PROCESS FOR CLEANING AND DEGREASING, PREMIX FOR USE AT THE PROCESS AND CLEANING COMPOSITION

Abstract: Process for cleaning and degreasing comprising treatment with a tenside and electrolyte containing water solution. The solution is prepared at the site of use by the mixing of a water free or nearly water free (below 20 weight %) premix, containing one or more nonionic tensides and one or more tensides with charge giving function of which at least part (25 to 100 weight %) has hydrotrope properties and eventually electrolyte in solution or in the shape of solid state, dispersed, finely divided particles, with water and, if the premix does not contain electrolyte, solid state electrolyte, liquid electrolyte or electrolyte solution at the site of use. The invention also concerns a spontaneously dispersing composition intended for use at the process, the resulting tenside/electrolyte mixture and its use.

Description: Process -for cleaning and degreasing, premix for use the process and cleaning composition. For a long time there have been automatic car cleaning equipments which to large extent have been based upon differe ko binations o- brushes together with spraying of cleaning solutions, run off and polish compositions etc. The differing designs of the cars makes automatic control of the movements the brushes very problematic and one has tried to use pressur water Jets instead, which give better accessibil ty with respect to hardly accessible corners. For trie cleaning of motors, chassis, wheel houses etc. nigh pressure Jets are the only realistic alternative to manual washing. With regard to heavier vehicles as trucks, lorries and busses the problem of automation of the brush movements is mainly still unsolved. If brushes are used the equipment is run manually. High demands must be met by the person who is runnin the equipment. One has often found it necessary to rely upon manual washing eventually assisted with manually directed high pressure guns. The road safety and the maintenance of the vehicles, however, demand very efficient cleaning at the same time as the costs of manual cleaning accelerate. New equipment for automatic cleaning of heavy vehicles work with ramps of high pressure jets. Though modern high pressure jets are very efficient the echanichal work they are able to bring about is- signi icantly less than what will be effected by brushes. The demand for efficient cleaning is, however, the same in both cases. The reduced mechanical work thus must be compensated by cleaning agents with higher efficiency. The agents must at the same tim be mild against finishes, plastics, bright metals etc. To this is added that the wastes from the cleaning plants must be environmentally acceptable. The earlier use of huge amounts of solvents of the cold degreasing agent type is therefore no longer possible. Most manu acturers of agents intended for use at vehicle cleaning have chosen to solve the problem by using emulsions, especially so called microe ulsions, which in themselves combine the activity of a solvent of the cold degreasing agent type and a tenside mixture and make it possible to reduce the solvent quantity to a fraction of what is needed, when using a conventional cold degreasing agent. Even those reduced amounts of solvents are frequently causing concern especially as the emulsions that w ll be the result when o l in the dirt is added to the micro emulsion and stabilized with finely divided particles in the dirt may be difficult to break. The concerns are first hand ascribed to hydrocarbon solvents including halαgenated hydrocarbon solvents. Thus there is a need for cleaning and degreasing agents that does not contain hydrocarbon solvents or halogenated hydrocarbon solvents. Further these agents must be mild against car finishes etc. and give an acceptable working environment. Still further the agents should give easily breakable emulsions with the oils that in the dirt to allow complete oil separation before the used cleaning solution is diverted to sewage. Most agents for vehicle cleaning have been based on anionic tensides, often in combination with nonionic tensides, especially of the ethoxylated alkyl phenol type. Tenside mixtures for degreasing purposes and personal car shampooing have been considered very critical systems with high demand for mixing exactitude not to be instabile. They are also thought to tend to forming gels difficult to dispers especially if their tenside concentrat on is high. Therefore they have been delivered ready-mixed with comparati ely high water contents. This has caused heavy costs for transport and storage. A system that from one or a few components, which are water free or contain just little water, with a minimum of mixing and dosing equipment is able to produce tenside/electro yte mixtures for degreasing and passenger car shampooing at the site of use has so far not been found. The inventor has studied the problem carefully and thereby found that a water free or nearly water free mixture of nonionic tensides and charge giving tensides with hydrotrope properties especially fatty amine ethoxylates and/or a pholyte or zwitterionic tensides or phosphoric acid partial ester tensides may be formulated in such a way that it becomes easil pouc— and pumpablβ and at mixing with electrolyte and water spontanously forms a clear solution with a minimum of agitatio that may be achieved by the added water either directly or via a simple propeller, which is driven by the water pressure. A considerable advantage with tenside mixtures instead of emulsions containing solvents is that tenside mixtures allow higher electrolyte content, which inter alia makes the emulsions formed with oils in the dirt easier to break. The higher electrolyte content may consist of complexing agents. Especially during winter, when calcium chloride containing road salt is part of the dirt, this will mean a considerably improved cleaning result even