WO2000008126A1 - Process for forming a stable non-phase separating rinse-aid dispersion - Google Patents
Process for forming a stable non-phase separating rinse-aid dispersion Download PDFInfo
- Publication number
- WO2000008126A1 WO2000008126A1 PCT/US1999/017816 US9917816W WO0008126A1 WO 2000008126 A1 WO2000008126 A1 WO 2000008126A1 US 9917816 W US9917816 W US 9917816W WO 0008126 A1 WO0008126 A1 WO 0008126A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rinse aid
- aid dispersion
- nonionic surfactant
- polymer
- weight
- Prior art date
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000006260 foam Substances 0.000 claims abstract description 21
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims abstract description 19
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000005187 foaming Methods 0.000 claims abstract description 17
- 239000003752 hydrotrope Substances 0.000 claims abstract description 17
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 229920000058 polyacrylate Polymers 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- -1 alkyl naphthalene sulfonate Chemical compound 0.000 claims description 11
- 150000002191 fatty alcohols Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 229940079842 sodium cumenesulfonate Drugs 0.000 claims description 7
- QEKATQBVVAZOAY-UHFFFAOYSA-M sodium;4-propan-2-ylbenzenesulfonate Chemical compound [Na+].CC(C)C1=CC=C(S([O-])(=O)=O)C=C1 QEKATQBVVAZOAY-UHFFFAOYSA-M 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229940048842 sodium xylenesulfonate Drugs 0.000 claims description 3
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 claims description 2
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WVFDILODTFJAPA-UHFFFAOYSA-M sodium;1,4-dihexoxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].CCCCCCOC(=O)CC(S([O-])(=O)=O)C(=O)OCCCCCC WVFDILODTFJAPA-UHFFFAOYSA-M 0.000 claims description 2
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 description 24
- 125000000217 alkyl group Chemical group 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 229920000867 polyelectrolyte Polymers 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000004851 dishwashing Methods 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 150000001720 carbohydrates Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical class NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920002257 Plurafac® Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical group OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical group OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 229930182830 galactose Chemical group 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- PSZAEHPBBUYICS-UHFFFAOYSA-N 2-methylidenepropanedioic acid Chemical compound OC(=O)C(=C)C(O)=O PSZAEHPBBUYICS-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical compound CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920013808 TRITON DF-16 Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000008195 galaktosides Chemical class 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MRXVCTWDXRBVLW-UHFFFAOYSA-N prop-2-enoylsulfamic acid Chemical class OS(=O)(=O)NC(=O)C=C MRXVCTWDXRBVLW-UHFFFAOYSA-N 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000021148 sequestering of metal ion Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/34—Organic compounds containing sulfur
- C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
- C11D1/721—End blocked ethers
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the polymer has a weight average molecular weight in a range of from about 1000 to about 50,000.
- the low foaming nonionic surfactant, the hydrotrope and the poly(meth)acrylic acid polymer are mixed together to form a rinse aid dispersion.
- the rinse aid dispersion is maintained in an acidic condition having a pH in a range of from about 2 to about 6. A stable, non phase-separating aqueous rinse aid dispersion is formed.
- the ethoxylated C 6 -C ⁇ 8 fatty alcohols and C 6 -C ⁇ 8 mixed ethoxylated/propoxylated fatty alcohols are highly preferred surfactants for use herein, particularly where water soluble.
- the ethoxylated fatty alcohols are the C ]0 -C ⁇ 8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the 2 -C ⁇ 8 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
- the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
- the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
- Examples of compounds of this type include certain of the commercially-available PluronicTM. surfactants, marketed by BASF.
- condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
- the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
- this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
- Nonionic alkylpolvsaccharide surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
- the low molecular weight acrylic acid containing polymer may be either a homopolymer or a copolymer including the essential acrylic acid or acrylic acid salt monomer units.
- Copolymers may include essentially any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
- the stable rinse aid dispersion does not phase separate upon storage for a reasonable time or under actual use conditions and permits each component to effectively reduce spotting and filming and improve sheeting action without interfering with the foaming and defoaming action of the surfactant.
- the process includes the step of forming a rinse aid dispersion as recited above wherein the rinse aid dispersion is free of a high molecular weight compatibilizing polymer and is free of an additional nonionic surfactant having a cloud point of at least 70 degrees C.
