EP0000215A1 - Low-phosphate detergent composition for fabric washing - Google Patents
Low-phosphate detergent composition for fabric washing Download PDFInfo
- Publication number
- EP0000215A1 EP0000215A1 EP78200034A EP78200034A EP0000215A1 EP 0000215 A1 EP0000215 A1 EP 0000215A1 EP 78200034 A EP78200034 A EP 78200034A EP 78200034 A EP78200034 A EP 78200034A EP 0000215 A1 EP0000215 A1 EP 0000215A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- ion exchange
- composition according
- compositions
- phosphate
- 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- Withdrawn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 103
- 239000003599 detergent Substances 0.000 title claims abstract description 55
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 20
- 239000010452 phosphate Substances 0.000 title claims abstract description 18
- 239000004744 fabric Substances 0.000 title description 8
- 238000005406 washing Methods 0.000 title description 6
- 239000000463 material Substances 0.000 claims abstract description 60
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 56
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 9
- 239000011976 maleic acid Substances 0.000 claims abstract description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims description 33
- 229920001577 copolymer Polymers 0.000 claims description 25
- 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 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 11
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000000344 soap Substances 0.000 claims description 7
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 7
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- 150000001768 cations Chemical class 0.000 claims description 5
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- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
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- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 16
- -1 "soaps" Chemical class 0.000 description 15
- 235000021317 phosphate Nutrition 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 7
- 150000008064 anhydrides Chemical group 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000004900 laundering Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
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- 239000002585 base Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
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- 239000003795 chemical substances by application Substances 0.000 description 4
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- 230000001105 regulatory effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 229940044600 maleic anhydride Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 2
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- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000005365 phosphate glass Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect 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
- 230000002797 proteolythic effect Effects 0.000 description 1
- VMXUWOKSQNHOCA-UKTHLTGXSA-N ranitidine Chemical compound [O-][N+](=O)\C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-UKTHLTGXSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011182 sodium carbonates Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
-
- 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
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
Definitions
- This invention relates to detergent compositions, and, in particular, to detergent compositions having only a specific low level of phosphorous-containing builder salt.
- compositions based on aluminosilicate and having specifically defined low levels of phosphate builder can have excellent all-round detergency performance provided that they also include a small amount of certain. specific polymeric materials, namely polymers including maleic acid or similar dibasic acid groups.
- Copolymers containing maleic acid moieties have already been suggested for use in detergent compositions containing aluminosilicate.
- a copolymer of maleic acid and methylvinylether is used at a high level essentially acting as a co-builder with the aluminosilicate.
- Belgian Patent No. 835, 492 there is a suggestion tnat such copolymers can be used in mixed aluminosilicate/tripolyphosphate systems to improve the processing characteristic of spray-dried detergent compositions.
- compositions containing various polymers also discloses compositions containing various polymers but these compositions normally contain substantial amounts of phosphate or, if free of phosphate, contain builder levels of the polymers. Furthermore, these polymers are normally polyacrylates and the polymers selected for use in the present invention have been shown to provide benefits in bleachable stain.removal not shared by polyacrylate materials.
- a detergent composition comprising:
- compositions of the invention contain from 1% to 4% of phosphate salts, especially a tripolyphosphate.
- Other water-soluble builder salts, while not excluded from the present invention are also preferably absent except in small amounts.
- Highly preferred compositions are in granular form and consain from 5% to 20% surfactant and from 15% to 50% of the aluminosilicate.
- the detergent compositions of the instant invention contain a surfactant selected from anionic, nonionic, zwitterionic and ampholytic surfactants.
- the surfactant is used in an amount from about 2% to about 60%, preferably from about 5% to about 50% of the detergent compositions.
- a typical listing of the classes and species of surfactants useful herein appears in U.S. Patent 3,929,678, incorporated herein by reference.
- the following list of detergent compounds and mixtures which can be used in the instant compositions is representative of such materials, but is not intended to be limiting.
- Water-soluble salts of the higher fatty acids are useful as the detergent component of the compositicns herein.
- This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 careon aton s end preferably from about 10 to about 20 carbon atoms. Soaps can be rase by direct saponificacion of fats and oils or by tne nautralization of free fatty acias.
- Particularly useful are the sodium and potassium salts cf the. mixtures of fatty acids derived from_coconut oil and tallow, "i.e. sodium or potassium tallow and coconut soap.
- Another class of detergents includes water-soluble salts, parti- lene glycol.
- Other suitable ncnionic synthetic desergents include polyethylene oxide condensates of alkyl phenols, e.g., the condensator products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or brancher chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
- the water-soluble condensation products of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms, are also useful nonionic detergents herein.
- Semi-polar nonionic detergents include water-soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon ators and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon. atoms; water-soluble moiety of from about 10 to 28 carbon atoms and a noiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
- Ampholytic detergents include derivatives of aliphati or alipta-
- Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphorium and sulfonium compounds in which the aliphatic moieties can be straight chain or branched, and wherein one of the aliphatic substimuents certains from about 8 to 18 carbon atoms and one centains an water solubilizing group.
- Other useful detergent compounds her a include the water-soluble salts of esters of ⁇ -sulfomater from a asica containing from about 6 to 20 carbon atoms in the factor and group and from about I to 10 carbon atoms in the ester group water-soluble salts of 2-acyl- oxy-alkane-l-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfenates containing from about 12 to 24 carbon atoms; and ⁇ -alkyloxy alKane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 caroon atoms in the alkane moiety.