if one for economical and environmental reasons is using recirculating water. With earlier cleaning compositions one is frequently forced to abstain from recirculation during the time of the year, when road salt is used. The mixture formed is particularly stabile at both low and high pH and may be completed with a many basic, acid or neutral electrolytes, especially of the complexing agent type, which makes the cleaning efficiency still better. The tenside/electrolyte mixture may be adapted for use as degreasing agent, car shampooing agent and general cleaning agent merely by adjusting the proportions of electrolyte/ tenside and/or dilution. A typical example of earlier technic is Swedish patent no 196938. According to this one uses a water solution containing condensed phosphate and a tenside mixture and eventually a solvent. In the one example that is given the tensides are specified to a mixture of 5 g/1 alkyl phenyl polyglykolether and 3,5 g/1 of alkylaryl sulphonate and other known aniαnic active surfactants and the condensed phosphates to 30 g/1 tetrasodium pyrophosphate. In the mixture is also included 2,5 g/1 hydrocarbon solvents with boiling point 250 to 320 °C. Salting out effects depending upon the lack of hydrαtrope properties in the used aπionic tenside makes it impossible to formulate this mixture as a not separating dilutable concentrate. This is true as well with as without solvents. Swedish laid open patent application no 368 933 concerns a process for vehicle cleaning at which one applies at the vehicle an acid solution containing tenside and fluoride ions. In preferred ways of carrying out the invention a cationic tenside is added to the composition. The acid solution is removed by an alcaline rinse solution that may contain complexing agents. European patent no 84 411 concerns a process for removal of oil from particles that have been released at oil drilling before depositing the particles. The composition is made up of (A) at least one alkoxylated alcohol, carboxylic acid, alkyl phenol or nonionic phosphate ester and <B) an ethylol amide. The composition is used without electrolyte addition. No charge giving tenside is added. Tests show that compositions according to this publication can't be mixed with electrolyte to a stabile not separating concentrate. European patent no 132 765 concerns a composition containing corrosion inhibitors for cleaning of metals in rolling mills and similar plants. In the composition there are tensides that may be nonionic and/or anionic. As nonionic tensides are mentioned polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters and glycerine fatty acid mono- and diesters. As anionic tensides are mentioned alkylaryl sulphonates, alkan sulphonates, alken sulphonates, sulphα- succinates, alfa-sulpho fatty acid esters, fatty acid salts, alkyl sulphates, al -αlefine sulphonates, polyoxyalkylene alkyl ether sulphates, polyoxyethylene alkylaryl sulphates an similar substances. Further the compositions contain a carboxylic acid or salt with the formula R-X-(CH2> m ~CQ0M, whe X stands for N-H, N<CH2>n-C00M eller CH-COOM. The composition according to the examples are neutral or acid. No hints are given to charge giving tensides with hydrαtrope properties. The French patent publication no 78 08611 concerns a process for cleaning of metals by spraying with weakly alcaline solutions containing soluble salts especially salts of alkano a ine and carboxylic acids that may be aromatic or alifatic with 6 to 12 carbon atoms, one or more nonionic tensides and one or more quaternary ammonium co puonds. The concentrate fo use according to the invention is said to have active content of 20 to 80 "/.. As preferred cationic tensides are mentioned alkyl dimethyl bensyl ammonium salts and alkyl trimethyl ammonium salts. These are lacking the hydrotrope properties that are essential to the present invention. The Japanese patent application 58-126992 (Patent Abstracts of Japan, vol. 7, (C-191)) concerns a composition for cleaning of plates in rolling mills. The composition contains 10 to 30 parts complexing agent, 10 to 30 parts tenside, 0.5 to 10 part organic sulphor compounds, 0.5 to 10 parts alumina gel without anorganic anions and 0.1 to 5 parts foam inhibitors. The components are mixed to a concentrate with 20 to 80 parts water. Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vαl A 7, Weinheim 1986, page 147 informs that car cleaning agents may contain 10 to 20 7. anionic tenside, 5 to 10 7. nonionic tenside, 2 to 5 % hydrotropes and 0 to 10 V. polyphosphate. One also mentions a polish that may contain nonionic- and cationic tensides and solvents of the white spirit type. It is said that the compositions are present in water solution without specifying any concentrations. The present invention concerns a process to produce at the sit of use an inter alia for cleaning purposes suitable stabil.e, water containing tenside/electrαlyte mixture, by the mixing of a premix, that is water free or contains relativly small water quantities (below 20 weight ., preferably below 10-weight */. an especially preferred below 5 weight '/.) and based upon a liquid mixture of one or more nonionic tensides, one or more tensides with charge giving function among which at least one tenside has hydrotrope properties, preferably a fatty a ine ethαxylate an ampholyte or zwitter ionic tenside or an anionic partial ester of phosphoric acid and eventually electrolyte in solutio or in the shape of solid dispersed particles, with water and, if the premix does not contain electrolyte already, solid or water solved electrolyte, at which the formation of a clear stabile solution will occur spontanously i.e. with the minimum of agitation that is required to avoid layering caused by the different densities of the liquids. Further the invention concerns a cleaning process that comprises application of a tenside/electrolyte mixture, produced according to