- the rinse aid dispersion is free of a high molecular weight compatibilizing polymer and is free of an additional nonionic surfactant having a cloud point of at least 70 degrees C.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Colloid Chemistry (AREA)
Abstract
A process for compatilization of a low foam nonionic surfactant without the aid of a high molecular weight compatilizing polymer and without requiring an additional nonionic surfactant having a cloud point of at least 70 degrees C to form a stable, non phase-separating aqueous rinse aid dispersion, is provided. The process includes the steps of providing, by weight of the rinse aid dispersion, a low foaming nonionic surfactant in an amount from about 2 % to about 80 %, a hydrotrope in an amount from about 0.5 % to about 20 %, and a poly(meth)acrylic acid polymer in an amount from about 0.1 % to about 15 %. The low foaming nonionic surfactant, the hydrotrope and the poly(meth)acrylic acid polymer are mixed together to form a rinse aid dispersion. The rinse aid dispersion is maintained in an acidic condition having a pH in a range of from about 2 to about 6. A stable, non phase-separating aqueous rinse aid dispersion is thus formed under acidic conditions.
Description
PROCESS FOR FORMING A STABLE NON-PHASE SEPARATING RINSE-AID DISPERSION
TECHNICAL FIELD The present invention relates to an automatic dishwashing machine rinse aid formulation which is useful for promoting the wetting of rinse water as well as preventing hard water precipitation on substrates and thus reducing or eliminating spotting and filming of the dried substrate surface. More particularly, the invention relates to a process for compatibilization of a low foaming nonionic surfactant without the aid of a high molecular weight compatibilizing polymer and without requiring an additional nonionic surfactant having a cloud point of at least 70 degrees C, to form a stable, non phase-separating aqueous rinse aid dispersion.
BACKGROUND OF THE INVENTION
Rinse aids are used in commercial and institutional machine dishwashers and very often, also in household automatic dishwashers. During the rinse cycle, a final rinse of fresh water serves to displace pre-final rinse water and its attendant detergent and soil residues. Rinse aid formulations are aqueous solutions containing a low foam nonionic surfactant. During the rinse cycle, the rinse aid is injected into the final fresh water rinse at a concentration of about 100 ppm to about 500 ppm. The surfactant in the rinse water lowers the surface tension of the rinse water and improves the wetting action of the rinse water on the somewhat hydrophobic substrate surfaces. Improved wetting reduces the tendency of the rinse water to form drops containing dissolved solids on the substrate surface which give rise to spots upon drying. Accordingly, the functions of the surfactant in the rinse aid are to effectively reduce the surface tension during the draining period and to be low foaming so as to avoid traces of foam on the rinsed substrate which result in a residue upon evaporation. While low foam surfactants have improved the wetting of rinse water on substrates, they have not completely eliminated spotting and streaking problems. It is known that the addition of a low molecular weight neutralized polyelectrolyte, such as polyacrylate, to the rinse water can further reduce spotting and filming or streaking.
It is known that poly(meth)acrylic acid polymers are especially useful because they do not contribute to foam formation and do not interfere with the soil defoaming activity of the low foam surfactants. It is also known that a major obstacle to the use of low molecular weight poly(meth)acrylic acid polymers in rinse aids is the incompatibility of these polymers in aqueous rinse aid formulations containing low foam surfactants. Combining such polymers and surfactants
in water results in phase separation. Upon standing for a short period of time the water containing these polymers and surfactants will form two or more layers of different compositions. This phase separation is obviously unsatisfactory since non-uniform addition of the desired components will occur as the formulation is injected into the dishwashing machine. For example, the formulation may contain too little surfactant to provide adequate wetting or too much surfactant, leading to excessive foam.
It is known to combine low molecular weight polyelectrolytes with low foam surfactants in detergent formulations. One reference discloses the desirability for combining polyelectrolytes with low foam surfactants in rinse aid concentrates. However, this reference requires the use of an alkali neutralized high molecular weight polymer to compatibilize the low foam nonionic surfactant with a low molecular weight neutralized poly(meth)acrylic acid in order to form a stable, non-phase separating aqueous rinse aid dispersion.
It is also known to formulate a stable rinse aid composition by mixing a low foam nonionic surfactant, an acrylic acid polymer of molecular weight 1000 to 250,000, and an additional nonionic surfactant having a cloud point of at least 70 degrees C, to serve as a stabilizer.
