SE412598B - LIQUID DETERGENT COMPOSITION WITH POWERFUL WASHING EFFECT - Google Patents

Description

7200741 -2 FJ long-lasting organic detergents and phosphate builders have had detrimental effects on such waters and watercourses. You surfactant organic compounds that do not decompose easily after being emptied from the sink or sink, washbasin or washing machine can be discharged into natural streams, rivers, lakes and lakes.

Most detergent manufacturers strive to remove from their products synthetic, organic detergents, such as highly branched alkylaryl sulfonates, which are not biodegradable, and have replaced them with comparatively readily degradable straight chain alkylbenzene sulfonates or similar materials which are destroyed within a short time.

Attempts have been made to modify the recipes for the detergent compositions to produce excellent detergents which do not contain any phosphates. However, this has been difficult to implement due to the particularly effective building, peptizing, soil suspending and cleaning effects of the polyphosphates, in particular pentasodium tripolyphosphate and tetrasodium pyrophosphate and analogous salts of polyphosphoric acid. At present, great efforts are being made to produce effective, safe and palatable detergent compositions which do not contain phosphate or nitrogen compounds as builder or builder. The present invention relates to such compositions.

The liquid detergents or detergents of the present invention are based on a simple, inexpensive and commercially available anionic detergent which is readily biodegradable. In addition, they do not contain any significant content of polyphosphates or other phosphate-containing detergent salts or any significant nitrogen compounds as detergents. Sodium citrate (or its equivalent) was used in these products for this purpose. A hydrotropic substance may conveniently be added to the preparation.

The different components of the products are interdependent in terms of miscibility, solubility, cleansing effects and detergency-enhancing effects.

By using the right materials in the right proportions in the areas listed below, effective, liquid laundry detergent compositions are obtained that are equivalent to or comparable to commercially available detergent products when tested on dirty clothes by existing controlled trials either in the laboratory or in washing machines for household washing. 3 72007111-2 Nevertheless, these detergents can be used and the washing water disposed of in the normal way, without giving rise to the ecological problems which arise in connection with the use of previously composed compositions.

The bulk laundry detergent composition of the present invention comprises 8 to 30% of an anionic, synthetic, organic detergent salt of the formula R 0 (C 2 H 2 O) n SO 3 M, wherein R is an alkyl of 10 to 20 carbon atoms, n is from 2 to 6 and constituting from 1/5 to 1/3 of the number of carbon atoms in R, and wherein M is a salt-forming ion, usually alkali metal, ammonium, lower alkylamino or lower alkanolamino; 10 - 30 Z citrate and optionally 1 - 15 2 of a hydrotrope, usually a salt consisting of cumene sulfonate, benzenesulfonate, toluenesulfonate or xylene sulfonate, the remainder of the composition consisting of water and conventional amounts (0.00l - 10 Z) of optical white matter, dyes, perfumes and other less important aids. The preferred compositions are clear, stable single phase liquids, of which only small amounts are required for washing whole batches in automatic washing machines. The invention also includes a method of washing clothes using the described liquid detergents or their ingredients.

The sulphated, ethoxylated higher fatty alcohol detergent has the formula R0 (C2HhO) nSO3M, where R is an alkyl having 1G - 20 carbon atoms, n is from 2 to 6 and constitutes from 1/5 to 1/3 of the number of carbon atoms in R, and where M is a solubilizing, salt-forming cation such as alkali metal, ammonium, lower alkylamino or lower alkanolamino. In order to make the anionic detergent very readily biodegradable and to have a better cleaning ability, the alkylene is end-linked to the polyoxyethylene chain, which is necessarily also end-linked to the sulfur to form a sulphate group. Although a slight branching of the higher alkyl can be tolerated - to an extent where at most about 10% of the carbon atoms of the alkyl are not present in a straight carbon chain - this minor deviation from linear structure should also be avoided.

Likewise, the bond of the ethylene oxy chain to the middle of the alkyl chain should be as small as possible, usually less than | 2, and also such a bond should preferably be concentrated to near the end of the alkyl chain. Within the stated range of IU - 20 carbon atoms in the alkyl groups, the alkyls having 12 to 15 carbon atoms are preferred, and of these, the one having a mixed alkyl group containing 12, 13, 14 and 15 carbon atoms is most preferred. The blax feed preferably has at least 10% of each chain length, but not more than 50 Z of any such chain length.

The ethylene oxide content of the anionic detergent is such that n is between 2 and 6, preferably between 2 and 4 and on average usually about 3, especially when R is an alkyl mixture of 12 to 15 carbon atoms. To maintain a desired hydrophilic-lipophilic equilibrium, when the carbon content of the alkyl chain is in the lower part of the 10 - 20 range, the ethylene oxide content can be reduced so that n is about 2, while n can be 4 - 6 when R contains 16 - 18 carbon - atoms. The salt-forming cation may be any suitable solubilizing metal or radical, but is usually alkali metal or ammonium. If alkylamine or lower alkanolamine groups are present, their alkyls and alkanols usually contain one to four carbon atoms and the amines and alkanolamines may be mono-, di- or trisubstituted, e.g. monoethanolamine, diisopropanolamine and trimethylamine.

