GB2160887A - Hard surface cleaning composition - Google Patents

Abstract

An aqueous cleaning composition comprising on a weight basis from 1 to 10% of an organic solvent having a boiling point of from about 120 to 285 DEG C; from 0.05 to 3.0% of a non-ionic surfactant system comprising (i) up to 25% of a water-soluble alcohol ethoxylate or water soluble alkyl ohenoxy ethoxylate surfactant and (ii) from 75 to 100% of a water-insoluble alcohol ethoxylate or water-insoluble alkyl phenoxy ethoxylate; an anionic surfactant which is an alkali metal, magnesium, triethanolamine or ammonium salt of aliphatic sulfates having from 10 to 20 carbons, and water, and concentrates of such compositions.

Description

SPECIFICATION Hard surface cleaning composition This invention relates to a spray and wipe hard surface cleaner composition. More specifically, the present invention relates to a hard surface cleaner composition containing a nonionic surfactant system comprising a surfactant selected from the group consisting of water soluble alcohol ethoxylates and alkyl phenoxy ethoxylates and a surfactant selected from the group consisting of water insoluble alcohol ethoxylates and alkyl phenoxy ethoxylates, and said composition further containing an effective amount of a high HLB anionic surfactant which is an alkali metal, magnesium, ammonium or triethanolamine salt of an aliphatic sulfate.Most specifically, the present invention relates to an aqueous ready- to-use hard surface cleaner composition wherein the nonionic surfactant system is a mixture of two linear primary alcohol ethoxylates, less than about 0.5% by weight of an alkali metal salt of an alkyl sulfate of 10 to 20 carbons as the high HLB anionic surfactant, and water.

Background of Invention Cleaning compositions disclosing mixtures of various surfactants are well known in the art. In particular, compositions comprising a mixture of primary linear alcohol ethoxylates having high and low HLB values, respectively, are known. Thus, for example, U.S. Patent 4,311,608 to Maurice discloses a cleaning composition containing a first primary alcohol ethoxylate of from 9 to 11 carbon atoms and having an average of 6 moles of ethylene oxide per mole of alcohol (Neodol 91-6) and a second primary alcohol containing 9 to 11 carbon atoms and having an average of about 2.5 moles of ethylene oxide per mole of alcohol (Neodol 91-2.5). The compositions disclosed in the Maurice patent contain from about 4.5 to 12.5% of each of said first and second primary alcohol ethoxylates.The Maurice compositions further contain about 43.75 to 70% of sodium lauryl sulfate, not more than about 4.5% of.dimethyl siloxane, about 6.25 to 18.75% isopropyl alcohol, about 0.5 to 1.5% of a linear dodecyl benzene sulfonic acid, and water. A concentrate is also disclosed. The concentrations stated in the Maurice patent appear to be on a volume basis.

U.S. Patent 4,018,699 to Lindy discloses a surfactant composition containing in aqueous solution an alkali metal, ammonium, or a magnesium salt of lauryl sulfate, and a mono- n-butyl ether of ethylene glycol. This composition has utility in the carpet industry, the Lindy composition being mixed with latex backsizing, which mixture is frothed and applied to the textile article and dried. The ratio of the sulfate salt to the ether is usually in the range of 75:25 to 50:50, calculated on a dry-weight basis.

U.S. Patent 4,201,686 to Augustijn discloses an aqueous liquid detergent composition containing mixtures of nonionic surfactants to improve stability, reduce foaming and viscosity, and provide clarity. The Augustijn patent specifically discloses a stable, low-foaming, nongelling unbuilt liquid detergent composition consisting essentially of three saturated fatty alcohol ethoxylates, the first ethoxylate being 50 to 80% of the composition and having 16 to 19 carbon atoms in the alcohol moiety condensed with 15 to 90 moles of ethylene oxide, the second being 5 to 25% of the composition and having 8 to 12 carbon atoms in the alcohol moeity condensed with 6 to 10 moles of ehtylene oxide, and the third being 5 to 25% of the composition and having 10 to 14 carbon atoms in the alcohol moiety condensed with 1 to 4 moles of ethylene oxide, the surfactant mixture being 25 to 45 by weight of the final liquid detergent composition.

U.S. Patents 3,625,909 to Berg and 4,247,425 to Egan, et al., also disclose detergent compositions wherein a mixed nonionic surfactant system is incorporated. The Berg patent concerns a spot-removing product containing 25 to 45% of a polyethoxypolypropoxy ethanol of a linear alcohol, 25 to 45% of an alkyl polyethoxy ethanol, and 2 to 10% by weight of a hydrotropic compound which is an alkyl benzene sulfonate, 0 to 15% water, and an organic solvent not exceeding 50% by weight. The Egan patent concerns a combination of an anionic surfactant and a nonionic surfactant which is an alkoxylated partial glycerol ester of detergent-grade fatty acid, the nonionic surfactant being characterized as having a polyoxyalkylene chain composed of randomly distributed oxyethylene and oxypropylene residues.The anionic surfactant is a salt of a higher alkyl sulfate, a higher alkyl ether sulfate, or a higher alkyl benzene sulfonate. The weight ratio of the nonionic surfactant to the anionic surfactant is between 1:1 and 4:1.

