WO2003020863A1 - Thickened toilet bowl cleaner - Google Patents
Thickened toilet bowl cleaner Download PDFInfo
- Publication number
- WO2003020863A1 WO2003020863A1 PCT/GB2002/003407 GB0203407W WO03020863A1 WO 2003020863 A1 WO2003020863 A1 WO 2003020863A1 GB 0203407 W GB0203407 W GB 0203407W WO 03020863 A1 WO03020863 A1 WO 03020863A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- hard surface
- surface cleaning
- composition according
- cleaning composition
- Prior art date
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title description 3
- 239000000203 mixture Substances 0.000 claims abstract description 150
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000004140 cleaning Methods 0.000 claims abstract description 49
- 239000000470 constituent Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 33
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims abstract description 31
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 28
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 27
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000230 xanthan gum Substances 0.000 claims abstract description 17
- 235000010493 xanthan gum Nutrition 0.000 claims abstract description 17
- 229920001285 xanthan gum Polymers 0.000 claims abstract description 17
- 229940082509 xanthan gum Drugs 0.000 claims abstract description 17
- 239000002562 thickening agent Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920002678 cellulose Polymers 0.000 claims abstract description 15
- 235000010980 cellulose Nutrition 0.000 claims abstract description 15
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 14
- 229920013820 alkyl cellulose Polymers 0.000 claims abstract description 14
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 14
- 239000004310 lactic acid Substances 0.000 claims abstract description 14
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 14
- 239000001630 malic acid Substances 0.000 claims abstract description 14
- 235000011090 malic acid Nutrition 0.000 claims abstract description 14
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 9
- 239000001361 adipic acid Substances 0.000 claims abstract description 9
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 9
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 235000010338 boric acid Nutrition 0.000 claims abstract description 9
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 9
- 239000011976 maleic acid Substances 0.000 claims abstract description 9
- 239000004334 sorbic acid Substances 0.000 claims abstract description 9
- 235000010199 sorbic acid Nutrition 0.000 claims abstract description 9
- 229940075582 sorbic acid Drugs 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims abstract description 7
- 239000003205 fragrance Substances 0.000 claims description 20
- -1 and Substances 0.000 claims description 19
- 239000002736 nonionic surfactant Substances 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 10
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 9
- 230000000249 desinfective effect Effects 0.000 claims description 9
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 9
- 229940071826 hydroxyethyl cellulose Drugs 0.000 claims description 9
- 239000003755 preservative agent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000003002 pH adjusting agent Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000006174 pH buffer Substances 0.000 claims description 5
- 230000002335 preservative effect Effects 0.000 claims description 5
- 239000004902 Softening Agent Substances 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000000344 soap Substances 0.000 abstract description 15
- 238000009472 formulation Methods 0.000 description 16
- 239000008233 hard water Substances 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 150000003839 salts Chemical group 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 239000012459 cleaning agent Substances 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
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- 235000021317 phosphate Nutrition 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 2
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- 229940071676 hydroxypropylcellulose Drugs 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000007928 solubilization Effects 0.000 description 2
- 238000005063 solubilization Methods 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 230000002110 toxicologic effect Effects 0.000 description 2
- 231100000027 toxicology Toxicity 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- 206010022998 Irritability Diseases 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000702670 Rotavirus Species 0.000 description 1
- 241001138501 Salmonella enterica Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
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- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
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- 159000000003 magnesium salts Chemical class 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
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- 235000011178 triphosphate Nutrition 0.000 description 1
- 125000002264 triphosphate group Chemical class [H]OP(=O)(O[H])OP(=O)(O[H])OP(=O)(O[H])O* 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0013—Liquid compositions with insoluble particles in suspension
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/042—Acids
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
- C11D1/24—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds containing ester or ether groups directly attached to the nucleus
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to improved cleaning compositions which find particular use in hard surface cleaning applications.
- Cleaning compositions are commercially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful with "hard surfaces".