The importance of using the proper anionic detergent in the present composition is demonstrated by the inability of corresponding alcohol sulfates in similar liquid detergent compositions to wash as well as the present compositions containing the higher alcohol-ethylene oxide sulfates described. For example, a higher alcohol sulfate, in which the alcohol is an alcohol mixed with 12 to 15 carbon atoms, exhibits a significantly poorer cleaning ability in liquid compositions similar to those of the present invention, compared to the corresponding ethoxylated sulfate in the same composition. Even in the preferred range of alcohol polyethylene oxysulfates, an improved cleaning ability is noted for those compositions which contain an alcohol polyethylene oxysulfate, where the alcohol is an alcohol mixed with 12 to 15 carbon atoms, compared to other higher alkyl ethylene oxysulfates such as a polyethylene oxysulfate mixed with 14 to 15 carbon atoms with the same length of ethyleneoxy chain. The preferred detergent is obtained by Shell Chemical Company and is referred to by them as Neodof 25-35, which product constitutes the sodium salt and is normally sold as a 60% active material containing about 40% of an aqueous solvent, of which a minor portion is ethanol. Although Neodof§š5-35 is the sodium salt, the potassium salt and other suitable soluble salts can also be used, either partially or completely substituted for the sodium salt. Examples of higher alcohol polyethylene oxysulfates which may be used as a major component of the anionic detergent of the liquid composition of the invention or as a partial substitute therefor include: normally, primarily, C1-215 mixed alkyltriethene oxysulfate, such as sodium salt; myristyltriethene oxysulfate, as potassium salt; n-decyl dietoxy oxulfate, as diethanolamine salt; lauryl dietoxy oxulfate, such as ammonium salt; palmityltetraethene oxysulfate, as sodium salt; normally, primarily, with C1-15 mixed tri- and tetraethenoxy sulfate in admixture, as sodium salt; stearyl pentaetheneoxy sulfate, as trimethylamine salt; and normally, primarily, C1-8 mixed alkyl triethylene oxy sulfate, such as potassium salt. Minor amounts of the corresponding branched chain and medially alkoxylated detergents, such as those described above, but modified to have ethoxylation at an intermediate carbon atom, e.g. located four carbon atoms from the chain end, can be used but the carbon atom content of the higher alkyl is the same. Similarly, the bonding of the normal alkyl may be at a secondary carbon atom at a distance of one or two carbon atoms from the end of the chain. In both cases, only the smaller, previously mentioned amounts are present.

The citrate component of the composition of the invention may be added as sodium citrate or as any other water-soluble salt, the cations being alkali metal (eg potassium, lithium), ammonium, amine, alkylolamine and the like. Citric acid can also be mentioned, especially where the composition was used on the acidic side. The citrate compounds can be used in the form of hydrates or in anhydrous form.

The hydrotropic salt has the ability to improve the solubility of the anionic detergent component to make it possible to produce a concentrated detergent liquid. The hydrotropic agent also helps to maintain the high concentration of builder or builder in solution and to prevent precipitation of other constituents which may conveniently be present in a separate phase, either as an insoluble precipitate or as a separate liquid phase. In addition, the hydrotropic agent helps to hold various aids with comparatively low solubility in solution, e.g. optical brighteners. As a further property it can be mentioned that the hydrotropic agent lowers the viscosity of the compositions, which is particularly advantageous at the higher concentration levels. The hydrotropic agents are preferably salts of aryl sulfonic acids, especially benzenesulfonic acids, where the benzene ring may be unsubstituted or substituted by one or more short chain alkyl groups. The short chain alkyls include those having 1 to 4 carbon atoms and are preferably methyl, ethyl or isopropyl. Up to three such substituents are present in the benzene ring, but none, one or two are preferred. The most preferred hydrotropic salt is a soluble cumene sulfonate salt, e.g. the sodium salt. Other similarly substituted aryl sulfonates and other such compounds in which the substituent consists of three carbon atoms are also useful hydrotropic agents, as are salts in which the salt-forming cations are of any of the types previously described in connection with the synthetic organic detergent component. Thus, alkali metal, lower alkylamine, lower alkanolamine and ammonium salts are preferred, although the free acids are also useful, especially in those compositions or washings in which sufficient alkali is present to convert them to a meza soluble salt form. .

Examples of hydrotropic agents useful in the large scale liquid detergent detergents of the invention are sodium cumene sulfonate, potassium cumene sulfonate, ammonium cumene sulfonate, ammonium benzenesulfonate, sodium toluenesulfonate, potassium xylene sulfonate, triethanolamine benzenesulfonate sulfonate and cethanolamine benzenesulfonate. Of course, one usually tries to use the hydrotropic agent that is most effective for the individual constituents and their constituent amounts. Of the hydrotropes listed, sodium cumin sulfonate is the most effective in the compositions described. Mixtures can, of course, be used where desired and in some cases the acidic form of the hycrotrope is added to the liquid detergent composition, but usually it is neutralized or otherwise transferred to soluble form before its use.

