Title of Invention

A LOW FOAMING CLEANING FORMULATION AND A METHOD OF CLEANING A HARD SURFACE WITH THE SAME

Abstract

The invention relates to a low foaming cleaning fonnulation which comprises at least one hydrotropic alkoxylated quaternary ammonium compound in combination with at least one nonionic surfactant based on ethoxylated short chain branched alcohols, wherein said hydrotropic alkoxylated quaternary ammonium compound is of formula II {CH<sub>2</sub>CHR<sub>5</sub>O)<sub>A</sub>.H J R<sub>1</sub>R<sub>2</sub>N. X' (CH<sub>2</sub>CHR<sub>5</sub>O)<sub>8</sub>H wherein R<sub>1</sub> is linear or branched, saturated or unsaturated C<sub>6</sub>-C<sub>22</sub> alkyl group; R<sub>2</sub> is a C<sub>1</sub>-C<sub>6</sub> alkyl group; X is an anion; each R<sub>5</sub> is independently at each occurrence C<sub>1</sub>-C<sub>2</sub> alkyl or H provided that at least one occurrence ofR<sub>5</sub> is a C<sub>1</sub>-C<sub>2</sub> alkyl; and A and B are integers greater than or equal to 1 and A+B is 2-50, and said nonionic surfactants of fonnula III R-o-(CH<sub>2</sub>CH<sub>2</sub>O)<sub>n</sub>H (III) wherein R is a branched alkyl group having 3-12 carbon atoms and n = 3-12. ,

