MXPA00006466A - Hard surface cleaner containing nonionic surfactants - Google Patents

Abstract

There is provided an aqueous hard surface cleaning composition comprising a) a water soluble organic solvent;b) a nonionic surfactant selected from the group consisting of an alcohol alkoxylate, an alcohol block alkoxylate, a polyoxyethylene polyoxypropylene block surfactant, and mixtures thereof, and c) a cleaning auxiliary selected from the group consisting of compounds having the general structure (HOOCCH2)2nch(R)COOH salts thereof, and mixtures thereof, wherein R is alkyl, hydroxyalkyl, or carboxyalkyl.

Description

Hard Surface Cleaner Containing Non-ionic Surfactants Cross Reference with Related Requests This request is a continuation of Serial Request No. 09 / 345,212, filed on June 30, 1999.

Field of the Invention The invention relates to a hard surface cleaner containing non-ionic surfactants, and especially to an effective cleaner for removing crusts of soap and other deposits without rubbing or scraping. It is desirable that a hard surface cleaner to clean surfaces of bathtubs, showers and baths be effective in removing soap scum and other deposits. The cleaner should easily remove deposits, and leave surfaces clean and free of stains. Additionally it is desirable that the cleaner work with a minimum of rubbing and scraping by the person who cleans the surface. It is also desirable that the cleaner be effective with a variety of materials found in bathrooms, such as porcelain, glass, and certain plastics such as polyvinyl chloride found in shower curtains, or styrenics such as those found in shower coatings. Applicants surprisingly found that a composition comprising an organic solvent, a non-ionic surfactant, and a cleaning aid is useful to achieve the desired goals previously.

Background of Invention Mills, US 5814591, provides aqueous cleaners for hard surfaces with non-ionic surfactants, EDTA-ammonium, and an organic solvent. Choy, US 5585342 supplies an aqueous hard surface cleaner containing solvent and a semi-polar non-ionic surfactant, buffered at a pH above 6.5. Graubart, US 5454984, provides a cleaning composition containing a quaternary ammonium compound component, a non-ionic surfactant, and a glycol ether component, with optional chelators. Sokol, US 4020016, provides aqueous cleansing compositions containing one or more nonionic surfactants, nitrogen containing salts of nitrilotriacetic acid or a polycarboxylic acid alkylene polyamine, and water, wherein the composition is substantially free of sodium ions.

Garabedian, US 5252245 and US 5437807, provide an aqueous cleaner for hard surfaces containing alkylene or alkylene glycol ether; a surfactant selected from amphoteric, nonionic, and anionic surfactants or mixtures thereof; and an effective amount of a nitrogen buffer. To avoid staining, sodium ions are avoided and the amount of surfactant is kept to a minimum. Garabedian, US 5468423, provides an aqueous hard surface cleaner containing alkanol or an alkylene glycol ether, a non-ionic surfactant, and an effective amount of a nitrogen-containing buffer. Black, US 5536452 and US 5587022, provides an aqueous rinse solution composition and a method of using it without scraping or rubbing, wherein the composition contains a nonionic surfactant with an HLB of 13 or less, a chelating agent, and optionally an alcohol and / or ammonium hydroxide and / or morpholine. Michael, US 5382376, discloses detergent compositions comprising a nonionic detergent surfactant, a hydrophobic solvent, and optionally comprises a polycarboxylated detergent generator.

Compendium of the Invention.

According to the invention a novel composition for cleaning hard surfaces is provided, which comprises a) a water soluble organic solvent b) a nonionic surfactant selected from an alcohol alkoxylate, a block alcohol alkoxylate, a block surfactant I of polyoxyethylene and polyoxypropylene, and mixtures thereof. c) an effective amount of up to 5% by weight of a cleaning aid selected from methyl glycine diacetic acid, hydroxyethylethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid, salts thereof, and mixtures thereof; and d) optionally, a thickening agent. In one embodiment, the invention is a non-aqueous mixture of the above-mentioned components. In another embodiment, the invention is an aqueous concentrate of the aforementioned components, ready for dilution to the desired point according to the final concentration. In yet another embodiment, the invention is an aqueous solution of the aforementioned components, diluted to the final use concentration for direct use by the final consumer. . * n e8- m, _, ^. ».. ,, j.