It is an object of the present invention to have a process for compatibilization of a low foam nonionic surfactant without the aid of a high molecular weight compatibilizing polymer to form a stable, non phase-separating aqueous rinse aid dispersion. It is also an object of the present invention to have a process for compatibilization of a low foam nonionic surfactant without requiring an additional nonionic surfactant having a cloud point of at least 70 degrees C in order to provide a stable non-phase separating rinse aid. It is finally an object of the invention to provide a stable aqueous rinse aid dispersion which reduces spotting and filming while improving sheeting action and drainage.
BACKGROUND ART
U.S. Pat. Nos. 3,563,901 and 4,443,270 disclose hydrotropes such as sodium xylene sulfonate, cumene sulfonate and short chain alkyl sulfates, used for raising the cloud point of low foam surfactants to permit the formulation of stable aqueous concentrates.
U.S. Pat. No. 4,203,858 discloses a low foaming, phosphate-free, dishwashing composition comprising an alkali metal or ammonium carbonate, such as sodium carbonate, a water soluble salt of a polyelectrolyte having a molecular weight of from about 500 and 4,000 and optionally up to 10 weight percent of a foam-suppressing nonionic surfactant. Typical of the polyelectrolytes are acrylic, methacrylic, maleic and itaconic acid polymers. Homopolymers and
copolymers of acrylic and methacrylic acid having a molecular weight ranging from 504 to 1291 are preferred. The '858 patent discloses that the major differences between this composition and prior polyelectrolyte-built dishwashing compositions are the low concentration of polyelectrolyte and the poor metal ion sequestering capability of these polyelectrolytes.
Other references disclosing poly(meth)acrylic acids and their salts in detergent and cleaning applications include U.S. Pat. Nos. 3,671,440; 3,853,981; 3,950,260; 3,933,673; 3,922,230 and 4,521,332. These references do not disclose the desirability of combining polyelectrolytes with low foam surfactants in rinse aid concentrates.
U.S. Patent No. 4,678,596 discloses the use of an alkali neutralized high molecular weight polymer to compatibilize the low foam nonionic surfactant with a low molecular weight neutralized poly(meth)ac_ylic acid in order to form a stable, non-phase separating aqueous rinse aid dispersion. Other related references include European Patent Nos. 245,987 and 308,221. All of these references either (i) require the use of a high molecular weight compatibilizing polymer, or (ii) require an additional nonionic surfactant having a cloud point of at least 70 degrees C as a co- surfactant, in order to provide a stable non-phase separating rinse aid.
SUMMARY OF THE INVENTION
The invention meets the needs above by providing a process for compatibilization of a low foam nonionic surfactant without the aid of a high molecular weight compatibilizing polymer and without requiring an additional nonionic surfactant having a cloud point of at least 70 degrees C, to form a stable, non phase-separating aqueous rinse aid dispersion. The process includes the following steps. A low foaming nonionic surfactant in an amount from about 2% to about 80% by weight of the rinse aid dispersion is provided. A hydrotrope in an amount from about 0.5% to about 20% by weight of the rinse aid dispersion is provided. A poly(meth)acrylic acid polymer in an amount from about 0.1% to about 15% by weight of the rinse aid dispersion is provided. The polymer has a weight average molecular weight in a range of from about 1000 to about 50,000. The low foaming nonionic surfactant, the hydrotrope and the poly(meth)acrylic acid polymer are mixed together to form a rinse aid dispersion. The rinse aid dispersion is maintained in an acidic condition having a pH in a range of from about 2 to about 6. A stable, non phase-separating aqueous rinse aid dispersion is formed.
DETAILED DESCRIPTION OF THE INVENTION
In the preferred embodiment of the present invention, the process for compatibilization of a low foaming nonionic surfactant without the aid of a high molecular weight compatibilizing polymer and without requiring an additional nonionic surfactant having a cloud point of at least 70
degrees C to form a stable, non phase-separating aqueous rinse aid dispersion, includes the steps of providing, by weight % of the rinse aid dispersion, a low foaming nonionic surfactant in an amount from about 2% to about 80%, a hydrotrope in an amount from about 0.5% to about 20%, and a poly(meth)acrylic acid polymer in an amount from about 0.1% to about 15%. The polymer has a weight average molecular weight in a range of from about 1000 to about 50,000. The low foaming nonionic surfactant, the hydrotrope and the poly(meth)acrylic acid polymer are mixed together to form a rinse aid dispersion. The rinse aid dispersion is maintained in an acidic condition having a pH in a range of from about 2 to about 6. Thus, a stable, non phase-separating aqueous rinse aid dispersion is formed under acidic conditions.