Full Text

Field of the Invention This invention relates to cleaning apptications that require low foam or non-foam cleaning formulations such as in automatic dishwashers. Cleaning in Place (CIP), automatic floor scmbbers, enclosed parts cleaning and the like. Any foam that is generated in these systems should be unstable and break down rapidly to prevent accumulation of foam during the process. Background of the Invention Typical hard surfece cleaning formulations consist of a nonionic surfactant or solvent component, an electi-olyte component (chelates or builders) and a hydrotropic co-surfactant (amphoteric, anionic or cationic surfactants). Quaternary ammonium compounds can function as the hydrotropic co-surfactants. In the cleaning industry there are several specialized categories of cleaning where foaming can be very detrimental to tiie application. Examples of such formulations include Cleaning In Place formulations, automatic floor scrubber formulations, automatic dishwasher formulations, re-circulatory metal parts cleaning and the like. These types of formulations demand low, fast breaking foams to avoid overflow, product loss, pump cavitation, and streaks/films on treated surfaces after drying. If the cleaning formulation shows any tendency to foam then the high turbulence caused by either brushes or water sprays will result in foam. In order to address the foaming issues, formulators often add oils or silicon defoamers to reduce or eliminate foam. Often these additives leave films and deposits on the surface, resulting in a poorly cleaned surface. Secondly at high concentrations of alkaline salts, such as in aqueous concentrates in which typically the cleaning compositions are supplied to the end user, these additives are not soluble. Formulators also use low foam or defoaming nonionic surfactants in these cleaning fonnulations to minimize foam. Examples include EO/PO block copolymers, branched alcohol ethoxylates, capped alcohol ethoxylates and the like. However, the addition of hydrotropes or hydrotropic co-surfactants that couple the electrolytic component and the low foam/defoam nonionic component together can result in foam stabilization, foam addition or foam boosting negating the effect of the low foaming or defoaming nonionic. This has resulted in many fomiulators avoiding the use of hydrotropes in their cleaning fonnulations. Additionally, these cleaning formulations have the lowest foam profile when the cleaning is done at temperatures above the formulations cloud points which results in cleaning solutions that are unstable and inefficient. Also, these fonnulations tend to have depletion problems especially in enclosed re-circulator systems. This requires that the nonionic surfactant be replenished in order to prevent flash foam occun^ence. The present invention has solved the deficiencies of the prior art by providing low foaming and/or defoaming formulations, which comprise an alkoxylated quaternary ammonium compound and at least one nonionic compound of a specific structure. Summary of the Invention The present invention generally relates to low foaming and/or defoaming cleaning formulations which comprise a synergistic combination of one or more hydrotropic alkoxylated quaternary ammonium compounds and at least one nonionic surfactant based on branched alcohols. The nonionic surfactant may be selected from stnjctures having 3 to 12 moles of ethoxylation, but preferably have an average of 3-6 moles of ethoxylation with either narrow or broad range distribution. Detailed Descriotion of the Invention The present invention generally relates to low foaming and/or defoaming cleaning fonnuiations which comprise a synergistic combination of one or more hydrotropic alI The hydrotropic alkoxylated quaternary ammonium compound is preferably selected from the group of compounds represented by General Fonnula 1, below. RIRSRSRAN-'X" (I) wherein Ri is a linear or branched, saturated or unsaturated C6-C22 alkyl group; Rais Ci-Ce alkyl group or Ri; R3 and R4 are C2-C4 random or block polyoxyalkylene groups; and X' is an anion, preferably chloride, methyl sulfate, bromide, iodide, acetate, carbonate, and the like. Preferred compounds within the scope of general Formula I are represented by General Formula II, below. (CHaCHRsOJAH (11) / R1R2N* X" \ (CH2CHR50)BH wherein Ri, R2, and X' are as defined above; each R5 is independently at each occurrence Ci-Ca alkyl or H, provided that R5 is a Ci - C2 alkyl in at least one occun^ence; and A and B are integers greater than or equal to 1 wherein A+B is 2-50. Most prefen"ed hydrotropic quaternary ammonium compounds within the scope of the present invention are as shown below where R ~ linear or branched, saturated or unsaturated C12-C22 alkyl, n+n' =0-10, m+m' =1-20, y+y'=0~20, and X" is an anion, preferably chloride or methyl sulfate, provided that when n+n'=Q, y+y' is at least 1. i ' R, ,.(CH2CH20)n(CH2CHO)m (CH^CH^OyH H3C' ^(CHjCH2O)n'{CH2CH0)m' {CH2CH20)y'H CH3 An especially preferred hydrotropic quaternary ammonium compound is Beroi CHLF available from Akzo Nobel Surface Chemistry LLC, Chicago, IL, USA: R^ ^.