Detailed Description of a Preferred Embodiment of the Invention The compositions of the invention are useful as aqueous cleaners for hard surfaces, and are especially suitable for cleaning vertical surfaces with soap scum of similar waste, with a minimum of rubbing or scraping. In itself, compositions that are intended to be applied to vertical surfaces by spraying them from a spray bottle, spray bottle, or any other dispensing system on the vertical surface, and allowing the compositions to drain and / or evaporate from the surface. the surface, leaving the surface clean and free of spots. It is understood that originally the surface may be dirty with soap crusts and similar residues where the user may need to do some scraping to remove this dirt, but then the compositions are designed to minimize the amount of rubbing and scraping when applied daily or after every shower. It is therefore contemplated that the compositions of the invention will be advantageously used to clean the shower surfaces daily, or after each bath. In itself, all of the compositions of the invention perform satisfactorily in a rinse test, described below, which measures the ability of the compositions to clean a surface without rubbing or scraping. The performance of the compositions of the invention is comparable to or exceeds the performance of commercially successful cleaning compositions. Preferred compositions perform quite well in a series of staining tests on different materials found in shower or bath environments. As discussed above, the compositions of the invention include aqueous solutions of the components mentioned in detail below. The compositions of the invention are also useful as mixtures of components as they would be for shipping to a bottler or packer for further processing to make the compositions that consumers would ultimately use. The invention also encompasses concentrated aqueous solutions of the components, such as those that would be sent from a mixing plant to another location for further dilution to reach the final concentrations used by the consumer. The compositions of the invention are also useful when diluting them in water to reach the final concentrations mentioned below. Optional ingredients may be added to the novel compositions of the invention, without departing from the scope of the invention. Such optional ingredients are well known to those skilled in the art, and include but are not limited to colorants, fragrances, preservatives, buffering agents, and antibacterial agents. A detailed description of the components of the invention is as follows: a) The water-soluble organic solvent The organic solvent useful in the invention enhances the cleaning performance by causing the compositions to rinse better or run off more easily on vertical surfaces. The solvent can also increase the rate of evaporation of the cleaning composition, which reduces staining and leads to a more lustrous looking surface. Therefore the organic solvent will be chosen based on its solubility in water, and its sufficient volatility for its good performance in cleaning. Preferred solvents have a solubility greater than 20% by weight in water to facilitate the formulation of the aforementioned aqueous concentrates. More preferably, the solvents are soluble in water by more than 30%. The greatest flexibility in the formulation is achieved when the solvent is miscible with water. Therefore, miscible organic solvents are also preferred. Additionally, it is naturally desired that the solvent is not toxic and that it does not have an offensive odor. Useful solvents are described in U.S. Pat. Nos. 5,814,591 and 5,585,342, which are incorporated herein by reference. Among the above parameters, a wide range of solvents is useful. Typical, but not limiting examples are alcohols with 1 to 6 carbons, alkylene glycols, alkylene glycols of alkylene glycols, alkanolamines, N-alkylalkanolamines, low molecular weight ketones and water-soluble alkylpyrrolidones. Examples of the above classes include ethanol, propanol, isopropanol, butanol and its isomers, ethylene glycol and its alkyl ethers such as ethylene glycol methyl ether and ethylene glycol monobutyl ether, propylene glycol alkyl ethers such as propylene glycol monopropyl ether , propylene glycol monobutyl ether and propylene glycol mono-t-butyl ether, acetone, butanone, and N-methylpyrrolidone. Examples of less desirable solvents are methanol due to its toxicity, and water soluble carboxylic acids such as acetic acid and butyric acid as well as organic amines soluble in water due to their annoying odor. Some solvents can be so volatile that their use is less preferred. An example of the above is acetone. Two solvents that are preferred because of their mixture of desirable properties such as commercial availability, ¿¿I ^ ^ ^ m ^ solubility in water, low toxicity, absence of annoying odor, and good performance in cleaning is isopropyl alcohol and monobutyl ether of ethylene glycol. b) The nonionic surfactant The nonionic surfactant is preferably selected from alcohol alkoxylates, block alcohol alkoxylates, polyoxyethylene and polyoxypropylene block surfactants, and mixtures thereof. Surfactants with a wide range in hydrophilic-lipophilic balance (HLB) can be used in the invention. The nonionic surfactant will preferably have an HLB greater than about 13, and more preferably equal to or greater than about 14. As is known in the prior art, alcohol alkoxylates are produced by using an alcohol as an initiator molecule, and then polymerizing an alkylene oxide or alkylene oxide mixtures on the initiator molecule to form a first block. Subsequently, a second alkylene oxide or alkylene oxide mixtures can optionally be added together to form a second block. You can also add subsequent blocks. Generally, the only condition is that the adjacent blocks have different relative alkylene oxide compositions.