Nonionic Surfactant
The nonionic surfactants useful in the process for forming a rinse aid dispersion may be any known low foaming nonionic surfactant used in machine dishwashing applications. Typical suitable nonionic surfactants include the following commercially available materials: Triton R™ CF-10 (an alkylaryl polyether) and Triton DF-16 (a modified polyalkoxylated alcohol) manufactured by Rohm and Haas Company; Plurafac LF404™, which is a mixed linear alcohol alkoxylate; and Pluronic R™ L-62 (a polyoxyethylene-polyoxypropylene block copolymer), both manufactured by BASF Wyandotte Corporation. The rinse aid formulation of the invention may contain one or a mixture of such low foaming nonionic surfactants.
Essentially any nonionic surfactants useful for detersive purposes can be included in the compositions. Exemplary, non-limiting classes of useful nonionic surfactants are listed below, (i) Nonionic polvhvdroxy fatty acid amide surfactant
Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R.CONRiZ wherein: R] is H, Ci -C hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferable C C alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5 -C3ι hydrocarbyl, preferably straight-chain C5 -Ci. alkyl or alkenyl, more preferably straight-chain C9-Cπ alkyl or alkenyl, most preferably straight-chain Cπ-Cπ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. (ii) Nonionic condensates of alkyl phenols
The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use herein. In general, the polyethylene oxide condensates are preferred. These compounds
include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 1 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
(iii) Nonionic ethoxylated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
(iv) Nonionic ethoxylated propoxylated fatty alcohol surfactant
The ethoxylated C6-Cι8 fatty alcohols and C6 -Cι8 mixed ethoxylated/propoxylated fatty alcohols are highly preferred surfactants for use herein, particularly where water soluble. Preferably the ethoxylated fatty alcohols are the C]0 -Cι8 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the 2 -Cι8 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
(v) Nonionic EO/PO condensates with propylene glycol
The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. Examples of compounds of this type include certain of the commercially-available Pluronic™. surfactants, marketed by BASF.
(vi) Nonionic EO condensation products with propylene oxide/ethylene diamine adducts
The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds, marketed by BASF.
(vii) Nonionic alkylpolvsaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The preferred alkylpolyglycosides have the formula:
wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose, (viii) Nonionic fatty acid amide surfactant
Fatty acid amide surfactants suitable for use herein are those having the formula:
O
II
R6— C— N(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, C C4 alkyl, Cι-C4 hydroxyalkyl, and —
(C2 tL 0)x H, where x is in the range of from 1 to 3.
The hydrotrope useful in the present rinse aid dispersion is selected from the group consisting of sodium cumene sulfonate, sodium xylene sulfonate, sodium toluenesulfonate, dioctyl sodium sulfosuccinate, alkyl naphthalene sulfonate and dihexyl sodium sulfosuccinate. Preferably, the hydrotrope is sodium cumene sulfonate.
Poly(meth.acrylic acid polymer
The low molecular weight poly(meth)acrylic acid polymer useful in the present process for forming a stable rinse aid dispersion is selected from the group consisting of polyacrylate homopolymer, polyacrylate copolymer, polyacrylate terpolymer, and mixtures thereof. Preferably, the poly(meth)acrylic acid polymer is a partially neutralized or non-neutralized poly(meth)acrylic acid polymer having a pH in a range of from about 3.0 to about 4.0. In the preferred embodiment,
the polyacrylate copolymer is desirably at least about 75% non-neutralized. Alternatively, the polyacrylate copolymer is non-neutralized. Still alternatively, a neutralized polyacrylate copolymer which is more than 25% neutralized, may also be used but an acid must be added in an amount sufficient to bring the pH value of the resultant dispersion within a range of from about 2 to about 6.
Typically the polyacrylate homopolymer is a polymer of acrylic or methacrylic acid, or a copolymer formed from at least about 50 weight percent acrylic acid and 50 weight percent or less of a suitable copolymerizable comonomer. Suitable comonomers include lower alkyl (C 2 -C4) acrylates; methacrylic acid and lower alkyl(C 2 -C ) methacrylates and amides, such as acrylamido sulfonic acids including 2-acrylamido-2 methylpropane sulfonic acid (AMPS). The poly(meth)acrylic acid is a low molecular weight polymer, or its alkali metal or ammonium salt, having a weight average molecular weight ranging from about 2,000 to about 40,000.