- Hard surfaces are those which are frequently encountered in lavatories such as lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc., as well as countertops, walls, floors, etc.
- lavatories such as lavatory fixtures such as toilets, shower stalls, bathtubs, bidets, sinks, etc.
- various forms of undesirable residues are known to form including hard water stains as well as "soap scum stains”.
- Hard water stains are mineral stains caused by the deposition of salts, such as calcium or magnesium salts, frequently present in hard water
- soap scum stains are residues of fatty acid soaps such as soaps which are based on alkaline salt of low fatty acids, which fatty acids are known to precipitate in hard water due to the presence of metal salts therein leaving an undesirable residue upon such surfaces.
- Various formulations in compositions of cleaning agents have been produced and are known to the art which cleaning agents are generally suited for one type of stain but not necessarily for both classes of stains. For example, it is known to the art that highly acidic cleaning agents comprising strong acids, such as hydrochloric acids, are useful in the removal of hard water stains.
- compositions and formulations are known to be useful upon soap scum stains, however, generally such compositions comprise an organic and/or inorganic acid, one or more synthetic detergents from commonly recognized classes such as those described in U.S. Patent No. 5,061 ,393; U.S. Patent No. 5,008,030; U.S. Patent No. 4,759,867; U.S. Patent No. 5,192,460; U.S. Patent No. 5,039,441.
- the compositions described in these patents are claimed to be effective in the removal of soap scum stains from such hard surfaces and may find further limited use in other classes of stains.
- an aqueous hard surface cleaning composition which comprises an acidic constituent which comprises either citric acid alone or citric acid in combination with an acid selected from the group consisting of sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, and mixtures thereof; 0.001 - 10% by weight of at least one anionic surfactant; 0.001 - 5% by weight of a thickener selected from the group consisting of cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, xanthan gum, and mixtures thereof; 0 - 10% by weight of one or more optional constituents; and the balance to 100% by weight, water
- the acid constituent is a combination of citric acid in combination with an acid selected from the group consisting of sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, and glycolic acid. More preferably, the acid constituent is a combination of citric acid with lactic acid, glycolic acid or malic acid.
- the amount of acid present in the composition should be in an amount such that the pH of the composition is less than 6, preferably less than 4, and more preferably less than 3.
- the thickener is a combination of hydroxy alkyl cellulose and xanthan gum, more preferably a combination of hydroxy ethyl cellulose and xanthan gum.
- the present invention also provides for an aqueous hard surface cleaning composition which comprises an acidic constituent which comprises citric acid in combination with an acid selected from the group consisting of sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, and mixtures thereof; 0.001 - 10% by weight of at least one anionic surfactant; 0.001 - 5% by weight of a thickener selected from the group consisting of cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, xanthan gum, and mixtures thereof; 0 - 10% by weight of one or more optional constituents; and the balance to 100% by weight, water; wherein the aqueous hard surface cleaning composition exhibits a pH of 6.0 or less.
- an acidic constituent which comprises
- the thickener is a combination of hydroxy alkyl cellulose and xanthan gum, more preferably a combination of hydroxy ethyl cellulose and xanthan gum.
- the compositions of the invention may also include one or more further optional constituents such as known art additives.
- such constituents include: low pH stable beads, nonionic surfactants, coloring agents, including dyes and pigment compositions, fragrances, fragrance adjuvants and/or fragrance solubilizers, pH adjusting agents, pH buffers, antioxidants, water softening agents, and preservative compositions.
- compositions according to the invention are preferably acidic in character, exhibiting a pH of less than 6.0, desirably the pH is in the range of from about 5.0 to about 1.0 and yet more desirably is a pH in the range of about 4.0 to about 1.0 and most desirably is a pH in from 3.0 - 1.0.
- improved process for cleaning surfaces especially hard surfaces which includes the step of applying to the surface an effective amount of a stain releasing composition as taught herein to such surface.
