WO 03/087281 PCT/US03/10802 LIQUID CLEANING COMPOSITION 5 Field of the Invention The present invention relates to liquid cleaning composition containing only surfactants that are considered as being biodegradable under anaerobic conditions. Despite that limited surfactant choice, the composition still has excellent grease cutting 10 proterties, excellent foam collapse and improved residue profile. Background of the Invention This invention relates to an all-purpose liquid cleaning composition which does not contain surfactants that are not biodegradable under anaerobic conditions but which still exhibits excellent foam collapse properties, excellent grease cutting 15 properties and improved residue profile and is designed in particular for cleaning hard surfaces. In recent years all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc. Such all-purpose liquids 20 comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts. In order to achieve comparable cleaning efficiency with granular or powdered all-purpose cleaning compositions, use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids. For example, such early phosphate-containing compositions are described in 25 U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739. In view of the environmentalist's efforts to reduce phosphate levels in ground water, improved all-purpose liquids containing reduced concentrations of inorganic phosphate builder salts or non-phosphate builder salts have appeared. A particularly useful self-opacified liquid of the latter type is described in U.S. Patent No. 4,244,840.
WO 03/087281 PCT/USO3/10802 2 However, these prior art all-purpose liquid detergents containing detergent builder salts or other equivalent tend to leave films, spots or streaks on cleaned unrinsed surfaces, particularly shiny surfaces. Thus, such liquids require thorough rinsing of the cleaned surfaces which is a time-consuming chore for the user. 5 In order to overcome the foregoing disadvantage of the prior art all-purpose liquid, U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed. However, such compositions are not completely acceptable from an environmental point of view based upon the phosphate content. On the other hand, another 10 alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent No. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the 15 need for thorough rinsing which has been found to be undesirable to today's consumers. Another approach to formulating hard surfaced or all-purpose liquid detergent composition where product homogeneity and clarity are important considerations involves the formation of oil-in-water (o/w) microemulsions which contain one or more 20 surface-active detergent compounds, a water-immiscible solvent (typically a hydrocarbon solvent), water and a "cosurfactant" compound which provides product stability. By definition, an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil" phase particles having a particle size in the range of 25 to 800 A in a continuous aqueous phase. 25 In view of the extremely fine particle size of the dispersed oil phase particles, microemulsions are transparent to light and are clear and usually highly stable against phase separation. Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 and WO 03/087281 PCT/USO3/10802 3 EP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al; and U.S. Patent No. 4,561,991 - Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent. It also is known from British Patent Application GB 2144763A to Herbots et al, 5 published March 13, 1985, that magnesium salts enhance grease-removal performance of organic grease-removal solvents, such as the terpenes, in o/w microemulsion liquid detergent compositions. The compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of 10 water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt. However, since the amount of water immiscible and sparingly soluble components which can be present in an o/w microemulsion, with low total active ingredients without impairing the stability of the microemulsion is rather limited (for 15 example, up to 18% by weight of the aqueous phase), the presence of such high quantities of grease-removal solvent tend to reduce the total amount of greasy or oily soils which can be taken up by and into the microemulsion without causing phase separation. The following representative prior art patents also relate to liquid detergent 20 cleaning compositions in the form of o/w microemulsions: U.S. Patents No. 4,472,291 Rosario; U.S. Patent No. 4,540,448 - Gauteer et al; U.S. Patent No. 3,723,330 Sheflin; etc. Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w 25 microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; and U.S. Patent Nos. 4,414,128 and 4,540,505. For example, U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight: WO 03/087281 PCT/US03/10802 4 (a) from 1% to 20% of a synthetic anionic, nonionic, amphoteric or zwitterionic surfactant or mixture thereof; (b) from 0.5% to 10% of a mono- or sesquiterpene or mixture thereof, at a weight ratio of (a):(b) being in the range of 5:1 to 1:3; and 5 (c) from 0.5% 10% of a polar solvent having a solubility in water at 15°C in the range of from 0.2% to 10%. Other ingredients present in the formulations disclosed in this patent include from 0.05% to 2% by weight of an alkali metal, ammonium or alkanolammonium soap of a C13-C24 fatty acid; a calcium sequestrant from 0.5% to 13% by weight; non-aqueous solvent, e.g., alcohols and glycol ethers, up to 10% by 10 weight; and hydrotropes, e.g., urea, ethanolamines, salts of lower alkylaryl sulfonates, up to 10% by weight. All of the formulations shown in the Examples of this patent include relatively large amounts of detergent builder salts which are detrimental to surface shine. Summary of the Invention 15 The present invention provides an improved, liquid cleaning composition which does not contain surfactants that are not biodegradable under anaerobic conditions but still having excellent foam collapse properties and improved residue profile, and excellent grease cutting property and which is suitable for cleaning hard surfaces such as plastic, vitreous and metal surfaces having a shiny finish, oil stained floors, 20 automotive engines and other engines. More particularly, the improved cleaning compositions, with excellent foam collapse properties and excellent grease cutting property exhibit good grease soil removal properties due to the improved interfacial tensions, when used in undiluted (neat) or dilute form and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping. The 25 latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art products. Surprisingly, these desirable results are accomplished even in the absence of polyphosphate or other inorganic or organic detergent builder salts and also in the complete absence or substantially complete absence of grease-removal solvent.
WO 03/087281 PCT/USO3/10802 5 In one aspect, the invention generally provides a stable, hard surface cleaning composition especially effective in the removal of oily and greasy oil. The cleaning composition includes, on a weight basis: (a) 0.5% to 4% of an ethoxylated nonionic surfactant formed from a C 9 5 Clalkanol and about 2 to about 3 moles of ethylene oxyde; (b) 2% to 7% of an ethoxylated nonionic surfactant formed from a C 8
-C,
1 8 alkanol and about 6 to 9, preferably about 7 to about 8.5 mole of ethylene oxyde; (c) 0 % to 6%, more preferably 0.05% to 5% of a C1-C4 alkanol such as ethanol and/or propanol and/or 0% to 6% of a propylene glycol ether; 10 (d) 0.1% to 5% of a solubilizer selected from the group consisting of sodium xylene sulfonate and/or sodium cumene sulfonate; (e) 0.25% to 6% of magnesium inorganic salt; (f) 0.05% to 2% of a fatty acid; (g) 0.1% to 5.0% of a perfume or essential oil; 15 (h) 0.05% to 2.5% of an alkali metal salt of a polycarboxylic acid having a molecular weight of about 5,000 to about 15,000; and (i) the balance being water, wherein the composition does not contain an amine having a pK value of more than 9, a furan-maleic anhydride copolymer sequestering agent or a water soluble detergency builder and the composition does not 20 contain a water-soluble polyethylene glycols having a molecular weight of 150 to 1000, polypropylene glycol of the formula HO(CH3CHCH20)nH wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropylene glycol (Synalox) and mono and di C1-C6 alkyl ethers and esters of ethylene glycol having the structural formulas R(X)nOH, R1(X)nOH, R(X)nOR and R1(X)nOR1wherein R is C1-C6 alkyl group, R1 is 25 C2-C4 acyl group, X is (OCH2CH2) or (OCH2(CH3)CH) and n is a number from 1 to 4, diethylene glycol, polyamino acids, monosuccinic acids selected from the group consisting of succinic acid, glutaric acid; and phosphoric acid and any salts thereof, ethylene diamine tetraacetic acid or any salt thereof, , enzymes, zeolite, alkali metal silicates, triethylene glycol, WO 03/087281 PCT/US03/10802 6 Also excluded from the instant all purpose cleaning compositions are grease release agents characterized by the formula: R2 R1 N R4 X 5 R3 