(CH2CH20)n(CH2CHO)m{CH3CH20)yH ■ H3C' ^(CH3CH20)n'[CH2CHO)m'(CH2CH20)y'H CH3 where R is tallow alkyl, n+n'=2, m+m'=12, y+y'=5 and X is methyl sulfate. The quaternary ammonium compound described in this invention may be prepared by quaternization of the starting amino compound described below using known methods such as that described in U.S. Patent No. 5,885,932 which is incorporated herein by reference. The fourth substituent added to the amino nitrogen by quaternization is preferably a group selected from alkyl, or alkenyl group having 1-4 carbons. Any suitable anion can be employed. Preferred anions include, but are not limited to, a member selected from the group consisting essentially of methyl sulphate, carbonate, chloride, fluoride, bromide, acetate and the like. The starting amino group can be prepared by reacting an amine selected from the group consisting of R1-NH2 and R1R2NH wherein Ri and R2 as in structure (1); with at least one propylene oxide and at least one alkylene oxide. Preferred alkylene oxides include but are not limited to ethylene oxide, propylene oxide, isobutylene oxide, butylene oxide and mixtures thereof. The compounds of the present invention are made in such a way as to introduce varying numbers of alkylene oxide units onto the amino nitrogen. The additional alkylene oxide groups may be all the same, such as, for example, one or more ethylene oxide units, or the groups may be different to fonn, for example, block copolymer chains of ethylene oxide and propylene oxide units, random copolymer chains consisting of several units of each of two or more different alkylene oxides, or alternating units of two or more alkylene oxides. Any conceivable combination of alkylene oxide units up to 50 units long may be employed at each available location on the amino nitrogen. For example, the amino nitrogen may contain two different ali In a preferred embodiment, block copolymer chains of ethylene oxide and one or more of propylene oxide or butytene oxide are employed. Preferably, the molar weight of the compounds used in the present invention is less than 8000 though higher molecular weight compounds can be employed. Typical compounds suitable for use in the present invention include, but are not limited to, bis(hydroxyethyl)methyltallow alkyl- ethoxylated, propoxylated, methyl sulphate; cocobis(2-hydroxyalkyl)methylammonium chloride; potyoxyalkylene (15) cocomethylammonium chloride; oleylbis(2-hydroxyalkyl)methyI ammonium chloride; polyoxyalkylene (15) stearytmethyl ammonium chloride; N,N-bis(2-hydroxyalkyl)-N-methyloctadecanaminium chloride; N-tailowalkyl-N,N"-dimethyl-N-N'-polyalkyteneglycol-propylenebis-ammonium-bis methylsulphate; polyoxyalkylene (3) tallow propylenedimonium dimethylsulphate; coconut penta-alkoxy methyl ammonium methyl sulphate; polyoxyalkylene (15) cocomonium methosulphate; isodecyfpropyl dihydroxyaikyl methyl ammonium chloride; isotridecylpropyi dihydroxyalkyl methyl ammonium chloride; methyl dihydroxyalkyl isoarachidaloxypropyi ammonium chloride; and mixtures thereof. The nonionic surfactant employed in the context of the present invention is preferably selected from the group of compounds represented by General Formula III, below R-0-(CH2CH20)nH III wherein R is a branched alkyl group with 3-12 carbon atoms, preferably derived -OH R-C-C-8-C- H- H- H, R from a Guerbet alcohol of the fomiula with 10 carbon atoms or less and/or mixtures thereof, and n = 3-12, but preferably 3-6 moles of ethoxylation with either narrow or broad range distribution. Specific examples of nonionic surfactants employable in the context of the present invention include but are not limited to: polyoxyethyiene (3) 2-ethylhexanol, polyethyleneglycoM ethylhexyl ether, polyethyleneglycol-5 ethylhexanol, polyoxyethyiene (4) 2-ethylheptyl, polyoxyethyiene (5) isodecanol and polyoxyethyiene (5) 2-propylhepanot. The formulation of the invention generally contains from about 0.1% to about 12% by weight nonionic surfactant, preferably from about 1 % to about 8% and still more preferably from about 2% to about 4%. The present formulation also preferably contains, in combination with said nonionic compound, from about 1% to about 20% by weight alkoxylated quaternary ammonium compound, preferably between 2 % to about 10%, and stilt more preferably between about 4% and about 8%. This synergistic combination of one or more hydrotropic alkoxylated quaternary ammonium compounds and at least one nonionic surfactant based on branched alcohols produces a clear and stable cleaning formulation, with unusual foam collapse properties in the presence of typical cleaning additives such as NaOH, EDTA, TKPP, glycols, corrosion inhibitors, phosphonates, solvents, carbonates, borates, citrates, acids, silicates and the like. The low foaming/defoaming cleaning compositions of the present invention are Ideal for applications that demand low, fast breaking foams to avoid overflow, product loss, pump cavitation, and streaks or films on treated surfaces after drying. Several specialized categories of cleaning which meet this criteria include but are not limited to Cleaning In Place formulations, automatic floor scrubber formulations, automatic dishwasher formulations, re-circulatory metal parts cleaning formulations and the like. The specialized cleaning formulations of the invention may