th invention, followed by a wash with water eventually containing cleaning agent. Those steps may be followed by rinsing, application of polish and run off agents et cetera in known ways. It concerns a premix too that contains one or more nonionic tensides, one or more tensides with charge giving function of which at least one has hydrotrope properties, preferably a fatty amine ethoxylate, an ampholyte or zwitter ionic tenside or an anjonic partial ester Df phosphoric acid, in for εpontanous formation of a clear solution at mixing with water appropiate proportions. Electrolytes may be added at the mixin or be present as waterfree particles homogenously dispersed i the tenside mixture. Further the invention concerns the resulting mixture that contains electrolytes too, preferably in the shape of alcalin alkali metal salts and/or salts of ammonium or substituted ammonium or acids and/or acid metal salts and/or komplexing agents for ultivalent metal ions, that improve the cleaning power. That the composition is water free or nearly water free shall be understood in the way that water is not an essential component of the premix. Part of the raw materials may be available merely in water solution or dispersion or need small quantities of water for their solution. These solutions or dispersions may without problems be used in the premix, at which they are the cause of the small quantities of water (below 20, preferably below 10 weight 7. and especially preferred below 5 weight '/.) in the premix that are mentioned above. The production of the mixture at the site of use may be made b all known processes for the mixing of two αr more liquids. Eve the agitation that is caused by the addition of water to the beforehand added premix is frequently sufficient. Another alternative is agitation with pressurized air but this is not preferred, as the tensides in the mixture may have a certain tendency to foam formation. This may lead to the scattering of liquid particles in the environment. If mechanical agitation is deemed appropiate simple propeller agitators are preferred. A preferred mixer for the making of a mixture according to the invention is constituted of a tank, which in its simplest version may be a slightly modified sheet-metal αr plastic barrel, equipped with an at the tank top mounted agitator. The agitator, which may have two or more blades, has a bearing in the shape of a tube connected to a pressure water pipe. The shaft of the agitator is hollow and the cavity is branched along the blades to at least two diametrally opposite blade points and opens out there in against the radius perpendicular directions in such a way that the reaction force caused by the escaping water makes the agitator rotate. Such an agitator is the subject of Swedish patent application no 9002609-7. As an equivalent alternati e to agitators may be used a specially designed supply arrangement for the water with distribution in different jets, which give water movement in the entire tank to avoid local stagnant areas where layering may be retained. A preferred mixer of this kind is described in Svedish patent application no 9102554-4. The demand for dosing accuracy at the final mixing is not large. It may for instance be sufficient with a simple level measurement, which may be made manually. Another preferred alternative is to use the packing volume as an estimate of premix and eventual liquid electrolyte volume and dilute with water to a fixed level afterwards. The application of the final mixture at the surfaces that are ' to be cleaned may be done by all known methods. For vehicles, for instance, manual guns, spray ramps, application as additiv to the water that sprinkles through the brushes and injection into the pipes that supply high pressure water may be proper alternatives. For other purposes as fire sanifying, degreasing etc. application by sprinkling or dipping may be appropiate. It is of course advantageous if the mixture after the application may have a suitable short time period to work before the next step of the cleaning process follows. The essential components of the premix are nonionic tenside and charge giving tenside with hydrotrope properties. The choice of nonionic type tenside is not critical. All known nonionic tenside types may be used. The choice is first-hand dictated by economical and environmental considerations. Where the disposition of waste water so allows, that is if there are no restrictions with the regard of tenside choice or if tenside and solvents can be removed from the waste water before treatment in waste water plants, alkoxylated alkyl phenols, especially those that are ethoxylated or prαpoxylated and ethoxylated are preferred. Such nonionic tensides give the best performance in proportion to their price. Other preferred nonionic tensides are alkoxylated higher alcohols, alkoxylated higher fatty acids and alkyl glycosides, which are environmentally better accepted and may be used in compositions that are equally effective as the alkyl phenol based ones but less favorable economically. Both primary and secundary alcohols may be used as well as so called oxα- alcohols. Even nitrogen-containing nonionic tensides such as alkoxylated alkyl amides, alkoxylated alkyl amines and tertiary alkyl amine oxides may . be used but are as a rule so expensive that they cannot be a dominating part of the composition. Small additions to modify the tenside properties may be of interest. To the extent that those tensides are able to add hydrogen to a tertiary nitrogen atom and at least temporar ly assume a quarternary con iguration they are regarded as potential cationic tensides in connection with the invention. Suitable nonionic tensides are relatively hydrophobe. With regard to the ethoxylates mentioned above they belong to the categories that normally are called low ethoxylated to middle ethoxylated ones. With regard to the alkyl phenols the proper range is 1 to 