The low molecular weight acrylic acid containing polymer may be either a homopolymer or a copolymer including the essential acrylic acid or acrylic acid salt monomer units. Copolymers may include essentially any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
Acid
When carrying out the process step of adding an acid to the rinse aid dispersion, any acid may be used although organic acids are more desirable and the preferred organic acid is citric acid.
It has been discovered that even in the absence of a compatibilizing high molecular weight polymer, but with the addition of a hydrotrope and in acidic conditions, the stable rinse aid dispersion does not phase separate upon storage for a reasonable time or under actual use conditions and permits each component to effectively reduce spotting and filming and improve sheeting action without interfering with the foaming and defoaming action of the surfactant.
In the preferred embodiment of the process of the present invention, the rinse aid dispersion is maintained in an acidic condition, desirably in a pH of from about 3 to about 6. Preferably, the pH is maintained within a range of from about 3 to about 5.
The process of the present invention is carried out by stirring the desired amount of the surfactant into an aqueous solution of the low molecular weight non-neutralized or only partially neutralized (no more than 25% neutralized) poly(meth)acrylic acid followed by the gradual
addition of the hydrotrope and if necessary, citric acid to bring the dispersion to within the desired pH range.
The rinse aid dispersion may also contain other additives including sequestants such as NTA, EDTA, or sodium citrate and water miscible solvents such as ethanol, isopropanol and propylene glycol. Ethanol is the preferred solvent, present desirably in a range of from about 0.1% to about 10% by weight of the rinse aid dispersion and preferably in a range of from about 2% to about 8% by weight.
In the most preferred embodiment of the present invention, the process includes the step of forming a rinse aid dispersion as recited above wherein the rinse aid dispersion is free of a high molecular weight compatibilizing polymer and is free of an additional nonionic surfactant having a cloud point of at least 70 degrees C. The following examples are intended to illustrate the invention.
EXAMPLE 1 A rinse aid dispersion according to the process of the present invention was made as follows, from the following composition, by weight percent:
Low foam nonionic surfactant 20.0%
Sodium cumene sulfonate hydrotrope 7.0%
Polyacrylate copolymer (20% neutralized) 4.5%
Ethanol 6.0%
Water 62.5%
EXAMPLE 2
Another rinse aid dispersion according to the process of the present invention was made as follows, from the following composition, by weight percent:
Low foam nonionic surfactant 15.0%
Sodium cumene sulfonate hydrotrope 7.0%
Polyacrylate copolymer (20% neutralized) 5.0%
Citric acid 2.5%
Ethanol 6.0%
Water 64.5%
EXAMPLE 3
In another example, a rinse aid dispersion was made according to the process of the present invention by the following procedure: 15.0 grams of a low foaming nonionic surfactant (Plurafac LF 404™), 15.0 grams of a 45% active sodium cumene sulfonate hydrotrope (45% active SCS), 10.0 grams of a 50% active polyacrylate copolymer (Acusol 480™, made by Rohm & Haas), 5.0 grams of a 50% active citric acid, 6.0 grams of ethanol and 49.0 grams of deionized water were added to a beaker and stirred sequentially. The resulting mixture obtained was a clear, single- phase dispersion and was found to be stable, with no phase separation occurring after the resulting mixture was kept undisturbed in a closed container for a period of 2 weeks at a temperature of 50 degrees C.
Accordingly, having thus described the invention in detail, it will be obvious to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.
Claims
1. A process for compatibilization of a low foam nonionic surfactant without the aid of a high molecular weight compatibilizing polymer and without requiring an additional nonionic surfactant having a cloud point of at least 70 degrees C, to form a stable, non-phase separating aqueous rinse aid dispersion, characterized by the steps of: providing a low foaming nonionic surfactant in an amount from 2% to 80% by weight of said rinse aid dispersion; providing a hydrotrope in an amount from 0.5% to 20% by weight of said rinse aid dispersion; providing a poly(meth)acrylic acid polymer in an amount from 0.1% to 15% by weight of said rinse aid dispersion, said polymer having a weight average molecular weight in a range of from 1000 to 50,000; mixing said low foaming nonionic surfactant, said hydrotrope and said poly(meth)acrylic acid polymer to form a rinse aid dispersion; and maintaining said rinse aid dispersion in an acidic condition having a pH in a range of from 2 to 6 to form a stable, non phase-separating aqueous rinse aid dispersion.