Similarly, U.S. Patent 4,240,921 to Kaniecki discloses an aqueous cleaning concentrate containing alkali metal hydroxide, at least two non ionic surfactants, and an alkylglycoside or alkoxylated glycidyl ether.

The nonionic surfactants each contains a polyoxyethylene group, for example, polyoxypropylene polyoxyethylene condensates, or the reaction product of propylene oxide and ethylene diamide, aliphatic alcohol, and alkylaryl alcohols The polyoxyethylene surfactants have 6 to 30 moles of ethylene oxide per mole of the hydrophobic compound. The hydroxide is present in an amount of about 10 to about 35% by weight, and the nonionic surfactant is from about 10 to about 50% by weight, while the ratio of the alkylglycoside or glycidyl ether to the nonionic surfactant is preferably from about 5:1 to about 10:1.

The Shell Development Company publications (1) "Performance of NeodolX Ethoxylates As Hard Surface Cleaners", June 1978 and (2) "Hard Surface Cleaners". "Performance of Normal And Blended Neo dol-; Ethoxylates", July 1979, consider the cleaning performance of NeodolQ ethoxylates, Neodol ethoxylate blends, ethoxy sulfates, and other industrial surfactants.Blends of Neodol 91-6 (a linear primary alcohol ethoxylate having between 9 and 11 carbon atoms in the alkyl moiety and about 6 moles of ethylene oxide per molecule) and Neodol 91-2.5 (a similar ethoxylate having 2.5 moles ethylene oxide per molecule), and blends of Neodol 23-6.5 (a linear primary alcohol ethoxylate having 12 or 13 carbon atoms in the alkyl moiety and 6.5 moles of ethylene oxide per molecule) and Neodol 23-3 (a similar ethoxylate having 3 moles of ethylene oxide per molecule) were shown to improve oily soil cleaning performance. All blends of the first composition out-performed unblended Neodol 91-6. The second blend did not improve performance with respect to Neodol 23-6.5. With respect to the first blend (Neodol 91-6/Neodol 91- 2.5), maximum performance was found for that system with an HLB in the range of from 10.2 to 12.5.

The second Shell publication discloses that in tetrapotassium pyrophosphate-containing formulations, the cleaning performance of detergent-range alcohol ethoxylates, having a hydrophobe carbon number ranging from 9 to 13, had maximum performance with respect to the Neodol 91 ethoxylates as the ethylene oxide- to-alcohol ratio reached values of 4.4 for unblended ethoxylates and 5.35 for blends. Neodol 91-8 or Neodol 91-6, properly blended with Neodol 91-2.5, performed synergistically at very high levels.

Peak performance was about constant at an HLB value of the blends ranging from a value of about 11.4 to a value of about 12.4, corresponding to 60!40 to 40160 mixtures, respectively, of Neodol 91-8 and 912.5. The compositions tested contained 0.12% by weight tetrapotassium pyrophosphate.

Summary of Invention It is an object of the present invention to provide a hard surface cleaning composition having utility in removing grease and other soils.

A further object of the present invention is to provide a cleaning product that avoids streaking and smearing on sensitive surfaces such as mirrors, chrome and stainless steel.

It is a primary object of the present invention to improve the cleaning efficiency of hard surface cleaning compositions containing ethoxylated alcohol and alkyl phenoxy ethoxylate nonionic surfactant blends, by including in the composition a high HLB anionic aliphatic sulfate surfactant, preferably sodium lauryl sulfate These and other objects and advantages of the present invention will be more fuly understood upon a reading of the complete specification herein, a summary of which follows.

The hard surface cleaning composition comprises on a weight basis: (a) from about 0.05 to about 3.0% of a nonionic surfactant system comprising: (i) from about 0 to 25% of a water soluble first surfactant selected from the group consisting of alcohol ethoxylates and alkyl phenoxy ethoxylates, and (ii) from about 75 to about 100% of a water insoluble second surfactant selected from the group consisting of alcohol ethoxylates and alkyl phenoxy ethoxylates; (b) an effective amount of an anionic surfactant which is an alkali metal, ammonium, or triethanolamine salt of an aliphatic sulfate of from 10 to 20 carbon atoms; (c) from about 1.0 to about 10% by weight of a water soluble organic solvent; (d) water.

Optional constituents include a smear-reducing material such as a low-molecular-weight polyacrylic acid and a wetting agent such as a fluorosurfactant, which reduces the surface tension of the spray as applied to the surface to be cleaned addition, the composition may contain fragrance and dye. In another aspect of the invention, the composition may be provided as a concentrate wherein the aforesaid readyso-use composition is obtained by diluting one part of a concentrate with up to about 16 parts water.

The organic solvent may be an individual glycol ether or alkoxyalcohol solvent component, or a mixture of two or more solvent components, having a boiling point between about 120 to about 285"C.Preferred solvents include, for example, ethylene glycol monobutyl ether, n-butoxypropanol, diethylene glycol butyl ether and n-propoxypropanol. Although not preferred for use singly as the solvent in the composition, the composition may also contain as a solvent component a low molecular weight aliphatic alcohol of from 1 to 5 carbon atoms.