10 moles, preferably 2 to 9 moles ethylene oxide if the alkyl part consists of 6 to 10 carbon atoms. With regard to alkanols the proper alkyl chain length is 8 to 18 carbon atoms and the number of ethylene oxide units 1 to 9, preferably 2 to 7. Alkoxylated nonionic tensides containing propylene and/or butylene oxide may be used if the ethylene oxide part is moiarly in surplus. Other usable tensides are the so called end group capped alkoxylated nonionic tensides, that is tensides, where the end OH-group has been esterified or etherified with conservation of the nonionic character. A nonionic tenside with a unitary degree of ethoxylation may be used but mixtures give advantages with regard to cold temperature stability and reduced gelling tendencies. An especially preferred mixture is nonyl phenol ethoxylate with 9 moles ethylene oxide together with nonyl phenol ethoxylate with 4 moles ethylene oxide. Another preferred environmentally better mixture is fatty alcohol ethoxylate with alkyl chain length 11 carbon atoms and 5 moles ethylene oxide together with fatty alcohol ethoxylate of the same fatty alcohol and 7 moles ethylene oxide in the proportions 1:1 to 2s 1. The performance of this latter mixture may be improved even further by adding a fatty alcohol ethoxylate with alkyl chain length 11 carbon atoms and 3 moles of ethylene oxide in quantities up to 45 % of the total quantity of nonionic tensides. Nonionic tensides with lower degrees of ethoxylation are useable but not preferred as the content of unethoxylated material increases and may cause working environment problems inter alia with regard to smell. This is especially obvious with regard to ethoxylated fatty alcohols. To the extent that so called narrow range alkoxylates becomes available to commercially acceptable prices the proper area of ethoxylation degree will probably be displaced downwards. In the compositions there are one or more tensides with capacity to give the tenside micelles a positive or negative charge included too. These other tensides are either cationic or anionic in character. One or more αf dessa charge giving tensides must have hydrotrope properties i.e. improve the solubility of the added electrolyte. Tensides with hydrotrope properties should constitute at least 25, preferably at least 50 weight '/. of total quantity of charge giving tensides. Especially suitable tensides of this type are quaternary fatty amine alkoxylates, ampholyte or zwitter ionic tensides and anjonic partial esters of phosphoric acid. Molecule structures of tensides that give rise to hydrotrope properties seem to be the presence of a charged nitrogen or phosphorus atom together with a relatively long alkoxy chain and/or presence of both cationic and anjonic charges in the same molecule. A suitable test if a charge giving tenside has sufficient hydrotrope properties is to make a mixture of it with nonionic tenside in intended proportions, add NTA-solution and dilute with cold water. See page 15, 1st paragraph regarding quantities and evaluation. Especially suitable are quaternary fatty amine ethoxylates containing a long alkyl chain, 8 to 22 carbon atomes, and a long ethoxy chain, 5 to 25 ethoxy units. Further quaternary imidazolinium carboxylates, betaines and sultaines and anionic partial phosphate esters of alkyl phenol ethoxylat with 6 to • 12 carbon atoms in the al yl part and 2 to 10 moles ethylene oxide respektively anionic partial phosphate esters of fatty alcohol ethoxylate with 8 to 24 carbon atoms and 2 to 16 ethylene oxide units. The compositions may further contain relatively low amounts of other hydrotropes that may wholly or partly consist of polar solvents. They have no or slight effect upon the cleaning process, but are modifying the properties of the premix especially with respect to viscosity, dispersion properties and cold stability. Compositions according to the invention contain different electrolytes as alkali, acids, complexing agents etc. For the cleaning of road vehicles pH should generally be within the range 8 to 12. For passenger cars the proper range is within the lower or middle part of this range. For lorries and other heavier vehicles within the middle and higher part. The compositions should contain a sufficient alkali reserv not to allow pH being effected by eventual acid components of the vehicle soil. pH adjustment and regulation of the alkalinity may be done by using a complex former solution with a surplus of alkali, addition of a solution of alkali metal hydroxide and/or ammonium or solid alkali as alkali metal carbonate. An interesting method is to let the premix be relatively acid for instance by the use of the acid form of one or more anionic tensides or by the addition of a hydrotrope in acid form. Premixes containing anionic tensides often show improved stability if they are present in acid form. Required alkalinity in the final mixture may be obtained by adjusting the electrolyte addition. For railway vehicles, where significant amounts of metal oxides especially iron oxide from the friction between wheels and rails may be a problem, acid composition are often preferred. The conditions may be of the same kind concerning cleaning of containers and goods, for instance cars and car parts that have been transported by rail. Acid compositions may also be preferred at a number of other potential areas of use of the invention as enhanched oil recovery, cleaning within the food and other industries etc. The choice of proper acid depends upon the area of use. Where strongly acid compositions are needed and corrosion no important concern strong inorganic acids as hydrochloric acid, sulphuric acid and nitric acids are preferred. In other cases relatively weaker unorganic acids as phosphoric acid, sulpha ic acid and acid metal salts as sodium bi-sulphate are suitable choices. In still other cases moderately strong to strong organic acids as formic acid, oxalic acid, citric