EP0745117A1 - Detergent composition containing graft copolymer - Google Patents
Detergent composition containing graft copolymerInfo
- Publication number
- EP0745117A1 EP0745117A1 EP95907629A EP95907629A EP0745117A1 EP 0745117 A1 EP0745117 A1 EP 0745117A1 EP 95907629 A EP95907629 A EP 95907629A EP 95907629 A EP95907629 A EP 95907629A EP 0745117 A1 EP0745117 A1 EP 0745117A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- composition
- nonionic surfactant
- graft copolymer
- vinyl acetate
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 84
- 239000003599 detergent Substances 0.000 title claims abstract description 40
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 25
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 41
- -1 polyethylene Polymers 0.000 claims abstract description 24
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000000740 bleeding effect Effects 0.000 claims abstract description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- 239000004743 Polypropylene Substances 0.000 claims abstract description 4
- 229920001748 polybutylene Polymers 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- 229920001155 polypropylene Polymers 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 27
- 239000004615 ingredient Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- 239000011800 void material Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002689 soil Substances 0.000 abstract description 7
- 238000010348 incorporation Methods 0.000 abstract description 6
- 239000000843 powder Substances 0.000 description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000007844 bleaching agent Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 7
- 229920002125 Sokalan® Polymers 0.000 description 7
- 239000000123 paper Substances 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000002304 perfume Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 4
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 4
- 229940120146 EDTMP Drugs 0.000 description 3
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229940096386 coconut alcohol Drugs 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000002366 lipolytic effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 230000002797 proteolythic effect Effects 0.000 description 2
- 229940045872 sodium percarbonate Drugs 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- 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 1
- WFRXSOIFNFJAFL-UHFFFAOYSA-N P1(OCCCCO1)=O.C(CN)N Chemical class P1(OCCCCO1)=O.C(CN)N WFRXSOIFNFJAFL-UHFFFAOYSA-N 0.000 description 1
- 108010081873 Persil Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Chemical class 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with 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
- C11D1/66—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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3788—Graft polymers
-
- 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
Definitions
- EP 219 048A discloses the use of graft copolymers of polyalkylene oxide with vinyl acetate as greying inhibitors in the washing and post-wash treatment of synthetic textile fabrics.
- the organic surfactant system comprises mobile ethoxylated nonionic surfactant in an amount of at least 10 wt% based on the whole composition
- the invention is of especial applicability to detergent powders of high bulk density, preferably at least 650 g/1, 20 more preferably at least 700 g/1 and most preferably at least 800 g/1.
- Preferred compositions of the invention have a void volume not exceeding 10%, more preferably not exceeding 5%; void volume may be measured by the known technique of mercury intrusion porosimetry.
- a 800 g sample of each powder was weighed out. Powder was poured to a depth of 1 cm into the base of a cylindrical container of diameter 15 cm, and an accurately weighed filter paper (Schleicher and Schull No. 589) placed on top of the powder. More powder was added to an approximate depth of 5 cm above the filter paper, and then covered with a second accurately weighed filter paper. The remainder of the powder sample was then used to cover the second filter paper.
- the container was tightly sealed and stored in a dry atmosphere at 37°C for 3 weeks. After the storage period the filter papers were removed and weighed, the increase in weight of each calculated, and the values for the two increases averaged.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
In a particulate detergent composition containing 10 wt % or more of mobile ethoxylated nonionic surfactant, the incorporation of a graft copolymer of polyethylene, polypropylene or polybutylene oxide with vinyl acetate/alcohol reduces bleeding out of nonionic surfactant as well as providing the known soil release benefit. Preferred compositions of the invention also contain sodium citrate and are of high bulk density.
Description
Detergent composition containing graft copolymer
TECHNICAL FIELD
The present invention relates to particulate detergent compositions containing a defined polymer conferring soil release benefits, for example, a graft copolymer of vinyl acetate units on a polyethylene oxide backbone. The compositions of the invention contain relatively high levels of mobile nonionic surfactants and are preferably of high bulk density.
BACKGROUND AND PRIOR ART
EP 219 048A (BASF) discloses the use of graft copolymers of polyalkylene oxide with vinyl acetate as greying inhibitors in the washing and post-wash treatment of synthetic textile fabrics.
EP 358 474A (Unilever) discloses that detergent compositions containing a graft copolymer of this type in conjunction with a low-HLB nonionic surfactant system exhibit surprisingly enhanced soil suspension (antiredeposition) properties on polyester/cotton fabrics.
EP 358 473A and EP 358 472A (Unilever) also relate to enhanced antiredeposition properties when the graft copolymer is used in conjunction with, respectively, aluminosilicate builder and acrylic polymer, or dipicolinic acid builder.