The solvent of said compound, which is included as a constituent of the liquid detergent, is an aqueous one and may be water alone or substantially water, with additional solvents added for particular constituents. Because water is available in unlimited quantities and also at low cost, water is preferred as the only solvent present. It is nevertheless possible to use other solvents in an amount which usually amounts to less than 20% and preferably less than 10 Z of the total amount of water and solvent. Such a complementary solvent is generally either a lower alkanol or a lower diol or polyol, e.g. ethanol, isopropanol, ethylene glycol, propylene glycol, glycerin. However, polyol ethers such as diethylene glycol and those known as "cellosolve", i.e. ethyl glycols.

The water used is preferably deionized water to avoid the presence of any reactive ionic materials which could form insoluble precipitates or colored deposits with other components of the liquid detergent. When the water is deionized, the content of metal ions is normally reduced to less than 10 parts per million, calculated as calcium carbonate. Although it is best to use such deionized water and it is available or can be produced in many factories, it is often possible to use ordinary tap water, provided that its hardness is low enough and is of such a nature that it does not cause any harm. effect on the preparation used. If desired, small amounts of sequestering agent (0.0l - 2.0 2) can be used to prevent or eliminate any potentially harmful or adverse effects caused by the hardness of the water and heavy metal ions. Illustrative of sequestrants are sodium nitrile triacetate, sodium EDTA, gluconates, lactates, inorganic phosphates and the like.

Most of the automatic washing machines used in homes are of the type that have an upper plug opening and a cylinder capacity of about 57 - 68 liters. Due to the agitator construction of these machines and the fact that the tube or cylinder is open at the top, the foam formed during washing will rise, which means that it does not participate in the washing of the laundry, which is usually the case with washing machines. with horizontal shaft or with front opening for stuffing laundry. The latter machines usually have a smaller water capacity, on average between 26.5 and SO liters, and the larger proportion of laundry in relation to washing water usually allows the use of less detergent to achieve the same degree of washing, provided that there is no foam barrier. which prevents good contact between the detergent solution and the laundry. Although the foam can help to carry dirt through the float in the form of large particles in an automatic washing machine with an upper filling opening and although the housewives have previously associated good foaming with good cleaning ability, it has in recent years been considered desirable to limit the amount of foam produced by laundry detergent products. Therefore, in the liquid laundry detergent compositions of the present invention, whether intended for use in automatic washing machines with an upper filling opening or with a front filling opening, it is often convenient or desirable to include a compound which limits foaming. Nevertheless, an additive which produces such a result should of course be compatible or compatible with the other components of the product and should not adversely affect the washing action.

In particular, in a product having different components in an equilibrium ratio to achieve a clear, single-phase, stable, liquid washing solution consisting of organic and inorganic components, sometimes close to the limits of their solubility, the addition of large men is usually avoided; - agents due to the fear that they could have adverse or detrimental effects on the preparation.

It has been found that the foam can be adjusted whenever desired so that little foam or no foam is generated while maintaining the high level of cleaning ability by adding a water-soluble soap of a higher fatty acid or a mixture of such soaps to the liquid detergents of the present invention. invention. The higher fatty acid soaps used usually consist of alkali metal salts, e.g. sodium and potassium salts, of mixed fatty acids such as the acid mixtures obtained from natural animal and vegetable fats and oils. Such soaps usually consist of a large proportion of saturated fatty acid soaps with chain lengths from 10 to 18 lol atoms.

The most preferred mixtures are obtained by mixing batches of pine oil and coconut oil. According to the present invention, such soaps usually contain more than 50% tall oil, preferably between 80 and 10 (Z), the remainder usually being coconut oil or a substitute therefor.

Other types of solubilizing cations can be used to achieve the desired soaps, such as e.g. ammonia, triethanolamine, trimethylamine and other lower amines and alkanolamines as previously described in conjunction with the synthetic detergent component.

As is well known, the higher fatty acid soaps, such as e.g. those currently used as antifoams in these liquid detergents also have good cleaning effects and their use to limit foaming does not affect the cleaning ability. With respect to certain soiling materials, for which the soaps are preferred detergents, the cleaning ability is improved by such use. 72007141-2 Various kinds of aids may be present in the liquid detergent to give it additional desired properties, either of a functional or aesthetic nature.

The preparation may thus include: soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, sodium carboxymethylcellulose, hydroxypropylmethylcellulose; optical brighteners or bleaches, e.g. cotton, amide and polyester bleaches (to be described in more detail below); complementary synthetic organic detergents, e.g. sodium lauryl sulfate; myristyl polyoxyethylene ethanol, in which the polyoxyethylene chain has a length of ten units, linear tridecylbenzenesulfonate; pH adjusting agents, e.g. sodium hydroxide, triethanolamine, sulfuric acid; buffering agents, e.g. sodium borate, sodium bisulfate; inorganic builder salts, e.g. borax, calcine soda and silicates; enzymes, e.g. proteases, amylases; thickeners, e.g. gummi, alginates, agar agar; foam improvers, e.g. lauric myristine diethanolamide, lauryl dimethylamine oxide; defoamers, e.g. silicon or silicon compounds; bactericides, e.g. tetrachlorosalieylanilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives; ultraviolet light absorber; fabric softeners, pearl or pigment forming agents; non-pacifying agents e.g. belenic acid, polystyrene suspensions, castor wax; and perfumes, The aids are selected to be compatible or tolerable with the main constituents of the detergent.