The nonionic ethoxylated alcohol surfactants suitable herein have from about 9 to about 15 carbon atoms in the alcohol moiety and from about 2.5 to about 15 moles ethylene oxide. The first ethoxylate herein is water soluble and has more than about 6 moles ethylene oxide per molecule, while the second is a water insoluble ethoxylate having less than about 5 moles ethylene oxide per molecule. The linear primary ethoxylates are most suitable herein.

The alkyl phenoxy ethoxylate most suitable herein are the octyl and nonyl phenoxy ethoxylates.The first phenoxy ethoxylate surfactant is water soluble and is characterized by having an HLB generally above about 12, there being more than about 6 moles ethylene oxide per molecule. The second phenoxy ethoxylate surfactant is water insoluble and is characterized by having an HLB of generally below about 10.8, there being less than about 5 moles ethylene oxide per molecule.

Use of the composition, after dilution as may be required, is by performance of the steps comprising applying the composition to the surface to be cleaned substantially uniformly over the surface to provide a thin film thereon, then shortly thereafter wiping the surface with a cloth, sponge, or paper towel to remove the thin film and the soils from said surface.

Brief Description of the Drawings Figure 1 is a graph of cleaning efficiency or percent stain removal verses total surfactant level, for mixed alcohol ethoxylate containing compositions of the present invention that also contain effective levels of the high HLB anionic surfactant, and for a composition comprising only a water soluble linear primary alcohol ethoxylate. The amount of high HLB anionic surfactant is included in the total surfactant level, for the compositions of the present invention.

Detailed Description of the Invention Compositions of the present invention are intended as ready-to-use cleaner compositions for hard surfaces such as glass, chrome, stainless steel, aluminum and plastic resins used in countertops, such as Formica. The composition may be also provided as a concentrate, dilution with tap water being required to provide said ready-to-use formulation. A hard-surface cleaner should be compatible with the surface to be cleaned, able to remove grease and other types of soils, should not streak or smear when the surface is wiped with a cloth or sponge, and should not leave a film or residue of the cleaning constituents.

The composition herein comprises a nonionic surfactant system comprising a water soluble first surfactant selected from the group consisting of alcohol ethoxylates, preferably the linear primary alcohol ethoxylates, and alkyl phenoxy ethoxylates and a water insoluble second surfactant selected from the group consisting of alcohol ethoxylates, preferably the linear primary alcohol ethoxylates, and alkyl phenoxy ethoxylates, an anionic surfactant having a high hydrophilic to lipophilic balance (HLB), a water soluble organic solvent or organic solvent system, and water.Preferably, said composition would include an alkalinity agent and, optionally, a builder, fluorocarbon surfactant, perfume and dye.

The nonionic surfactant system contains on a weight basis of said system from about 0 to about 25% of the water soluble surfactant and from about 75 to about 100% of the water insoluble surfactant. With regard to the alcohol ethoxylates, the water soluble ethoxylate has from about 9 to about 15 carbon atoms in the alcohol moiety and has more than about 6 moles of ethylene oxide per molecule, while said water insoluble alcohol ethoxylate has from about 9 to about 15 carbon atoms in the alcohol moiety and has less than about 5 moles ethylene oxide per molecule. The alkyl phenoxy ethoxylates. most suitable herein are the octyl and nonyl phenoxy ethoxylates.The water soluble phenoxy ethoxylate has more than about 6 moles of ethylene oxide per molecule, the HLB thereof being generally above about 12, while the water insoluble phenoxy ethoxylate has less than about 5 moles of ethylene oxide per molecule, the HLB thereof being generally below about 10.8.

Examples of said second nonionic surfactant are Neodol surfactants, types 25-3, 91-2.5 (manufactured by Shell Chemical Company); plurafac surfactants, types A-24, RA-40, RA-43 (manufactured by BASF Wyandotte); Siponic L-Series surfactants (manufactured by Alcolac, Inc.); Triton surfactants, types X- 35, X-45; N-42, N-60 (manufactured by Rohm & Haas Company); and Igepal surfactants, types CA-420, CA520, CO-210, CO-430, CO-520, CO- 530 (manufactured by GAF Corp.). Examples of the first nonionic surfactant in the system include Neodol surfactants, types 25- 7, 25-9, 25-12, 45-13, 91-6 and 91-8; Triton surfactants, types X-100, X-102, N-101, N-111, N-401; and Igepal surfactants, types CA-620, CA-630, CA720, CO-610, CO-630, CO-660, CO-710, CO- 730.

The preferred nonionic surfactants are the linear primary alcohol ethoxylates, the most preferred thereof being surfactants in such class having from about 9 to 11 carbon atoms in the alcohol moiety.

The HLB of the nonionic surfactant system containing alcohol ethoxylates as the first and second surfactants is from about 2.5 to about 12.5.