also be formulated with ingredients know in the art. As nonlimiting examples, such formulations may include hydrotropes or coupling agents, surfactants, thickening agents, chelating agents, builders, defoamers and anti-foam agents, corrosion inhibitors and the like. Hydrotropes or coupfing agents include but are not limited to glycol ethers, alcohols, acrylic polymers, sodium xylene sulphonate, phosphate esters, amphoteric surfactants, alkoxylated carboxylates, aminopropionates, glycerine, alkylpolyglucostdes, alkanolamides, quatemary ammonium compounds or mixtures thereof. Surfactants, include but are not limited to, amphoteric, cationic, nonionic, anionic classes and mixture thereof. Thickening agents Include, but are not limited to, associative polymers and copolymers, acrylic polymers, amides, xanthan gums, cetlulosic polymers, modified clays, amine oxides, ettioxylates amines, silica, silicates, polyvinyl pyrrolidone and mixtures thereof. The electrolytic components can consist of chelating agents or builders. Chelating agents include but are not limited to gluconates, citric acid, sodium ethylenediaminetetraacetic acid, phosphonates, phosphonic acids, phosphates, polyphosphates, nitrotnacetic acid, ethylenediaminebis(2-hydroxyphenylacetic acid) and mixtures thereof. Builders include, but are not limited to soda ash, acrylic polymers, silicates, phophonates, phosphates, carbonates, citrates, sodium hydroxide, potassium hydroxide, triethanotamine and mixture thereof. Corrosion inhibitors include but are not limited to alkanolamides, aliphatic carboxyiic acids, amides, amines, diamines, polyamines, phosphoric acid, borates, oxazoUnes, phosphate esters, benzotnazoie, azoles, Imidazolines, amphotenc surfactants, silicates, phophonates, gluconates, fatty acids, thioazoles and mixtures thereof. other optional components may be included in the fomiulations of the present invention. These include but are not limited to liquid carriers such as water, pH modifiers, enzymes, bleaching agents, bieacfi activators, optical brighteners, soil release agents, antistatic agents, lubricants, preservatives, peri'umes, colorants, anti-redeposition agents, dispersing agents, acidifying agents and solvents. The invention will now be illustrated by the following nonlimiting examples. The following chemicals were utilized in the examples and their 'identities are provided below. From Akzo Nobel Surface Chemistn/ LLC. Berol® 260 - C9-11 alcohol with 4 moles of ethoxylation (narrow range) Berol® 840 - 2-ethylhexyl witti 4 moles of ethoxylation (narrow range) Berol OX-91-4- C Ethoquad" T/25 - tallowme^yi ethoxylated (15) ammonium cMoride Propoquad® C/12 - cocomethyt-bis-(2-hydroxy-2-methylethyl) quaternary ammoniun methyisulphate Ampholak"' YJH-4Q - a low foam hydrotrope octylimtnodipropionate From Condea Vista Novel* II 12-4 - 2-butyloctanol alcohol made with 4 moles of ethoxylation (narrow range) From Akcros Chemicals Versilan" MX332 - proprietary blend of anionic and nonionic surfectants intended for low foam cleaning of metal parts From Harcros T-Det A-134 - isotndecyl alcohol with 4 moles of ethoxylate (standard range) From BASF Pluronic L-62 - nonionic block polymer a low foam detergent for metal cleaning Pluronic L-64 - nonionic block polymer a dispersantfor metal cleaning From Union Carbide fPow^ Teroftol" 15-S-3 - CIMS secondary alcohol with 3 moles of ethoxylation (standard range) Terqitot* 15-S-5 - Cn .15 secondary alcohol with 5 moles of ethoxylation (standard range) Terqitol* 15-S-40 - Cn .15 secondary alcohol with 40 moles of ethoxylation (standard range) Others SXS - sodium xylene sulphonate a standard hydrotrope. EDTA - 40% solution of sodium ethylenediaminetetraacetic acid TKPP - tetrapotassium pyrophosphate (TKPP) Example 1 Table 1 compares cleaning ability of the vanous formulations desaibed previoustv with respect to cleaning ability, formulation stability and foaming properties. Table 1: Summary Table of Cleaning Formulations Cleaning Formula Type Traditional Low foam Nonionic Silicon defoamer Invention Cleaning Good-Excellent Medium- poor Medium-poor Good-Excellent Stability Yss No No Stable Foam Too High Low' Low- Rapid collapse *Need to be replenished To demonstrate the above invention, cleaning formulations with the following ingredients were prepared: Formulation A 7% EDTA (40% solution of sodium salt) 4% TKPP 2.5% Nonionic (may be varied from 0.5 to 4%) 6% Hydrotrope (or X amount until clear and stable) The test fomiulations were diluted 1:10 with distilled water and 100 ml samples were placed into the blender. The test solutions were blended for 60 sec at 1600 rpm and decanted into a measuring cylinder. The foam volume was determined initially, then after intervals of 1 and 5 minutes. The collapse rate was determined by taking the initial foam volume and dividing it by the time in seconds that it took to reach zero foam. If foam was still present at five minutes, the final foam volume was subtracted from initial volume and divided by 300 seconds. This test method was chosen to demonstrate the stability of any foam generated by the cleaning fonnulation under mechanical agitation. The rnfiuence of nonionic surfactant type, hydrotrope type and variations of