Of the aids mentioned, the optical brighteners are perhaps the most important for functional effect, as the modern housewife expects that washed clothes should no longer be only clean and white, but they should also have a luminous or shiny appearance. The optical brighteners are substantive to fabrics that have been washed (such substantivity or adhesion can be selective) and they sometimes show relatively low solubility. Consequently, they are important in reading the liquid ether and even more important are that they must be immediately dispersed in the wash water to avoid the creation of a wash which contains markedly lightened spots instead of a wash which has a skinance look.

Accordingly, the composition of the invention, the ingredients of which facilitate the dissolution of the whitening or bleaching agents, may advantageously contain these additives. Here, the choice of bleach to achieve the best results will be determined by those skilled in the art. It has been shown that relatively small amounts of bleach should be used so that the solubility limits are not exceeded. Likewise, within the class of these materials, certain bleaches have been found to be particularly readily soluble and are highly suitable for incorporation into the products of the invention. Fortunately, such preferred whitening agents contain both cotton and amide polyester whitening agents, making them suitable for use in laundry containing a variety of natural and synthetic materials. Although a single bleach can be used in the compositions of the present invention, it is generally desirable to use a blend of bleach to have good luster or whiteness effects on cotton, nylon, polyester and blends of such materials. and so that the luster or whiteness activity is maintained even in the presence of bleach.

A good description of the different types of optical brighteners or x-rays, which are suitable for obtaining these results, is given in the article "Optical Brighteners and Their Evaluation", by Per S Stensby and reprints of articles published in "Soap and Chemical § pecialties ", April, May, July, August and September 1967, in particular p. 3 - 5.

The cotton bleaches are often referred to as GQ / DAS bleaches and are obtained by the reaction product of eyanuric chloride and the disodium salt of diaminostilbene disulfonic acid. The compounds usually differ from each other with respect to triazine and aromatic rings. Bleach stable bleaches usually include benzidine sulfonic disulfonic acids, a naphthotriazolyl stilbenzulfonic acid or a nensimidazolyl derivative. Polyamide whitening agents usually include either aminocoumarin or diphenylparazoline derivatives, and polyester whitening agents, which are also applicable to polyamides, may be naphthotriazolyl stilbenes. The whitening or bleaching agents are normally present in the form of their soluble salts, but can be added as corresponding acids. The wool bleaches usually comprise a drier part of the bleach system and are generally accompanied by a minor portion of the amide polyestoryl binder. The bleaches used in the systems according to the present invention include the following: "Calcofluor white ALF" (American Cyanamid); "ALF-N" (American Cyanamid); "SOF A-2001" (CIBA); "CWDF (Hilton ~ Davis); "Phorwite H" (Verona), "CSL", powder, acid (American Cyanamid); "CSL", liquid, mon ethanolamine salt (American Qyanamid) - "FB 766" (Veroni); Blancopnor n * (oAz- fi; "UNPA" (Geigy), "rinopal mas" (Geigy); and "mas zoo" (Geigy).

Among the complementary or complementary organic detergents which are useful, the anionic detergents are those which are most compatible or tolerable with the synthetic organic main detergent component of the present compositions. Of the anionic detergents, the higher alkyl benzene sulfonates are preferred, preferably straight chain and having 12 to 16 carbon atoms in the alkyl moiety of the molecule, higher fatty alcohol sulfates, higher olefin sulfonates, higher fatty acid soaps (additional function as defoamers) and higher alkyl toluene sulfonates. The higher alkyl groups usually contain 10 to 18 carbon atoms, preferably 12 to 16 carbon atoms. Of the non-ionic detergents, the following are considered to be the best: polyethoxylated higher alcohols, the middle or higher alkylphenol polyethylene ethanols, the block copolymers of ethylene oxide and propylene oxide (Pluoronics (R), and heterocyclic polymers of ethylene oxide and propylene oxide, which have either ether or ether) substances, such as imidazolines, pyrazolines, imides and "Mannheimers" amphoteric substances, can be used.The use of cationic active compounds is generally not preferred as they react with the anionic compounds and impair the cleaning ability of both types of materials. .

Of the inorganic builders or builder additives, various additional materials can be used such as borax, calcined sod, sodium carbonate and silicates. Fillers such as sodium sulfates and bisulfates may also be included in the compositions. It should of course be ensured that the inorganic materials used are not reactive together with the other constituents or that they are not substantially insoluble in the detergent medium.

The pH of the liquid detergent may vary between about 2 and 12, with particularly pronounced cleaning ability being in the range of 7 to 9. Slightly higher alkalinity may be prescribed by the presence of aids requiring a pH above 7-9 to achieve the required solubility.

An example of this is the sparingly soluble bleaches.