We have now unexpectedly discovered that incorporation of these graft copolymers in certain particulate detergent compositions can additionally confer another, quite different benefit, unconnected with antiredeposition or soil suspension: when high levels of mobile nonionic surfactants are present, especially in powders of high bulk density, bleeding out of the nonionic surfactant can be substantially reduced. Delivery into the wash may also be improved.
EP 358 474A (Unilever) mentioned above discloses compositions containing ethoxylated nonionic surfactants. However, the benefit concerned (enhanced antiredeposition) is obtained only with nonionic surfactants having a low cloud point and a low HLB value. No benefit is observed, for example, with C12.15 alcohol ethoxylated with an average of 7 or more moles of ethylene oxide per mole of alcohol. Furthermore, the preferred level of nonionic surfactant disclosed is from 3 to 10 wt% based on the whole composition, and the compositions specifically described in the Examples contain only 4 wt% of nonionic surfactant. The specific disclosures of EP 358 473A and EP 358 472A (Unilever) are similar.
WO 92 06152A and WO 93 19145A (Procter & Gamble) disclose the use of soil release polymers, including the graft copolymer, in compositions in which the surfactant systen includes a polyhydroxy fatty acid amide. Powders of high bulk density are exemplified in WO 92 06152A but these contain only low levels of ethoxylated nonionic surfactant (less than 2.5 wt%) .
EP 455 468A (Protein Technologies International) discloses a new proteinaceous soil release material and compares it with graft copolymers of the type discussed above. Powder compositions specifically disclosed contain 5 wt% of nonionic surfactant (C12.15 alcohol, 9EO) .
DEFINITION OF THE INVENTION
The present invention accordingly provides a particulate detergent composition comprising an organic surfactant system, a detergency builder system and optionally other detergent ingredients, wherein
(a) the organic surfactant system comprises mobile ethoxylated nonionic surfactant in an amount of at least 10 wt% based on the whole composition, and
(b) the composition also comprises a graft copolymer of
(i) polyethylene, polypropylene or polybutylene oxide with
(ii) vinyl acetate (optionally partially saponified) ,
in a weight ratio of (i) to (ii) of from 1:0.2 to 1:10.
The invention also provides a process for the preparation of a particulate detergent composition as defined above, which comprises preparing a substantially homogeneous granular base by mixing and granulation, then optionally postdosing further ingredients, the graft copolymer being incorporated in aqueous solution form during the mixing and granulation process.
The invention further provides the use of a copolymer as defined above to reduce or prevent the bleeding out of nonionic surfactant from a particulate detergent composition containing at least 10 wt% of mobile ethoxylated nonionic surfactant.
DETAILED DESCRIPTION OF THE INVENTION
The particulate detergent compositions of the invention contain a graft copolymer as described and claimed in EP 219 048A (BASF) .
The compositions also contain a relatively high level of mobile ethoxylated nonionic surfactant. These surfactants give substantial performance benefits, but in such compositions the phenomenon known as "bleeding" of nonionic surfactant can be a major problem. The mobile nonionic surfactant can migrate through the powder, becoming unevenly distributed, leading to loss of performance, loss of powder flow, and caking; where porous (eg cardboard) packaging is used, the nonionic surfactant tends to move to the narrow capillaries of the pack material leading to penetration and external staining. Bleeding is a particular problem with powders of high bulk density and correspondingly low particle porosity.
According to the invention, the presence of a graft copolymer as previously defined, and as discussed in more detail below, can reduce or prevent nonionic surfactant bleeding. The effect is enhanced if a water-soluble salt of citric acid, preferably sodium citrate, is present.
The σraft copolvmer
The graft copolymers, used in the compositions of the present invention are described and claimed in EP 219 048A (BASF) . They are obtainable by grafting a polyalkylene oxide of molecular weight (number average) 2000 - 100 000 with vinyl acetate, which may be partially saponified, in a weight ratio of polyalkylene oxide to vinyl acetate of 1:0.2 to 1:10. The vinyl acetate may, for example, be saponified to an extent of up to 15%.
The polyalkylene oxide may contain units of ethylene oxide, propylene oxide and/or butylene oxide; polyethylene oxide is preferred.
Preferably the polyalkylene oxide has a number-average molecular weight of from 4000 to 50 000, and the weight ratio of polyalkylene oxide to vinyl acetate is from 1:0.5 to 1:6. Especially preferred are polymers derived from polyethylene oxide of molecular weight 2000-50 000 and having a weight ratio of polyethylene oxide to vinyl acetate of from 1:0.5 to 1:6.
