of the plus detergent. ..or colored deposits could form; When de ionizing '.... the content of metal ions is generally reduced to below 10 ppm as calcium carbonate. So although deionized water is best used and this is available or can be manufactured in many production facilities, it is often also possible to use normal tap water if its hardness is low enough and of such a nature that.:. it has no adverse effect on the - .. ·· product to be manufactured. In addition, small amounts, ie from 0.1 to 2 wt. #, Of a sequestering agent can also be used in order to eliminate possible adverse effects, water hardness and heavy metal ions. Suitable sequestering agents include nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), gluconates, lactates, phosphates and the like.

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It should be noted that NTA and phosphates and polyphosphates, when used as sequestering agents are only present in very small amounts, which are absolutely not act as builders in the detergents produced. Consequently are the liquid detergents according to the invention, themselves if they are used for sequestering purposes small amounts of polyphosphate or HTA, still practically free of phosphate and nitrogen-containing builders.

Furthermore, the detergents according to the invention can be adjusted so that they are either strong or weak or have a medium foaming power. These different foam behaviors are important, as most household washing machines do are of the head-fed type and fit from 55 to 70 liters, but also have a considerable number of front-loading washing machines lower water capacity is in use. For these front-loading washing machines, the ratio is Laundry larger than washing water and usually only a smaller amount of detergent is used to achieve the same washing effect needed. Although foam is useful for washing away particulate debris in head-loaded machines is and although housewives generally associate good foaming power with good detergency, it generally is Desired both from the ecological point of view and from the point of view of good cleaning effect, the amount of To limit the foam generated by detergents.

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It has been found that the foaming power can be adjusted as desired: can regulate that little or no foam is produced while maintaining a high washing effect, if you give the liquid detergents according to the invention a soluble soap of a higher fatty acid or a mixture of such soaps. The higher fatty acid soaps are common Alkali salts, i.e. potassium or sodium salts, a mixture of higher fatty acids, such as from natural animal or Fatty acid mixtures obtained from vegetable fats and oils. ..- Such Soaps generally contain a major proportion of saturated fatty acid soaps with chain lengths of 10 "to : 18 carbon atoms. Particularly preferred mixtures are by mixing tallow and coconut oil fatty acids and saponifying Made from mixed tallow / coconut oil batches. For the -: ■ purposes according to the invention, soaps are generally used: which are about $ 50 sebum and especially about $ 80 to $ 100 sebum and otherwise contain coconut oil or a substitute for this oil. Other solubilizing cations can also be used Making the desired soaps can be used, such as

for example ammonia, triethylamine, trimethylamine or

other lower amines or alkanolamines. These higher fatty acid soaps act as anti-foaming agents in addition to their properties also good washing properties, so that the use of these soaps to limit the foaming the cleaning effect not affected. In addition, under certain circumstances, these soaps are even preferable surfactants and their use can indeed improve the detergency of the product as a whole in certain cases.

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Although the liquid laundry detergent according to the invention from consist of a clear, single-phase stable liquid, which at elevated temperatures and over long periods of time a shows excellent stability, the incorporation of large amounts of additives should be avoided as such Additives affect the total solubility of the agent can. However, it is often useful to add various auxiliaries to the liquid detergents in order to help them to impart further advantageous properties with regard to their function or their appearance. So you can get the means For example, add substances such as dirt dispersants or agents that prevent dirt redeposition, e.g., polyvinyl alcohol, sodium carboxymethyl cellulose, and Hydroxypropylmethylcellulose, means for adjusting the pH value, e.g. sodium hydroxide, triethanolamine and sulfuric acid, Buffer substances, e.g. sodium borate and sodium bisulfate, inorganic builder salts, e.g. borax, soda and silicates, enzymes, e.g. proteases and amylases, thickeners, e.g. gums, Alginates and agar-agar, foam improvers, e.g. lauric acid diethanolamide, myristic acid diethanolamide and Lauryldimethylamine oxide, foam destroyers, e.g. silicones, bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, Fungicides, dyes, pigments (dispersible in water), preservatives, ultraviolet absorbers, fabric softeners, Pearlescent substances, opacifiers, e.g. behenic acid, polystyrene suspensions and castor wax, and perfumes.

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These auxiliaries are selected so that they with the anion-active sulfated surfactant are compatible.