- the acidic constituent of the present invention comprises either citric acid alone or citric acid in combination with an acid selected from the group consisting of sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid and mixtures thereof.
- the acid constituent is citric acid in combination with an acid selected from the group consisting of sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, and mixtures thereof. More preferably, the acid constituent is citric acid in combination with lactic acid, glycolic acid or malic acid.
- These acids provide free acidity within the cleaning composition which free acid reacts with the fatty acid metal salts which are comprised within soap scum stains releasing the metal ions and freeing the fatty acid, which facilitates the removal of these undesired stains from hard surfaces. These acids also sequester the resulting free metal ions which are released from the soap scum stains. Also where the acids are selected to feature disinfecting properties, they concomitantly provide anti-microbial activity necessary to disinfect the cleaned surface.
- the acid constituent is desirably present in the formulations such that with the presence of optional ingredients taken into account, the pH of the formulation is at a pH of less than 6, more preferably, the pH is in the range of from about 5.0 to about 1.0 and most desirably is a pH in from 3.0 - 1.0.
- the pH range represents an amount of acid from about 0.5 to about 10% by weight based on the total weight of a composition.
- Compositions of the present invention also includes at least anionic surfactant.
- Suitable anionic surfactants include, for example, alcohol sulfates (e.g. alkali metal or ammonium salts of alcohol sulfates) and sulfonates, alcohol phosphates and phosphonates, alkyl sulfates, alkyl ether sulfates, sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl sulfonates, alpha-olefin sulfonates, beta-alkoxy alkane sulfonates, alkyl ether sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkyl benzene sulfonates, alkyl monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to 5 mo
- Preferred anionics include alkyl sulfates.
- the anionic surfactant is present in the compositions of the present invention in an amount of from about 0.1 to about 10% by weight, more preferably from about 0.5 to about 4% by weight.
- the composition of the present of invention is thickened to a viscosity range of from about 100 to about 2000 centipoise, preferably to a viscosity of from about 750 to about 1000 centipoise, more preferably about 900 centipoise, at room temperature, measured by a Brookfield RVT viscometer, spindle #2, at 60 rpm.
- Thickeners useful in the present invention to achieve this viscosity are selected from the group consisting of cellulose, alkyl celluloses, alkoxy celluloses, hydroxy alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses, carboxy alkyl hydroxy alkyl celluloses, xanthan gum, and mixtures thereof.
- the cellulose derivatives include ethyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose, carboxy methyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxy propyl methyl cellulose, and ethyl hydroxy ethyl cellulose.
- the thickener is a mixture of hydroxy ethyl cellulose and xanthan gum.
- the amount of thickener present in the composition ranges from about 0.1 to about 4% by weight, more preferably from about 0.1 to about 2% by weight.
- the compositions according to the invention are aqueous in nature.
- Water is added to the above constituents in order to provide 100% by weight of the composition.
- the water may be tap water, but is preferably distilled and is most preferably deionized water. If the water is tap water, it is preferably substantially free of any undesirable impurities such as organics or inorganics, especially minerals salts which are present in hard water which may thus interfere with the operation of Constituents A, B, C, as well as any other optional components of the aqueous
- compositions according to the invention may comprise one or more of the following optional components, the total weight of such optional constituents not exceeding about 10% by weight of the total weight of the composition, more preferably not exceeding about 5% by weight and is most preferably less than 5% by weight based on the total weight of the composition according to the invention.
- Non-ionic surfactants of the conventionally known and used variety in this class of cleaning agents may be added in effective amounts, i.e., amounts which are shown to be effective in the cleaning compositions in facilitating the removal of greasy soils. Such greasy soils are to be differentiated from the hard water stains and the soap scum stains described earlier in this specification. However, it is also to be appreciated that the non- ionic surfactants of this optional constituent may be also at least partially effective in the solubilization and removal of soap scum stains.