Alcohol alkoxylates are commercially available, such as for example the Plurafac® surfactants from BASF Corporation. An example are surfactants represented by the general formula R - (oxidol) a - OR 'wherein R is the alkyl residue of an alcohol having between 6 and 24 carbon atoms; a represents the average number of alkylene oxide units in the structure; oxydol is an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide and a mixture thereof; and wherein R 'is hydrogen, an alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group, or a mixture thereof. As used herein, butylene oxide refers to any of 1,2-butylene oxide, 2,3-butylene oxide, and isobutylene oxide, and mixtures thereof. Here and throughout the specification, it will be understood that R and R 'may also refer to mixtures of alcohols or alkyl groups. These surfactants are produced by adding the ethylene oxide or mixture of ethylene oxides to an alcohol R-OH. Useful surfactants are obtained when a is less than or equal to about 30. It is more preferable that a is less than about 20. The oxidol is preferably a heteric mixture of ethylene oxide and propylene oxide, SkiÜiA. present the ethylene oxide by more than 50%, preferably by more than 70% of the total number of the a-units of the alkylene oxide in the structure. The R group preferably contains between 8 and about 16 carbon atoms, and more preferably between about 10 and about 16 carbon atoms. A preferred surfactant is that where R contains between 10 and 12 carbon atoms, R 'is hydrogen and a is about 15, that among the 15 alkylene oxide units, about 13 are ethylene oxide and about 2 are propylene oxide. Alcohol alkoxylates of two and three blocks are also useful. The two-block alcohol alkoxylate can be represented as R - (oxidol) to - (oxide2) b - OR ' while the three-block alcohol alkoxylate can be represented as R - (oxidol) a - (oxide2) b - (oxide3) c - OR ' wherein R is an alkyl or aralkyl group containing between 6 and 24 carbon atoms; oxydol, oxide2, and ox3 do3 each represent an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, and a mixture thereof, provided that the relative alkylene oxide composition of oxide2 differs from oxidol and oxide3; a, b, and c are each between approximately 1 and 35; and R 'is hydrogen, an alkyl group with 1 to 18 carbon atoms, a hydroxyalkyl group with 1 to 18 carbon atoms, or a mixture thereof. Examples of useful block alcohol alkoxylates are the two-block alcohol alkoxylates wherein the blocks are essentially all ethylene oxide or all propylene oxide. These can be represented by the general formulas R - (eo) a - (po) b - OR 'or R - (po) a - (eo) b - OR' where R is the alkyl or aralkyl residue of an alcohol containing between 6 and 24 carbon atoms; a and b are each between approximately 1 and 30; eo represents a unit of ethylene oxide; po represents a propylene oxide unit; and R 'is hydrogen, an alkyl group with 1 to 18 carbon atoms, a hydroxyalkyl group with 1 to 18 carbon atoms, or a mixture thereof. One class of polyoxyethylene and polyoxypropylene block surfactants useful in the invention is that of three block surfactants represented by the general formula R - (eo) a "(po) b - (eo) c - R 'where a, b, and c each represents the number of units of ethylene oxide or propylene oxide in each of the blocks, and wherein R and R 'are each, independently, hydrogen, alkyl Ci-is, hydroxyalkyl C? _? 8, or mixtures thereof Members of this class of surfactants are commercially available as PLURONIC® surfactants from BASF Corporation When such a three-block surfactant is subject to further reaction with propylene oxide in such a manner that groups of polyoxypropylene are added to the ends of the three-block surfactant, another useful polyoxyethylene and polyoxypropylene block surfactant is obtained, which can be represented similarly as R - (po) a - (eo) b- (po) c - (eo) d - (po) e - R 'where a, b, c, d and e each represents the number of units of ethylene oxide and propylene oxide in each of the blocks, and wherein R and R 'are each, independently, hydrogen, alkyl C? ? s, hydroxyalkyl C? _i8, or a mixture thereof. Preferred polyoxyethylene and polyoxypropylene block surfactants include those where a, b, c, d and e have values such that the nominal average molecular weight of the polyoxyethylene and polyoxypropylene block surfactant ranges from about 1800 to about 6000, more preferably between 2000 and 4000 approximately. The block surfactants preferably comprise between about 20 and 60% by weight of polyoxyethylene blocks, and more preferably between about 25 and 50%. A preferred block surfactant is a five-block polyoxyethylene and polyoxypropylene surfactant with a molecular weight of about 3200, and wherein the polyoxypolyethylene blocks comprise approximately 34% of the total weight. c) The Cleaning Aid The cleaning aids useful in the present invention include methyl glycine diacetic acid (MGDA), ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl ethylenediamine t-acetic acid, diethylenetriamine pentaacetic acid, and nitrilotriacetic acid, as well as the salts of these. Mixtures of the above are also useful. Useful salts include metalalkaline salts, alkaline earth salts, ammonium salts, amine salts, alkylamine salts and alkanolamine salts. Useful metalalkaline salts include sodium and potassium. The salts useful in the invention can be monovalent, divalent, trivalent, tetravalent, or pentavalent. For example, when sodium is the opposite ion, examples of EDTA salts useful in the invention include sodium EDTA, disodium EDTA, trisodium EDTA, and tetrasodium EDTA. Similarly, by way of illustration, the pentasodic salts of diethylenetriamine pentaacetic acid may be used. The salts, including the meta-alkaline salts, of the cleaning aid can be added to the cleaning compositions in their salt state. Alternatively, the free acid state of the cleaning aid can be added, and the salts can be formed in themselves by the addition of a basic neutralizing compound, such as an alkali metal hydroxide. Finally, the compositions of the invention can be adjusted to a desired pH by the addition of buffering agents. An advantage of the compositions of the present invention is that they are not sensitive to the presence of sodium ions. Therefore, common materials containing metalalkalines, such as sodium hydroxide and sodium-containing buffering agents, can easily be used to adjust the pH. Preferred cleaning aids include MGDA, EDTA, its salts, and mixtures thereof. A preferred salt is the sodium salt, due to its easy availability fifteen • Ji ^ iít ^^ - K ^ d ^ íÍÉlíiiÉliiWáiUiíiíiíi commercial. Examples of preferred cleaning aids are sodium EDTA and sodium MGDA. The Thickener The compositions of the invention optionally and advantageously contain a thickening agent. The thickening agent increases the viscosity of the aqueous compositions of the invention, which leads to desired soaking, run-off and retention times on the vertical surfaces on which they are applied. Water soluble thickeners useful in the invention include cellulose thickeners, water soluble gums, and acrylic polymers. Examples include carboxymethylcellulose, carboxyethylcellulose, Irish moss, tragacanth gum, starch, hydroxyethylpropylcellulose, hydroxybutylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose (eg, available as Natrosol®, a water soluble polymer from Hercules, Inc.), sodium carboxymethylcellulose, poly (methylvinyl ether) / maleic anhydride) available as Gantrez® AN 139 (GAF Corporation), and carboxyvinyl polymer such as Carbopol® 934, Carbopol® 940, or Carbopol® 941 (BF Goodrich). Other suitable water-soluble thickeners include the general type of polyoxyalkylenes. These may include high molecular weight polyethylene glycols, such as also alkoxylates of polyfunctional alcohols, such as ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, and the like. A preferred thickening agent is the type of nonionic associative thickeners. These are described in US Patent Nos. 4,904,466, 4,810,503, 4,673,518, 4,411,819, 4,649,224, 4,665,239 and 4,709,099, which are incorporated herein by reference. As known in the state of the art, these thickeners are produced by reacting an epoxide compound of about 6 carbons or more with a polyoxyalkylene polyol. Useful epoxies are those with 6 carbons and even those with 20 to 45 carbon atoms. A wide range of polyoxyalkylene polyols can be used and can be diols, trioles, or more functionality. The product of the reaction is a polyol with large alkyl groups at its ends, these groups being large alkyl groups on the aforementioned epoxides. It is estimated that in aqueous solution the large alkyl groups associate with each other to form micelle-like structures, which form an extensive network through the solution and act to increase viscosity. The preferred nonionic associative thickeners are those with detergent properties. The detergent properties can be introduced into the associative thickener by choosing a polyoxyalkylene polyol for the reaction described in the preceding paragraph which alone has detergent properties. A polyoxyalkylene polyol has detergent properties when it has a relatively more hydrophobic part and a relatively more hydrophilic part. It is common to introduce these hydrophilic and hydrophobic parts into polyoxyalkylene polyols when preparing polyols with polyoxyalkylene blocks, wherein adjacent blocks have different relative concentrations of alkylene oxide. This principle, which is well known to those skilled in the art, is illustrated by the above discussion of the nonionic surfactants useful in the invention. Useful nonionic associative thickeners used in the Examples are Pluracol® AT 299 and Pluracol® AT301, commercially available from BASF Corporation. Formulating the Components of the Invention To produce the compositions of the invention, the ingredients mentioned above are combined together by means well known in the state of the art. The relative levels of the ingredients are selected to give the required performance of the composition for a hard surface cleaning application, with caution in ensuring that on the one hand a component is present at a sufficient level to be effective, but on the other hand avoid excessive cost by limiting the upper range of the component. Given the above considerations, the Applicants have found that the organic solvent (a) is advantageously used at a level between 0.1 and 10 parts by weight approximately; the nonionic surfactant (b) is useful at levels between 0.5 and 10 parts by weight approximately; and the cleaning aid (c) can be used at an effective amount of up to 5 parts by weight approximately. When a thickening agent is used, between 0.1 and 10 parts by weight, preferably between 0.2 and 10 parts by weight, may be present. By combining the ingredients according to the above levels, one achieves useful hard surface cleaning compositions, especially suitable for being diluted with water and used to clean bath surfaces having soap crusts and other deposits using minimal rubbing and scraping effort. As noted above, another object of the invention is to provide aqueous concentrates of the components of the invention. For this purpose, water is added to the mixture of components which are present in the ranges of parts by weight given above. The water can be added to an amount wherein the percentage by weight of the components (a), (b), and (c), and optionally d) in the composition containing water is numerically equal to the parts by weight of the components given above. Another way to state this is to note that water can be added to a mixture that comprises components (a), (b), and (c), and optionally d) up to an amount where the sum of the concentrations of all the components , including water, add 100 parts by weight. It is readily observed that the parts by weight given above for components (a), (b), and (c), and optionally d) are numerically equal to the percentage composition by weight in the aqueous composition. For many reasons, it may be desirable to add water to components (a), (b), and (c), and optionally d), but to add less water than necessary to dilute the components and reach their final use concentration. For example, it may be desirable to add half the water or less to produce a cleaning concentrate which can be sent to a customer for later dilution with water and bottling and packaging for the consumer. Accordingly, the invention encompasses concentrates comprising components (a), (b), (c), optionally d) and water. twenty ** - - * - * - * - Preferred compositions that will be discussed below refer to percentages by weight in the final aqueous solution that will be used by the consumer, based on the above discussion also refer to the parts by weight of the components in the non-aqueous mixture The water-soluble organic solvent (a) can be used at any effective level Preferably, the level ranges from about 0.1% to about 10% The upper level has some arbitrariness, but as practical matter, in the amount of solvent should be limited based on considerations of costs and volatility.Most preferably the solvent is present at a level ranging between 1% and 10% approximately, most preferably between 2% and 6%. % The nonionic surfactant is generally present at levels between approximately 0.1% and 10%, higher levels would probably be effective in performance, but would be less than desirable due to cost considerations. Preferably the nonionic surfactant is present in more than 0.2%, and more preferably in more than 0.5%. The cleaning aid is present in an amount in the compositions of the present invention in such a way that the 21 *. & ^^^ dilute them to the final use concentration, the cleaning aid will be present in an effective amount. At the end-use concentration by the final consumer, the minimum level of cleaning aid will generally be approximately more than 0.1%. It is preferable that the minimum amount is more than 0.25%, and more preferably more than 0.4%. Likewise, the maximum level must be selected in such a way that the cleaning aid is present in an effective amount. This level is more limited due to cost considerations. Generally, it is preferred to use up to 5% of the cleaning aid. Preferably, up to 3% should be used. All the percentages for the cleaning aid are referred to the weight in the composition completely diluted with water up to its final use concentration for the final consumer's use. The compositions of the invention may optionally contain additional ingredients which are conventional additives found in cleaning compositions. Such ingredients may include fragrances, dyes, and preservatives. Additionally, the compositions of the invention can be adjusted with mineral acids or organic acids to achieve the desired pH, or they can contain buffer systems to keep the pH constant at a desired level.