A material within this definition, based on polyethylene oxide of molecular weight 6000 (equivalent to 136 ethylene oxide units), containing approximately 3 parts by weight of vinyl acetate units per 1 part by weight of polyethylene oxide, and having itself a molecular weight of 24 000, is commercially available from BASF as Sokalan (Trade Mark) HP22.
The polymers are suitably present in the compositions of the invention in amounts of from 0.1 to 10% by weight, preferably from 0.2 to 5% by weight and more preferably from 0.3 to 2% by weight.
The graft copolymer is available in aqueous solution form, suitable for use in the preparation of detergent compositions in accordance with the present invention, as described in more detail below.
The surfactant system
In the compositions of the invention, at least 10 wt% of mobile ethoxylated nonionic surfactant is present. Preferred compositions contain at least 12 wt% of mobile ethoxylated nonionic surfactant.
Preferably the ethoxylated alcohol nonionic surfactant has an average alkyl chain length of C8-C18, preferably C12-C16. Especially preferred are C12-C15 aliphatic alcohols ethoxylated with from 2.5 to 8.0 moles of ethylene oxide per mole of alcohol. The benefit associated with the present invention is especially marked with C12-C15 alcohols having an average degree of ethoxylation of from 6.5 to 8.0.
A preferred surfactant system for use in the compositions of the invention comprises ethoxylated nonionic surfactant in combination with primary alcohol sulphate (PAS) .
In this embodiment, the ethoxylated nonionic surfactant preferably constitutes from 30 to 90 wt% of the surfactant system, more preferably from 40 to 70 wt%; and the PAS preferably constitutes from 10 to 70 wt%, more preferably from 30 to 60 wt%, of the surfactant system. Preferably the whole composition contains at least 5 wt% of PAS.
The compositions of the invention may also advantageously contain fatty acid soap, suitably in an amount of from 1 to 5 wt%. The presence of soap is beneficial because of its behaviour as a powder structurant, giving crisp free-flowing powder. However, the presence of soap in the compositions of the invention is not essential.
Water-soluble salts
According to a preferred embodiment of the invention, the compositions contain at least one water-soluble salt. The presence of a water-soluble salt appears to be highly beneficial with respect to the reduction of nonionic surfactant "bleeding", and may also simultaneously fulfil other functions within the composition.
For example, the compositions may contain sodium carbonate, which in any case is useful for increasing detergency and can ease processing. Sodium carbonate may generally be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%, and most suitably from 2 to
13 wt%. However, compositions free of alkali metal carbonate are also within the scope of the invention.
According to a highly preferred embodiment of the invention, the compositions contain a water-soluble salt of citric acid, more preferably sodium citrate. Citrate is of course valuable as a detergency builder as well as enhancing the anti-"bleeding" effect associated with the present invention.
Citrate is suitably present in an amount of from 0.5 to 40 wt% (as sodium citrate dihydrate, based on the whole composition) .
Especially preferred is citrate having a Rosin-Rammler particle diameter of less than 800 μm, preferably from 100 to 500 urn, incorporated within the homogeneous base granules of the composition rather than admixed.
Other ingredients
The compositions of the invention contain a detergency builder system, which preferably comprises an alkali metal, preferably sodium, aluminosilicate. Sodium aluminosilicates may suitably be incorporated in amounts of from 10 to 60 wt% (anhydrous basis) .
The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
0.8-1.5 Na20. A1203. 0.8-6 Si02
These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 Si02 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
Other builders may also be included in the detergent compositions of the invention as necessary or desired. As mentioned above, citrates are especially preferred.
Another class of builders that may be included is comprised by polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, which may suitably be used in amounts of from 0.5 to 15 wt%, especially 5 from 1 to 10 wt%.
»
Other ingredients which may be present include fluorescer; sodium silicate; bleach components such as sodium perborate or percarbonate, bleach activators and bleach 10 stabilisers; proteolytic and lipolytic enzymes; dyes; foam control granules; coloured speckles; perfumes; and fabric softening compounds. This list is not intended to be exhaustive.
15
Bulk density and powder -properties
The invention is of especial applicability to detergent powders of high bulk density, preferably at least 650 g/1, 20 more preferably at least 700 g/1 and most preferably at least 800 g/1. Preferred compositions of the invention have a void volume not exceeding 10%, more preferably not exceeding 5%; void volume may be measured by the known technique of mercury intrusion porosimetry.
25
Advantageously, the content of "fines", that is to say, particles smaller than 180 micrometres, does not exceed 10 wt%, and more preferably it does not exceed 5 wt%.