acids etc. may be appropiate. pH in acid compositions according to the invention may be between .5 and 4, preferably between .5 and 3.0. Addition of complexing agents to break the the bonds caused by multivalent metal ions is generally appropiate as soon as alkaline compositions are concerned. The complexing agents may be oligomer or polymer phosphates as pyrophosphate, tripoly- phosphate, metaphoεphate etc., amine pαlycarboxylates as nitrilo triacetic acid (NTA) , ethylene di-amine tetraacetic acid (EDTA) etc., phosphonates and a ino phophonates. Part of these may in several cases be replaced by oligomer or polymer carboxylatβ compounds and/or cation exchanging zeolites. In acid compositions the need for complexing agents is generally less. To the extent that the electrolyte in its water free state is solid it may be present as dispersed small particles suspended in the tenside mixture, but this requires generally an advance mixing apparatus including fine-grinding of the particles and is not preferred. In water free state is included the cases too, where the main part of the water is present as crystal water. Most suitable complexing agents are available on the market in the form of concentrated solutions at a price per active substance that is below the price of the water free product. In these cases it is preferred to add the complexing agents as a concentrated water solution directly at the mixing of the water containing mixture. Even when the complexing agent may b bought to competitive price in its water free state it is usually preferred to add it in connection with the final mixin either as powder or as water solution as the presence of finel ground particles strongly increases the viscosity of the tenside premix, rises the turbidity point and reduces the stability and gives the premix increased tendencies to gelling. Besides the additives mentioned the premixes according to the invention may contain other common additives to this type of agents as f ' luor tensides to enhance the wetting of plastic surfaces etc., corrosion inhibitors, stabilizing agents, solubilizers (hydrotropes) , viscosity adjusters, freezing point reducing agents etc. The proportion of nonionic tenside to cationic tenside if it is added should be at least 2:3 and preferably at least 1:1. As the nonionic tenside is less costly than the cationic tenside it is preferred to increase its proportion as much as possible without seriously deteriorating the performance of the product. The possibilities of this are far better, when the nonionic tenside wholly or to considerable extent consists of alkoxylated nonyl phenols. In these cases one is able to create very efficient mixtures with a proportion of nonionic tenside to cationic tenside of 100:1 or sometimes even higher. Concerning mixtures based upon alkoxylated higher alcohols the conditions are not equally favorable and appropiate mixing proportions are therefore closer to the lower values above. Suitable mixing proportions concerning nonionic tensides to cationic tensides are thus from 2:3 to 150:1, preferably from 1:1 to 100:1 and more preferably from 1:1 to 80:1. To the extent that anionic tensides are used as charge giving tensides that is not solely as counter ions to cationic tensides the proportion nonionic tenside to anionic tenside should be at least 2:3, preferably 1:1. In this case too the proportion of charge giving tenside may be rather small. Proportions nonionic tenside to anionic tenside of 100:1 are well usuable. Generally seen, however, the proportion should not exceed 80: 1. Besides the already mentioned areas of use , cleaning of road vehicles and railway vehicles, processes and agents accordin to the invention are suitable for a large number of different applications as degreasing within the industry, cleaning of machines in work shops and industry, cleaning Df agricultural and excavating machines, cleaning of aeroplanes, sanifying after fires, enhanched oil recovery etc. The tenside containing premix does in most cases not need any separate adjustment but has a generally seen universal usability. The adjustment to special areas of use is mainly done by the choice of electrolyte additives. This adjustment is thus to a high degree simplified by the method of final mixing directly in connection with the site of use. Compositions according to the invention will to large extent be used in locations, where the temperature at winter may be very low. Therefore it is advantageous if both the concentrate and the ready-made mixtures remain stable down to or below the freezing point. Starting instability is shown by turbidity. Stability should be present down to +10 °C, preferably down to 0 °C, and more preferably to -8 °C. Empirically, compositions with good stability in the final mixture seems to be satisfactory regarding stability in concentrate form too. Further the compositions should be able of being diluted with cold water without showing gelling tendencies. As a fast test of suitability mixing of 15 grammes concentrate, 6 grammes 38 NTA-solution and diluting to 100 grammes with tap water (+B ° while agitating with magnetic stirrer is applied. Of these 100 grammes 10 grammes are taken and diluted to 100 grammes. At both tests a time of 1 minute to complete dispersion and formation of a clear, slightly opalescent liquid is considere as satisfactory. Belling at the first test and turbidity at t second one shows that the composition does not contain appropiate combinations of nonionic tenside and charge giving tenside with hydrotrope properties. Example 1. A premix consisting of 33,6 weight 7. alkyl phenol ethoxylate with about 10 carbo atoms in the alkyl part and 4 moles ethylene oxide, 28,0 weight 7. nonyl phenol ethoxylate with 9 moles ethylene oxide, 31,4 weight 7. phenol ethoxylate with 4 moles ethylene oxide, 1,6 weight % quaternary cocoa fatty amine ethoxylate with about 10 moles ethylene oxide, 0,6 weight 7. cetyl tributyl ammonium bromide, 4,8 weight 7. prαpylene glykol was produced. The mixture was a clear pDurable liquid. 