Examples A main waste recipe is made initially with the following ingredients Ivory® bar soap 3.90% by weight Shampoo (a) 0.35 Clay residue (b) 0.06 Sebaceous secretion (c) 0.15 Hard water (d) 95.54 (Ivory® is a registered trademark of Procter &Gamble Company) Annotations: (a) a single commercial mop-up cleaning shampoo containing alkyl ethoxy sulfates is recommended. A suitable shampoo is Johnson & Jcnnson, which can be purchased in retail stores. Shampoos containing conditioners or special hair treatment additives should be avoided. (b) Potter or plastic clay supplied by H.C. Spinks Co., Paris, TN. (c) Spangler, et al., "A laboratory method for testing detergency in laundry products", JAOCS, Vol. 42, August 1965, pp 723-727. (d) 20,000 ppm, 2: 1 calcium: magnesium, such as CaCO3, using calcium chloride dihydrate and magnesium chloride hexahydrate.

Procedure 1. Shave soap bar and place in suitable container. 2. Add the rest of the components, in order, and shake with a three-blade propellant mixer. 3. Heat the entire mixture to 45-50 ° C. 4. Mix until a smooth suspension is achieved. 5. Filter the suspension with a Buchner funnel with Whatman # 1 filter paper. 6. Resuspend all the filtered residue in deionized water using the same volume of water that was used to produce the waste. 7. Dry the filter cake overnight in an oven at 45 ° C. 8. Spray the cake dry and keep it in a closed container away from environmental humidity. This will be the main waste.

