EP0812904A2 - Cleaning compositions - Google Patents
Cleaning compositions Download PDFInfo
- Publication number
- EP0812904A2 EP0812904A2 EP96870088A EP96870088A EP0812904A2 EP 0812904 A2 EP0812904 A2 EP 0812904A2 EP 96870088 A EP96870088 A EP 96870088A EP 96870088 A EP96870088 A EP 96870088A EP 0812904 A2 EP0812904 A2 EP 0812904A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- surfactant
- liquid cleaning
- weight
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 126
- 238000004140 cleaning Methods 0.000 title claims abstract description 52
- 239000004094 surface-active agent Substances 0.000 claims abstract description 80
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 229920005646 polycarboxylate Polymers 0.000 claims abstract description 22
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 24
- -1 alkyl sulphates Chemical class 0.000 claims description 23
- 230000002209 hydrophobic effect Effects 0.000 claims description 14
- 239000007844 bleaching agent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 6
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 229920006037 cross link polymer Polymers 0.000 claims 1
- 150000001412 amines Chemical class 0.000 description 16
- 235000014113 dietary fatty acids Nutrition 0.000 description 14
- 239000000194 fatty acid Substances 0.000 description 14
- 229930195729 fatty acid Natural products 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 6
- 239000003518 caustics Substances 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000005708 Sodium hypochlorite Substances 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- ILUJQPXNXACGAN-UHFFFAOYSA-N ortho-methoxybenzoic acid Natural products COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910003202 NH4 Inorganic materials 0.000 description 2
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- UZZYXUGECOQHPU-UHFFFAOYSA-N octyl hydrogen sulfate Chemical compound CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- MCFGYHKPYCQXJH-UHFFFAOYSA-N 2-hydroxy-3,5-dimethylbenzoic acid Chemical compound CC1=CC(C)=C(O)C(C(O)=O)=C1 MCFGYHKPYCQXJH-UHFFFAOYSA-N 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- AFPHTEQTJZKQAQ-UHFFFAOYSA-N 3-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC([N+]([O-])=O)=C1 AFPHTEQTJZKQAQ-UHFFFAOYSA-N 0.000 description 1
- TUXYZHVUPGXXQG-UHFFFAOYSA-N 4-bromobenzoic acid Chemical compound OC(=O)C1=CC=C(Br)C=C1 TUXYZHVUPGXXQG-UHFFFAOYSA-N 0.000 description 1
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 1
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000010480 babassu oil Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0043—For use with aerosol devices
-
- 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
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/37—Mixtures of compounds all of which are anionic
-
- 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
- C11D1/75—Amino oxides
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/90—Betaines
-
- 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
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3749—Polyolefins; Halogenated polyolefins; Natural or synthetic rubber; Polyarylolefins or halogenated polyarylolefins
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/395—Bleaching agents
- C11D3/3956—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
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic 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
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- 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
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/29—Sulfates of polyoxyalkylene ethers
Definitions
- the present invention relates to cleaning compositions, especially to thickened liquid cleaning compositions exhibiting effective cleaning performance and viscosity.
- Efficient cleaning performance and viscosity of the cleaning compositions are two requirements which drive consumer acceptance of cleaning products. Indeed, viscosity enables cleaning compositions to remain long enough on the surface to provide an effective cleaning action. Such a requirement is of particular utility in cleaning compositions intended to be applied "as is” to non-horizontal structural surfaces such as walls, windows and sanitary fittings such as sinks, baths, showers, wash basins and WCs. More particularly, viscosities of 10 cps to 4000 cps are suitable. On the other hand, effective cleaning is important, especially on greasy and oily soils and/or where the composition is thereafter diluted.
- the Applicant has now found that the combination of a surfactant system, comprising a short chain surfactant and a long chain surfactant, and a polycarboxylate polymer in a liquid cleaning composition fulfills such a need.
- Another advantage of the present invention is that it provides stable compositions, especially in presence of a bleach component.
- Another advantage of the present invention is that it provides liquid cleaning compositions which are safe to the user when said composition is sprayed onto the surface to be treated.
- the present invention is a liquid cleaning composition comprising:
- the present invention further encompasses the use of a polycarboxylate polymer in a liquid cleaning composition, in a sprayed form, for preventing or reducing inhalation of said composition by the user as said composition is sprayed.
- a surfactant system is an essential feature of the invention.
- the surfactant system comprises a short chain surfactant and a long chain surfactant. All surfactants have in common that they comprise a hydrophobic portion and a hydrophilic portion.
- the short chain and the long chain surfactant are present in a weight ratio of said short chain to said long chain surfactant of less than 4:1, preferably less than 2:1, more preferably less than or equal to 1:1.
- short chain surfactant it is meant herein surfactants which comprise a C 6 -C 10 alkyl chain as their hydrophobic portion. Such short chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain.
- Suitable short chain surfactants for use herein are selected from the group consisting of C 6 -C 10 alkyl sulphates (C 6 -C 10 SO 4 ), alkyl ether sulphates (C 6 -C 10 (OCH 2 CH 2 )eSO 4 ), alkyl sulphonates (C 6 -C 10 SO 3 ), alkyl succinates (C 6 -C 10 OOCCH 2 CH 2 COOZ), alkyl carboxylates (C 6 -C 10 COOM), alkyl ether carboxylates (C 6 -C 10 (OCH 2 CH 2 ) e COOM), alkyl sarcosinates (C 6 -C 10 CON (CH 3 )R), alkyl sulpho
- e is from 0 to 20
- f is from 1 to 16, preferably 1 to 5
- Z is M or R
- M is H or any counterion such as those known in the art, including Na, K, Li, NH 4 , amine, R and R' are C 1 -C 5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably C 1 -C 3 , most preferably methyl.
- the compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof, depending on the end use envisioned.
- Preferred short chain surfactants for use herein are hypochlorite compatible, e.g surfactants which contain no functionalities (such as ether linkages, unsaturation, some aromatic structures or hydroxyl groups) which are susceptible of oxidation by the hypochlorite bleach. More preferably, the short chain surfactants for use herein are anionic short chains. Preferably, the anionic short chain surfactants comprise a C 7 -C 9 alkyl chain as their hydrophobic portion. Preferred anionic short chain surfactants among the one above disclosed are the alkyl sulphates and alkyl sulphonates.
- anionic short chain surfactants are selected from the C 7 -C 9 alkyl sulphates, C 7 -C 9 alkyl sulphonates and mixtures thereof.
- a most preferred short chain surfactants for use herein is octyl sulphate.