It has been found that cleaning efficacy of compositions containing said nonionic surfactant system may be improved by incorporating therein an anionic surfactant having an HLB of at least about 30. It has further been found that such improvement in cleaning is achieved with a minor amount of said anionic surfactant, and that not all anionic surfactants are effective in so doing. Thus, the anionic surfactants of the present invention are selected from the group consisting of alkali metal, ammonium and triethanol ammonium salts of aliphatic sulfates, preferably the alkyl sulfate salts, having from about 10 to about 20 carbon atoms.The most preferred anionic surfactant is sodium lauryl sulfate.

The nonionic surfactant system is present by weight of the composition in an amount of from about 0.05 to about 3.0%, while the anionic surfactant is preferably present in an amount effective to achieve optimum improvement in cleaning performance. Preferred levels of the nonionic surfactant system is from about 0.1% (for a relatively light-duty cleaner) to about 0.5% (for a heavy-duty cleaner). Effective levels of a sodium lauryl anionic surfactant for these particular light-and heavy-duty compositions are about 0.035% and 0.14%, respectively.Further discussion concerning the optimum improvement of cleaning performance appears below.

The organic solvent is a water soluble solvent, preferably a glycol ether or an alkoxyalkanol or a mixture of such solvent agents, present in an amount of from about 1.0 to about 10% by weight of the ready-to-use composition, the solvent or solvent mixture having a boiling point of from about 120 to about 285 C. Preferably, the solvent concentration is in the range of from about 3 to about 6% by weight.Suitable for use as the solvent are, for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, n-butoxypropanol, n-propoxypropanol, ethylene glycol butyl ether, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol hexyl ether, dipropylene glycol methyl ether, propylene glycol phenyl ether, triethylene glycol butyl ether, tripropylene glycol methyl ether, ethylene glycol phenyl ether, triethylene glycol methyl ether, and triethylene glycol ethyl ether. Preferred solvents are ethylene glycol monobutyl ether, diethylene glycol butyl ether, n-butoxypropanol and n-propoxypropanol. In addition, the solvent may comprise up to about 5.0% of a low molecular weight Cl to C, alcohol, for adjusting the evaporation rate of the solution from the surface to which it is applied.

The compositions of the present invention may contain an alkalinity agent, in an amount of less than about 2% by weight, which agent enhances cleaning, especially in the removal of greasy soils. Preferably, the alkalinity agent is present in an amount of less than about 0.25% by weight for the compositions designated herein as light-duty cleaners, and less than about 0.5% for compositions designated as heavyduty cleaners herein. Typical alkalinity agents include sodium, potassium and ammonium hydroxide, ethylene diamine tetraacetic acid, nitrilotriacetic acid, morpholine and inorganic carbonates.

A builder agent may be incorporated herein as an optional constituent Certain builder agents also provide alkalinity to the composition, and in such event an alkalinity agent may not be required as an added constituent, or may be present in low levels. The concentration of the builder agent is dependent upon which such agent is incorporated, but is typically in an amount of less than about 1%.Typical builders include phosphates, such as tetrapotassium pyrophosphate (TICPP), tetrasodium pyrophosphate (TSPP), nitrilotriacetate (also an alkalinity agent, as noted above), a polyacrylic acid or polyacrylic acid salt having a molecular weight of less than about 8,000, ethylene diamine tetraacetic acid, and silicates.Silicates are not preferred, however, inasmuch as they may form insoluble films on glass surfaces if the composition is allowed to dry without wiping the surface. Preferred amounts of the builder range from about 0.01 to about 0.2% by weight. The preferred builder is a polyacrylic acid or salt thereof.

Other optional constituents include fragrance, dye, and the like. These adjuvants are typically included in low levels, generally less than 0.1% by weight.

Water accounts for the remainder of the composition. In a further embodiment, the composition of the present invention may be a concentrate, requiring dilution with tap water, one part of the concentrate being diluted with up to about 16 parts water to obtain the ready-to-use composition herein.

Use of the composition in the ready-to-use formulation is by spraying the composition or otherwise applying the composition to the surface to be cleaned, allowing the film thus formed to react with the dirt of the surface, typically several seconds, and wiping the surface with a cloth, paper towel, or sponge.

Because silicates, on drying, have a tendency to form a difficult to remove film on some surfaces, e.g., glass, caution is required when silicates are included as a builder material.

The minimum effective amount of high HLB anionic surfactant for incorporation in the composition is that amount required to provide a clear solution of the mixed nonionic surfactants. Thus, said first nonionic surfactant is a water soluble ethoxylate, while the second nonionic surfactant is a water insoluble, oil soluble ethoxylate, the nonionic surfactant system formed by their admixture being incompletely soluble. By providing the effective amount of the anionic surfactant, complete solubilization of the surfactant system is obtained, and the solution thus obtained is clear.The amount of anionic surfactant required increases with increasing concentration of the second nonionic surfactant. it has been found that, for a blend of Neodol 91-8 as the first nonionic surfactant and Neodol 2.5 as the second nonionic surfactant, optimum cleaning efficiency is achieved at a ratio of the first surfactant to the second surfactant of about 1:9. This corresponds to an HLB of about 8.8. The effective amount of sodium lauryl sulfate, the anionic surfactant, was 0.022% by weight. The Shell reference, Ilard Surface Cleaners".Performance of Normal And Blended Neodoi EtnwWlates, at Table 3 indicates that optimum Neodol 91-8 and Neodol 91-2.5 is at a ratio of from about 3:2 to about 2:3, the HLB thereof ranging from 12.4 to about 11.4, said composition not containing an anionic surfactant as taught herein.