Then, a reconstituted waste is made from the main waste. Main waste 4.50% by weight Hard water (according to the above) 9.00 HCl (37%) 0.77 Acetone 85.73 24 - ^ jj ^ igg. 1. Combine the previous ingredients. 2. Homogenize the suspension until its color changes from white to gray.

Soak test First, ceramic tiles are prepared by washing, drying and cooling at room temperature; air brushes are applied 0.1-0.15 grams of reconstituted residue on the tiles; Bake at 320 ° C for about 2 minutes; and cool overnight at room temperature. To carry out the soaking test, the tiles prepared according to the previous paragraph are soaked in the test formula for 5 minutes, and the cleaned percentage is evaluated qualitatively.

Vinyl and glass cleaning To carry out the test, the reconstituted residue is sprayed onto a 7.62 cm by 20.32 cm piece of glass or a vinyl bath curtain material. The test piece is left to dry for 24 hours, and then it is evaluated qualitatively according to the scale below. The proof ^^ - ^^^^^^^ j ^ g is repeated for five days, and the ranking is reported after the fifth day. The qualitative test scale is 1 very stained; I quite accumulate 2 some spots; slight accumulation 3 uniform distribution of a thick film 4 uniform distribution of a light film uniform distribution with semi-gloss The higher the numerical value of the qualitative classification, the more desirable the result.