- Such short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralisation, but said anionic short chain surfactants are more conveniently commercially available, for instance from Rhone Poulenc under the trade name Rhodapon® OLS, from Witco under the trade name Witconate ®, or from Albright and Wilson under the trade name Empimin®.
- a preferred commercially available compound is Empimin® LV33.
- compositions comprise from 0.1% to 5%, preferably 0.3% to 4% by weight, more preferably from 0.6% to 2.5% by weight, of short chain surfactants.
- Long chain surfactants for use herein are those which comprise a C 11 -C 20 alkyl chain as their hydrophobic portion. Suitable long chain surfactants are selected from C 11 -C 20 alkyl sulphates (C 11 -C 20 SO 4 ), alkyl ether sulphates (C 11 -C 20 (OCH 2 CH 2 )eSO 4 ), alkyl sulphonates (C 11 -C 20 SO 3 ), alkyl succinates (C 11 -C 20 OOCCH 2 CH 2 COOZ), alkyl carboxylates (C 11 -C 20 COOM), alkyl ether carboxylates (C 11 -C 20 (OCH 2 CH 2 ) e COOM), alkyl sarcosinates (C 11 -C 20 CON(CH 3 )R), alkyl sulpho succinates (C 11 -C 20 OOCCH(SO 3 M)CH 2 COOZ), capped alkyl ethoxylates (C 11
- e is from 0 to 20
- f is from 1 to 16, preferably 1 to 5
- Z is M or R
- M is H or any counterion such as those known in the art, including Na, K, Li, NH 4 , amine, R and R' are C 1 -C 5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably C 1 -C 3 , most preferably methyl.
- the compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof, depending on the end use envisioned.
- Preferred long chain surfactants for use herein are hypochlorite compatible, e.g surfactants which contain no functionalities (such as ether linkages, unsaturation, some aromatic structures or hydroxyl groups) which are susceptible of oxidation by the hypochlorite bleach. More preferably, the long chain surfactants for use herein are anionic long chains. Preferably, the long chain anionic surfactants for use herein comprise a C 11 -C 18 , more preferably a C 12 -C 14 alkyl chain as their hydrophobic portion. A preferred anionic long chain surfactant among the one above disclosed is alkyl sulphate. A most preferred is the C 12 -C 14 alkyl sulphate. Preferred alkyl sulphates for use herein are selected from sodium tallow alkyl sulphate, sodium lauryl sulphate and mixtures thereof. A preferred commercially available compound is Empicol ® 0298/F from Albright and Wilson.
- compositions according to the present invention comprise from 0.1% to 5%, preferably from 1% to 3% by weight of the total compositions of said long chain surfactants.
- amine oxide is used as a long chain surfactant
- the level of said long chain amine oxide surfactant is present at a level of from 0.1% to 2% by weight of the composition. Above such levels, the composition may tend to be too viscous to be easily usable.
- long chain amine oxide surfactants in the cleaning composition of the invention which provide effective cleaning and viscosity performance is especially surprising as the Applicant has found that in the absence of a polycarboxylate polymer, a problem encountered with the use of such amine oxide is that the activity of the short chain surfactant is hindered by said long chain amine oxide surfactant, so that the cleaning performance of the short chain surfactant does not act to its best performance.
- the amine oxide surfactant especially long chain amine oxides, and the short chain surfactant are trapped in the cylindrical micellar system, formed by the amine oxide surfactants, that generates the viscosity.
- the short chain surfactant is not completely free to move and loses part of its cleaning power.
- polycarboxylate polymer Another essential component of the invention is a polycarboxylate polymer.
- the polycarboxylate polymers contrary to cellulosic polymers such as guar gum or xanthum gum, are more stable in presence of hypochlorite bleach, provide better thickening efficiency and also a higher yield value. Such high yield value is of particular utility where the composition is packaged in a spray-type dispenser.
- the polymers for use herein preferably have a molecular weight of from 500.000 to 4.500.000, preferably from 1.000.000 to 4.000.000. Most preferred polymers for use herein contain from 0.5% to 4% by weight of a cross-linking agent, wherein the cross-linking agent tends to interconnect linear strands of the polymers to form the resulting cross-linked products.
- Suitable cross-linking agents include the polyalkenyl polyethers.
- Polycarboxylate polymers include the polyacrylate polymers. Other monomers besides acrylic acid can be used to form these polymers including such monomers as maleic anhydride which acts as a source of additional carboxylic groups.
- the molecular weight per carboxylate group of monomers containing a carboxylate group typically varies from 25 to 200, preferably from 50 to 150, more preferably from 75 to 125. Further other monomers may be present in the monomeric mixture, if desired, such as ethylene and propylene which act as diluents.
- Preferred polycarboxylate polymers for use herein are the polyacrylate polymers.
- Commercially available polymers of the polyacrylate type include those sold under the trade names Carbopol®, Acrysol® ICS-1, Polygel®, and Sokalan®.
- Most preferred polyacrylate polymers are the copolymer of acrylic acid and alkyl (C 5 -C 10 ) acrylate, commercially available under the tradename Carbopol® 1623, Carbopol® 695 from BF Goodrich, and copolymer of acrylic acid and maleic anhydride, commercially available under the tradename Polygel® DB from 3V Chemical company.
- the polymer is present in an amount of from 0.1% to 4% by weight, preferably 0.3 to 4% by weight, more preferably 0.4% to 1.5% by weight of the composition.
- the present polymer performs dual functions when it is incorporated in the composition herein, said functions being not only to thicken but also to support the cleaning performance of the surfactant system.
- compositions according to the present invention may comprise a number of optional ingredients such as bleaching agents, fatty acids, radical scavengers, antimicrobial compounds, builders, chelants, buffers, bactericides, solvents, enzymes, hydrotropes, colorants, bleach activators, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
- optional ingredients such as bleaching agents, fatty acids, radical scavengers, antimicrobial compounds, builders, chelants, buffers, bactericides, solvents, enzymes, hydrotropes, colorants, bleach activators, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
- a highly preferred optional ingredient according to the present invention is a hypochlorite bleaching agent, preferably an alkali metal hypochlorite.
- the compositions of the invention are stable in presence of this bleaching agent.
- alkali metal hypochlorites are preferred other hypochlorite compounds may also be used herein and can be selected from calcium and magnesium hypochlorite.
- a preferred alkali metal hypochlorite for use herein is sodium hypochlorite.
- Compositions according to the present invention comprise said hypochlorite bleaching agents such that the content of active chlorine in the compositions is from 0.1% to 4%, preferably from 1% to 2% by weight.