Example 1 Compositions 1 to 5 and 7 to 10 in Table I are in accordance with the present invention, while Composition 6 not containing the anionic surfactant is not within the scope of this invention. Compositions 1 to 6 are light-duty formulations having about 0.09% of the nonionic surfactant system, while Compositions 7 to 10 are heavy-duty formulations having about 0.15% of the mixed nonionic surfactant system. In each of these compositions, sodium lauryl sulfate, a high HLB anionic surfactant, was included in the formulation, which amount of anionic surfactant increases as the concentration of Neodol 91-2.5 also increases.

Composition 6 containing a level of Neodol 91-2.5 outside the range herein specified for said second nonionic surfactant contains no anionic surfactant, the nonionic surfactant system being soluble in said composition.

TABLE 1 Weight %, As Is Basis Heavy Duty Formulation Light Duty Formulation Constituent 1 2 3 4 5 6(1) 7 8 9 10 Propasol B (2) 3.4 3.4 3.4 3.4 3.4 3.4 4.1 4.1 4.1 4.1 Neodol 91-8 (3) 0.0495 0.0405 0.0225 0.009 0 0.0675 0.0375 0.024 0.015 0 Neodol 91-2.5(4) 0.0405 0.0495 0.0675 0.081 0.090 0.0225 0.1125 0.126 0.135 0.150 Equex S (5) 0.024 0.038 0.062 0.076 0.10 0 0.0655 0.076 0.090 0.076 Potassium Hydroxide 45% Solution 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 Acrysol LMW 45X (6) 0.025 0.025 0.25 0.25 0.25 0.25 0.025 0.025 0.025 0.025 FC-129 (7) 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 Water q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 Total 100 100 100 100 100 100 100 100 100 100 Nonionic Surfactant System:: % Neodol 91-8 55 45 25 10 0 75 25 16 10 0 % Neodol 91-2.5 45 55 75 90 100 25 75 84 90 100 HLB 11.4 10.8 9.6 8.7 8.1 12.6 9.6 9.06 8.7 8.1 Cleaning Value 0.958 1.017 2.227 3.365 1.837 -1.100 -0.313 0.50 1.096 0.638 Notes: (1) Composition not in accordance with present invention.

(2) n-butoxypropanol; 100% active; Union Carbide Co.

(3) Water soluble linear alcohol ethoxylate having 9 to 11 carbons in alcohol moiety and about 8 moles ethylene oxide per molecule; HLB = 14.1; 100% active.

(4) Water insoluble linear alcohol ethoxylate having 9 to 11 carbons in alcohol moiety and about 2.5 moles ethylene oxide per molecule; HLB = 8.1; 100% active.

(5) Sodium lauryl sulfate; 29% active; Procter & Gamble Company.

(6) Partially neutralized sodium salt of polyacrylic acid resin; M.W. = about 4,500; 48% active; Rohm & BR< Haas Co.

(7) Fluorosurfactant; 50% active; 3M Company.

Performance of these compositions was measured in the following manner. Three test panels or plates made of glass, high gloss enamel laminate and matte finish laminate were thoroughly cleaned and soiled with a Blaisdell orange wax pencil 969T. Lines were drawn across the width of the panels at 3/4" intervals, and the soil aged for 24, 4 and 2 hours, respectively. A strip of masking tape was placed lengthwise through the center of the plate, and each half labeled with a code corresponding to the composition to be used to clean the plate. the plate was placed in a Gardner Straight Line Washability and Abrasion machine with dual head carrier, and equal amounts of composition evenly applied to each half of the plate. The plates were cleaned for 30 to 60 seconds, corresponding to the toughness of the soil. Each side of the plate was dried by gentle blotting with a lint free towel.

All panels thus cleaned were placed in a well lit area on a nonglare surface, Ten panelists having experience in evaluating hard surface cleaning composition performance rated each side of each panel comparatively by assigning a value of zero to four, the value zero indicating no difference between sides, the value four indicating substantial superiority of one side over the other, and the values to one to three being intermediate thereto. The mean cleaning score for each composition tested on each surface was then calculated.

The cleaning scores for the average of the three substrates tested is included in Table 1. As seen by a review of that data, the optimum cleaning value was 3.365 for Composition 4 containing Neodol 91-8 and Neodol 91- 2.5 in the ratio of 1:9, corresponding to an HLB value of about 8.8. As the level of Neodol 918 increased, the cleaning values decreased to a low of 0.0958 for Composition 1 containing Neodol 91-8 and Neodol 91-2.5 in the ratio of 55/45. Similarly, Composition 5 containing all Neodol 91-2.5 had a cleaning value of +1.837. Thus, improvement in the cleaning level increased with decreasing HLB until a value of HLB of about 8.7, the cleaning value decreasing with further decrease in HLB. With respect to Composition 6, having an HLB of about 12.6, the cleaning value was -1.10, far lower than that of any of the Compositions 1 to 5.