- nonionic surfactants include known nonionic surfactants which generally consist of a hydrophobic moiety, such as C6-C20 primary or secondary, branched or straight chain monoalcohols, C8-C18 mono- or dialkyphenols, C6-C20 fatty acid amides, and a hydrophilic moiety which consists of alkylene oxide units.
- These nonionic surfactants are for instance alkoxylation products of the above hydrophobic moieties, containing from 2 to 30 moles of alkylene oxide.
- alkylene oxides ethylene-, propylene- and butylene oxides and mixtures thereof are used.
- nonionic surfactants are C9-C11 primary, straight- chain alcohols condensed with 5-9 moles of ethylene oxide, C12-C15 primary straight chain alcohols condensed with from 6-12 moles of ethylene oxide, or with 7-9 moles of a mixture of ethylene oxide and propylene oxide, C11-C15 secondary alcohols condensed with from 3-15 moles of ethylene oxide, and C10-C18 fatty acid diethanolamides, and tertiary amine oxides such as higher alkyl di(lower alkyl or lower substituted alkyl)amine oxides.
- nonionic surfactants include certain alkoxylated linear aliphatic alcohol surfactants which are believed to be the condensation products of a C8 -C10 hydrophilic moiety with alkylene oxides, especially polyethylene oxide and or polypropylene oxide moieties.
- alkoxylated linear alcohol surfactants are presently commercially available under the tradename PolyTergent® (BASF, Mt. Olive, NJ).
- Such nonionic surfactants are known to the art, and are more particularly described in McCutcheon's Detergents and Emulsifiers.
- fragrances may be added in any conventional manner, admixing to a composition or blending with other constituents used to form a composition, in amounts which are found to be useful to enhance or impart the desired scent characteristic to the composition, and/or to cleaning compositions formed therefrom.
- compositions which include a fragrance it is frequently desirable to include a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base.
- a fragrance solubilizer which assists in the dispersion, solution or mixing of the fragrance constituent in an aqueous base.
- These include known art compounds, including condensates of 2 to 30 moles of ethylene oxide with sorbitan mono- and tri-CI0-C20 alkanoic acid esters having a HLB of 8 to are also known as nonionic surfactants.
- Suitable surfactants include water soluble nonionic surfactants of which many are commercially known and by way of non-limiting example include the primary aliphatic alcohol ethoxylates, secondary aliphatic alcohol ethoxylates, alkylphenol ethoxylates and ethylene-oxide-propylene oxide condensates on primary alkanols, and condensates of ethylene oxide with sorbitan fatty acid esters.
- This fragrance solubilizer component is added in minor amounts, particularly amount which are found effective in aiding in the solubilization of the fragrance component, but not in any significantly greater proportion, such that it would be considered as a detergent constituent.
- Such minor amounts recited herein are generally up to about 0.5% by weight of the total composition but is more generally an amount of about 0.1% by weight and less, and preferably is present in amounts of about 0.05% by weight and less.
- constituents are one or more coloring agents which find use in modifying the appearance of the compositions and enhance their appearance from the perspective of a consumer or other end user.
- Known coloring agents may be incorporated in the compositions in any effective amount to improve or impart to compositions a desired appearance or color.
- Such a coloring agent or coloring agents may be added in a conventional fashion, i.e., admixing to a composition or blending with other constituents used to form a composition.
- pH adjusting agents including minor amounts of mineral acids, basic compositions, and organic acids
- An exemplary composition includes citric acid, such as is available in an anhydrous salt form of an alkali metal citric acid.
- citric acid such as is available in an anhydrous salt form of an alkali metal citric acid.
- the addition of an effective amount such a pH adjusting agent is useful in establishing a targeted pH range for compositions according to the invention.
- the addition of an effective amount of a pH buffering composition so to maintain the pH of the inventive compositions may also be added. While the composition of the invention generally does not require a pH buffering composition, the use of such a pH buffering composition may provide the benefit of hard water ion sequestration.