- Another optional component of the present invention is an alkali metal salt of a C 8 -C 18 fatty acid.
- Said fatty acids are used as suds suppressors.
- Suitable fatty acids for use herein can be any C 8 -C 18 fatty acid, preferably fully saturated, preferably a sodium, potassium or lithium salt, more preferably the sodium salt.
- Suitable fatty acids may be selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and mixtures of fatty acids suitably hardened, derived from natural sources such as tallow, coconut oil, ground oil and babassu oil.
- Compositions according to the present invention comprise from 0.1% to 2%, preferably less than 0.6% by weight of the composition of fatty acids.
- a further optional component of the present invention is a radical scavenger.
- Said radical scavengers are used as stabilisers.
- a suitable radical scavenger for use herein is the aromatic molecule containing a carboxylic group ring substitution.
- Suitable examples of radical scavengers for use herein include the meta and para-chlorobenzoic acid, benzoic acid, meta- ortho- and para-methoxybenzoic acid, meta nitrobenzoic acid, para bromobenzoic acid, salicylic acid, 5-sulphosalicylic acid, 3,5-dimethyl salicylic acid and paratoluic acid. Of the above materials, ortho-methoxybenzoic acid is preferred.
- Compositions according to the present invention comprise from 0.01% to 1.5% by weight, preferably from 0.1% to 0.8% by weight and more preferably from 0.2% to 0.5% by weight of the composition of radical scavengers.
- compositions according to the present invention are preferably greater than 10, preferably greater than 11, more preferably greater than 12. This is achieved by the addition of from 0.4% to 2% of a caustic alkali. Suitable caustic alkalis for use herein include sodium and potassium hydroxide.
- compositions according to the present invention comprising hypochlorite preferably have a pH greater than 12 for hypochlorite stability.
- compositions according to the present invention are preferably aqueous and preferably comprise from 80% to 95%, more preferably from 85% to 90% of water.
- compositions according to the present invention are prepared by methods well known in the art such as the methods described in GB 1 329 086 with the exception of the polymer being pre-dispersed in an acidic water solution of pH 3 and then neutralised up to pH 7 before starting adding the other components.
- the compositions according to the present invention can then be prepared by mixing all of the ingredients in a non-metallic apparatus at room temperature or in warm water. If fatty acid is used, it is melted before being added to the mixture.
- the surfactant blend is first prepared by adding the short chain surfactant to the long chain surfactants. Other optionals such as perfume and the alkali metal hypochlorite are then added whilst stirring. Colourants, if present, are added after all the other ingredients have been mixed.
- compositions according to the present invention preferably have a viscosity of from 10 cps to 4000 cps, more preferably from 50 cps to 2000 cps, most preferably from 150 cps to 1000 cps measured with a Carrimed Rheometer at a temperature of 25°C and a shear rate of 15-35 s -1 .
- the viscosity of said spraying compositions is preferably of from 15 cps to 40 cps.
- compositions of the present invention may be used for a variety of cleaning purposes such as cleaning hard surfaces whereby said compositions thickened nature results in longer adhesion to the surface than non-thickened compositions.
- hard surface it is meant herein any surface like bathroom, sanitary fittings such as sinks, showers, wash basins and WCs, kitchen, sinks, cooker tops, table tops, refrigerators, walls, windows and the like.
- compositions herein may be packaged in a variety of suitable detergent packaging known to those skilled in the art.
- the liquid compositions herein may desirably be packaged in manually operated spray dispensing containers, which are usually made of synthetic organic polymeric plastic materials.
- the present invention also encompasses liquid cleaning compositions of the invention packaged in a spray dispenser, preferably in a trigger spray dispenser.
- said spray-type dispensers allow to uniformly apply to a relatively large area of a surface to be cleaned the liquid cleaning compositions suitable for use according to the present invention; thereby contributing to the cleaning properties of said compositions.
- Such spray-type dispensers are particularly suitable to clean vertical surfaces.
- the cleaning composition is as defined hereinbefore. Accordingly, the use of a polycarboxylate polymer in a liquid cleaning composition is provided, said composition being in a sprayed form, for preventing or reducing inhalation of said composition by the user as said composition is sprayed.
- the liquid cleaning composition is as defined hereinbefore.
- Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al. and US-4,646,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500® or T 8900® commercially available from Continental Spray International or T 8100® commercially available from Canyon, Northern Ireland. In such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated.
- the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
- an obstacle e.g. a grid or a cone or the like
- the present invention further encompasses a method for cleaning a hard surface by applying on said surface an effective amount of a composition of the invention.
- the said composition may be applied in its neat form or after having been diluted with water.
- Preferably said composition is diluted up to 200 times its weight of water, preferably into 50 to 150 times its weight of water and more preferably 75 to 95, before it is applied to said surface.
- the composition When the composition is diluted prior to use (to reach a total active level in the order of 1.2%), the composition will still advantageously provide effective cleaning performance.
- compositions were prepared: Components A B C D E F G 24 AS 1.0 1.0 2.0 2.0 1.0 1.0 1.0 C8 AS 1.0 1.0 1.0 2.0 2.0 2.0 2.0 Polymer 0.8 0.8 1.2 1.0 1.0 1.5 0.3 Caustic - 1.4 1.4 1.5 1.4 - 1.0 Sodium hypochlorite - 1.4 1.0 1.4 1.4 1.4 Fatty acid - 0.2 0.3 0.3 0.2 - - Water and minors up to 100
- compositions are in accordance with the invention H I J K L C8 AS 1.0 1.0 2.0 2.0 2.0 24AE3S 2.0 2.0 1.0 1.0 1.0 1.0 1.0 Polymer 0.8 1.0 1.2 1.0 0.4 nonionic 0.5 0.5 1.0 1.0 0.5 fatty acid 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Caustic 1.4 1.4 1.4 1.0 sodium hypochlorite 1.4 1.6 1.6 1.4 1.4 Water and minors up to 100
- compositions are in accordance with the invention M N O amine oxide 0.4 0.4 0.8 24 AS - 2.0 2.0 C8 AS 2.0 2.0 2.0 Polymer 0.8 0.8 0.8 Caustic 1.4 1.4 1.4 Sodium hypochlorite 1.4 1.4 1.4 Water and minors up to 100
- compositions were made and packaged in a spray-trigger dispenser T 8500®: G L P C8 AS 2.0 2.0 3.0 24AS 1.0 - 0.3 24AE3S - 1.0 - Polymer 0.3 0.4 0.4 nonionic - 0.5 - fatty acid - 0.3 - Caustic 1.0 1.0 1.0 sodium hypochlorite 1.4 1.4 1.4 Water and minors up to 100
- compositions, in a sprayed form exhibited reduced inhalation of said composition by the user as said composition was sprayed as compared to compositions, in a sprayed form, which did not contain the polycarboxylate polymer.