The pH of the liquid heavy duty detergents according to the invention is normally practically neutral or only slightly alkaline. A pH measurement, with a glass electrode and a calomel "reference" electrode shows a maximum of a pH of about 8. Because the system, despite the presence of a small amount of water is essentially non-aqueous, the pH reading can often be incorrect. You will get a better ad if you have the Measures the pH value in a 1% solution in water, i.e. roughly the concentration in which the liquid / ash agent is added practical use. This measurement should generally be in the range of about 6.8 to 8.8. in the In the wash bath in the presence of the textiles to be washed, the pH value is generally in the same range.

The proportions of the various components in the liquid heavy duty detergents of the present invention is important because of the absence of major amounts of builder What is important is a means with a good coarse washing effect and at the same time to get a consistent product. Since there is only a minimal amount of builder present, the product must be used Achievement of the desired washing and cleaning effect is necessary contain a considerable amount of surfactant. To continue the solubility of the fluorescent brighteners and other components to support ur.d a clear homogeneous

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and to obtain easily pourable liquid product must be in the products according to the invention, the anion-active alkyl polyethene oxysulfate be contained in an amount of 30 Ms 70% by weight of the total concentrate. The preferred amount of anionic surfactant is in the range of 35 Ms 60 wt. $, with a concentration of about 50 $ sulfated anionic surfactant in particular is preferred. By combining it with isopropyl alcohol At this high concentration of anionic surfactant, a fairly thin liquid product is still obtained, which is compatible with other components, so that a clear liquid detergent can be made. IM the best To achieve an effect, the amount of additional surfactant, preferably nonionic alkylpolyäthenoxy surfactant, should be im Range from 0 to 25%. The additional surfactant can while also being omitted entirely, the product preferably contains up to about 15% of the preferred nonionic Surfactants and especially about 10 $ of this surfactant. When this preferred nonionic surfactant is replaced by one of the The above-mentioned other nonionic, amphoteric or anionic surfactants should be replaced, the proportion of these surfactants preferably less than $ 5, although kengen up to $ 15 can be used.

The fluorescent added to the agents according to the invention or optical brighteners should be based on its active substance in amounts from 0.5 to 5 $, preferably from about 1 up to $ 3 and especially from about $ 2. These

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Amounts become readily soluble in the aqueous-alcoholic base of the anionic detergent of the present invention made. Generally, "at least $ 25, and preferably at least $ 50, the optical brightener consists of a brightener for cotton, and in particular a brightener "is preferred, which is 51% to $ 90 from cotton lightener and im the rest of one or more polyamide or polyester brighteners or chlorine-resistant brighteners.

The lower monohydric alcohol is used in such an amount as to keep the surfactants in a non-gelled state holds and enough alcohol to stabilize and dissolve various other components are present in the product. As has already been said, the addition of a lower monovalent makes it possible Alcohol, preferably isopropanol, the formation of a thin or less viscous concentrated product, the alcohol generally being used in an amount of from 7 to 15% by weight and preferably around 10% by weight. The one in the The proportion of water used in products according to the invention between 5 and 50 wt. $, with the range of 25 to 40 wt. $ being preferred.

The sequestering agents and adjuvants added should and generally will not exceed a total of $ 10 kept under $ 5 and preferably under $ 3. Each individual component should not exceed $ 5, preferably $ 3 and especially below $ 1 of the product.

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The heavy-duty liquid detergents of the present invention are easy to manufacture and do not require complicated equipment or expensive operations. A typical manufacturing process involves first slurring the optical brighteners in the alcohol. Then adding water and, if necessary, a small amount of alkali or other Base is added, which supports the partial dissolution of the previously suspended material, but does not yet result in a clear solution. The remainder of the brightener is dissolved by adding the surfactant combination and a clear solution is obtained. The sequestering agent is then optionally added in the form of the acid or a salt (preferably as the sodium, potassium or amine salt) and stir until the solution clears, which usually takes about 5 to 10 minutes, at which point perfume and coloring can be added to give the product the desired look and feel To give smell. All these operations ge can be carried out at room temperature, obv / OHL, optionally, other suitable temperatures are in the range of 10 ° can be applied to 80 ⁰ C. The adjuvants can be added at any convenient point in the process, but in most cases they are added at the end. The product thus obtained normally has a pH in the range from 6.5 to 8, for example 7.0, and a density in the range from 0.9 to 1.1, preferably from 0.95 to 1.05 and in particular from 0.98 to 1.02. The viscosity of the product at 25 ⁰ G is usually between 20 and 200 cP and preferably between 50 and 150 cP.