wherein R1 is a methyl group and R2, R3 and R4 are independently selected from the group consisting of methyl, ethyl, and CH2CH2Y, wherein Y is selected from the group consisting of Cl, Br, CO2H, (CH20)nOH wherein n=1 to 10, OH, CH2CH9OH and x is selected from the group consisting of Cl, Br, methosulfate 10CH30 AO 10 0 and _HCO3 Also excluded from the instant all purpose cleaning compositions are grease 15 release agents which are an ethoxylated maleic anhydride-alpha-olefin copolymer having a comblike structure with both hydrophobic and hydrophilic chains and is depicted by the formula: CO2H H) (C HC H) I (tH2)x 20 x CH3 (CH2 CH2 OMH y wherein n is about 5 to about 14, preferably about 7 to 9, x is about 7 to 19, preferably 8 to 19 and y is of such a value as to provide a molecular weight about 10,000 to about 25 30,000. Detailed Description of the Invention The present invention relates to a stable optically hard surface cleaning composition comprising approximately by weight: 0.5% to 4% of a first nonionic surfactant; 2% to 7% of a second nonionic surfactant; 0.1% to 5% of a solubilizer; WO 03/087281 PCT/US03/10802 7 0.05% to 2.5% of an alkali metal salt of a polycarboxylic acid; 0.05% to 2% of a fatty acid; 0.25% to 6% of magnesium sulfate heptahydrate; 0.1% to 5% of an essential oil or a perfume, , and the balance being water. As used herein and in the appended claims the term "perfume" is used in its 5 ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances. Typically, perfumes are complex mixtures of blends of various organic compounds such as alcohols, 10 aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume. In the present invention the precise composition of the perfume is of no 15 particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor. Naturally, of course, especially for cleaning compositions intended for use in the home, the perfume, as well as all other ingredients, should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.. The instant compositions show a marked improvement in ecotoxocity as compared to 20 existing commercial products. Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic 25 technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69 0 C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun WO 03/087281 PCT/USO3/10802 8 balsam, Heliotropin, Isobornyl acetate, Isolongifolene, Juniper berry oil, L-methyl acetate, Lavender oil, Lemon oil, Lemongrass oil, Lime oil distilled, Litsea Cubeba oil, Longifolene, Menthol crystals, Methyl cedryl ketone, Methyl chavicol, Methyl salicylate, Musk ambrette, Musk ketone, Musk xylol, Nutmeg oil, Orange oil, Patchouli oil, 5 Peppermint oil, Phenyl ethyl alcohol, Pimento berry oil, Pimento leaf oil, Rosalin, Sandalwood oil, Sandenol, Sage oil, Clary sage, Sassafras oil, Spearmint oil, Spike lavender, Tagetes, Tea tree oil, Vanilin, Vetyver oil (Java), Wintergreen The cleaning composition also contains an inorganic or organic salt of oxide of a multivalent metal cation, particularly Mg++. The metal salt or oxide provides several 10 benefits including improved cleaning performance in dilute usage, particularly in soft water areas, and minimized amounts of perfume required to obtain the microemulsion state. Magnesium sulfate, either anhydrous or hydrated (e.g., heptahydrate), is especially preferred as the magnesium salt. Good results also have been obtained with magnesium oxide, magnesium chloride, magnesium acetate, magnesium 15 propionate and magnesium hydroxide. These magnesium inorganic salts can be used with formulations at neutral or acidic pH since magnesium hydroxide will not precipitate at these pH levels. Although magnesium is the preferred multivalent metal from which the salts (inclusive of the oxide and hydroxide) are formed, other polyvalent metal ions also can be used provided that their salts are nontoxic and are soluble in the aqueous 20 phase of the system at the desired pH level. The cleaning compositions include from about 0.05% to about 2.0% by weight of the composition of a C8-C22 fatty acid or fatty acid soap as a foam suppressant. The addition of fatty acid or fatty acid soap provides an improvement in the rinseability of the composition whether applied in neat or diluted form. Generally, 25 however, it is necessary to increase the level of cosurfactant to maintain product stability when the fatty acid or soap is present. If more than 2.5 wt. % of a fatty acid is used in the instant compositions, the composition will become unstable at low temperatures as well as having an objectionable smell.