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Abstract
Description
- The present invention relates to cleaning compositions, especially to thickened liquid cleaning compositions exhibiting effective cleaning performance and viscosity.
- Efficient cleaning performance and viscosity of the cleaning compositions are two requirements which drive consumer acceptance of cleaning products. Indeed, viscosity enables cleaning compositions to remain long enough on the surface to provide an effective cleaning action. Such a requirement is of particular utility in cleaning compositions intended to be applied "as is" to non-horizontal structural surfaces such as walls, windows and sanitary fittings such as sinks, baths, showers, wash basins and WCs. More particularly, viscosities of 10 cps to 4000 cps are suitable. On the other hand, effective cleaning is important, especially on greasy and oily soils and/or where the composition is thereafter diluted.
- It is therefore an object of the present invention to provide cleaning compositions having effective cleaning performance and viscosity.
- The Applicant has now found that the combination of a surfactant system, comprising a short chain surfactant and a long chain surfactant, and a polycarboxylate polymer in a liquid cleaning composition fulfills such a need.
- Another advantage of the present invention is that it provides stable compositions, especially in presence of a bleach component.
- Another advantage of the present invention is that it provides liquid cleaning compositions which are safe to the user when said composition is sprayed onto the surface to be treated.
- The present invention is a liquid cleaning composition comprising:
- i)-a surfactant system comprising a short chain surfactant and a long chain surfactant, said surfactants comprising a hydrophobic portion and a hydrophilic portion, wherein the chain length of the hydrophobic portion of the short chain surfactant is C6 to C10 and the chain length of the hydrophobic portion of the long chain surfactant is C11 to C20 carbon atoms; and
- ii)-a polycarboxylate polymer;
- The present invention further encompasses the use of a polycarboxylate polymer in a liquid cleaning composition, in a sprayed form, for preventing or reducing inhalation of said composition by the user as said composition is sprayed.
- In a further aspect of the invention, there is provided a method for cleaning a hard surface by applying on said surface an effective amount of a composition of the present invention.
- A surfactant system is an essential feature of the invention. The surfactant system comprises a short chain surfactant and a long chain surfactant. All surfactants have in common that they comprise a hydrophobic portion and a hydrophilic portion.
- For the purpose of the invention, where the chain length of the hydrophobic portion of the short chain surfactant is C6 to C8, the short chain and the long chain surfactant are present in a weight ratio of said short chain to said long chain surfactant of less than 4:1, preferably less than 2:1, more preferably less than or equal to 1:1.
- By short chain surfactant, it is meant herein surfactants which comprise a C6-C10 alkyl chain as their hydrophobic portion. Such short chain surfactants are accordingly those conventionally used in this field, but with a shorter alkyl chain. Suitable short chain surfactants for use herein are selected from the group consisting of C6-C10 alkyl sulphates (C6-C10SO4), alkyl ether sulphates (C6-C10(OCH2CH2)eSO4), alkyl sulphonates (C6-C10SO3), alkyl succinates (C6-C10OOCCH2CH2COOZ), alkyl carboxylates (C6-C10COOM), alkyl ether carboxylates (C6-C10(OCH2CH2)eCOOM), alkyl sarcosinates (C6-C10CON (CH3)R), alkyl sulpho succinates (C6-C10OOCCH(SO3M)CH2COOZ), capped alkyl ethoxylates (C6-C10(OCH2CH2)fOR, capped alkyl ethoxylates carboxylates (C6-C10(OCH2CH2)f(CH2)COOR, amine oxides (C6-C10RR'NO), and betaines (C6-C10N+(CH3)2CH2COO-). In the formulae in brackets, e is from 0 to 20, f is from 1 to 16, preferably 1 to 5, Z is M or R, M is H or any counterion such as those known in the art, including Na, K, Li, NH4, amine, R and R' are C1-C5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably C1-C3, most preferably methyl. The compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof, depending on the end use envisioned.
- Preferred short chain surfactants for use herein are hypochlorite compatible, e.g surfactants which contain no functionalities (such as ether linkages, unsaturation, some aromatic structures or hydroxyl groups) which are susceptible of oxidation by the hypochlorite bleach. More preferably, the short chain surfactants for use herein are anionic short chains. Preferably, the anionic short chain surfactants comprise a C7-C9 alkyl chain as their hydrophobic portion. Preferred anionic short chain surfactants among the one above disclosed are the alkyl sulphates and alkyl sulphonates. Most preferred anionic short chain surfactants are selected from the C7-C9 alkyl sulphates, C7-C9 alkyl sulphonates and mixtures thereof. A most preferred short chain surfactants for use herein is octyl sulphate. Such short chain anionic surfactants can be made by well known sulphation or sulphonation processes followed by neutralisation, but said anionic short chain surfactants are more conveniently commercially available, for instance from Rhone Poulenc under the trade name Rhodapon® OLS, from Witco under the trade name Witconate ®, or from Albright and Wilson under the trade name Empimin®. A preferred commercially available compound is Empimin® LV33.
- According to the present invention, the compositions comprise from 0.1% to 5%, preferably 0.3% to 4% by weight, more preferably from 0.6% to 2.5% by weight, of short chain surfactants.
- Long chain surfactants for use herein are those which comprise a C11-C20 alkyl chain as their hydrophobic portion. Suitable long chain surfactants are selected from C11-C20 alkyl sulphates (C11-C20SO4), alkyl ether sulphates (C11-C20(OCH2CH2)eSO4), alkyl sulphonates (C11-C20SO3), alkyl succinates (C11-C20OOCCH2CH2COOZ), alkyl carboxylates (C11-C20COOM), alkyl ether carboxylates (C11-C20(OCH2CH2)eCOOM), alkyl sarcosinates (C11-C20CON(CH3)R), alkyl sulpho succinates (C11-C20OOCCH(SO3M)CH2COOZ), capped alkyl ethoxylates (C11-C20(OCH2CH2)fOR, capped alkyl ethoxylates carboxylates (C11-C20(OCH2CH2)f(CH2)COOR, amine oxides (C11-C20RR'NO), and betaines (C11-C20N+(CH3)2CH2COO-). In the formulae in brackets, e is from 0 to 20, f is from 1 to 16, preferably 1 to 5, Z is M or R, M is H or any counterion such as those known in the art, including Na, K, Li, NH4, amine, R and R' are C1-C5 alkyl groups, possibly functionalized with hydroxyl groups, R and R' are preferably C1-C3, most preferably methyl. The compositions according to the present invention may comprise any of the above surfactants alone, or any combination thereof, depending on the end use envisioned.