30
Preparation of the compositions
The high bulk density powders to which the present invention is especially applicable are not generally the 35 direct product of spray-drying processes, although they may be prepared by densification of a spray-dried base powder.
A preferred method of preparation, however, involves preparation of a dense, substantially homogeneous granular base by a non-tower (non-spray-drying) process in which liquid and solid ingredients are mixed and granulated together. Other ingredients may subsequently be postdosed if desired.
Of the ingredients listed above, the surfactants, aluminosilicate, fluorescer, sodium carbonate, sodium silicate and other salts may suitably be incorporated in the base, while bleach ingredients, enzymes, perfumes, dyes, foam control granules and fabric softening compounds will generally be postdosed.
According to a preferred process, the preparation of the granular base is carried out in a high-speed mixer/granulator having both a stirring and a cutting action. The high-speed mixer/granulator, also known as a high-speed mixer/densifier, may be a batch machine such as the Fukae (Trade Mark) FS, or a continuous machine such as the Lδdige (Trade Mark) Recycler CB30. Suitable processes are described, for example, in EP 544 492A, EP 420 317A and EP 506 184A (Unilever) .
Incorporation of sodium citrate
As previously indicated, according to a preferred embodiment of the invention, sodium citrate (or other alkali metal citrate) is incorporated within the granular base, as described and claimed in our International Patent Application No. PCT/EP94/03613 filed on 2 November 1994.
The citrate in the base powder should desirably amount to at least 0.5 wt%, preferably from 0.5 to 40 wt%, of the total composition; and desirably at least 3 wt%, more preferably at least 5 wt% and most preferably from 3 to 15 wt%, of the total composition.
Sodium citrate incorporated in the base powder is preferably finely divided, having a Rosin-Rammler particle size not exceeding 800 micrometres, preferably not exceeding 500 micrometres, and most preferably from 100 to 500 micrometres.
Generally the inorganic builders and other inorganic materials (for example, zeolite, sodium carbonate) are granulated with the surfactants, which act as binders and granulating or agglomerating agents. The finely divided citrate may suitably be incorporated at this stage. Fatty acid soap may be prepared by in situ neutralisation with sodium hydroxide solution during the mixing and granulation process.
Optionally, the citric acid salt may be incorporated in the form of an intimate mixture with surfactant, more preferably nonionic surfactant. Alternatively it may be added in solid form. Fatty acid may also be added in the form of a premix with surfactant, again preferably nonionic surfactant.
Any optional ingredients as previously mentioned may be incorporated at any suitable stage in the process.
In these processes, any PAS present may be already neutralised, that is to say in salt form, when dosed into the high-speed mixer/granulation, or alternatively may be added in acid form and neutralised in situ. If desired, PAS and nonionic surfactant may be introduced in the form of a homogeneous liquid blend, as described in EP 265 203A and EP 507 402A (Unilever). EP 420 317A and EP 506 184A (Unilever) disclose a different process wherein PAS acid, which is a liquid, is mixed and reacted with a solid inorganic alkaline material, such as sodium carbonate, in a continuous high-speed mixer. The resulting granule or "adjunct" is then dosed into another high-speed mixer with the nonionic surfactants and solid ingredients.
All these processes are suitable for the preparation of compositions of the invention.
In accordance with normal detergent powder manufacturing practice, bleach ingredients (bleaches, bleach precursor, bleach stabilisers), proteolytic and lipolytic enzymes, coloured speckles, perfumes and foam control granules are most suitably postdosed to the base powder after it has left the high-speed mixer/granulator.
Additional citrate may if desired be among the postdosed ingredients. That should not be finely divided, and preferably is of comparable particle size to the rest of the composition.
Incorporation of the graft copolvmer
As indicated previously, in the general process outlined above, the preferred route for incorporation of the graft copolymer comprises including a solution (preferably aqueous) of the graft copolymer among the liquid ingredients in the mixing and granulation process used to prepare the base powder.
Thus the preferred process of the invention comprises preparing a substantially homogeneous granular base by mixing and granulation, then optionally postdosing further ingredients, the graft copolymer being incorporated in aqueous solution form during the mixing and granulation process.
Sokalan HP22 is commercially available as a 20 wt% aqueous solution which is highly suitable for incorporation by this route.