Results Comparative examples 1, 2 and 3 show the performance in the soak test and in the glass and vinyl cleaning tests of three formulations currently in commercial use. The formulations of comparative examples 1-3 were obtained by purchasing them at a retail store. Examples 1-28 are within the scope of the present invention. It can be seen that the compositions of the invention offer performance comparable to or superior to that of commercially successful products. The Examples show compositions that offer a cleanliness rating of 85% -100% in the soak test. Compositions within the scope of the present invention should preferably offer a 50% cleanliness rating in the soak test. More preferably, the results of the soak test should be at least 80% or more, with 100% cleaning being the most preferred result. With the compositions of the present invention, the results in the curtain test and in the glass test should preferably be at least equal to that of the commercial products, which in this case is a classification 1 in the glass test and a classification of 1 or 2 in the curtain test.

Clean Shower® is a registered trademark of Automation, Inc., of Jacksonville, Florida. Tilex® is a registered trademark of Clorox Company, Oakland, California.

Examples 1-2i 27 -. ^ ^. ^ A. ^ ..... ^ S & In Examples 1-28, water is added to bring the total to 100 parts. Accordingly, the numbers in the table represent percentage by weight of the composition. Solvent 1 is monobutyl ether of ethylene glycol, also known as butyl carbitol. Solvent 2 is isopropanol. Thickener 1 is Pluracol® AT301, commercially available from BASF Corporation. Thickener 2 is Pluracol® AT299, commercially available from BASF Corporation. MGDA is the sodium salt of diacytic acid methylglycine. Surfactant A is block copolymer po / eo / po / eo / po, molecular weight about 3200, about 34% ethylene oxide. The HLB of surfactant A is 14. The value of the cleaned% is the result in the soak test, described above. The classifications of the curtain test and the glass test are the test results of the glass and vinyl test described above.

Examples Examples EXAMPLES 29-36 Examples 29-36, including 36b, compare the performance of several polycarboxylated detergent generators with the cleaning aids of the present invention. In Examples 29-36, the formulations are given based on a total of 500 g. Therefore, to calculate the corresponding percentages by weight, the quantities must be divided by 5. For example, in all examples 29-36, there is 22 g of solvent 1, which corresponds to 4.44% by weight. Similarly, surfactant A, at 7.5 g, is present at 1.5% by weight in the compositions. The solvent 1 and the surfactant A are as defined in examples 1-28. Trilon® C is pentasodium diethylenetriamine pentaacetic acid. Trilon® D is the triacetic acid of trisodium hydroxyethylethylene diamine. Trilon® M is the sodium salt of diacytic acid methylglycine. Trilon® B is tetrasodium ethylenediamine tetraacetic acid.

Trilon® products are commercially available from BASF Corporation. The classification of the curtain and glass tests are as defined in examples 1-28. Among all the polycarboxylated detergent generators in Examples 29-36, only tetrasodium EDTA and sodium MGDA, both cleaning aids of the present invention, give acceptable results in the soaking test at a level of 0.44%. At a level of 3%, the cleaning aids of the present invention gave an acceptable performance (examples 32b, 33b, 34b, 35b and 36b), while others gave an unacceptable performance (examples 29b, 30b, and 31b). 31 • ßfiÜ = i EXAMPLES 29-36 * The sample of Example 31b was not a homogeneous solution.

Claims (23)

CLAIMS:

1. An aqueous hard surface cleaning composition comprising: (a) an organic solvent soluble in water; (b) a nonionic surfactant selected from alcohol alkoxylates, block alcohol alkoxylates, or polyoxyethylene and polyoxypropylene block surfactants, and mixtures thereof; (c) an effective amount of up to 5% by weight of a cleaning aid selected from methyl glycine diacetic acid, hydroxyethylethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, salts thereof, and mixtures thereof; and d) water.

2. The cleaning composition according to claim 1, wherein said nonionic surfactant is selected from: (a) alcohol alkoxylate with the general structure R- (oxidol) a-OR '(b) alcohol alkoxylate two-block structure general R- (oxydol) a- (oxide2) b-0R '(c) three-block alcohol alkoxylate with the general structure R- (oxydol) a- (oxide2) b- (oxide3) C-0R' and mixtures of the same, wherein R is an alkyl or aralkyl group containing between 6 and 24 carbon atoms; a, b, and c are each between approximately 1 and 35; R 'is hydrogen, an alkyl group with 1 to 18 carbon atoms; a hydroxyalkyl group; or a mixture thereof; and wherein oxidol, oxide2, and oxide3 each represent at least one alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, with the proviso that the relative composition of alkylene oxide for oxide2 differed from oxidol and oxide3.