- Preferred long chain surfactants for use herein are hypochlorite compatible, e.g surfactants which contain no functionalities (such as ether linkages, unsaturation, some aromatic structures or hydroxyl groups) which are susceptible of oxidation by the hypochlorite bleach. More preferably, the long chain surfactants for use herein are anionic long chains. Preferably, the long chain anionic surfactants for use herein comprise a C11-C18, more preferably a C12-C14 alkyl chain as their hydrophobic portion. A preferred anionic long chain surfactant among the one above disclosed is alkyl sulphate. A most preferred is the C12-C14 alkyl sulphate. Preferred alkyl sulphates for use herein are selected from sodium tallow alkyl sulphate, sodium lauryl sulphate and mixtures thereof. A preferred commercially available compound is Empicol ® 0298/F from Albright and Wilson.
- Compositions according to the present invention comprise from 0.1% to 5%, preferably from 1% to 3% by weight of the total compositions of said long chain surfactants.
- Where amine oxide is used as a long chain surfactant, it is preferred for convenient use of the composition that the level of said long chain amine oxide surfactant is present at a level of from 0.1% to 2% by weight of the composition. Above such levels, the composition may tend to be too viscous to be easily usable.
- Furthermore, the use of long chain amine oxide surfactants in the cleaning composition of the invention which provide effective cleaning and viscosity performance is especially surprising as the Applicant has found that in the absence of a polycarboxylate polymer, a problem encountered with the use of such amine oxide is that the activity of the short chain surfactant is hindered by said long chain amine oxide surfactant, so that the cleaning performance of the short chain surfactant does not act to its best performance.
- Not to be bound by theory, it is believed that the amine oxide surfactant, especially long chain amine oxides, and the short chain surfactant are trapped in the cylindrical micellar system, formed by the amine oxide surfactants, that generates the viscosity. As a result, the short chain surfactant is not completely free to move and loses part of its cleaning power.
- The Applicant has now found that the use of a polycarboxylate polymer not only overcomes the problem but also supports the cleaning efficiency of the surfactant system, even in the presence of long chain amine oxide surfactants.
- Another essential component of the invention is a polycarboxylate polymer. The polycarboxylate polymers, contrary to cellulosic polymers such as guar gum or xanthum gum, are more stable in presence of hypochlorite bleach, provide better thickening efficiency and also a higher yield value. Such high yield value is of particular utility where the composition is packaged in a spray-type dispenser.
- The polymers for use herein preferably have a molecular weight of from 500.000 to 4.500.000, preferably from 1.000.000 to 4.000.000. Most preferred polymers for use herein contain from 0.5% to 4% by weight of a cross-linking agent, wherein the cross-linking agent tends to interconnect linear strands of the polymers to form the resulting cross-linked products. Suitable cross-linking agents include the polyalkenyl polyethers. Polycarboxylate polymers include the polyacrylate polymers. Other monomers besides acrylic acid can be used to form these polymers including such monomers as maleic anhydride which acts as a source of additional carboxylic groups. The molecular weight per carboxylate group of monomers containing a carboxylate group typically varies from 25 to 200, preferably from 50 to 150, more preferably from 75 to 125. Further other monomers may be present in the monomeric mixture, if desired, such as ethylene and propylene which act as diluents.
- Preferred polycarboxylate polymers for use herein are the polyacrylate polymers. Commercially available polymers of the polyacrylate type include those sold under the trade names Carbopol®, Acrysol® ICS-1, Polygel®, and Sokalan®. Most preferred polyacrylate polymers are the copolymer of acrylic acid and alkyl (C5-C10) acrylate, commercially available under the tradename Carbopol® 1623, Carbopol® 695 from BF Goodrich, and copolymer of acrylic acid and maleic anhydride, commercially available under the tradename Polygel® DB from 3V Chemical company.
- Mixtures of any of the polycarboxylate polymers, herein before described, may also be used.
- The polymer is present in an amount of from 0.1% to 4% by weight, preferably 0.3 to 4% by weight, more preferably 0.4% to 1.5% by weight of the composition.
- The Applicant has now surprisingly found that the present polymer performs dual functions when it is incorporated in the composition herein, said functions being not only to thicken but also to support the cleaning performance of the surfactant system.
- The compositions according to the present invention may comprise a number of optional ingredients such as bleaching agents, fatty acids, radical scavengers, antimicrobial compounds, builders, chelants, buffers, bactericides, solvents, enzymes, hydrotropes, colorants, bleach activators, soil suspenders, dye transfer agents, brighteners, anti dusting agents, dispersants, dye transfer inhibitors, pigments, perfumes and dyes.
- A highly preferred optional ingredient according to the present invention is a hypochlorite bleaching agent, preferably an alkali metal hypochlorite. Advantageously, the compositions of the invention are stable in presence of this bleaching agent. Although alkali metal hypochlorites are preferred other hypochlorite compounds may also be used herein and can be selected from calcium and magnesium hypochlorite. A preferred alkali metal hypochlorite for use herein is sodium hypochlorite. Compositions according to the present invention comprise said hypochlorite bleaching agents such that the content of active chlorine in the compositions is from 0.1% to 4%, preferably from 1% to 2% by weight.
- Another optional component of the present invention is an alkali metal salt of a C8-C18 fatty acid. Said fatty acids are used as suds suppressors. Suitable fatty acids for use herein can be any C8-C18 fatty acid, preferably fully saturated, preferably a sodium, potassium or lithium salt, more preferably the sodium salt. Suitable fatty acids may be selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and mixtures of fatty acids suitably hardened, derived from natural sources such as tallow, coconut oil, ground oil and babassu oil. Compositions according to the present invention comprise from 0.1% to 2%, preferably less than 0.6% by weight of the composition of fatty acids.
- A further optional component of the present invention is a radical scavenger. Said radical scavengers are used as stabilisers. A suitable radical scavenger for use herein is the aromatic molecule containing a carboxylic group ring substitution. Suitable examples of radical scavengers for use herein include the meta and para-chlorobenzoic acid, benzoic acid, meta- ortho- and para-methoxybenzoic acid, meta nitrobenzoic acid, para bromobenzoic acid, salicylic acid, 5-sulphosalicylic acid, 3,5-dimethyl salicylic acid and paratoluic acid. Of the above materials, ortho-methoxybenzoic acid is preferred. Compositions according to the present invention comprise from 0.01% to 1.5% by weight, preferably from 0.1% to 0.8% by weight and more preferably from 0.2% to 0.5% by weight of the composition of radical scavengers.