The proportions between the constituents of the detergents according to the invention are important in order to be able to maintain a uniform product with a good active effect on laundry. In the absence of phosphate builders, it is important that the product contains a significant proportion of the fatty alcohol ethylene oxide sulfate and citrate builders. To provide the clear, homogeneous and readily durable liquid product, it contains from 8 to 30% of anionic, synthetic, organic detergent salt of the formula? 200 '? 1§1 -2 12 RO (C2H40) nSO3M, preferably 20% of the same, with about 15 Z being the most preferred amount. By such an amount, in connection with the amount of citrate used, the desired product is obtained. For maximum utility, the amount of supplemental detergent or surfactant used in the product should be limited to about 30% of the concentration of the main detergent and care should be taken to avoid the presence of additional or complementary materials which do not are tolerable or compatible with the other constituents or which cause phase separations at the concentrations used.

The content of citrate builder amounts to about 10 - 30% of the liquid detergent and preferably 15 l of it, the most preferred content being 20 X of the product, calculated as sodium citrate dihydrate for the most preferred citrate. When other substitutes for the washing sprayers are used, usually in only minor partial exchange for the citrate, the total content of citrate and substitutes is within the ranges indicated above.

In the compositions of the invention, the amount of citrate that is soluble will often determine the upper limit of its concentration within given ranges, while a useful minimum amount is determined by the amount that should be sufficient for the agent to be an effective detergent builder for the synthetic organic. the detergent.

The hydrotropic agent, which is optional but usually desirable to use to improve the miscibility or combinability of the various constituents of the liquid detergent, may constitute about 1 to 15% of the weight and preferably 5 to 10 x of this, wherein the most preferred amount is 8 - 9 X Larger amounts than the given limits are usually not necessary and may adversely affect the purifying ability of the product by causing a limitation of the amount of alkylene ethoxy sulfate or citrate to maintain a condition with a single-phase, clear liquid, while, when smaller amounts are used, the hydrotropic effect may be insufficient to produce a composition which has a long and stable storage life. In accordance with the other components of the present liquid detergents, the amounts can of course be adjusted within the given ranges in order to take advantage of the best properties in terms of the characteristics of the individual compounds used and to obtain the best products. Thus, in most systems, the amount of sodium cumene sulfonate used may be less than for other hydrotropes, such as potassium xylene sulfonate, to have the same dissolving effect. The diluted solvent medium, which is preferably water, but which may also contain minor amounts, e.g. up to 30% of the same, of mono-, di-, and polyhydroxyl alcohol and similar solvents, may be present in an amount of about 15-30% of the liquid detergents and preferably 40 ~ 60% of the same, the most preferred amount being about 50%. Often - 60% of the water of the diluted solvent is present together with the other constituents as they are added, the remaining part being added, preferably as deionized water, during the mixing process in which the present detergent is prepared. Although the amount of dilute solvent used is controllable in a fairly wide range, it will be seen that this amount is limited by the solubility of the various components in the presence of the hydrotropic agent. In addition, since a substantial content of active ingredient is required to have the desired effect, highly diluted liquid detergent solutions will not be sufficiently useful.

The water-soluble soap, which is used to reduce foaming and for its complementary washing effects, constitutes a minor component of the liquid detergent, usually 0.5 - 5% and preferably 1 - 2% of the same. The fluorescent whitening system consists of about 51 - 90% cotton whitening, the remaining part consisting of one or more polyamide whitening agents, polyester whitening agents and chlorine-stable whitening agents. The content of fluorescent whitening agent in the liquid is normally 0.2 - 2%, preferably 0.4 - 1 L, with about 0.7 X being the most preferred content. Such concentrations are soluble in the described liquid detergents and are effective in giving the washed clothes a noticeable luster or shine.

The levels of other additives or auxiliaries should generally not exceed% and are preferably kept at 15% and below and preferably below about 10% in the phosphate-free, large-scale synthetic detergent liquids. The individual components should not exceed 10%, preferably 5%, with the most preferred amount being less than 3 Z of the product. The use of such compounds in amounts greater than those indicated above can often significantly alter the properties of the liquid detergent and should therefore normally be avoided. The use of the clear, large-scale liquid detergent of the present invention is both simple and exceptionally effective. Relatively small amounts of the liquid are used and the product is useful in washing machines with upper filling openings as well as in those with front openings for filling washing clothes. When using a typical preparation according to the present invention, which contains about 50% solids and 50 Z of water, although products with larger or smaller amounts of solids can be used, e.g. about 1/3 cup of the liquid for a full automatic washing machine with washing cylinder, in which the water volume is about 57 ~ 68 liters (15 - 18 gallons). Correspondingly, only 1/6 cup is used when using a washing machine equipped with a front filling opening with a volume that is half as large as the top filling machine. The concentration of the liquid detergent in the washing water is thus only about 1-2 g / l, preferably 1.5 g / l. The kits weigh about 50 grams for a horizontal cylinder machine and about 100 grams for a vertical cylinder machine. The amount used generally corresponds to about 0.1 - 0.3 g / l of the higher fatty alcohol ethoxylate sulphate, 0.1 - 0.5 g / l of the citrate, 0.07 - 0.2 g / l of the hydrotropic agent, 0.01 - 0.1 g / l of soap, 0.01 - 0.02 g / l of optical brightener and 0.01 - 0.1 g / l of other aids. The amount of the active cleaning materials and the filling and filler materials used in the washing water can also be achieved by using more dilute or more concentrated liquid detergents than those described above, but in such cases other problems are sometimes encountered. As an example, it can be pointed out that the more dilute the liquid, the more water must be transported unnecessarily and the more space the product takes up, while when highly concentrated solutions are used these cfta become too thick while some of the components may become insoluble during storage. It is, however, to be understood that the use of more dilute or more concentrated products is within the scope of the invention when the desired wash waters are provided by such products and the relative proportions between the components are maintained.