- pH buffer compounds examples include the alkali metal phosphates, polyphospates, pyrophosphates, triphosphates, tetraphosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures of the same.
- Certain salts such as the alkaline earth phosphates, carbonates, hydroxides, can also function as buffers. It may also be suitable to use buffers such materials as aluminosilicates (zeolites), borates, aluminates and certain organic materials such as gluconates, succinates, maleates, citrates, and their alkali metal salts.
- Such buffers keep the pH ranges of the compositions of the present invention within acceptable limits. Others, not particularly elucidated here may also be used.
- citric acid such as is available in an anhydrous salt form of an alkali metal citric acid is added as it is readily commercially available, and effective.
- the addition of such a buffering agent is desirable in certain cases wherein long term, i.e., prolonged storage, is to be anticipated for a composition, as well as insuring the safe handling of said aqueous composition.
- Preservatives may also be added in minor amounts in the formulations according to the invention which preservative compositions do not include a disinfectant component.
- Known art compositions may be used. Examples of such preservatives compounds include those which are presently commercially available under the tradenames KathonX CG/ICP (Rohm & Haas, Philadelphia PA), SuttocideX A (Sutton Labs, Chatham NJ) as well as MidtectX TFP (Tri-K Co., Emerson, NJ).
- Such preservatives are generally added in only minor amounts, i.e., amounts of about 0.5% by weight of the total composition, more generally an amount of about 0.1% by weight and less, and preferably is present in amounts of about 0.05% by weight and less.
- Another optional ingredient are low pH stable beads. These beads provide a visual effect and can provide the user of the composition with an indicatin that the composition has been evenly applied to the surface to be treated.
- One example of these beads is calcium alginate from geniaLabs, Germany. These beads can be in a variety of colors.
- compositions described in this specification include particularly: good removal of hard water stains, good removal of soap scum stains, relatively low toxicity, as well as ease in handling of the composition due to its readily pourable or pumpable characteristic, and when needed, disinfection. Further, when one or more of the optional constituents is added, i.e., fragrance, bead, and coloring agents, the esthetic and consumer appeal of the product is favorably improved.
- compositions according to the invention are useful in the cleaning and/or disinfecting of hard surfaces, having deposited soil thereon.
- cleaning and disinfecting of such surfaces comprises the step of applying a stain releasing and disinfecting effective amount of a composition as taught herein to such a stained surface.
- the compositions are optionally but desirably wiped, scrubbed or otherwise physically contacted with the hard surface, and further optionally, may be subsequently rinsed from the surface.
- the hard surface cleaner composition provided according to the invention can be desirably provided as a ready to use product in a pourable or manually squeezed bottle (deformable bottle).
- squeezed bottles include United States Design Patent Nos. D406.530, D406.531 , D410,847, and D383.678
- the consumer generally applies an effective amount of the cleaning composition and within a few moments thereafter, wipes off the treated area with a rag, towel, brush or sponge, usually a disposable paper towel or sponge.
- the cleaning composition according to the invention may be left on the stained area until it has effectively loosened the stain deposits after which it may then be wiped off, rinsed off, or otherwise removed. For particularly heavy deposits of such undesired stains, multiple applications may also be used.
- Exemplary formulations illustrating certain preferred embodiments of the inventive compositions and described in more detail in Table I below were formulated generally in accordance with the following protocol.
- a measured amount of water was provided after which the constituents were added in the following sequence: thickening agent, surfactant, acid and lastly the coloring and fragrance constituents.
- Mixing which generally lasted from 5 minutes to 120 minutes was maintained until the particular formulation appeared to be homogeneous.
- the exemplary compositions were readily pourable, and retained well mixed characteristics (i.e., stable mixtures) upon standing for extended periods, even in excess of 120 days.
- the constituents may be added in any order.
- Cellosize is hydroxyethyl cellulose from Union Carbide, Division of Dow Chemical.