- An optional requirement of the compositions according to the present invention is that the pH is greater than 10, preferably greater than 11, more preferably greater than 12. This is achieved by the addition of from 0.4% to 2% of a caustic alkali. Suitable caustic alkalis for use herein include sodium and potassium hydroxide. Compositions according to the present invention comprising hypochlorite preferably have a pH greater than 12 for hypochlorite stability.
- The compositions according to the present invention are preferably aqueous and preferably comprise from 80% to 95%, more preferably from 85% to 90% of water.
- The compositions according to the present invention are prepared by methods well known in the art such as the methods described in GB 1 329 086 with the exception of the polymer being pre-dispersed in an acidic water solution of pH 3 and then neutralised up to pH 7 before starting adding the other components. The compositions according to the present invention can then be prepared by mixing all of the ingredients in a non-metallic apparatus at room temperature or in warm water. If fatty acid is used, it is melted before being added to the mixture. Preferably, the surfactant blend is first prepared by adding the short chain surfactant to the long chain surfactants. Other optionals such as perfume and the alkali metal hypochlorite are then added whilst stirring. Colourants, if present, are added after all the other ingredients have been mixed.
- The compositions according to the present invention preferably have a viscosity of from 10 cps to 4000 cps, more preferably from 50 cps to 2000 cps, most preferably from 150 cps to 1000 cps measured with a Carrimed Rheometer at a temperature of 25°C and a shear rate of 15-35 s-1. Where the composition is in a sprayed form, the viscosity of said spraying compositions is preferably of from 15 cps to 40 cps.
- The compositions of the present invention may be used for a variety of cleaning purposes such as cleaning hard surfaces whereby said compositions thickened nature results in longer adhesion to the surface than non-thickened compositions. By "hard surface" it is meant herein any surface like bathroom, sanitary fittings such as sinks, showers, wash basins and WCs, kitchen, sinks, cooker tops, table tops, refrigerators, walls, windows and the like.
- The compositions herein may be packaged in a variety of suitable detergent packaging known to those skilled in the art. The liquid compositions herein may desirably be packaged in manually operated spray dispensing containers, which are usually made of synthetic organic polymeric plastic materials. Accordingly, the present invention also encompasses liquid cleaning compositions of the invention packaged in a spray dispenser, preferably in a trigger spray dispenser. Indeed, said spray-type dispensers allow to uniformly apply to a relatively large area of a surface to be cleaned the liquid cleaning compositions suitable for use according to the present invention; thereby contributing to the cleaning properties of said compositions. Such spray-type dispensers are particularly suitable to clean vertical surfaces. Surprisingly, the spraying of a liquid composition containing a polycarboxylate polymer, contrary to compositions which do not contain the polycarboxylate polymer, has been seen beneficial for preventing or reducing inhalation of the composition by the user as said composition is sprayed.
- The present avantage is preferably observed where the cleaning composition is as defined hereinbefore. Accordingly, the use of a polycarboxylate polymer in a liquid cleaning composition is provided, said composition being in a sprayed form, for preventing or reducing inhalation of said composition by the user as said composition is sprayed. Preferably, the liquid cleaning composition is as defined hereinbefore.
- Suitable spray-type dispensers to be used according to the present invention include manually operated foam trigger-type dispensers sold for example by Specialty Packaging Products, Inc. or Continental Sprayers, Inc. These types of dispensers are disclosed, for instance, in US-4,701,311 to Dunnining et al. and US-4,646,973 and US-4,538,745 both to Focarracci. Particularly preferred to be used herein are spray-type dispensers such as T 8500® or T 8900® commercially available from Continental Spray International or T 8100® commercially available from Canyon, Northern Ireland. In such a dispenser the liquid composition is divided in fine liquid droplets resulting in a spray that is directed onto the surface to be treated. Indeed, in such a spray-type dispenser the composition contained in the body of said dispenser is directed through the spray-type dispenser head via energy communicated to a pumping mechanism by the user as said user activates said pumping mechanism. More particularly, in said spray-type dispenser head the composition is forced against an obstacle, e.g. a grid or a cone or the like, thereby providing shocks to help atomise the liquid composition, i.e. to help the formation of liquid droplets.
- The present invention further encompasses a method for cleaning a hard surface by applying on said surface an effective amount of a composition of the invention. The said composition may be applied in its neat form or after having been diluted with water. Preferably said composition is diluted up to 200 times its weight of water, preferably into 50 to 150 times its weight of water and more preferably 75 to 95, before it is applied to said surface. When the composition is diluted prior to use (to reach a total active level in the order of 1.2%), the composition will still advantageously provide effective cleaning performance. In the preferred embodiment of the method of the present invention wherein said composition is applied to a hard-surface to be cleaned in its diluted form, it may not be necessary to rinse the surface after the composition has been applied.
- In the detergent compositions of the invention, the abbreviated component identifications have the following meaning:
- C8 AS
- : Octyl sulphate, available from Albright and Wilson, under the tradename Empimin® LV33
- 24 AS
- : Sodium C12 - C14 alkyl sulphate, available from Albright and Wilson, under the tradename Empicol® 0298/F
- 24E3S
- : C12 - C14 sodium alkyl sulphate condensed with an average of 3 moles of ethylene oxide per mole
- Amine oxide
- : C12 - C14 amine oxide, commercially available under the tradename Genaminox® LA from Hoechst
- Polymer
- : Copolymer of acrylic acid and alkyl (C5-C10) acrylate, commercially available under the tradename Carbopol® 1623 from BF Goodrich
- Fatty acid
- : C8-C18 fatty acid
- nonionic
- : Capped ethoxylated carboxylate of formula C12-C14(OCH2CH2)xCH2COOR, wherein x is an integer ranging from 2 to 4
- The invention is illustrated in the following non-limiting examples, in which all percentages are on a weight basis unless otherwise stated.