Berol CHLF structure on the collapse rate of the cleaning fomiula was studied. Also, the percentage of nonionic in the fomnulation w/as varied to detemnine its contribution to collapse rate. Table 2: Foam Generation plus Collapse Rates for Various Nonionic and Hydrotropes Formulation Foam Volume(ml) after minute Col laps e Rate (ml/sec) Nonionic Hydrotrope 0 min. 1 min. 5 min. Berol 840" 0- 0 0 N/A - Berol CHLF 200 86 0 1.6 - - 40 12 4 0.12 Berol 840 Berol CHLF 205 0 0 6 Novell 12-4 Berol CHLF 190 120 40 0.5 T-DETA~134 Berol CHLF 194 104 48 0.5 Berol 260 Berol CHLF 200 170 52 0.5 Berol 840 SXS 350 320 166 0.6 Novel 112-4 sxs 170 124 52 0.4 T-OeTA-134 SXS 168 106 54 0.4 *CIoudy unstable formulation The above results show that the Berol CHLF alone in this fonnulation has a collapse rate of -1.6 ml/sec {average of five batches, values range from 1.2-2.1 ml/sec). When this hydrotrope was combined with various low foam nonionic surfactants in the majority of the cases the collapse rate drops to -0.5 mi/sec or less. However, when Berol CHLF was combined with Berol 840 the collapse rate increased by three-fold to ~6 ml/sec (average of five batches values range from 4.7-8.7 ml/sec). However, combination of Berol 840 with a traditional hydrotope such as sodium xylene sulfonate (SXS) results in a boost of foam volume and a reduction in collapse rates, due to foam stabilization, as seen in Table 2. The other two nonionic surfactants tested show no significant change in foam stability or amount of foam generated based on hydrotrope selected. Table 3: Structure Variations on Berol CHLF and Various Hydrotropes Influence on Collapse Rates with Berol 840 Hydrotrope Type Collapse Rate (ml/sec) Berol CHLF 2E0 + 12 PO + 5 EO Methyl sulfate 6 Berol CHLF Type 2E0 + 12 PO + 5 EO Chloride 5.2 Berol CHLF Type 5 E0 +12 PO Methyl sulfate 5.2 SXS Sodium xylene suiphonate 0.6 Ampholak YJH-40 Amphoteric - octyliminodipropionate 0.4 Ethoquad C/25 MS Cocoquat 15 EO 0.7 Ethoquad T/25 Tallow quat 15 EO 0.6 Propoquad C/12 Coco quat 2 PO 0.5 Adjusting the atkoxylated cationic hydrotrope structure by varying the EO/PO content or the counter ion preserves the rapid collapse rate seen with Berol CHLF and Berol 840 formulations (Table 3). Use of more traditional hydrotropes results in the decline in ihe collapse rate of the cleaning formulations, even when a low foam hydrotrope such as Ampholak YJH-40 was used. The above-data suggest that propoxylation in the aikoxyiated group is a critical factor in foam collapse behavior. Table 4: The Effect of Various Nonionics Surfactant Types on the Formulation Collapse Rates with Berol CHLF Alky) type Moles of EO EtfioxylatJon Types HLB Collapse Rate (ml/sec) 2-ethyihexyl R 1.2 6 2-ethylhexyl R 3 4.5 2-ethylhexyl R 0.6 2-ethylhexyi R B 2 2-ethylhexyl R 6 2 2-propylheptyi R .3 2-BiJtyloctyl R 0 .5 CB-IO ,5 R 0.5 Cs-no .5 R 1 0.7 CB R 1.6 2 Cio R 0.5 1 C9.11 R 0.5 0.5 Methyl capped Co-io R Benzyl capped 09.1, R Iso tridecyl R ,5 Cins (Secondary) R 0.6 .5 C11.16 (Secondary) R .3 1 .5 NR= narrow range ethoxylate; SR= standard (broad) range ethoxylate Adjusting the nonionlc surfectant type in the fonnulation indicates that two moles of EO on the 2-ethylhexanol was not sufficient to provide rapid defoaming such as seen with higher ethoxyiates (Berol 840). However, the distribution of the ethoxylation, a result of process conditions, does not affect the defoaming ability of the ethoxylated 2-ethylhexyi in these formulations. This is illustrated with the 2-ethylhexyl plus 5 moles EO based formulation, which gave results similar to the Berol 840 based fomiulation. 2-ethylhexyl plus 5 moles EO is produced by traditional ethoxylation techniques that produce a broad distribution of EO. Berol 840 is processed under conditions that result In a nan-ow distribution of EO as seen in Table 4. Slightly higher Guerbet alcohol based nonionlcs such as 2-propylheptyl with 5 moles of EO exhibit the same behavior as 2-ethylhexyi. However, longer Guerbet alcohols like 2-butyloctyl do not behave in the same manner with the Berol CHLF in these formulations. Higher levels of ethoxylation cause a decrease in the defoaming rate as illustrated by the use of 2-ethylhexyl plus eight mole of ethoxylate, which gives a collapse rate similar to the formulation with just the Berol CHLF. Screening results for other types of nonionlcs surfectants with various alkyl groups, HLBs, moles of EO and ethoxylation type can also be seen in Table 4. Branched alkyl groups other than short Guerbet alcohols do not provide the same rapid foam collapse. Linear fetty alkyl chains do not boost the collapse rate, but in general as the chain length decreases, the influence on collapse rate of the Berol CHLF decreases. Capping of the ethoxylate does not appear to affect the collapse rate, as seen with the benzyl methyl capped nonionic in Table 4. The amount of nonionic has a dramatic impact on the collapse rate of this fomiulation type as can be seen in Figure 1. As the amount of Berol 840 increases the collapse rate of the formulation increases. The collapse rate dramatically increases above 2% nonionic and it reaches a maximum between about 2.5% and 3.5% Berol 840. However, the opposite trend was seen with two other branched