The wash water used is preferably a fairly soft water or of reasonable hardness and is usually used at elevated temperature. The compositions of the present invention are also useful for washing clothes in very hard water and at lower temperatures. the hardness of the water can thus range from 0 to over 300 parts per million, calculated as calcium carbonate, and the washing temperatures can be from 10 ° C to 900 ° C. The washing temperatures are preferably between 20 ° C and 70 ° C and the washing can be performed in an automatic washing machine, in which the washing is followed by rinsing and centrifugation or other drainage or twisting cycles or operations. The liquid detergent according to the invention can of course also be used for hand washing of clothes, in which case full strength can sometimes be used on certain stains on the laundry clothes or the laundry clothes can be soaked in a detergent solution with a higher concentration before washing. Washing processes generally take between three minutes and an hour, depending on the type of fabric being washed and the degree of soiling observed. After completed washing and spinning, draining or twisting processes, it is preferable to dry the laundry in an automatic drying device shortly afterwards, but drying on a line or line can also be used. A rinse with fabric softener can be placed between washing and drying or carried out at other suitable stages during the washing process.

The detergent according to the present invention dissolves very easily in the washing water, whether it is hot or cold and very effectively cleans various kinds of fabrics, clothes and other laundry items. It can be used in washing machines with either top filling or front filling and can be advantageously adapted to foam to the right extent. The product is an appealing clear, stable liquid that retains its active effect and uniformity during a long storage time on a shelf, for example. In experiments, where its effects have been compared with the effects of commercially available pre-laundry detergents, it has been found to be very advantageous, especially when the fact has been taken into account that the composition according to the invention does not require any special treatment. before disposal via standard sewers or sewer systems. The composition according to the invention is often preferred because it is convenient to use and for excellent and superior cleaning ability. Nevertheless, even if the washing results of the present product are not as good as those obtained with commercial products overfilled with polyphosphates, the value of the development of this anti-polluting detergent is a significant and important advance to justify. that this new product replaces the phosphate-based compositions intended for large-scale washing. Therefore, when the cleaning ability obtained is of the same extent as that obtained with phosphate-containing detergents, the significance of the progress made is much greater in this context. 7200741 -2 m: The invention is described in more detail by the following examples, which dcck do not limit the same. All parts are parts by weight and all temperatures are in degrees Celsius unless otherwise stated.

Example 1 ® Percent Ro (c2H40) 3so3Na Üueodol "25 - as, so x aqueous solution containing 14% ethanol, 1% unsulfated alcohol, R = with 12, 13, 14 and 15 carbon atoms mixed primary alkyl 25.0 Sodium citrate dihydrate 20.0 Sodium cumin sulphonate, 43% aqueous solution (of which 1% is sodium sulphate) 20.0 Water, deionized 35.0 100 g, A clear liquid detergent according to the above recipe is prepared by adding the sodium cumin sulphonate solution, the citrate and Neodol at room temperature, 250 ° C. the solution to the water The order of addition of the various constituents can be changed as desired as well as the temperature A single phase, clear, liquid detergent is obtained which is stable for long storage periods The pH of the product is 8.5.

Using tap water from New Bunswick, New Jersey, which contained about 100 parts per million (expressed as calcium carbonate) of magnesium and calcium hardness, the cleaning ability of the main components of the liquid detergent was determined in comparison with a commercially acceptable detergent. In one series of experiments, cotton clothes were repeatedly soiled by periodically rubbing against the skin during the day, after which the soiled clothes containing dirt, grease, skin flakes and tallow secretions were uniformly divided and washed with a solution of ingredients of either the experimental product or the control product, less hydrotrope, in a Terg-o-tometer washing machine for laboratory use. Reflectometer readings were performed on the washed clothes and compared to determine the extent to which the dirt had been removed, after which a statistical analysis was made of the results to determine whether there was a difference between the washing abilities of the tested materials or not.

The statistical analysis of the results proved and established that the liquid detergent composition, free of polyphosphate builder salts, is as good a detergent as the commercial product, which contains% of such polyphosphate. When the experiments were repeated by re-soiling clothes and washing them several times, the same results were obtained.