2. A process of claim 1, including the step of adding an acid in an amount from 0.1% to 20% by weight of said rinse aid dispersion.
3. A process of claims 1-2, wherein said acid is citric acid.
4. A process of claims 1-3, wherein said acid is in the form of one or more of a non- neutralized polyacrylate polymer, a partially neutralized polyacrylate polymer, said neutralization being no more than 25%, and mixtures thereof.
5. A process of claims 1-4, including the step of adding ethanol in an amount from 0.1% to 10% by weight of said rinse aid dispersion.
6. A process of claims 1-5, wherein said hydrotrope is selected from the group consisting of sodium cumene sulfonate, sodium xylene sulfonate, sodium toluenesulfonate, dioctyl sodium sulfosuccinate, alkyl naphthalene sulfonate and dihexyl sodium sulfosuccinate.
7 A process of claims 1-6, wherein said poly(meth)acrylic acid polymer is selected from the group consisting of polyacrylate homopolymer, polyacrylate copolymer, polyacrylate terpolymer, and mixtures thereof.
8. A process of claims 1-7, wherein said low foaming nonionic surfactant is selected from the group consisting of nonionic ethoxylated alcohols, nonionic ethoxylated fatty alcohols, nonionic propoxylated fatty alcohols, nonionic ethoxylated alcohol condenstaes with propylene glycol, nonionic propoxylated alhohol condensates with propylene glycol, and mixtures thereof.
9. A process of claims 1-8, wherein the step of maintaining said rinse aid dispersion in an acidic conditions includes maintaining said pH of said rinse aid dispersion in a range of from 3 to
5.
10. A process of claims 1-9, wherein said poly(meth)acrylic acid polymer is at least 75% non- neutralized.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000563753A JP2002522592A (en) | 1998-08-03 | 1999-08-03 | Method for producing stable non-phase separated rinse aid dispersion |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US9516098P | 1998-08-03 | 1998-08-03 | |
| US60/095,160 | 1998-08-03 |
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| WO2000008126A1 true WO2000008126A1 (en) | 2000-02-17 |
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| PCT/US1999/017816 WO2000008126A1 (en) | 1998-08-03 | 1999-08-03 | Process for forming a stable non-phase separating rinse-aid dispersion |
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| US9567551B2 (en) | 2012-06-22 | 2017-02-14 | Ecolab Usa Inc. | Solid rinse aid composition and method of making same |
| US9011610B2 (en) | 2012-06-22 | 2015-04-21 | Ecolab Usa Inc. | Solid fast draining/drying rinse aid for high total dissolved solid water conditions |
| BR112016004119B1 (en) * | 2013-08-27 | 2021-06-29 | Ecolab Usa Inc | SOLID RINSING AID COMPOSITION, METHOD FOR PRODUCING THE SAME AND METHOD FOR RINSING A HARD SURFACE IN A CLEANING APPLICATION |
| BR112017004221B1 (en) * | 2014-08-29 | 2022-11-29 | Ecolab Usa Inc | SOLID RINSE AUXILIARY COMPOSITION COMPRISING POLYACRYLIC ACID AND METHOD FOR PRODUCING SUCH COMPOSITION |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4316744A1 (en) * | 1993-05-19 | 1994-11-24 | Huels Chemische Werke Ag | Rinse aids with biodegradable polymers |
| EP0659871A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Rinsing compositions |
| EP0659872A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Rinsing compositions |
| EP0659873A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Rinsing compositions |
| GB2311537A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Rinse composition for dishwashers |
| EP0851021A2 (en) * | 1996-12-28 | 1998-07-01 | Basf Corporation | Improved rinse aid compositions |
-
1999
- 1999-08-03 WO PCT/US1999/017816 patent/WO2000008126A1/en active Application Filing
- 1999-08-03 JP JP2000563753A patent/JP2002522592A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4316744A1 (en) * | 1993-05-19 | 1994-11-24 | Huels Chemische Werke Ag | Rinse aids with biodegradable polymers |
| EP0659871A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Rinsing compositions |
| EP0659872A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Rinsing compositions |
| EP0659873A1 (en) * | 1993-12-23 | 1995-06-28 | The Procter & Gamble Company | Rinsing compositions |
| GB2311537A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Rinse composition for dishwashers |
| EP0851021A2 (en) * | 1996-12-28 | 1998-07-01 | Basf Corporation | Improved rinse aid compositions |
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