low foaming nonionic tested. Both Novel H 12-4 and T-Det A134 nonionic surfactants show a decrease in collapse rate as the amount of nonionic was increased in the test formulations. The results are in Table 5. Table 5: Influence of Nonionic Surfactant Level on Collapse Rates of Berol CHLF Nonionic Amount {%) Foam Volume (ml) Timo to zero Foam Collapse rate (ml/sec) Initial 5min Berol 840 0.5 230 0 135 0.9 1 220 0 120 1.3 1,5 220 0 110 1.8 2 220 0 77 2.5 2.5 210 0 45 4.7 3 220 0 42 4.9 3,5 220 0 67 3.3 4 240 0 206 1.2 Novel 1112-4 0.5 210 0 140 1.5 1 210 0 225 0.9 1.5 210 3d - 0.6 2 220 40 - 0.6 2.5 190 40 - 0.5 T-DetA134 0.5 210 0 246 0.9 t 21Q 30 - 0,6 1.5 210 48 - 0.5 2 210 5a - 0.5 2.5 194 48 - 0.5 Cleaning Performance Test solutions of cleaning Formulation A were prepared with three nonionic surfactants with two being known degreasers as shown in Table 6. These test formulations were diluted 1:10 with distilled water and their ability to degrease a real world soil (greasy/oily soil obtained from train engines) was detenmined using the method described below. The results indicated that the combination of Berol CHLF with Berol 840 gives statistically similar cleaning to both Berol 260 and T-DET A-134 both of which are considered excellent degreasers. Formulation A: 7% EDTA (40% solution of sodium salt) 4% TKPP 2.5% Nonionic surfactant 6% Berol CHLF Table G: Cleaning ability of Formulation A with Various Nonionic Surfactants. Nonionic Degreasing (%) Berol 840 58 ±11 Berol 260 70 ±5 T-DET A-134 69±11 Example 2 Two formulations were compared using the Formulation B-t and Formulation Bz shown below. The foaming and cleaning ability of these two surfactant systems were compared as described previously. Fonnulation Bi combines 3.5% Berol 840 and 6% Berol CHLF and Fonnulation Bz contains 9.5% Versilan MX332 (Akcros) with the same builders. Versilan MX332 has been described as a low foam cleaning surfactant blend recommended for metal cleaning. Versilan MX332 low foaming character is dependent on temperature as shown in Table 7. Results indicate that the combination of Berol 840/Berol CHLF was at least eight time more effective at degreasing under non-mechanical conditions than Versilan MX332. Formulation Bi: 7% EDTA (40% solution of sodium salt) 4% TKPP 3.5% Berol 840 6% Berat CHLF compared with Formulation Bz 7% EDTA (40% solution of sodium salt) 4% TKPP 9.5% Versilan MX332 Table 7: Comparison of Invention Formulation with a Low Foam Formulation Formula Foam Voiume(ml) Collapse Rat (mi/sec) Degreasing i'A) Appe aran ce min min min Berol 84Q/Berol CHLF 20 * ,3 0±1Q tear at 13CrF 0 6 * ,3 lear Versilan MX332 34 6 0 ,3 ±2 lear at 1 SOT 30 5 8 .3 loudy Time to zero foam was 67 seconds and at 130°F the time was 240 seconds. The results also indicate that the combination of Berol 840 and Berol CHLF generate very unstable foam at low temperatures and significantly lower foam volumes at higher temperature with slightly more stable foam. The fon-nulation containing Versilan MX332 has a small reduction in foam volume Uiat appears to be quite stable after an initial decline. The formulation containing Versilan MX332 also shows less stability than the combination of Berol 840 and Berol CHLF. Example 3 Parts Cleanino Test A fonnuiation containing Berol CHLF was submitted to an external laboratory for testing in a "Cycio Jet I Tumbling System." Parts Information Parts description: Automotive Engine and transmission parts Material: Steel, Aluminum Throughput per day : Various Shifts : 8 hours Contamination to be removed : oil, grease, dirt Any holes ? yes Are holes to be cleaned ? yes Process information Next process: Re-assemble Loading parts into machine: Manually Existing cleaning method : Manually Stages Requested for Test Cleaning: Wash ; Yes Rinse: Yes Dry; Yes Results shown in Table 8 indicated that Berol CHLF fomiulations can clean soiled car parts without foam generation or leaving any streaks or film on the parts after cleaning in a "CycIo Jet I Tumbling System". Table 8: Cycle Parameters and Cleaning Results Cycle Parameters Test Wash Rinse Dry Time (min) Temp. fF) Time (min) vrater Time (min) Temp. {"F) 1 3 170 2 Fresh 3 275 Results : Parts appear clean and dry 2 4 j 170 1.5 Fresh 3 250 Results : Parts appear clean and dry 3 8 160 1.5 Fresh 3 250 Results : Parts appear clean and dry Example 4 Test solutions of cleaning FormuiaUon Cj were prepared with several nonionic surfactants, SXS and a caflonic hydrotrope. These test formulations were diluted 1:100 with distilled water and their ability to disperse particulate (Sanders-Lambert soil) was determined using the method describe below. The results indicate that unlike other hydrotropes, Berol CHLF has the ability to disperse particles and aid in the cleaning of low foam surfactants such as Berol 840. Formulation Ci: 4% Sodium metasilicate 6% TKPP 9% Surfectant Table 9: Cleaning ability of Formulation Ci with Various Nonionic Surfactants. Nonionic Removal {%) Berol OX-91-4 43 ±6 BeroiOX-91-8 54 ±5 Berol 260 40 + 10 Tergitol 15-S-5 48 ±8 Tergitol 15-S-15 55 + 8 Tergitol 15-S-40 28 + 7 Pluronic L-62 27 + 6 Piuronic L-64 28 ±6 Hydrotrope Sodium Xylene Sulphonate 31 ±1 Berol CHLF 69 ±14 Cleaning Test Method Non-Mechanical