Referring to Compositions 7 to 10, the maximum cleaning value again occurred at a Neodol 91-8 to Neodol 91-2.5 ratio of 1:9, the value being 1.096. The cleaning value for Composition 7 was -0.313. At 100% Neodol 91-2.5, the cleaning value was +0.638. It should be noted that the cleaning values reported in Table 1 are not comparative as between the light-duty and the heavy-duty formulations, although they are comparative within each type of formulation.

Example 2 Further examples of the compositions of the present invention are tubulated in Table 2. In Compositions 11 to 13, the ratio of the first nonionic surfactant to the second nonionic surfactant is 1:6.14. In Composition 11 the mixed nonionic surfactant system comprises as the first nonionic surfactant Igepals CO 710 and as the second nonionic surfactant Igepal CO 430; in Composition 11 the first nonionic surfactant is Triton 100, and the second non- ionic surfactant is Triton X35, and in Composition 13 the first nonionic is Neodol 91.8 and the second nonionic surfactant, Neodol 91-2.5. The HLB for these nonionic surfactant systems is 9.47, 8.6 and 8.9, respectively.The effective amounts of sodium lauryl sulfate required to provide a clear solution, i.e., a solution wherein the nonionic surfactant system is soluble, is 0.188%, 0.251% and 0.091%, respectively.

TABLE 2 Weight /0, As Is Basis Constituent 11 12 13 Propasol B 1.2 1.2 1.2 Butyl Cellosolve (8) 2.5 2.5 2.5 Igepal CO 710 (9) 0.014 Igepal CO 430 (10) 0.086 Triton X100 (11) 0.014 Triton X35 (12) 0.086 Neodol 91-8 0.014 Neodo191-2.5 0.086 Equex X (29%) 0.188 0.251 0.091 Potassium Hydroxide, 45% Solution 0.13 0.13 0.13 Acrysol LMW 45X 0.04 0.04 0.04 Water q.s.100 q.s.100 q.s.100 Total 100 100 100 Notes: (8) Ethylene glycol n-butyl ether; 100% active; Union Carbide.

(9) Nonylphenoxypoly (ethyleneoxy) ethanol; 100% active water soluble nonionic surfactant; GAF Corportion; HLB 13.6.

(10) Nonylphenoxypoly (ethyleneoxy) ethanol; 100% active water insoluble nonionic surfactant; GAF Corporation; HLB 8.8.

(11) Octyl phenoxy polyethoxy ethanol; 100% active water soluble nonionic surfactant; Rohm & Haas Co.; HLB 13.5.

(12) Octyl phenoxy polyethoxy ethanol; 100% active water insoluble nonionic surfactant; Rohm & Haas Co., HLB 7.8.

Cleaning tests were conducted as follows. Clean white high-gloss Formica plastic laminates divided into three sectors 7" x 20" corresponding to the number of compositions to be tested and were marked with Blaisdell grease pencil 969T to provide two parallel wavy lines 1 1/2" apart in each of the five sections. The soils were allowed to age for about 20 minutes, and each section then cleaned by hand with equal amounts of compositions 11- 13, using a cheesecloth pad and the same number of cleaning cycles.

A panel of 4 judges rated the sections as to the percent stain removed. The laminate was cleaned and 3 replicates were performed. The average cleaning score was then calculated.

It was found that Composition 11 had a 59.5% soil removal, Composition 12 had a 71.7% soil removal, and Composition 13 had an 82.3% soil removal efficiency. It is seen that the linear primary alcohol ethoxylates are preferred to the alkylphenol ethoxylate systems of igepal CO and Triton X, both in terms of the level of anionic required and the level of cleaning.

Example 3 In Table 3 compositions containing other anionic surfactants are identified. The amount of anionic surfactant contained in these examples is the effective amount required to provide clear solutions. Composition 18 contains sodium lauryl sulfate and is in accordance with the present invention. Each of the Compositions 14 to 18 contains that amount of nonionic surfactant system identified in Composition 4, which composition provided the maximum cleaning efficiency for the light-duty formulation.

TABLE 3 Weight /O, Active Basis Anionic Surfactant 14 15 16 17 18 Sodium Toluene Sulfonate 0.956 Klearfac AA420 (13) 0.360 Klearfac AA270 (14) 0.302 Sodium Xylene Sulfonate 0.384 Sodium Lauryl Sulfate 0.022 Cleaning Score +1.825 -1.654 -0.325 -0.669 +1.600 Notes: (13) Free acid of organic phosphate ester; BASF Wyandotte.

(14) Free acid of organic phosphate ester; BASF Wyandotte.

* Compositions adjusted with additional potassium hydroxide to obtain pH of 11.7, same as control, composition 4.

It is seen that the effective amount of the anionic surfactant required to obtain clear solution was far greater for each of the Compositions 14 to 17 than for Composition 18. These Compositions 14 to 18 were evaluated according to the procedure of Example 1. It is further seen that the comparative cleaning values reported in Table 3 for Compositions 15 to 17 is far lower than that reported for Composition 18 of the present invention. The cleaning score for Composition 14, containing 0.956% sodium toluene sulfonate, is somewhat better than Composition 18. However, Composition 14 had about 43 times the amount of anionic surfactant than Composition 18.