WO 03/087281 PCT/US03/10802 9 As example of the fatty acids which can be used as such or in the form of soap, mention can be made of distilled coconut oil fatty acids, "mixed vegetable" type fatty acids (e.g. high percent of saturated, mono-and/or polyunsaturated C18 chains); oleic acid, stearic acid, palmitic acid, eiocosanoic acid, and the like, generally those fatty 5 acids having from 8 to 22 carbon atoms being acceptable. The C1-C4 alkanol is preferably ethanol and/or isopropanol. The final essential ingredient in the inventive cleaning compositions or all purpose hard surface cleaning compositions is water. The proportion of water in the all purpose hard surface cleaning composition compositions generally is in the range of 10 20% to 97%, preferably 70% to 97% by weight. The liquid cleaning composition of this invention may, if desired, also contain other components either to provide additional effect or to make the product more attractive to the consumer. The following are mentioned by way of example: Colors or dyes in amounts up to 0.5% by weight; bactericides in amounts up to 1% by weight; 15 preservatives or antioxidizing agents, such as, 5-bromo-5-nitro-dioxan-1,3; 5-chloro-2 methyl-4-isothaliazolin-3-one, 2,6-di-tert.butyl-p-cresol, etc., in amounts up to 2% by weight; and pH adjusting agents, such as sulfuric acid or sodium hydroxide, as needed. Furthermore, if opaque compositions are desired, up to 4% by weight of an opacifier may be added. 20 In final form, the cleaning compositions exhibit stability at reduced and increased temperatures. More specifically, such compositions remain clear and stable in the range of 40C to 500C, especially 2'C to 430C. Such compositions exhibit a pH in the acid or neutral range depending on intended end use. The liquids are readily pourable and exhibit a viscosity in the range of 6 to 60 milliPascal second (mPas.) as measured 25 at 250C with a Brookfield RVT Viscometer using a #1 spindle rotating at 20 RPM. Preferably, the viscosity is maintained in the range of 10 to 40 mPas. The compositions are directly ready for use or can be diluted as desired and in either case no or only minimal rinsing is required and substantially no residue or streaks are left behind. Furthermore, because the compositions are free of detergent WO 03/087281 PCT/USO3/10802 10 builders such as alkali metal polyphosphates they are environmentally acceptable and provide a better "shine" on cleaned hard surfaces. Environmental profile is also greatly improved by the fact that the composition does not contain surfactants that are non biodegradable under anaerobic conditions. 5 When intended for use in the neat form, the liquid compositions can be packaged under pressure in an aerosol container or in a pump-type sprayer for the so called spray-and-wipe type of application. Because the compositions as prepared are aqueous liquid formulations and since no particular mixing is required to form the microemulsion, the compositions are 10 easily prepared simply by combining all the ingredients in a suitable vessel or container. The order of mixing the ingredients is not particularly important and generally the various ingredients can be added sequentially or all at once or in the form of aqueous solutions of each or all of the surfactants and amphiphiles can be separately prepared and combined with each other and with the perfume. The 15 magnesium salt, or other multivalent metal compound, when present, can be added as an aqueous solution thereof or can be added directly. It is not necessary to use elevated temperatures in the formation step and room temperature is sufficient. The instant cleaning compositions explicitly exclude alkali metal silicates and alkali metal builders such as alkali metal polyphosphates, alkali metal carbonates, alkali 20 metal phosphonates and alkali metal citrates because these materials, if used in the instant composition, would cause the composition to have a high pH as well as leaving residue on the surface being cleaned. The following examples illustrate liquid cleaning compositions of the described invention. Unless otherwise specified, all percentages are by weight. The exemplified 25 compositions are illustrative only and do not limit the scope of the invention. Unless otherwise specified, the proportions in the examples and elsewhere in the specification are by weight.
WO 03/087281 PCT/US03/10802 11 Example 1 The following compositions in wt. % were prepared by simple mixing at 25 0 C: A B C9-C11 alcohol EO 2-3:1 1 2 Ethanol 0 1 C8-18 alcohol EO7.5-8:1 4 4 Polycarboxylic acid sodium salt 0.25 0.5 Coconut fatty acid 0.2 0.5 Sodium cumene sulfonate 40% 4 4 MgSO4 7 H20 0.5 1 Perfume 0.65 0.65 Water Balance Balance Grease cutting Neat 84% 93% Dilute 88% 99% Residue Better than reference Better than reference 5