Cleaning Evaluations (Black Box Test) SCOPE: A non-mechanical cleaning test method for dilutable industrial Cleaners that can be used to evaluate the influence of surfactants in the cleaning solution. DESCRIPTION: Reagents 1.1 General Chemical Berol 226 40% solution of Sodium Ethylenediaminetetraacetic acid (EDTA) Tetrapotassium Pyrophosphate (TKPP) Distilled/deJonized water Isopropyl alcohol (IPA) Control solution Tap water for rinsing Soils Urban Lambert soil (sources of reagents are describe below) 1.2 Control Solution Berol 226 Standard Formulation D: Berol 226 9% EDTA (40%) 9% TKPP 4% Water 78% 1.3 Soils 1.3.1 Real World Soils Soils obtained from train engines in Europe and the US. 1.3.2 Synthetic Soil SoU Formulation: Sander-Lambert Soil (particulate mix) 16 g Non detergent motor oil 7 g Isopropyt alcohol 200 g The Sander-Lambert soil particulate mix contains the following ingredients: Hyperhumus 38%, Portland cement 15%, low-fumace carbon black 1.5%, synthetic red iron pigment 0.3%, powdered silica 200-300 mesh 15%, bandy black clay 16.7%, stearic acid 1.5%, oleic acid 1.5%, palm oil 3%, cholesterol 1%, vegetable oil 1%, octadecene 2% linolecic acid 2% and mineral oil 1.5%. This particulate mix can either be prepared In house as follows or ordered pre-made from SGS U.S. Testing Company Inc, Fairfield, New Jersey. The above components are mixed together and transferred to a ball mill, then mixed for 18 hours using both large (1.25 inch diameter by 1.25 inch) and small (0.5 inch diameter by 0.5 inch) ceramic cylinders. The soil is transferred by a shallow pan and allowed to air-dry. Once the soil is completely dry it is pulverized and passed through a 300 mesh screen. Equipment 1. 100 ml and 25 ml Pyrex beakers 2. Spectrophotometer or reflectometer (any instrument capable of accurately measuring changes in substrates reflectance, such as Minolta CM-508D spectrophotometer) 3. 1 inch paint bnjsh 4. Aerosol sprayer 5. Sink with a water spray nozzle 6. 1 X 140 X 220 mm steel plates, which were primed, painted (white) plus two coats of lacquer, not unlike a car surface. Propedures 1. The panels are washed with detergent, then cleaned with IPA and allowed to dry before use. 2- The spectrophotometer is placed on the marked sections and a base reading is taken (marked as MB. ABB or Abs - the base reading), 3. If required the synthetic soil is prepared as stated above or a real World soil sample is selected for the test 4. The real World soil is applied on to tfie test panel with a brush, then the soil is smoothed over the surface to obtain an even coating as possible using a Kimwipe. If using the Synthetic soil, the soil is sprayed across the test panel once using an aerosol sprayer, once the IPA has evaporated off the surface a second coat is applied. The plates are then allowed to stand for 12 hour before testing. 5. The spectrophotometer is placed on the marked sections of the soiled panels and the soiled reading is taken (marked as ALs, Aas or Abg - the soiled reading). 6. 100 mis of the test solutions are prepared and the solution is diluted between 1:10 to 1:120 with distilled/deionized water. 7. Twenty ml of each diluted test cleaner is poured onto the soiled plate (three solutions per plate). Oneach test plate twenty mis of the control solution at 1:10 dilution is tested and used as a reference for product/plate performance. 8. The test solution is left for twenty seconds. The plates are then cleaned using a low-pressure water spray. The plates are cleaned from the bottom up to remove the emulsified dirt. 9. The panels are allowed to air dry. The spectrophotometer is placed on the marked sections and the final reading is taken (marked as ALc, Aac or Abe - the cleaned reading). 10. The Delta values are used to calculated the amount of soil removed from the panel using the CLE. Lab or L*a*b Color Space standard. 11. Each fonnulation was then tested at three times and the standard deviation calculated. However, if the standard deviation of a single test is greater than 15%, the formulation is re-tested and any outlying points eliminated. In some cases the repeated studies show/ no outlying points and both data sets are combined. The contra) solution should qive 95±7 % soil removal. 12. WE CLAIM: 1. A low foaming cleaning formulation which comprises at least one hydrotropic alkoxylated quaternary ammonium compound in combination with at least one nonionic surfactant based on ethoxylated short chain branched alcohols, wherein said hydrotropic alkoxylated quaternary ammonium compound is of formula II 2. The formulation as claimed in claim 1 wherein said nonionic surfactant has an average of 3-12 moles of ethoxylation with either narrow or broad range distribution. 3. The formulation as claimed in claim 1 wherein R is derived from a Guerbet alcohol having up to 12 carbon atoms, and wherein the ethoxylation of said nonionic surfactant has either narrow or broad range distribution. 4. The formulation as claimed in claim 1 wherein said nonionic surfactant is selected from the group consisting of polyoxyethylene (3) 2-ethylhexanol, polyethyleneglycol-4 ethylhexyl ether, polyethyleneglycol-5 ethylhexanol, polyoxyethylene (4) 2-ethylheptyl, polyoxyethylene (5) isodecanol, polyoxyethylene (5) 2-propylheptanol and mixtures thereof. 