250 liters of the premix were mixed with 25 liters NTA-solutio (38 weight 7.) that further contained a lye surplus of 1 to 5 weight "/.. The mixture was diluted to 1000 liters with cold water from a water tap. No gelling tendencies were observed at th dilution. The composition, which was a clear liquid with very slight opalescens, was applied by spraying at greasy and dirty machine parts. After flushing with high pressure water the parts were both clean and effectively de-greased. 150 litres of the premix were mixed with 25 litres NTA-solution (3B weight 7.) containing lye surplus. The mixture was diluted to 1000 litres with cold water. The composition was a clear liquid with very slight opalescence and was applied by spraying upon dirty car chassis. Flushing with high pressure jets gave an extraordinarily efficient cleaning. The composition was used for injection into a high pressure wash for passenger cars too and showed highly improved cleaning efficiency. 50 litres of the premix were mixed with 5 litres NTA-solution (38 weight 7.) . The mixture was diluted to 1000 litres with cold water. The composition was like in other cases a clear, very slightly opalescent solution. It was applied by a spray ramp at covered lorries. Following wash in a wash plant with high pressure jets completed with manually operated hand operated guns at for ramp— ounted guns in-accessible places showed improved result compared with microemulsions that were delivered ready-mixed. 5 litres of the premix were mixed with 2.5 litres NTA-solution (38 weight "/.) and diluted to 1000 litres with cold water. The composition was like in other cases a clear, very slightly opalescent solution. It was applied by a spray ramp upon passenger cars. The following wash in a brush washing plant showed improved result compared with microemulsions that were delivered ready-made. Example 2. A premix of 16,3 weight 7. ethoxylated fatty alcohol with 11 carbon atoms in the alcohol chain and 7 moles ethylene oxide per ol fatty alcohol, 32,7 weight 7. ethoxylated fatty alcohol with 11 carbon atoms in the alcohol chain and 5 moles ethylene oxide per mol fatty alcohol, 41,5 weight 7. cationic tenside of the quaternary cocoa fatty amine ethoxylate type with about 15 moles ethylene oxide, 0,5 weight 7. monocetyl tributyl ammonium bromide, 2,5 weight 7. propylene glykol, 6,5 weight 7. εodi m-N-l uryl sarcosinate (35 7. solution), was prepared. The product was a clear, pourable liquid. It was used in the same way as the product according to example 1 and showed equal properties with respect to dispersion without gelling and cleaning result. Example 3. Trial 2 was repeated with the difference that the content of nonionic tenside was increased to 55,5 weight "/. and entirely constituted of fatty alcohol ethoxylate with 11 carbon atoms i alcohol chain and 5 moles ethylene oxide per mol fatty alcohol At the same time the addition of natrium-N-laurylsarkosinat wa cancelled. The composition was a clear liquid and could be use in the same way and with equal results as the composition according to example 2. Samples of the composition according t example 2 and example 3 were diluted in the proportions 15 grammes premix, 3 grammes NTA-solution (38 weight 7.) and cold water to 1 liter. The resulting mixtures were subjected to cooling tests. The composition according to example 2 did not became turbid until at -5 °C the one according to example 3 became turbid at +8 °C. Example 4. Trial 3 was repeated with the difference that the entire nonionic tenside quantity now was made up of fatty alcohol ethoxylate with 11 carbon atoms in the alcohol chain and 7 moles ethylene oxide per mol fatty alcohol. The premix was diluted in the same way as according to example 3. The resulting mixtures showed better cold stability than the ones according to example 3 but showed larger tendencies to gelling at dilution with water (did not pass the gelling test above). Example 5. A premix of 63,4 weight 7. ethoxylated fatty alcohol with 11 carbon atoms in the alcohol chain and 5 moles ethylene oxide per mol fatty alcohol, 5,8 weight 7. fatty alcohol with 9 carbon atoms in the alcohol chain and alkoxylated with 3 moles propylene oxide and 9 moles ethylene o ide, 18,7 weight 7. cationic tenside of the quaternary cocoa fatty amine ethoxylate type with about 15 moles ethylene oxide, 3.0 weight 7. monocetyl tributyl ammonium bromide, 9.1 weight 7. ethanol was prepared. The product was a clear, easy-flowing liquid. It was used in the same way as the product according to example 1 and showed equal results. Example 6. A premix was prepared from 54.3 weight 7. fatty alcohol ethoxylate with 11 carbon atoms in the alcohol chain and on an average 5 moles ethylene oxide, 31.4 weight 7. cationic tenside of the quaternary cocoafatty amine ethoxylate type with about 15 moles ethylene oxide, 14,3 weight 7. ethanol. The product was a clear, easy-flowing liquid. It was used in the same way as the product according to example 1 and showed equal properties. It was further mixed with NTA-solution (38 weight 7.) containing lye surplus in the proportions 5 7. concentrate and 25 "A NTA-solution, rest to 100 7. water. The mixture was used as a 5 to lO 7. additiv to water. This mixture was used as a car shampoo in an automatic wash plant and showed excellent cleaning properties. Example 7. Trial 6 was repeated with the exchange of the NTA-solution against a clear liquid mixture of 49.5 7. NTA-solution (38 %> , 49,5 7. kalipol (50 7. potassium tripolyphosphate solution) and 1 "/. 50 7. potassium lye. The mixture was used as car shampoo i the same way as the earlier one and showed an excellent cleaning result. Example 8. 5 liters of the premix according to example 6 were mixed with 70 liters of water. 