- Kelzan is Xanthan gum from Kelco.
- Stepanol WAC is sodium lauryl sulfate from Stepan Company.
- Formulations of the present invention are expected to have good cleaning efficacy.
- Ex. 10 was tested in a limescale removal test. Therein, marble tiles, measuring 5 3/4" x 2 7/8" x 3/8", were washed and dried for 1 hour @ 80C. The tiles were then weighed, immersed in 900 mis of test formula for 10 seconds, removed and allowed to sit for 10 minutes. The tiles were then rinsed thoroughly, towel dried and dried for another hour @ 80C. The tiles were then cooled completely and reweighed.
- Formulations of the present invention are expected to have good antimicrobial efficacy.
- Ex. 10 was tested against Rotavirus at 30 sec and 10 minute contact times under current US EPA guidelines.
- the tox level was 3.5 and Virus recovered was 6.67.
- a 3.17 log reduction was recorded with no virus detected above tox. The same results were recorded for the sample tested at 10 minute contact time.
- Ex. 10 was tested under the AOAC Use Dilution Test against four standard test organisms, (Staphylococcus aureus, Pseudomonas aeruginosa, Salmonella choleraesuis, and Eschenchia coli). Test was performed at a 1 :25 dilution. The results are shown in the table below.
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Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
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MXPA04001760A MXPA04001760A (en) | 2001-08-31 | 2002-07-25 | Thickened toilet bowl cleaner. |
EP02751326A EP1423497B1 (en) | 2001-08-31 | 2002-07-25 | Thickened toilet bowl cleaner |
PL367726A PL200532B1 (en) | 2001-08-31 | 2002-07-25 | Thickened toilet bowl cleaner |
DE60222441T DE60222441T2 (en) | 2001-08-31 | 2002-07-25 | DILUTED TOILET BASIN CLEANER |
CA002452962A CA2452962C (en) | 2001-08-31 | 2002-07-25 | Thickened toilet bowl cleaner |
AU2002361849A AU2002361849B2 (en) | 2001-08-31 | 2002-07-25 | Thickened toilet bowl cleaner |
BR0212164-6A BR0212164A (en) | 2001-08-31 | 2002-07-25 | Thickened toilet cleaner |
US10/789,018 US7196046B2 (en) | 2001-08-31 | 2004-02-27 | Hard surface cleaner comprising a suspension of alginate beads |
US10/789,075 US7119055B2 (en) | 2001-08-31 | 2004-02-27 | Hard surface cleaners comprising a thickening gum mixture |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB0121111.9 | 2001-08-31 | ||
GB0121111A GB2379223A (en) | 2001-08-31 | 2001-08-31 | Cleaning composition comprising citric acid |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/GB2004/000589 Continuation-In-Part WO2004074420A1 (en) | 2001-08-31 | 2004-02-17 | Hard surface cleaning compositions |
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PCT/GB2004/000589 Continuation-In-Part WO2004074420A1 (en) | 2001-08-31 | 2004-02-17 | Hard surface cleaning compositions |
US10/789,075 Continuation-In-Part US7119055B2 (en) | 2001-08-31 | 2004-02-27 | Hard surface cleaners comprising a thickening gum mixture |
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WO2003020863A1 true WO2003020863A1 (en) | 2003-03-13 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/GB2002/003407 WO2003020863A1 (en) | 2001-08-31 | 2002-07-25 | Thickened toilet bowl cleaner |
Country Status (15)