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The compositions of the invention are extremely simple "and effective in use. Compared to the known powdered heavy-duty detergents significantly rich smaller volumes of fluids of the invention for washing dirty textiles. So" is needed, for example, by a ^'r typical preferred product of the present invention, which Contains about 50% sulfonated anionic surfactant and 10% nonionic alkyl polyetheneoxy compound, only about 60 CHT ^ or 1/4 cup liquid for a full washing machine load with a water volume of 55 to 70 liters. The concentration of the liquid detergent in the washing water is thus of the order of 0.1 or 1 g per liter or 1000 ppm. In general, the amount to be used is between 0.7 and 1.5 g per liter, which corresponds to a concentration of 0.3 to 0.6 g / l of sulfated anionic surfactant, 0.075 to 0.15 g / l of nonionic surfactant, 0, 01 to 0.05 g / l of fluorescent or optical brightener, 0.05 to 0.4 g / l of alcohol and 0.005 to 0.03 g / l of organic sequestering agent. The proportion of the other components of the liquid detergent can vary accordingly. Of course, the same results can be achieved using larger amounts of a more dilute liquid detergent, however; The required larger volumes then require more packaging and transport space and are less pleasant to use for the consumer. However, the use of such more dilute products is within the scope of the invention if the relative

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The proportions of the components are preserved ". With In other words, simply adding water to the liquid detergent does not circumvent the present invention diluted as the same results are obtained because the washing water also serves to add the detergent to a Use concentration to be diluted.

Although Y / ash water in the normal hardness range and at an elevated temperature is preferably used, the present invention is also suitable for washing items of laundry and other textiles in hard and extremely soft water and in water at room temperature and below. The "water hardness may thus in the range of 0 to about 300 ppm, calculated as calcium carbonate, and the Y / vary aschtenperatur in the range of 10 to 80 ⁰ C. Preferably, the washing temperature of from room temperature, ie 20 ° to 25 ⁰ C, and 70 detergent according to the invention can furthermore ⁰ C., although they v normally used in washing machines with subsequent to the wash rinse and spin transitions or drainage and Wringgängen / earth, even to the Y / äschev;. as <vhen be used by hand in these cases A stronger concentration of the liquid detergent is usually used in the Y / ater and sometimes it can also be used at full strength to support the washing out of dirt or stains that are otherwise difficult to remove. ash generally afterwards in an automatic dryer, otherwise such a special drying process is not necessary,

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If the liquid detergent is put into water, regardless of whether it is hot or cold, it will dissolve immediately evenly throughout the water, even if it is not moved significantly. The detergent substances and Brighteners are brought into contact with the entire laundry and there are no local over-concentrations of these components on. The textiles washed according to the normal methods are exceptionally clean and in comparative tests the product was rated as good as some of the best commercial laundry detergents on the market. Although the products according to the invention have little or no Foaming detergents are and therefore extremely suitable for front-loading washing machines, and are also excellent Washing results achieved in top-loaded washing machines, in which foaming detergents are normally used will. Repeated tests with soiled and again soiled textiles in which the inventive Products used in comparison to larger quantities of commercially available heavy-duty detergents with phosphate or NTA builders showed that the dirt was removed again and again and no undesirable accumulation thereof occurred. In most cases, consumers did not actually represent any significant differences between the washing properties of the tested products according to the invention and those of the tested commercially available products. In fact, a significant preference for the products according to the invention was found.

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The discovery of the Y / ash agents according to the invention "and their exceptionally good properties was unexpected, as those skilled in the art did not expect that it would be possible to produce a builder-free To produce heavy duty detergents without inorganic builder salts or the substitutes for these builders HDTA or ITTA. This discovery was "particularly surprising in view of the fact that the organic So far, surfactants have only been used in mild detergents and cleaning products, as their ability to remove dirt from laundry in To remove coarse washing methods, had not yet recognized. It was also a realization that many believed other researchers in the field of detergents and cleaning agents was the opposite. The use of the invention Means without ITTA does not adversely affect substantivity the optical brightener, while sequestering agents of the NTA or polyphosphate type the uniform absorption of the Brighteners can interfere with the fabric. In fact, with the unique combination according to the invention, the described anion-active and non-ionic surfactants surprisingly achieved exceptionally good whiteness values. The surfactants do not react with hypochlorite bleach, whereas UTA can be subject to such reactions. After all, they wear various components, as already said above, contribute to the mutual mediation of solutions and form a pourable clear liquid. The lower monohydric alcohol and the water make the brightener system soluble and the i