5. The formulation as claimed in claim 3 wherein X' is selected from the group consisting of chloride, methyl sulfate, bromide, iodide, acetate and carbonate. 6. The formulation as claimed in claim 1 wherein said hydrotropic alkoxylated quaternary ammonium compound is of the formula: 7. The formulation as claimed in claim 6 wherein X" is chloride or methyl sulfate. 8. The formulation as claimed in claim 6 wherein R is tallow alkyl, n+n'=2, m+m'=12, y+y'=5 and X is methyl sulfate. 9. The formulation as claimed in claim 1 wherein said hydrotropic alkoxylated quaternary ammonium compound is selected from the group consisting essentially of bis(hydroxyethyl)methyltallow alkyl, ethoxylated, propoxylated, methyl sulphate; cocobis(2-hydroxyalkyl)methylammonium chloride; polyoxyalkylene (15) cocomethylammonium chloride; oleylbis(2-hydroxyalkyl)methyl ammonium chloride; polyoxyalkylene (15) stearylmethyl ammonium chloride; N,N-bis(2-hydroxyalkyl)-N- methyloctadecanaminium chloride; N-tallowalkyl-N,N'-dimethyl-N-N'- polyalkyleneglycol-propylenebis-ammonium-bis methylsulphate; polyoxyalkylene (3) tallow propylenedimonium dimethylsulphate; coconut penta-alkoxy methyl ammonium methyl sulphate; polyoxyalkylene (15) cocomonium methosulphate; isodecylpropyl dihydroxyalkyi methyl ammonium chloride; isotridecylpropyl dihydroxyalkyl methyl ammonium chloride; methyl dihydroxyalkyi isoarachidaloxypropyl ammonium chloride; and mixtures thereof. 10. A method of cleaning a hard surface which comprises applying to said surface a cleaning effective amount of a low foaming cleaning formulation which comprises at least one hydrotropic alkoxylated quaternary ammonium compound of formula II A and B are integers greater than or equal to 1 wherein A+B is 2-50 in combination with at least one nonionic surfactant based on branched alcohols of formula III wherein R is a branched alkyl group having 3-12 carbon atoms and n = 3-12, and thereafter removing said cleaning formulation from said surface. 11. The method as claimed in claim 10 wherein said nonionic surfactant has an average of 3-6 moles of ethoxylation with either narrow or broad range distribution. 12. The method as claimed in claim 10 wherein R is derived from a Guerbet alcohol having up to 12 carbon atoms, and wherein the ethoxylation of said nonionic surfactant has either narrow or broad range distribution. 13. The method as claimed in claim 12 wherein said nonionic surfactant is selected from the group consisting of polyoxyethylene (3) 2-ethylhexanol, polyethyleneglycol-4 ethylhexyl ether, polyethyleneglycol-5 ethylhexanol, polyoxyethylene (4) 2-ethylheplyl, polyoxyethylene (5) isodecanol, polyoxyethylene (5) 2-propylheptanol and mixtures thereof. 14. The method as claimed in claim 10 wherein X" is selected from the group consisting of chloride, methyl sulfate, bromide, iodide, acetate and carbonate. 15. The method as claimed in claim 10 wherein said hydrotropic alkoxylated quaternary ammonium compound is of the formula: 18. A low foaming cleaning formulation which comprises at least one hydrotopic alkoxylated quaternary ammonium compound in combination with at least one nonionic surfactant based on short chain branched alcohols, wherein said hydrotropic alkoxylated quaternary ammonium compound is selected from the group consisting essentially of bis {hydroxyethyl)methyltallow alkyl, ethoxylated, propoxylated, methyl sulphate; cocobis(2-hydroxyalkyl) methylammonium chloride; polyoxyalkylene (15) cocomethylammonium chloride; oleylbis(2-hydroxyalkyl)methyl ammonium chloride; polyoxyalkylene (15) stearylmethyl ammonium chloride; N,N-bis(2-hydroxyalkyl)-N- methyloctadecanaminium chloride; N-tallowalkyl-N,N'-dimethyl-N-N'- polyalkyleneglycol-propylenebis-ammonium-bis methylsulphate; polyoxyalkylene (3) tallow propylenedimonium dimethylsulphate; coconut pentaalkoxy methyl ammonium methyl sulphate; polyoxyalkylene (15) cocomonium methosulphate; isodecylpropyl dihydroxyalkyl methyl ammonium chloride; isotridecylpropyl dihydroxy-alkyl methyl ammonium chloride; methyl dihydroxyalkyl isoarachidaloxypropyl ammonium chloride; and mixtures thereof. 19. The formulation as claimed in claim 1 which comprises from 0.1% to 12% by weight nonionic surfactant and from 1% to 20% by weight alkoxylated quaternary ammonium compound. 20. The formulation as claimed in claim 19 which comprises from 2% to 4% by weight nonionic surfactant and from 4% to 8% by weight alkoxylated quaternary ammonium compound. 21. The formulation as claimed in claim 1 wherem n is an integer of from 3-6. 22. The method as claimed in claim 10 wherein n is an integer of from 3-6.

Documents:

1591-chenp-2003 abstract-duplicate.pdf

1591-chenp-2003 abstract.pdf

1591-chenp-2003 claims-duplicate.pdf

1591-chenp-2003 claims.pdf

1591-chenp-2003 correspondence-others.pdf

1591-chenp-2003 correspondence-po.pdf

1591-chenp-2003 descritpion (complete)-duplicate.pdf

1591-chenp-2003 descritpion (complete).pdf

1591-chenp-2003 form-1.pdf

1591-chenp-2003 form-18.pdf

1591-chenp-2003 form-26.pdf

1591-chenp-2003 form-3.pdf

1591-chenp-2003 form-5.pdf

1591-chenp-2003 pct search report.pdf

1591-chenp-2003 pct.pdf

1591-chenp-2003 petition.pdf