The results of the Terg-o-tometer experiments were confirmed when the complete, clear and liquid detergent product was tested against a commercial product by so-called "bundle tests", in which a variety of soiled fabric articles of cotton, polyester-cotton blends, rayon and nylon were used instead, and during washing in a full-size commercial automatic washing machine. Similar results are obtained when in instead of "Neodol 25-38" uses the other higher fatty alcohol ethylene oxyulfulates, including those in which the higher fatty alkyl is mixed Cl2_13 or Cl4_15 but it appears that the mixture of Cl2_15 is a better detergent in the present compositions than the narrower types of the higher fatty alcohol derivatives.

Regarding the ethoxylation, comparable results are obtained when the higher fatty alcohol is ethoxylated from two to four times provided that the hyophilic-lipophilic equilibrium is maintained at approximately the same equilibrium as for "Neodol 25-38. Thus, when the higher carbonaceous alkyls of the higher alkyl the group used, the degree of ethoxylation should be higher, eg 4, 5, while in the lower carbon content of the higher alkyl groups the ethoxylation can be from 2 to 4. Good cleaning ability is obtained even when in one of the described fatty alkylene ethoxylate sulphates the cation is potassium. , ammonium, lower alkylamine or lower alkanolamine.

When concentrations are used which far exceed the concentrations of the main active ingredients in the dezergent indicated above, solubility problems may arise and the liquid detergent will often not be clear or may be divided into two phases. This can also occur when more than about% "Neoïgâà ll is added to the recipe as a substitute for a certain amount of water." Neodšå '4511 is a higher alkyl (C14-15) ethoxylated alcohol (11 ethoxy groups). Poorer stability and phase separation have also been noticed when the alcohol ethenoxylate sulphate is replaced by higher alcohol sulphate. Instead of the sodium citrate dihydrate, other forms of citric acid and intermediate salts, including potassium, ammonium and lower alkanolamine salts, may be used, giving similar results.

When sodium cumene sulfonate is replaced with potassium xylene sulfonate or ammonium benzenesulfonate, a good detergent is also obtained which is clear and stable. The amounts of the hydrotropic agent are varied within the entire range specified above as well as the amounts of the citrate and good, stable and clear liquid detergents are obtained which all have an excellent and excellent cleaning ability.

Modifications to the recipe are made in which soluble optical brighteners include extensive cotton brighteners and polyester-nylon brighteners. Such compositions are good cleaning agents, form clear single-phase solutions and also help to make the cleaned, washed laundry clothes light, clear and shiny.

In the experiments described above, the concentrations of the liquid detergent used are L / 3 measuring cup for the top-loading washing machine, but can be reduced to half this quantity for horizontal cylinder-filling machines with front-filling. In both cases, an equally good cleaning is obtained. In current use on soiled fabrics and garments, the concentration of the liquid detergent used can be from 1 to 2.5 g / l depending on the extent to which the laundry is soiled. 1 - 2 g / l is generally sufficient to clean an average wash. The washing time can vary depending on the materials to be washed and the extent to which these materials are soiled. Washing times between 3 minutes and one hour are used, however, with the most common washing time being about 45 minutes. Better cleaning is achieved in warm water, but the product can also be used very well in cold water, as the liquid dissolves very quickly and easily. The water temperatures used in the experiments have been about 65 ° C. Under such conditions the pH of the washing water is normally between 7 and 9 and in most of these experiments the pH has been about 8.5 at the beginning of the wash and is lowered about one pH unit during the wash, the extent of such a pH decrease depending on the nature of the wash and its acid or buffer content.

After the washing itself has been completed, the clothes are of course rinsed with water, sometimes using as many as three rinses, after which the water is removed by centrifugation, vacuum technique or by twisting and the laundry is dried, preferably in an automatic drying plant, although the line drying can also be considered.

Example 2 Example 1 is repeated but with the difference that the sodium citrate is replaced by Z citric acid. The resulting liquid composition has a pH of 1.3. In this case, the cleaning ability is slightly worse than that of the composition according to Example 1.

Example 3 Example 1 is repeated again, but with the difference that sodium cumene sulfonate is excluded and the amount of water is increased to 55%. This product is more viscous than that obtained according to Example 1, but its effect is comparable.

Example 4 Example 1 is repeated once more, but with the difference that instead of 20% cumene sulfonate 10 Z sodium xylene sulfonate (40% aqueous solution) and 10% water were used.

Example 5 The following compositions are prepared:% of constituents of E 2 2 of Alcoholser sulfac acc. ex. 1 25.0 25.0 29.5 20.0 25.0 Neurium myrrh - 21020 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 C14-14 alcohol and 11 moles of ethylene oxide (Neodol 4511) 3.0 3.0 Isopropyl alcohol 1.0 Water 50.0 54.0 35.0 37.0 32.0 Example 6 A composition is prepared as follows : - '72007h1-2 _ 20 Alcohol ether sulphate acc. ex. Sodium citrate ° 2H 2 O 10 Sodium cumene sulphonate (43%) 20 Sodium carbonate 10 Sodium silicate 10 Water 25 Example 7 Example 6 is repeated, but with the difference that the sodium carbonate is excluded and instead 10 l of citrate are added (for a total amount of 20%).