10 liters of this mixture were diluted to 100 liters. The mixture was used as car shampoo. The cleaning seemed at the beginning good, i.e. the dirt was dispersed. At rinsing, however, firmly adhering dirt stripes were formed. After addition of NTA-solution according to example 6 and new application the dirt could be removed by flushing in the same way as at the trial according to example 6. Example 9. A premix was prepared from 35,5 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the fatty alcohol and on an average 5 moles ethylene oxide, 12,0 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol and on an average 7 moles ethylene oxide, 37,2 weight 7. quaternary cocoa fatty amine ethoxylate with about 15 moles ethylene oxide, 6,2 weight 7. sodium~N-lauryl sarcosinate (35 7. solution), 9,1 weight 7. ethanol. The premix was a clear easy-flowing solution. It was used in the same way as the premix according to example 1 and showed equal properties. Example 10. A premix was prepared from 27,4 weight 7. fatty alcohol alkoxylate containing a mixture of ethylene oxide and propylene oxide (Miravon B12DF, biologically degradable low-foaming nonionic tenside) , 36,1 weight 7. fatty alcohol alkoxylate containing a mixture of ethylene oxide and propylene oxide (Miravon B79R) , biologically degradable low-foaming nonionic tenside) , 9,5 weight 7. cumene sulphonate (water free), 9,5 weight 7. water, 17,5 weight 7. sodium-N-lauryl sarcosinate (35 7. solution), The premix was a clear, easy—flowing solution. It was used in the same way as the product according to example 1 and showed equal properties. Example 11. A premix was prepared from 10,9 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol chain and on an average 5 moles ethylene oxide, 14,8 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol and 7 moles ethylene oxide, 18,2 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol chain and on an average 3 moles ethylene oxide, 19,8 weight % phosphate ester of nonyl phenol ethoxylate ' with 4 moles ethylene oxide, 16.5 weight 7. dipropylene glykol methyl ether, 14,8 weight 7. cumene sulphonate (water free), 5,0 weight 7. water, Thw premix was a clear, easy-flowing solution. It was used in the same way as the premix according to example 1 and showed equal properties. Example 10. A premix was prepared from 12,4 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol chain and on an average 5 moles ethylene oxide, 16,0 weight % fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol and on an average 7 moles ethylene oxide, 19.6 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol chain and on an average 3 moles ethylene oxide. 21,4 weight 7. phosphate ester mixture consisting of 50 weight 7. phosphate ester of a fatty alcohol ethoxylate of a fatty alcohol with 12 to 14 carbon atoms and ethoxylated with 3 moles ethylene oxide and 50 weight 7. phosphate ester of a fatty alcoholethoxylate of a fatty alcohol with 14 to 20 carbon atoms and ethoxylated with 8 to 12 moles ethylene oxide, 9,1 weight 7. dipropylene glykol methyl ether, 16,0 weight 7. cumene sulphonate (water f ee), 5,5 weight 7. water, The premix was a clear, easy-flowing solution. It was used in the same way as the premix according to example 1 and showed equal properties. Example 13. A premix was prepared from 38,5 weight % fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol chain and on an average 5 moles ethylene oxide, 11,5 weight 7. fatty alcohol ethoxyl te with on an average 11 carbon atoms in the alcohol and on an average 7 moles ethylene oxide, 14,4 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the alcohol chain and on an average 3 moles ethylene oxide, 20,0 weight 7. phosphate ester of nonyl phenol ethoxylate with 4 moles ethylene oxide, 11,3 weight 7. dipropylene glykol methyl ether, 4,3 weight 7. cumene sulphonate (water free), The premix was a clear, easy-flowing solution with pH between and 4. 15 grammes of the pre ixen were mixed with 2 grammes NT (38 7. solution) and diluted to 100 ml with tap water. The mixture was turbid but cleared up at the addition of small amounts of potassium lye. If the potassium lye was added to the NTA-solution beforehand the mixture became clear directly at the dilution. Ex am 1 e 1 To test different cold stabilizing additives the following tests were made. A start mixture containing 52,0 weight 7. fatty alcohol ethoxylate with on an average 11 carbon atoms in the fatty alcohol and on an average 5 moles ethylene oxide, 42,5 weight 7. quaternary cocoa fatty amine ethoxylate with about 15 moles ethylene oxide, 0,5 weight 7. monocetyl tributyl ammonium bromide, was prepared. The missing 5 weight 7. were constituted of a row of different solvents respectively other additives which are thought to be cold cold stabilizing. The mixtures were diluted in the earlier mentioned proportions 15 grammes premix, 3 grammes NTA (38 7. solution) and the remainder to 1 liter tap water. The zero sample where the extra 5 weight 7. were constituted of water became turbid at +10 °C while the samples with each 5 weight 7. addition of propyl lactate, sodium-N-l uryl sarcosinate (35 weight 7.) and fatty alcohol with on an average 11 carbon atoms ethoxylated with on an average 7 moles ethylen oxide did not became turbid until at -5 °C. Other additives ha as a rule a certain effect upon the cold stability but this effect was smaller compared to the one of the three mentioned. A row of different dilution proportions were tested beside the mentioned one. The turbidity point showed to be generally speaking independent of the dilution proportions. Example 15. The premix according to example 1 was mixed with oxalic acid i the weight proportions premix to oxalic acid 10:1 and diluted with water in the weight proportions premix to water 1:6. The resulting composition had pH about 2 and was used for the cleaning of railway cars and showed an excellent effect especially for the removal of of firmly adhering iron oxide.