EXAMPLES
The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated. Ingredients used in the Examples are abbreviated as follows:
CocoPAS coconut alcohol sulphate
Nonionic 3EO coconut alcohol ethoxylated with 3 moles of ethylene oxide per mole of alcohol
Nonionic 7EO coconut alcohol ethoxylated with 7 moles of ethylene oxide per mole of alcohol
Zeolite MAP zeolite MAP powder, as described and claimed in EP 384 070A (Unilever), Si:Al ratio 1.00
Percarbonate sodium percarbonate having a protective coating of sodium metaborate and sodium metasilicate, as disclosed in GB 2 123 044B (Kao)
TAED tetraacetylethylene diamine (granules)
EDTMP ethylenediamine tetramethylene phosphonate, Ca salt: Dequest (Trade Mark) ex Monsanto.
SCMC sodium carboxymethylcellulose
Mn catalyst bleach catalyst granule as described and claimed in International Patent Application No. PCT/GB94/01904 filed on 2 September 1994
PVP polyvinyl pyrrolidone
The following test methods were used to compare nonionic surfactant bleeding and delivery characteristics.
Test for nonionic surfactant bleeding
The test used gives an estimate of the degree of bleeding during a three week storage period at 37°C by measuring the amount of nonionic surfactant absorbed by preweighed filter papers placed near the top and bottom of a powder column.
A 800 g sample of each powder was weighed out. Powder was poured to a depth of 1 cm into the base of a cylindrical container of diameter 15 cm, and an accurately weighed filter paper (Schleicher and Schull No. 589) placed on top of the powder. More powder was added to an approximate depth of 5 cm above the filter paper, and then covered with a second accurately weighed filter paper. The remainder of the powder sample was then used to cover the second filter paper. The container was tightly sealed and stored in a dry atmosphere at 37°C for 3 weeks. After the storage period the filter papers were removed and weighed, the increase in weight of each calculated, and the values for the two increases averaged.
Test 1 for delivery in the wash: g g es
Delivery characteristics of the powders were compared using a model system which simulates the delivery of a powder in an automatic washing machine, under more adverse conditions (low temperature, minimal agitation) than those normally encountered in a real wash situation.
For this test a cylindrical vessel having a diameter of 4 cm and a height of 7 cm, made of 600 micrometre pore size stainless steel mesh, and having a top closure made of Teflon and a bottom closure of the mesh just described, was used.
The top closure had inserted therein a 30 cm metal rod to act as a handle, and this handle was attached to an agitator arm positioned above 1 litre of water at 20°C in an open container. By means of this agitator apparatus the cylindrical vessel, held at 45 degrees, could be rotated through a circle with a 10 cm radius over a period of 2 seconds and allowed to rest for 2 seconds, before the start of the next rotation/rest cycle.
A 50 g powder sample was introduced into the cylindrical vessel which was then closed. The vessel was attached to the agitator arm which was then moved down to a position such that the top of the cylindrical vessel was just below the surface of the water. After a 10 second delay, the apparatus was operated for 15 rotation/rest cycles.
The cylindrical vessel and handle were removed from the water and and the vessel detached from the handle. Surface water was carefully poured off, and any powder residues transferred to a preweighed container and dried for 24 hours at 100°C. The weight of dried residue as a percentage of the initial powder weight (50 g) was then calculated.
Test 2 for delivery to the wash: delivery device test
Delivery characteristics of the powders were also compared using a model system which emulates the delivery of a powder in an automatic washing machine from a flexible delivery device of the type supplied with Lever's Persil (Trade Mark) Micro System powder in the UK: a spherical container of flexible plastics material having a diameter of approximately 4 cm and a top opening of diameter approximately 3 cm.
In this test the delivery device was attached in an upright position (opening uppermost) to an agitator arm positioned above water (5 litres at 20°C) . By means of this apparatus the device could be moved vertically up and down through a distance of 30 cm, the lowest 5 cm of this travel being under water. Each up or down journey had a duration of 2 seconds, the device being allowed to rest 5 cm under water for 4 seconds at the lowest position, and at the highest position being rotated through 100° and allowed to rest in the resulting tilted orientation for 2 seconds before redescending.
A preweighed powder sample was introduced into the device in its highest position, and the apparatus then allowed to operate for six cycles and stopped when the device was again in its highest position. Surface water was carefully poured off, and any powder residues transferred to a preweighed container. The container was then dried at 100°C for 24 hours, and the weight of dried residue as a percentage of the initial powder weight calculated.
EXAMPLES 1 and 2. COMPARATIVE EXAMPLES A to C
Bleaching detergent powders of high bulk density were prepared to the formulations shown in Table 1. Examples 1 and 2 were in accordance with the invention, while Examples A to C were comparative.
Base powders were prepared using a continuous high-speed mixer/granulator, and other ingredients were postdosed as shown. The Sokalan HP22 was incorporated as a 20 wt% aqueous solution, but the amounts quoted here are for 100 wt% material. Sodium citrate dihydrate incorporated in the base had a Rosin Rammler particle diameter of 415 micrometres.