Example 8 Example 1 is repeated, the following being varied under the corresponding A w HUQ w G the ethoxylated component according to the change in the amount of water: 8% ethoxylated sulphate according to Example 1 2 ethoxylated 50% ethoxylated sulphate according to Example 1 Sulphate according to Example 1% % ammonium lauryl diethyl oxysulfate X diethanolamine salt of stearyl pentaethylene oxysulfate% potassium myristyltriethene oxysulfate Excellent results are obtained in all cases.

Examples 9 Examples 8A - 8G are varied individually with respect to the citrate component as follows under corresponding increase or decrease in water content: IIWUOEU G% sodium citrate - 2H 2 O% sodium citrate, anhydrous% potassium citrate, anhydrous% diethanolammonium citrate% citric acid% trimitonium citrate each example. Example 10 Each of the foregoing examples is modified to include separate preparations as follows: A 0.05% sodium mnT / x (ethylenedienine ceracetic acid) B 1.0 L sodium nitrilotriacetate C 1.0% sodium tripolyphosphate D 0, 08% tetrachotassium pyrophosphate The compositions are comparable to those of Examples 1-9.

Examples 11 Examples 1 and 3 are repeated using a sodium soap of tallow coconut fatty acid (80:20 ratio) in the amounts indicated and with a corresponding reduction in the water content.

A 1.074 B 2.074 C 3.0% Example 12 Examples 1, 3, 8C and 8 E are repeated using the following additional detergents and with a corresponding reduction in the water content: A 3.5% sodium lauryl sulphate B 3.0% linear sodium tridecylbenzenesulphonate C 4.0% myristylnonaethenoxyethanol Example 13 Examples 8C and 8E are repeated, adding as in Example 12 7.5% sodium lauryl sulphate in the first place, 7.5% sodium dodecylbenzene sulphonate in the second place and finally 7.5% dodecanol and moles of ethylene oxide.

Claims (8)

7200741 -2 22 P a t e n t k r a v Liquid detergent liquid detergent composition, which is free of phosphate and nitrogenous builders, characterized in that it comprises 8 to 30% of a water-soluble, anionic, synthetic, organic detergent salt of the formula R0 ( C 2 H 2 O) n SO 3 M, where R represents alkyl having 10 to 20 carbon atoms, n is from 2 to 6 and represents between 1 / S and 1/3 of the number of carbon atoms in R, and where M is salt-forming ion; 10 - 30 2 of a citrate scrubber; 0 - 15 Z of a hydrotropic agent; 0 ~ 5 Z of a water-soluble soap; 0 - 10 2 water-soluble silicate; 0 - 10 Z water-soluble carbonate; and 15 - 80 2 aqueous solvent medium. Detergent composition according to claim 1, characterized in that it contains 8 to 30 Z of the water-soluble, anionic, synthetic, organic detergent salt of said formula, wherein M represents alkali metal, ammonium, lower alkylamino and lower alkanolamino; 10 - 30 2 citrate wash- enhancer salt; S - 15 2 hydrotropic salt comprising cumene sulfonates, benzenesulfonates, toluenesulfonates and xylene sulfonates; and 15 ~ 80 2 aqueous solution medium. Detergent composition according to any one of the preceding claims, characterized in that it contains 10 - 2 2 of said water-soluble detergent salt of the formula R 0 (C 2 H 2 O) n SO 3 M, wherein R is a straight chain alkyl having 12 to 15 carbon atoms, n is from 2 to Ä and M. is an alkali metal; 15 - 25 Z of an alkali metal citrate; 5-10% hydrotropic alkali metal salt; and # 0 - 60 2 aqueous solvent medium. Ä. Detergent composition according to any one of the preceding claims, characterized in that it contains 10 - 2 2 of said water-soluble detergent salt having the formula R 0 (C 2 H 2 O) n SO 3 M, wherein R is a mixture of straight chain alkyls having 12 to 15 carbon atoms which via oxygen is end-linked to the polyethoxy chain, n is 3 and M is sodium; 15 - 25 Z sodium citrate; 5 - 10% sodium cumene sulfonate; and H0 - 60 2 water. Detergent composition according to any one of the preceding claims, characterized in that it contains 2 of said water-soluble detergent salt of the formula R 0 (C 2 H 2 O) 3 SO 3 Na; 20% sodium citrate; 8 - 10 2 sodium cumensulfonate, varvid 2; The remainder consists of optical brighteners, dyes, perfumes and other minor auxiliaries, which composition is present as a clear, single-phase, stable liquid. Detergent composition according to any one of the preceding claims, characterized in that it contains 0.5 '5 2 of a water-soluble alkali metal soap, which composition is substantially non-foaming and leaves only traces of foam in a rinsing water used for to rinse off detergent and dirt from washed laundry. Detergent composition according to any one of the preceding claims; characterized in that it is in clear single-phase form and contains U, b - 1% of an optical brightener system comprising a cotton bleach as a major component and a polyester-amide bleach as a minor component. Detergent composition according to any one of the preceding claims, characterized in that the water in said aqueous solvent medium is substantially deionized or is a low hardness water. PUBLICATIONS MADE: US 2,264,103 (210-58)