3. The composition of claim 1, wherein said nonionic surfactant is selected from a polyoxyethylene and polyoxypropylene block surfactant of the general structure R- (eo) a- (po) b- (eo) cR 'a block surfactant of polyoxyethylene and polyoxypropylene of the general structure R- (po) a- (eo) b- (po) c- (eo) d- (po) eR 'and mixtures thereof, wherein a, b, c, d, e each represents the number of units of ethylene oxide and propylene oxide in each of the blocks; and wherein a, b, c, d, and e have values such that the nominal average molecular weight of the polyoxyethylene and polyoxypropylene block surfactant ranges from about 1800 to about 6000.

4. A cleaning composition of claim 2, wherein the nonionic surfactant has the general formula R- (oxidol) a-OH wherein R is an alkyl group containing between 6 and 18 carbon atoms, ranging from 3 to 30 and oxidol is selected from ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof.

5. A cleaning composition according to claim 4, wherein oxidol is a mixture of ethylene oxide and propylene oxide comprising more than 50% ethylene oxide.

6. A cleaning composition according to claim 4, wherein the mixture comprises more than 70% ethylene oxide.

7. A cleaning composition according to claim 1, wherein said cleaning aid is selected from methyl glycine diacetic acid, ethylenediamine tetraacetic acid, salts thereof, and mixtures thereof.

8. A cleaning composition according to claim 1, wherein said cleaning aid is selected from the methyl glycine diacetic acid, salts thereof, and mixtures thereof.

9. A cleaning composition according to claim 1, wherein said cleaning aid comprises the sodium salt of the methyl glycine diacetic acid.

10. A composition according to claim 1, wherein said organic solvent has more than 30% by weight of water solubility.

11. A composition according to claim 1, wherein said organic solvent is miscible in water.

12. A composition according to claim 1, further comprising a thickening agent.

13. A composition according to claim 12, wherein said thickening agent is a non-ionic associative thickener.

14. A composition according to claim 13, wherein the nonionic associative thickener is the reaction product of a Ce epoxide or greater with a polyoxyalkylene polyol.

15. A composition according to claim 1, which comprises between 1 and 10% by weight of said organic solvent; and between 0.5 and 10% by weight of said nonionic surfactant.

16. A composition according to claim 15, further comprising between 0.1 and 10% by weight of a thickening agent.

17. A composition according to claim 1, which comprises an effective amount up to 3% by weight of said cleaning aid.

18. A composition according to claim 17, wherein said cleaning aid is selected from methyl glycine diacetic acid, ethylenediamine tetraacetic acid, salts thereof, and mixtures thereof.

19. A composition according to claim 18, wherein said cleaning aid comprises the sodium salt of the methyl glycine diacetic acid.

20. A composition according to claim 1, wherein the hydrophilic-lipophilic balance of said nonionic surfactant is greater than or equal to about 13.

21. A composition according to claim 1, wherein the hydrophilic-lipophilic balance of said nonionic surfactant is greater than or equal to about 14.

22. A water-dilutable cleaning composition, which comprises: a) between about 1 and 10 parts of a water-soluble organic solvent; b) between about 0.5 and 10 parts of a nonionic surfactant selected from a group consisting of alcohol alkoxylates, alcohol block alkoxylates, polyoxyethylene and polyoxypropylene block surfactants, and mixtures thereof; c) between about 0.1 and 5 parts of a cleaning aid selected from methyl glycine diacetic acid, hydroxyethylethylenediamine triacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, salts thereof, and mixtures thereof; and d) optionally, water, in any amount up to an amount where the total weight of the composition is 100 parts.

23. A composition according to claim 22, further comprising between 0.1 and 10 parts of a thickening agent. 39 - •• - "" "• - - ^ s--