Table 2 shows the bleeding and delivery characteristics of the base powders prior to the postdosing of the ingredients in the lower part of Table 1.
Detergencies of all the powders (full compositions) were very similar, but the Sokalan HP22 gave a noticeable boost to oily soil removal from polyester and polyester/cotton fabrics.
EXAMPLES 3 to 8
Table 3 shows some examples of non-bleaching formulations in accordance with the invention.
These formulations also contained postdosed sodium citrate dihydrate of larger particle size than the sodium citrate dihydrate incorporated in the base powders.
Examples 1 and 2. Comparative Examples A to C Table 1: formulations
Base
CocoPAS 5.82 5.98 5.55 5.82 6.04 Nonionic 3EO 5.27 5.65 5.25 - -
10 Nonionic 7EO 7.91 8.38 7.78 13.18 14.16 Sokalan HP22 - - 0.74 - 0.79 Soap 2.05 1.40 1.30 2.05 -
Zeolite MAP 36.65 39.17 38.85 36.65 38.98 Sodium citrate - 4.25 4.18 - 4.85
15 Sodium carbonate 1.16 1.20 1.11 1.16 1.20 SCMC 0.90 - - 0.90 - Water/salts 5.49 0.47 0.43 5.49 0.47
Total 65.25 66.49 65.18 65.25 66.48
20
Postdosed
Sodium carbonate 2.23 - 2.30 2.23 - 25 Antifoam/fluorescer 3.00 4.00 3.00 3.00 4.00
TAED granule 4.75 4.75 4.75 4.75 4.75
Mn catalyst 1.70 1.70 1.70 1.70 1.70
Percarbonate 20.50 20.50 20.50 20.50 20.50
EDTMP 0.37 0.37 0.37 0.37 0.37 30 Enzymes 1.75 1.75 1.75 1.75 1.75
Perfume 0.45 0.45 0.45 0.45 0.45
Examples 1 and 2. Comparative Examples A to C
Table 2: properties and test results
A B 1 £ 2.
Citrate in base I I I
Sokalan HP22 solution in base / /
10
Nonionic 3EO/7EO / / /
Nonionic 7EO only / /
15
Bleeding 36.0 35.0 0 45.0 11.0
Cage test residue 47.2 24.8 23.7 70.0 26.1
20 Delivery device test 62.3 0 0 50.0 0
Table 3: Examples 3 to 8: non-bleaching formulations
1 i 5_ £ 7
Base
COCOPAS 6.16 5.84 10.66 9.44 6.46 6.46
Nonionic 3EO 5.78 - 4.24 3.83 5.86 - 10 Nonionic 7EO 5.78 13.74 6.37 5.76 8.78 14.64
Sokalan HP22 0.68 0.65 0.62 0.65 0.51 0.51
Soap 1.84 2.03 1.85 1.64 2.25 2.25
Zeolite MAP 38.66 38.49 30.91 31.52 40.15 40.15
Sodium citrate 4.95 4.71 - 4.30 - - 15 Sodium carbonate 1.31 1.31 2.18 1.83 1.26 1.26
SCMC - - - - 0.72 0.72
Water/salts 44..7722 66..0033 55..3322 55..9922 66..2222 66..2222
Total 72.80 72.80 62.15 64.89 72.22 72.22
20
Postdosed
Sodium citrate 20.62 20.62 30.47 27.73 21.53 21.53 25 Antifoam/PVP 3.20 3.20 4.00 4.00 3.15 3.15 EDTMP 1.43 1.43 1.43 1.43 1.43 1.43 Enzymes 1.50 1.50 1.50 1.50 1.50 1.50 Perfume 0.45 0.45 0.45 0.45 0.45 0.45
Claims
1 A particulate detergent composition comprising an organic surfactant system, a detergency builder system and optionally other detergent ingredients, characterised in that
(a) the organic surfactant system comprises mobile ethoxylated nonionic surfactant in an amount of at least 10 wt% based on the whole composition, and
(b) the composition also comprises a graft copolymer of
(i) polyethylene, polypropylene or polybutylene oxide with
(ii) vinyl acetate (optionally partially saponified) ,
in a weight ratio of (i) to (ii) of from 1:0.2 to 1:10.
2 A detergent composition as claimed in claim 1, characterised in that it contains at least 12 wt% of mobile ethoxylated nonionic surfactant.
3 A detergent composition as claimed in claim 1, characterised in that the nonionic surfactant consists of one or more C12_15 aliphatic alcohols ethoxylated with from 2.5 to 8.0 moles of ethylene oxide.