Claims: Patent claims 1. Process for cleaning and de-greasing comprising treatment with a tenside and electrolyte containing water solution characterized in that the solution is prepared at the site of use by the mixing of an easy-flowing water free or nearly wate free (below 20 weight 7.) premix, containing one or more nonionic tensides and one or more tensides with charge giving function of which at least part (25 to 100 weight 7.) has hydrotrope properties and preferably is constituted of cationi fatty amine ethαxylates, ampholyte or zwitterionic tensides or anionic partial ester of phosphoric acid and eventually electrolyte in solution or in the shape of solid state, dispersed, finely divided particles, with water and, if the premix does not contain electrolyt, solid state electrolyte, liquid electrolyte or electrolyte solution at the site of use, at which the dispersing will occur spontanously that is withou agitation or with the minimum αf agitation only that is needed for the elimination of layering caused by the different densities of the liquids. 2. Process according to claim 1 characterized in that the charge giving tenside is cationic and that the proportion between the total content of nonionic tensides, apart from nitrogen containing nonionic tensides that are able to assume cationic charge, and cationic tenside lies within the range 2: to' 150:1, preferably within the range 1:1 to 100:1 and more preferred 1:1 to 80:1. 3. Process according to claim 1 characterized in that the charge giving tenside is anionic and that the proportion between the total content of nonionic tenside and anionic tenside lies within the range 2:3 to 100:1, preferably within the range- 1:1 to 80:1. 4. Process according to claim 1 to 3 characterized in that separate electrolyte or electrolyte solution is added at the mixing and contains alkaline substances and/or complexing agents for ultivalent metal ions and that pH in the final solution is within the range S to 12. 5. Process according to claim 1 to 3 characterized in that separate electrolyte or electrolyte solution is added at the mixing and contains acids and/or acid salts and/or complexing agents and that pH in the final solution is between .5 and 4.0, preferably between 1.0 and 3.0. 6. Spontanously dispersing composition intended as premix for the preparation of a stabile water and electrolyte containing mixture by a simple mixing equipment at the site of use characterized in that the composition is easy-flowing and water free or nearly water free and contains one or more nonionic tensides and one or more tensides with charge giving function of which at least part (25 to 100 weight 7 has hydrotrope properties and preferably is constituted αf cationi fatty amine ethoxylates, ampholyte or zwitterionic tensides or anionic partial ester of phosphoric acid and eventually one or more electrolytes in solution or in the shape of solid state, finely divided particles, at which the final solution contains electrolyte and the premix has been given such properties that the dispersing will occur spontanously that is without agitation or with the minimum of agitation that may be needed to avoid layering caused by the different densities of the 1iqui s. 7. Composition according to claim 6 characterized in that the charge giving tenside is cationic and that the proportion between the total content of nonionic tensides, apart from nitrogen containing nonionic tensides that are able to assume cationic charge, and cationic tenside is within the range 2:3 tα 150:1, preferably within the range 1:1 to 100:1 and more preferred 1:1 to 80:1. 8. Composition according to claim 6 characterized in that the charge giving tenside is anionic and that the proportion between the total content of nonionic tenside and anionic tenside is within the range 2:3 to 100:1, preferably within t range 1:1 to 80: 1. 9. Water containing tenside/electrolyte mixture, obtained by the mixing of a spontanously dispersing premix with water and eventually electrolyte characterized in that the preparation made in a mixing equipment at the site of use and that the premix is easy-flowing and water free or nearly water free an contains one or more nonionic tensides, one or more solvents and one or more tensides with charge giving function αf which at least part (25 to 100 weight 7.) has hydrotrope properties and preferably is constituted of cationic fatty amine ethoxylates, ampholyte or zwitterionic tensides or anionic partial ester of phosphoric acid and eventually one or more elektrolytes and that the mixture is containing electrolyte a the dispersing will occur spontanously, that is without agitation, or with the minimum of agitation that may be needed to avoid layering caused by the different densities of the liquids. 9. Use for cleaning purposes of a water containing tenside/ electrolyte mixture characterized in that the mixture is obtained by the mixing of a spontanously dispersing premix wit water and eventually electrolyte, at which the preparation is .made in a mixing equipment at the site of use and the premix i easy-flowing and water free or nearly water free and contains one or more nonionic tensides and one or more tensides with charge giving function of which at least part (25 to 100 weigh 7.) has hydrotrope properties and preferably is constituted of cationic fatty amine ethoxylates, ampholyte or zwitterionic tensides αr anionic partial ester of phosphoric acid and eventually one or more electrolytes in solution or in the shap of solid state finely divided particles and that the final mixture is containing electrolyte and the the dispersing occur spontanously that is without agitation or with the minimum of agitation that may be needed to avoid layering caused by the different densities of the liquids.

Inventors: ERIKSSON TORD GEORG, ERIKSSON, TORD, GEORG
Applicants: ERIKSSON TORD GEORG, ERIKSSON, TORD, GEORG
Application year: 1991
Main classification: C23G1
IPC codes: C11D1, C23G5, E21B41