In addition, it was found that Atlas G-271 and Atlas G- 263, cationic surfactants, did not achieve solubilization, although the HLB of these materials is above 30.

Other surfactants that provided clear solutions at low levels of addition were Conoco Sulfate P (a potassium lauryl sulfate), Conoco Sulfate C (a sodium cetyl sulfate), Conoco Sulfate M (a magnesium lauryl sulfate), Sipon LT6 (a triethanolamine lauryl sulfate), Sipon L22 (an ammonium lauryl sulfate), Sipex CAV (sodium alkyl sulfate), Sipex TDS (sodium tridecyl sulfate), and Sipex OS (sodium oleyl sulfate). Each of these anionic surfactants has an HLB of from about 31 for Sipon L22 to about 42 for Sipex OS.

Example 4 To determine whether the compositions of the present invention compare in cleaning efficacy against a composition containing a single nonionic surfactant, the Compositions 19 to 26 were prepared. Compositions 19 to 22 contained different amounts of the mixed nonionic surfactant system, each with an effective amount of sodium lauryl sulfate required to obtain clear solutions. Compositions 23 to 26 contain only Neodol 91-6, a water soluble nonionic surfactant having an HLB of 12.5. The level of Neodol 91-6 in each of these compositions was made equal to the total surfactant concentration including the concentration of the anionic surfactant, of the corresponding Compositions 19 to 22.

TABLE 4 Weight %, As Is Basis This Invention Neodol 91-6 Surfactant Only Constituent 19 20 21 22 23 24 25 26 Propasol B 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Butyl Cellosolve 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Neodol 91-8 0.014 0.028 0.070 0.210 Neodol 91-2.5 0.086 0.172 0.430 1.290 Neodol 91-6 (15) Equex S 0.119 0.20 0.484 1.432 Potassium Hydroxide 45% Solution 0.25 0.25:n0.25 0.25 25 0.25 0.25 0.25 Acrysol LMW 45X 0.040 0.040 0.040 0.040 0.040 0.040 0.040 0.040 Water q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 q.s.100 Total 100 100 100 100 100 100 100 100 Total Surfactant, % (16) 0.135 0.258 0.640 1.915 0.135 0.258 0.640 1.915 % Stain Removal 46 58 76 92 36 44.8 61.3 78.3 Notes: (15) Water soluble linear primary alcohol ethoxylate having 9 to 11 carbons in alcohol moiety and about 6 moles ethylene oxide par molecule; HLB 12.5; 100% active;Shell chemical Company.

(16) Active basis.

The eight Compositions 19 to 26 were evaluated for cleaning ability, in ccordance with the test method described in Example 2.

The values of the percent stain removal in these cleaning tests are included in Table 4, and plotted in Figure 1. As seen in Table 4 and in the Figure, the compositions of the present invention containing less Neodol surfactant but containing an effective amount of anionic surfactant were superior to the compositions containing only Neodol 91- 6, at equal total surfactant levels.

Example 6 Tests comparing the cleaning efficacy of the compositions of the present invention and competitive products were carried out. The compositions of the present invention used in the tests are reported in Table 5, Composition 27 being a light-duty formulation and Composition 28 being a heavy- duty formulation.

TABLE 5 Weight /0, As Is Basis Constituent 27 28 Propasol B 1.2 1.0 Butyl Cellosolve 2.5 5.1 Neodol 91-8 0.014 0.021 Neodol 91-2.5 0.086 0.129 Equex S 0.115 0.225 Potassium Hydroxide 45% Solution 0.130 0.270 Acrysol LMW 45X 0.04 0.04 Ethanol, 100% 0.50 Fragrance 0.014 0.014 Water, Deionized 95.901 92.701 Total 100. 100.

The competitive products were Fantastiks containing 2.8% butyl Cellosolve, 0.53% nonionic surfactant which is an ethoxylated alkyl phenol, 0.24% sodium metasilicate, 0.27% tetraacetic acid, 0.15% sodium hydroxide and the remainder water and Clorox 409 containing 3.2% butyl Cellosolve, 0.3% isopropyl alcohol, 1.08% anionic surfactant which is sodium lauryl ether sulfate, 0.89% sodium metasilicate, 0.73% tetrasodium salt of ethylene diamine, 0.1% sodium carbonate, and the balance water. The results are tubulated in Table 6.

TABLE 6 Soil Removal Score (17) Flat Enamel Substrate Baked No. Smooth Matte Stainless Wall Wall Wax Composition Enamel Vinyl Formica Formica Steel Chrome Glass Paint Paint Composition 27 +0.475 -1.375 -0.975 -1.275 -1.900 -1.000 -1.350 +0.225 -0.475 Composition 28 +2.225 -1.550 +2.175 +2.45 +1.975 +2.925 pl2.225 +1.150 +0.850 Fantastic -1.050 +0.388 -1.175 -1.675 -0.800 -2.025 -1.300 -0.450 -0.650 Clorox 409# -1.650 +2.538 -0.025 +0.500 +0.725 +0.100 +0.425 -0.925 +0.275 Note: (17) Comparisons between different substrates not valid.