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condensate helps to achieve the best solubility and of a clear product ". The lower monohydric alcohol prevents the liquid detergent from gelling, which is of great importance, and reduces the viscosity of the concentrate. Preventing gel formation means preventing staining, otherwise the laundry will be stained Gel deposits could occur, which hold the whitening agent in only a few places on the laundry. The invention Liquid detergents are easily "biodegradable and bring" no large amounts of phosphate or NTA builder in the wash water a.

The invention is illustrated in more detail by the following examples, but is not restricted to the same. Not so far otherwise noted, all quantities in the examples relate to parts or percentages by weight.

example 1

It became a clear liquid detergent of the following composition manufactured. For this purpose, a mixture of optical brighteners was first slurried in isopropanol and then mixed with water while stirring. Then the .. anion-active surfactant was added, whereupon the solution after a few Minutes stirring at moderate speed became clear:

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Neodol 25-3S (C-j2 - J5 ~ ^A lkolioltriäthenoxysulfat, sodium salt, SOFO active substance) 51.5

I so per pyl aiko hol 8.6

Brightener 1.1

Water difference to 100

The product was a clear, single-phase, low-viscosity liquid detergent which dissolved quickly and completely in washing water at 38 ^° C. without stirring. In comparative tests with other biodegradable detergents with or without a builder, the product showed the same washing and cleaning properties.

Comparative Example 1

A product of the same composition as in Example 1 produced, but the Isopropylaiko hol was made left out of the formula and increased the water content accordingly.

The product was a clear single-phase liquid of medium viscosity which "hildete when poured into distilled water at 38 ⁰ C a gel which broke up with gentle stirring. The washing and cleaning properties were adequate, but less than" in the product after Example 1. In addition, some "staining" was observed since the brighteners and surfactants tended to form local overconcentrations on initial contact with the water.

3 : 3 8 8 S / 1 1 ν 2

Example 2

Products with the same composition as in Example 1 prepared, but the Neodol 25-3S was used in the following amounts "or by the following combinations of Neodol 25-3S with other synthetic ensides replaces:

a) 52.2 $ Neodol 25-3S plus 1 $ Neodol 4511 (non-ionic C ₁ , _{1 (} - alkyl polyethenox; y compound with 11 mol of ethylene oxide),

b) 7Ο? έ Neodol 25-3S,

c) $ 35 Neodol 25-3S plus $ 15 I'Teodol 4511,

d) 50 $ normal primary mixed C ₁ ._ _{1 (} - -alkyl tri / tetraethene oxysulphate,

e) 45 $ stearylpentaethenoxysulfate, triethanolamine salt, plus 10 $ normal primary mixed C _12-1 C-AIlCyI with 7 ethylene oxide groups,

f) $ 31.0 Neodol 25-3S plus $ 10.3 Neodol 4511 plus $ 4.7 linear dodecyl benzene sulfonate.

All products thus obtained were clear single phase ZLüssigwaschmittel low viscosity and is broken down when poured into distilled water at 38 ⁰ C quickly and without stirring. Furthermore, all of the products obtained showed excellent washing properties and performed favorably in comparisons with phosphate-containing liquid heavy-duty detergents.

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Comparative example 2

It was again a product of the same composition as made in Example 1, but the isopropyl alcohol replaced by propylene glycol.

Although the product had a lower viscosity than that obtained according to Comparative Example 1, it "formed when poured." in distilled water of about 38 0 also a gel. Although this gel dissolved quickly when stirred gently, it can be caused by local overconcentrations of brightener and Surfactant lead to a certain staining of the laundry, even if it is otherwise generally clean and clear.

Comparative example 3

Products with the same composition as in Example 2 prepared, but the isopropanol was omitted from all formulas. In all cases the Viscosity of the product increased significantly and all liquid detergents formed a gel when poured into water of 38 0, which more or less formed with gentle stirring quickly dissolved.