- The following compositions, according to the invention, were prepared:
Components A B C D E F G 24 AS 1.0 1.0 2.0 2.0 1.0 1.0 1.0 C8 AS 1.0 1.0 1.0 2.0 2.0 2.0 2.0 Polymer 0.8 0.8 1.2 1.0 1.0 1.5 0.3 Caustic - 1.4 1.4 1.5 1.4 - 1.0 Sodium hypochlorite - 1.4 1.0 1.0 1.4 1.4 1.4 Fatty acid - 0.2 0.3 0.3 0.2 - - Water and minors up to 100 - The following compositions are in accordance with the invention
H I J K L C8 AS 1.0 1.0 2.0 2.0 2.0 24AE3S 2.0 2.0 1.0 1.0 1.0 Polymer 0.8 1.0 1.2 1.0 0.4 nonionic 0.5 0.5 1.0 1.0 0.5 fatty acid 0.3 0.3 0.3 0.3 0.3 Caustic 1.4 1.4 1.4 1.4 1.0 sodium hypochlorite 1.4 1.6 1.6 1.4 1.4 Water and minors up to 100 - The following compositions are in accordance with the invention
M N O amine oxide 0.4 0.4 0.8 24 AS - 2.0 2.0 C8 AS 2.0 2.0 2.0 Polymer 0.8 0.8 0.8 Caustic 1.4 1.4 1.4 Sodium hypochlorite 1.4 1.4 1.4 Water and minors up to 100 - The following compositions were made and packaged in a spray-trigger dispenser T 8500®:
G L P C8 AS 2.0 2.0 3.0 24AS 1.0 - 0.3 24AE3S - 1.0 - Polymer 0.3 0.4 0.4 nonionic - 0.5 - fatty acid - 0.3 - Caustic 1.0 1.0 1.0 sodium hypochlorite 1.4 1.4 1.4 Water and minors up to 100 - The above compositions, in a sprayed form, exhibited reduced inhalation of said composition by the user as said composition was sprayed as compared to compositions, in a sprayed form, which did not contain the polycarboxylate polymer.
Claims (17)
- A liquid cleaning composition comprising:i)-a surfactant system comprising a short chain surfactant and a long chain surfactant, said surfactants comprising a hydrophobic portion and a hydrophilic portion, wherein the chain length of the hydrophobic portion of the short chain surfactant is C6 to C10 and the chain length of the hydrophobic portion of the long chain surfactant is C11 to C20 carbon atoms; andii)-a polycarboxylate polymer;with the proviso that where the chain length of the hydrophobic portion of the short chain surfactant is C6 to C8, the short chain and the long chain surfactant are present in a weight ratio of said short chain to said long chain surfactant of less than 4:1.
- A liquid cleaning composition according to Claim 1, wherein said short chain surfactant is an anionic surfactant selected from the group consisting of alkyl sulphates, alkyl sulphonates and mixtures thereof, preferably alkyl sulphates.
- A liquid cleaning composition according to either one of Claim 1 or 2, wherein said short chain surfactant contains from 7 to 9 carbon atoms.
- A liquid cleaning composition according to any one of Claims 1-3, wherein said short chain surfactant is in amount of 0.1% to 5% by weight, preferably 0.3% to 4% by weight, more preferably from 0.6% to 2.5% by weight of the composition.
- A liquid cleaning composition according to any one of Claims 1-4, wherein said long chain surfactant is an anionic surfactant, preferably an alkyl sulphate surfactant.
- A liquid cleaning composition according to any one of Claim 1-5, wherein said long chain surfactant contains from 11 to 18 carbon atoms, preferably from 12 to 14 carbon atoms.
- A liquid cleaning composition according to any one of Claims 1-6, wherein said long chain surfactant is in amount of 0.1% to 5% by weight, preferably from 1% to 3% by weight of the composition.
- A liquid cleaning composition according to any one of Claims 1-7, wherein said polycarboxylate polymer is a polyacrylate polymer.
- A liquid cleaning composition according to Claim 8, wherein said polyacrylate polymer is a cross-linked polymer.
- A liquid cleaning composition according to any one of Claims 1-9, wherein said polycarboxylate polymer is in amount of 0.1% to 4% by weight, preferably 0.3 to 4% by weight, more preferably 0.4% to 1.5% by weight of the composition.
- A liquid cleaning composition according to any one of Claims 1-10, wherein said composition further comprises an alkali metal hypochlorite bleach.
- A liquid cleaning composition according to Claim 11, wherein said hypochlorite bleach is present in an amount such that the content of active chlorine in the compositions is from 0.1% to 4% by weight of the composition.
- A liquid composition according to any one of Claims 1-12, wherein said composition has a viscosity of from 10 cps to 4000 cps, preferably from 50 cps to 2000 cps, more preferably from 150 cps to 1000 cps.
- A liquid composition according to any one of Claims 1-13, wherein said composition is packaged in a spray dispenser, preferably in a trigger spray dispenser.
- The use of a polycarboxylate polymer in a liquid cleaning composition, for preventing inhalation of the composition by the user as said composition is sprayed.
- The use of a polycarboxylate polymer in a liquid cleaning composition as defined in Claim 14, for preventing inhalation of the composition by the user as said composition is sprayed.