4 A detergent composition as claimed in claim 3, characterised in that the nonionic surfactant consists of one or more C12.15 aliphatic alcohols ethoxylated with from 6.5 to 8.0 moles of ethylene oxide.
5 A detergent composition as claimed in any preceding claim, characterised in that the organic surfactant system consists essentially of:
(i) the ethoxylated nonionic surfactant (60-100 wt% of the surfactant system) , and
(ii) optionally primary alcohol sulphate (0-40 wt% of the surfactant system) .
6 A detergent composition as claimed in claim 5, characterised in that the surfactant system consists essentially of from 30 to 90 wt% (based on the surfactant system) of ethoxylated nonionic surfactant and from 10 to 70 wt% (based on the surfactant system) of primary alcohol sulphate.
7 A detergent composition as claimed in any preceding claim, characterised in that the graft copolymer is obtainable by grafting a polyalkylene oxide of molecular weight (number average) 2000 - 100 000 with vinyl acetate (optionally partially saponified) in a weight ratio of polyalkylene oxide to vinyl acetate of 1:0.2 to 1:10.
8 A detergent composition as claimed in any one of claims 1 to 7, characterised in that the graft copolymer is obtainable by grafting a polyethylene oxide of molecular weight (number average) 2000 - 50 000 with vinyl acetate (optionally partially saponified) in a weight ratio of polyethylene oxide to vinyl acetate of 1:0.5 to 1:6.
9 A detergent composition as claimed in any preceding claim, characterised in that the graft copolymer is present in an amount of from 0.1 to 10 wt%.
10 A detergent composition as claimed in any preceding claim, which further comprises a water-soluble salt of citric acid.
11 A detergent composition as claimed in claim 10, characterised in that the composition contains from 0.5 to 40 wt% of sodium citrate.
12 A detergent composition as claimed in claim 11, comprising a substantially homogeneous granular base and optionally postdosed ingredients, characterised in that the granular base contains at least 0.5 wt% (based on the whole composition) of sodium citrate.
13 A detergent composition as claimed in claim 12, characterised in that the substantially homogeneous granular base contains from 3 to 15 wt% (based on the whole composition) of sodium citrate.
14 A detergent composition as claimed in claim 12 or claim 13, characterised in that the sodium citrate in the substantially homogeneous granular base has a Rosin-Rammler particle size not exceeding 800 micrometres.
15 A detergent composition as claimed in any preceding claim, characterised in that the detergency builder system comprises from 10 to 60 wt% (based on the whole composition) of crystalline or amorphous alkali metal aluminosilicate.
16 A detergent composition as claimed in claim 15, characterised in that the alkali metal aluminosilicate is zeolite P having a silicon to aluminium ratio not exceeding 1.33 (zeolite MAP) .
17 A detergent composition as claimed in any preceding claim, characterised by a bulk density of at least 650 g/litre.
18 A detergent composition as claimed in any preceding claim, characterised in that it is not the direct product of a spray-drying process.
19 A detergent composition as claimed in any preceding claim, characterised by a void volume not exceeding 5%.
20 A process for the preparation of a particulate detergent composition as claimed in any preceding claim, characterised in that it comprises preparing a substantially homogeneous granular base by mixing and granulation, then optionally postdosing further ingredients, characterised in that there is incorporated during the granulation process an aqueous solution of the graft copolymer (b) .
21 A process as claimed in claim 20, characterised in that a water-soluble salt of citric acid is also incorporated within the substantially homogeneous granular base.
22 A process as claimed in claim 21, characterised in that the water-soluble salt is sodium citrate and is incorporated in an amount of at least 0.5 wt% based on the whole composition.