Example 3

A liquid detergent was made which contains 53, Neodol 25-3S, $ 1.8 tallow / Oocos (80/20) soap, $ 8.9 isopropyl alcohol and 35.7 ^ "/ water as well as impurities and brighteners

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contained. When this product is placed in an overhead washing machine with no laundry in 65 liters of 49 C water
51 g of product only developed so much foam that
only $ 50 of the air space in the washing machine was filled with it, and there was no foam at all in the rinse water. If, however, a product of the same composition but without sebum / coconut soap was used in the same amount, the foam filled the entire air space in the washing machine within 3 minutes and a certain amount of foam appeared in the rinse water.

Example 4

Products of the following compositions were prepared and in a concentration of $ 0.1 against a comparative product, which was $ 15 linear tridecylbenzenesulfonate, $ 35
Containing pentasodium tripolyphosphate and $ 50 sodium sulfate, tested at a concentration of $ 0.15:

Table I.

$ Active ingredient

A E C D E P

Neodol 25-3S 53.6 46.2 54.6 42.1 31.0 36.9

Neodol 4511 .. - 11.5 - 10.3 -

linear tridecylbenzenesulfonate - - - 10.5 10.3 -

C _{12 5} alcohol sulfate - - - - - 9.2

Tallow / coconut (80/20) soap 1.8 1.9

Isopropanol 8.9 9.6 10.0 8.8 8.6 7.7

35 £ JM J ^ j. JQ ^ J ^ S 46.2

100.0 100.0 100.0 100.0 100.0 100.0. 309885/1272

The following results were obtained for the test specimen in the Spangler dirt test, in which A Rä is a measure of the grain content on a scale "from 1" to 100 (100 = white) in an automatic G-ardner FarMifferensmesser . A difference of about one Rd unit can be visually recognized.

Tabel

II

Δ Ed (units for removing sorrow ζ) _

Product A, 0.1 ^ 20.4

Product B, 0.1 # 20.5

Product C, 0.1 ^ 21.2

Product D, 0.1? B 21.0

Product E, $ 0.1 20.7

Product P, 0.1 $ 21.0

Comparative product, 0.15 ^ 20.7

example 5

In the products according to Example 4A to F, the amount was Isopropanol reduced to the following proportion and the water content increased accordingly:

A. B. "

C. 15 #

D. 11 °

E. 2fo

α.

R.

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All of the oMgen products had good cleaning effects, however only the products A, B, C, D, G- and H showed an acceptable one Viscosity and dispersibility in distilled water. However, with the formulas G- and H the viscosity did not appear to be reduced any further than with the lower ones Concentrations.

Example 6

In the products according to Example 5A "to F, the isopropyl alcohol replaced by the following monohydric or polyhydric alcohols:

A. Ethanol

B. n-propanol

C. n-butanol

D. sec butanol

E. tert-butanol
P. eth3 ^r lenglycol
G. Propylene Glycol

With additives A to E, the viscosity was reduced and gel formation was prevented, even if not in some cases as strong as "for isopropanol. The ones obtained according to P and G- Products "formed" gels on standing, which are heavy allowed to disperse.

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Claims (6)

P a t e η t a η s ρ r ü ehe (T) Liquid heavy-duty detergents without substantial content of phosphates and nitrogen-containing builders, characterized in that it consists essentially of 30 "to 70 wt. I ° anion-active surfactant of general formula RO (C ₂ H ₄ O) _n SO ₃ M wherein R an alkyl group with 10 "to 20 carbon atoms, η a number from 2" to 6 and M is an alkali, ammonium, alkaliolamine or alkylamine cation, 0 "to 25% by weight of additional surfactant, 5" to 50% by weight of water and 7 to 15% by weight of lower mono-alcoholic alcohol ". 2. Detergent according to claim 1, characterized in that the additional surfactant consists of a nonionic surfactant of the general formula RO (CpH ^ O) _n H, where R is an alkyl group with 10 to 20 carbon atoms and η is a number from 5 to 14. 3. Y / ash means according to claim 1 or 2, characterized in that that it is the anionic surfactant in an amount of 35 to 60 wt. ^ and the additional surfactant in an amount of 0 to 15 wt. ^ Contains. 309885/1272 4. Detergent according to claims ΐ to 3, characterized in that that it still contains a foam suppressant. 5. V / ash agent according to claims 1 to 4, characterized shows that it still contains an optical brightener system. 6. Detergent according to Claims 1 to 5 _}, characterized in that it contains isopropanol as the monohydric alcohol. 309885/1272