- A method of cleaning a hard surface, wherein an effective amount of a composition as defined in any one of Claims 1-14 is applied onto said surface.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96870088A EP0812904A3 (en) | 1996-06-10 | 1996-07-01 | Cleaning compositions |
| AT97929872T ATE259408T1 (en) | 1996-06-10 | 1997-06-06 | CLEANING SUPPLIES |
| PCT/US1997/009957 WO1997047714A1 (en) | 1996-06-10 | 1997-06-06 | Cleaning compositions |
| EP97929872A EP0906390B1 (en) | 1996-06-10 | 1997-06-06 | Cleaning compositions |
| ES97929872T ES2212112T3 (en) | 1996-06-10 | 1997-06-06 | CLEANING COMPOSITIONS. |
| DE69727567T DE69727567T2 (en) | 1996-06-10 | 1997-06-06 | CLEANING SUPPLIES |
| US09/202,248 US6066614A (en) | 1996-06-10 | 1997-06-06 | Cleaning compositions |
| CA002257955A CA2257955C (en) | 1996-06-10 | 1997-06-06 | Cleaning compositions |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP96870071 | 1996-06-10 | ||
| EP96870071 | 1996-06-10 | ||
| EP96870088A EP0812904A3 (en) | 1996-06-10 | 1996-07-01 | Cleaning compositions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0812904A2 true EP0812904A2 (en) | 1997-12-17 |
| EP0812904A3 EP0812904A3 (en) | 1999-05-26 |
Family
ID=26144398
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96870088A Withdrawn EP0812904A3 (en) | 1996-06-10 | 1996-07-01 | Cleaning compositions |
| EP97929872A Revoked EP0906390B1 (en) | 1996-06-10 | 1997-06-06 | Cleaning compositions |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP97929872A Revoked EP0906390B1 (en) | 1996-06-10 | 1997-06-06 | Cleaning compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (2) | EP0812904A3 (en) |
| AT (1) | ATE259408T1 (en) |
| CA (1) | CA2257955C (en) |
| DE (1) | DE69727567T2 (en) |
| ES (1) | ES2212112T3 (en) |
| WO (1) | WO1997047714A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999028427A1 (en) * | 1997-12-04 | 1999-06-10 | The B.F. Goodrich Company | Thickened bleach compositions |
| WO2000011128A1 (en) * | 1998-08-19 | 2000-03-02 | Jeyes Group Limited | Liquid bleaching compositions |
| EP0992573A1 (en) * | 1998-10-05 | 2000-04-12 | The Procter & Gamble Company | Cleaning with short-chain surfactants |
| WO2000077145A1 (en) * | 1999-06-11 | 2000-12-21 | Henkel Kommanditgesellschaft Auf Aktien | Bleaching and disinfecting agents |
| WO2014160590A1 (en) * | 2013-03-26 | 2014-10-02 | The Procter & Gamble Company | Cleaning compositions for cleaning a hard surface |
| US9757006B2 (en) | 2013-03-26 | 2017-09-12 | The Procter & Gamble Company | Articles for cleaning a hard surface |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2051162A (en) * | 1979-05-30 | 1981-01-14 | Reckitt & Colmann Prod Ltd | Thickened aqueous alkali metal hypochlorite solutions |
| GB2219596A (en) * | 1988-06-09 | 1989-12-13 | Procter & Gamble | Liquid automatic dishwashing compositions having enhanced stability |
| US4941988A (en) * | 1989-02-13 | 1990-07-17 | The Procter & Gamble Company | Liquid automatic dishwashing compositions having an optimized thickening system |
| US4933101A (en) * | 1989-02-13 | 1990-06-12 | The Procter & Gamble Company | Liquid automatic dishwashing compositions compounds providing glassware protection |
| US5169552A (en) * | 1989-10-04 | 1992-12-08 | The Procter & Gamble Company | Stable thickened liquid cleaning composition containing bleach |
| WO1993021298A1 (en) * | 1992-04-13 | 1993-10-28 | The Procter & Gamble Company | Process for preparing thixotropic liquid detergent compositions |
| EP0656936B1 (en) * | 1992-08-25 | 1997-05-14 | Unilever Plc | Liquid cleaning compositions comprising primary alkyl sulphate and non-ionic surfactants |
| EP0916719A3 (en) * | 1992-11-03 | 1999-07-14 | The Procter & Gamble Company | Cleaning with short-chain surfactants |
| CA2107938C (en) * | 1993-01-11 | 2005-01-11 | Clement K. Choy | Thickened hypochlorite solutions with reduced bleach odor and methods of manufacture and use |
| EP0694058A1 (en) * | 1993-04-27 | 1996-01-31 | The Procter & Gamble Company | Liquid or granular automatic dishwashing detergent compositions |
| DE69415972T2 (en) * | 1993-04-27 | 1999-08-12 | The Procter & Gamble Co., Cincinnati, Ohio | LIQUID OR GRANULAR MACHINE DISHWASHER |
| JPH09503012A (en) * | 1993-09-20 | 1997-03-25 | ザ、プロクター、エンド、ギャンブル、カンパニー | Thickened aqueous detergent composition having improved cleaning performance |
| US5384061A (en) * | 1993-12-23 | 1995-01-24 | The Procter & Gamble Co. | Stable thickened aqueous cleaning composition containing a chlorine bleach and phytic acid |
| US5602092A (en) * | 1994-07-06 | 1997-02-11 | Colgate-Palmolive Company | Concentrated aqueous liquid detergent compositions containing deflocculating polymers |
-
1996
- 1996-07-01 EP EP96870088A patent/EP0812904A3/en not_active Withdrawn
-
1997
- 1997-06-06 WO PCT/US1997/009957 patent/WO1997047714A1/en not_active Ceased
- 1997-06-06 CA CA002257955A patent/CA2257955C/en not_active Expired - Fee Related
- 1997-06-06 EP EP97929872A patent/EP0906390B1/en not_active Revoked
- 1997-06-06 ES ES97929872T patent/ES2212112T3/en not_active Expired - Lifetime
- 1997-06-06 AT AT97929872T patent/ATE259408T1/en not_active IP Right Cessation
- 1997-06-06 DE DE69727567T patent/DE69727567T2/en not_active Revoked
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999028427A1 (en) * | 1997-12-04 | 1999-06-10 | The B.F. Goodrich Company | Thickened bleach compositions |
| US6083422A (en) * | 1997-12-04 | 2000-07-04 | The B.F. Goodrich Company | Thickened bleach compositions |
| EP1348755A3 (en) * | 1997-12-04 | 2003-11-05 | Noveon IP Holdings Corp. | Thickened bleach compositions |
| WO2000011128A1 (en) * | 1998-08-19 | 2000-03-02 | Jeyes Group Limited | Liquid bleaching compositions |
| EP0992573A1 (en) * | 1998-10-05 | 2000-04-12 | The Procter & Gamble Company | Cleaning with short-chain surfactants |
| WO2000020543A1 (en) * | 1998-10-05 | 2000-04-13 | The Procter & Gamble Company | Cleaning with short-chain surfactants |
| WO2000077145A1 (en) * | 1999-06-11 | 2000-12-21 | Henkel Kommanditgesellschaft Auf Aktien | Bleaching and disinfecting agents |
| WO2014160590A1 (en) * | 2013-03-26 | 2014-10-02 | The Procter & Gamble Company | Cleaning compositions for cleaning a hard surface |
| CN105073967A (en) * | 2013-03-26 | 2015-11-18 | 宝洁公司 | Cleaning compositions for cleaning a hard surface |
| US9757006B2 (en) | 2013-03-26 | 2017-09-12 | The Procter & Gamble Company | Articles for cleaning a hard surface |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997047714A1 (en) | 1997-12-18 |
| CA2257955A1 (en) | 1997-12-18 |
| DE69727567T2 (en) | 2004-12-16 |
| EP0906390A4 (en) | 1999-05-26 |
| CA2257955C (en) | 2002-04-16 |
| EP0906390B1 (en) | 2004-02-11 |
| EP0812904A3 (en) | 1999-05-26 |
| DE69727567D1 (en) | 2004-03-18 |
| EP0906390A1 (en) | 1999-04-07 |
| ATE259408T1 (en) | 2004-02-15 |
| ES2212112T3 (en) | 2004-07-16 |
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