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US (1) | US7196046B2 (en) |
EP (1) | EP1423497B1 (en) |
CN (1) | CN100487099C (en) |
AR (1) | AR037499A1 (en) |
AT (1) | ATE373075T1 (en) |
AU (1) | AU2002361849B2 (en) |
BR (1) | BR0212164A (en) |
CA (1) | CA2452962C (en) |
DE (1) | DE60222441T2 (en) |
ES (1) | ES2289127T3 (en) |
GB (1) | GB2379223A (en) |
MX (1) | MXPA04001760A (en) |
PL (1) | PL200532B1 (en) |
WO (1) | WO2003020863A1 (en) |
ZA (1) | ZA200309804B (en) |
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US7119055B2 (en) | 2001-08-31 | 2006-10-10 | Reckitt Benckiser Inc. | Hard surface cleaners comprising a thickening gum mixture |
US7196046B2 (en) | 2001-08-31 | 2007-03-27 | Reckitt Benckiser Inc. | Hard surface cleaner comprising a suspension of alginate beads |
US7256167B2 (en) | 2001-08-31 | 2007-08-14 | Reckitt Benckiser Inc. | Hard surface cleaner comprising suspended particles and oxidizing agent |
US7291586B2 (en) | 2003-02-22 | 2007-11-06 | Reckitt Benckiser Inc. | Hard surface cleaning compositions comprising suspended alginate inclusions |
US7186676B2 (en) | 2003-02-22 | 2007-03-06 | Reckitt Benckiser Inc. | Hard surface cleaning compositions comprising alginate materials and xanthan gum |
CN100381549C (en) * | 2004-04-27 | 2008-04-16 | 天津科技大学 | Cleaning agent for flush toilet |
WO2006097666A1 (en) * | 2005-03-15 | 2006-09-21 | Reckitt Benckiser Inc. | Improvements in or relating to cleaning compositions |
EP2031048B1 (en) | 2007-08-31 | 2015-09-16 | The Procter and Gamble Company | Liquid acidic hard surface cleaning composition |
EP2031048B2 (en) † | 2007-08-31 | 2019-05-01 | The Procter and Gamble Company | Liquid acidic hard surface cleaning composition |
EP2206766B1 (en) | 2008-12-23 | 2015-11-11 | The Procter and Gamble Company | Liquid acidic hard surface cleaning composition |
WO2011026718A1 (en) * | 2009-09-02 | 2011-03-10 | Unilever Nv | Composition and process for treatment of a fabric |
AU2010291392B2 (en) * | 2009-09-02 | 2013-07-11 | Unilever Plc | Composition and process for treatment of a fabric |
EA022063B1 (en) * | 2009-09-02 | 2015-10-30 | Юнилевер Нв | Liquid composition for treatment of a fabric, process for preparation thereof and method of washing a fabric using the same |
EP3327107A1 (en) | 2016-11-25 | 2018-05-30 | Henkel AG & Co. KGaA | Hard surface cleaner comprising abrasive particles |
WO2018095810A1 (en) | 2016-11-25 | 2018-05-31 | Henkel Ag & Co. Kgaa | Hard surface cleaner comprising abrasive particles |
Also Published As
Publication number | Publication date |
---|---|
EP1423497B1 (en) | 2007-09-12 |
ZA200309804B (en) | 2004-12-20 |
GB0121111D0 (en) | 2001-10-24 |
PL367726A1 (en) | 2005-03-07 |
ES2289127T3 (en) | 2008-02-01 |
US20040186037A1 (en) | 2004-09-23 |
US7196046B2 (en) | 2007-03-27 |
ATE373075T1 (en) | 2007-09-15 |
GB2379223A (en) | 2003-03-05 |
MXPA04001760A (en) | 2004-05-31 |
CN100487099C (en) | 2009-05-13 |
CN1539008A (en) | 2004-10-20 |
DE60222441T2 (en) | 2008-06-12 |
PL200532B1 (en) | 2009-01-30 |
AR037499A1 (en) | 2004-11-17 |
DE60222441D1 (en) | 2007-10-25 |
CA2452962C (en) | 2009-11-03 |
EP1423497A1 (en) | 2004-06-02 |
CA2452962A1 (en) | 2003-03-13 |
BR0212164A (en) | 2004-07-13 |
AU2002361849B2 (en) | 2007-11-15 |
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