It is seen that, as compared to the competitive products, both of the compositions of the present invention are preferred for baked enamel and flat wall paint. The heavy- duty formulation is preferred with enamel wall paint, chrome, stainless steel, smooth and matee Formica, and glass. The competititve products tested are preferred over compositions of the present invention for no-wax vinyl floors. It is noted that the competitive products have a higher tool surfactant level than either of the Compositions 27 and 28. Furthermore, the light-duty Compositions 27 is intended for easy-to-remove stains associated with normal cleaning soon after the soil has been deposited and before aging of the soil.

Claims (24)

1. An aqueous cleaning composition comprising on a weight basis: (a) from about 1 to about 10% of a water soluble organic solvent having a boiling point of from about 120 to about 285"C, (b) from about 0.05 to about 3.0% of a nonionic surfactant system comprising: (i) from about 0 to about 25% of a first nonionic surfactant selected from the group consisting of water soluble alcohol ethoxylates and water soluble alkyl phenoxy ethoxylates, and (ii) from about 75 to 100% of a second nonionic surfactant selected from the group consisting of water insoluble alcohol ethoxylates and water insoluble alkyl phenoxy ethoxylates, (c) an effective amount of an anionic surfactant selected from the group consisting of alkali metal, magnesium, ammonium, and triethanolamine salts of aliphatic sulfates having from about 10 to about 20 carbons, and (d) water.

2. The composition of Claim 1 wherein said first nonionic surfactant is a linear primary alcohol ethoxylate having more than about 6 but less than about 15 moles ethylene oxide per molecule and wherein said second nonionic surfactant is a linear primary alcohol ethoxylate having less than 5 moles ethylene oxide per molecule.

3. The composition of Claim 1 or 2 wherein said first and second nonionic surfactants have from about 9 to about 11 carbon atoms in the alcohol moiety.

4. The composition of Claim 3 wherein said first nonionic surfactant has about 8 moles ethylene oxide per molecule and said second nonionic surfactant has about 2.5 moles of ethylene oxide per molecule.

5. The composition of Claim 1 wherein said first nonionic surfactant is an alkyl phenoxy ethoxylate having more than about 6 but less than about 15 moles ethylene oxide per molecule and wherein said second nonionic surfactant is an alkyl phenoxy ethoxylate having less than 5 miles ethylene oxide per molecule.

6. The composition of Claim 5 wherein the alkyl group is selected from the group consisting of octyls and nonyls.

7. The composition of any of claims 1 to 6 wherein the second nonionic surfactant is present in an amount of from about 85 to 95% by weight of the nonionic surfactant system.

8. The composition of any of claims 1 to 7 wherein the anionic surfactant is selected from the group consisting of sodium lauryl sulfate, sodium cetyl sulfate, sodium oleyl sulfate, and sodium tridecyl sulfate.

9. The composition of any of claims 1 to 8 wherein the anionic surfactant is present in an amount of from about 0.02 to about 0.5% by weight.

10. The composition of Claim 9 wherein the anionic surfactant is sodium lauryl sulfate.

11. The composition of any of claims 1 to 10 wherein the surfactant system is present in an amount of from about 0.1 to about 1.5% by weight of the composition.

12. The composition of any of claims 1 to 11 wherein the organic solvent is selected from the group consisting of ethylene glycol monobutyl ether, ethylene glycol ethyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, propylene glycol phenyl ether, ethylene glycol methyl ether, n-butoxypropanol, n-propoxypropanol, and combinations of same.

13. The composition of Claim 12 wherein the organic solvent is ethylene glycol monobutyl ether.

14. The composition of any of claims 1 to 13 wherein the organic solvent is present in an amount of from about 3 to about 6% by weight.

15. The composition of any of claims 1 to 14 further comprising less than about 5% of a low molecular weight aliphatic alcohol of 1 to 5 carbons.

16. The composition of any of claims 1 to 15 further comprising less than 2% by weight of the composition of an alkalinity agent.

17. The composition of Claim 16 wherein the alkalinity agent is selected from the group consisting of an alkali metal or alkaline earth metal hydroxide, ammonium hydroxide and morpholine.

18. The composition of any of claims 1 to 17 further comprising less than about 2% of a builder.

19. The composition of Claim 18 wherein the builder is selected from the group consisting of tetrapotassium pyrophosphate, a polyacrylic acid resin or salt thereof having a molecular weight of less than 8,000, ethylenediamine tetraacetic acid and nitrilotriacetate.

20. The composition of Claim 19 wherein the builder is a polyacrylic acid or salt thereof present in an amount of from about 0.01 to about 0.20% by weight on an active basis.

21. A concentrate cleaner which, when diluted with up to 16 parts water, provides the composition of Claim 1.

22. A concentrate cleaner which, when diluted with up to 16 parts water, provides the composition of any of claims 2 to 20.

23. A method of cleaning a hard surface comprising the steps of applying the composition of any of claims 1 to 20 to said surface to be cleaned, and wiping said surface with a cloth, towlette or sponge.

24. Any composition as claimed in claim 1 whose formulation is substantially as indicated in the foregoing Examples section.