23 Use of a graft copolymer of
(i) polyethylene, polypropylene or polybutylene oxide with
(ii) vinyl acetate (optionally partially saponified) ,
in a weight ratio of (i) to (ii) of from 1:0.2 to 1:10,
to prevent or reduce the bleeding out of nonionic surfactant from a particulate detergent composition comprising an organic surfactant system comprising a mobile ethoxylated nonionic surfactant in an amount of at least 10 wt% based on the whole composition, a detergency builder system and optionally other detergent ingredients.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9403155 | 1994-02-18 | ||
| GB9403155A GB9403155D0 (en) | 1994-02-18 | 1994-02-18 | Detergent compositions |
| PCT/EP1995/000318 WO1995022593A1 (en) | 1994-02-18 | 1995-01-28 | Detergent composition containing graft copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0745117A1 true EP0745117A1 (en) | 1996-12-04 |
| EP0745117B1 EP0745117B1 (en) | 1997-12-10 |
Family
ID=10750575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP95907629A Expired - Lifetime EP0745117B1 (en) | 1994-02-18 | 1995-01-28 | Detergent composition containing graft copolymer |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0745117B1 (en) |
| JP (1) | JPH09509203A (en) |
| AU (1) | AU1577295A (en) |
| CA (1) | CA2177057A1 (en) |
| CZ (1) | CZ239796A3 (en) |
| DE (1) | DE69501208T2 (en) |
| ES (1) | ES2110314T3 (en) |
| GB (1) | GB9403155D0 (en) |
| HU (1) | HU218497B (en) |
| PL (1) | PL177812B1 (en) |
| SK (1) | SK281380B6 (en) |
| WO (1) | WO1995022593A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL185641B1 (en) * | 1995-09-04 | 2003-06-30 | Unilever Nv | Detergent compositions and method of obtaining them |
| US5750483A (en) * | 1995-12-06 | 1998-05-12 | Basf Corporation | Non-phosphate machine dishwashing compositions containing polycarboxylate polymers and nonionic graft copolymers of vinyl acetate and polyalkylene oxide |
| EP1085080B1 (en) * | 1998-06-04 | 2006-04-05 | Kao Corporation | Surfactant composition |
| CA2590434A1 (en) | 2004-12-17 | 2006-06-22 | The Procter & Gamble Company | Hydrophobically modified polyols for improved hydrophobic soil cleaning |
| EP1838825A1 (en) | 2004-12-17 | 2007-10-03 | The Procter and Gamble Company | Hydrophilically modified polyols for improved hydrophobic soil cleaning |
| JP2009538946A (en) † | 2006-05-31 | 2009-11-12 | ビーエーエスエフ ソシエタス・ヨーロピア | Amphiphilic graft polymers based on polyalkylene oxides and vinyl esters |
| US20090023625A1 (en) † | 2007-07-19 | 2009-01-22 | Ming Tang | Detergent composition containing suds boosting co-surfactant and suds stabilizing surface active polymer |
| EP2823029A1 (en) * | 2012-03-09 | 2015-01-14 | The Procter & Gamble Company | Detergent compositions comprising graft polymers having broad polarity distributions |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8821035D0 (en) * | 1988-09-07 | 1988-10-05 | Unilever Plc | Detergent compositions |
| US5049302A (en) * | 1988-10-06 | 1991-09-17 | Basf Corporation | Stable liquid detergent compositions with enchanced clay soil detergency and anti-redeposition properties |
-
1994
- 1994-02-18 GB GB9403155A patent/GB9403155D0/en active Pending
-
1995
- 1995-01-28 WO PCT/EP1995/000318 patent/WO1995022593A1/en not_active Application Discontinuation
- 1995-01-28 DE DE69501208T patent/DE69501208T2/en not_active Expired - Fee Related
- 1995-01-28 HU HU9602274A patent/HU218497B/en not_active IP Right Cessation
- 1995-01-28 SK SK1059-96A patent/SK281380B6/en unknown
- 1995-01-28 AU AU15772/95A patent/AU1577295A/en not_active Abandoned
- 1995-01-28 EP EP95907629A patent/EP0745117B1/en not_active Expired - Lifetime
- 1995-01-28 PL PL95316075A patent/PL177812B1/en unknown
- 1995-01-28 CA CA 2177057 patent/CA2177057A1/en not_active Abandoned
- 1995-01-28 JP JP7521533A patent/JPH09509203A/en active Pending
- 1995-01-28 ES ES95907629T patent/ES2110314T3/en not_active Expired - Lifetime
- 1995-01-28 CZ CZ962397A patent/CZ239796A3/en unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9522593A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB9403155D0 (en) | 1994-04-06 |
| SK105996A3 (en) | 1997-07-09 |
| HU9602274D0 (en) | 1996-10-28 |
| SK281380B6 (en) | 2001-03-12 |
| CZ239796A3 (en) | 1996-12-11 |
| CA2177057A1 (en) | 1995-08-24 |
| PL177812B1 (en) | 2000-01-31 |
| WO1995022593A1 (en) | 1995-08-24 |
| HUT75198A (en) | 1997-04-28 |
| HU218497B (en) | 2000-09-28 |
| AU1577295A (en) | 1995-09-04 |
| PL316075A1 (en) | 1996-12-23 |
| JPH09509203A (en) | 1997-09-16 |
| ES2110314T3 (en) | 1998-02-01 |
| DE69501208T2 (en) | 1998-04-02 |
| DE69501208D1 (en) | 1998-01-22 |
| EP0745117B1 (en) | 1997-12-10 |
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