- a highly preferred mixture of surfactants is an anicnic/nonlonic mixture, especially sulfonate and a C 10 - C 20 alkanol ethoxylated with-from 3 to 30 moles of ethylene oxide per mole of alkanol.
- Highlyprefarmed mixtures include C 12 alky. benzene sulfonate and C 14 - C 15 alcohol-(7)ethoxylate, in ratios of from 5:1 to 1:3, preferably 5:1 to will in still more preferred compo sitions, a fatty acid soap is added to the above-dascribed mixture, preferably a C 10 - C 20 soap as a level of from if to 5%.
- the aluminosilicate on exchange materials used herein are pre- higher calcium ion exchange capacity and a higher exchange is the than similar materials previously suggested as detergency builders. Such high calcium ion exchange rate and capacity appear to be a function of several interrelated factors which result from the method of preparing said aluminosilicate ion exchange materials.
- these ion exchange builder materials are in the "sodium form".
- a second essential feature of the ion exchange builder materials herein is that they be in a hydrated form, i.e. contain 10%-28%, preferably 10%-22%, of water.
- Highly preferred aluminosilicates herein frequently contain from about 18% to about 22% water in their crystal matrix. It has been found, for example, that less highly hydrated aluminosilicates, e.g. those containing about 6% water, do not function effectively as ion exchange builders when employed in the context of a laundry detergent composition.
- a third essential feature of the ion exchange builder materials herein is their particle size range. Proper selection of small particle sizes results in fast, highly efficient builder materials.
- a highly preferred synthetic aluminosilicate ion exchange material for use in the present invention is known under the commercial denomination ZEOLITE A; in the dehydrated form is can be used as a molecular sieve and catalyst carrier.
- the synthetic aluminosilicate known commercially as ZEOLIT X is also suitable for use in the present invention, as are the amorphous synthetic aluminosilicates.
- a preferred synthetic aluminosilicate ion exchange material has the formula Examples of aluminosilicates having a molar ratio: A102:Si02 1, suitable for use in the instant compositions include: and Although completely hydrated aluminosilicate ion exchange materials are preferred herein, it is recognized that the partially dehydrated aluminosilicates having the general formula given hereinbefore are also excellently suitable for rapidly and effectively reducing the water hardness during the laundering operation. Of course, in the process of preparing the instant aluminosilicate ion exchange material, reaction-crystallization parameter fluctuations can result in such partially hydrated materials. As pointed out previously, aluminosilicates having about 6% or less water do not function effectively for the intended purpose in laundering context. The suitability of particular partially dehydrated water-insoluble aluminosilicates for use in the compositions of this invention can easily be asserted and does only involve routine testing as, for example, described herein (Ca-ion exchange capacity; rate of exchange).
- the ion exchange properties of the aluminosilicates herein can conveniently be determined by means of a calcium ion electrode.
- the rate and capacity of Ca ++ uptake from an aqueous solution containing a known quantity of Ca ++ ion is determined as a function of the amount of aluminosilicate ion exchange material added to the solution.
- the water-insoluble, inorganic aluminosilicate ion exchange materials prepared in the foregoing manner are characterized by a particle size diameter from about 0.1 micron to about 100 microns.
- Preferred ion exchange materials have a particle size diameter from about 0.2 micron to about 10 microns.
- the term "particle size diameter” herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination, scanning electron microscope (SEM).
- aluminosilicate ion exchangers herein are further characterized by their calcium ion exchange capacity, which is at least about 200 mg. equivalent of CaC0 3 hardness/gram of aluminosilicate, calculated on an anhydrous basis, and which general- ly lies within the range of from about 300 mg. eq./g. to about 352 mg. eq./g.
- the ion;exchange materials herein are still further charac- terized by their calcium ion exchange rate, which is at least about 2 grains (Ca )/gallon/minute/gram of aluminosilicate (anhydrous basis), and lies within the range of about 2 grains/ gallon/minute/gram to about 6 grains/gallon/minute/gram, baser on calcium ion hardness.
- Optimum aluminosilicate for builder purposes exhibit a Ca++ exchange rate of at least about 4 grains/ gallon/minute/gram.
- Preferred detergent compositions of the present inventior contain from 15% to 50% of the aluminosilicate, more preferably from 20% to 45%.
- compositions contain from 1% to 3% of a polyphosphate salt, especially sodium or potassium tripolyphosphate or higher poly- phosphates, such as the tetra-,penta-, and hexaphosphates up to the so called glassy metaphosphates with some 12-14 or more phosphorous atoms in the molecule.
- a polyphosphate salt especially sodium or potassium tripolyphosphate or higher poly- phosphates, such as the tetra-,penta-, and hexaphosphates up to the so called glassy metaphosphates with some 12-14 or more phosphorous atoms in the molecule.
- the use of such phosphates does of course reduce the economy of phosphate usage achieved by the compositions, but it also improves some aspects oi their cleaning power, especially whiteness maintenance and removal c i par ticulate soils, such as clay-like materials.
- Preferred compositions contain from 1% to 3% of tripolyphosphate, or from 0.5% to 2% pentaphosphate.
- phosphates are obtainable commercially under trade names, such as those of Messrs. Albright and Wilson, viz. Phosphate Glass 627 (believed to be sodium pentaphosphate) Calgon N12 (believed to be the P 12 glassy phosphat tively known as glassy sodium phosphate, sodium hexametaphosphate or Graham's Salts.
- the fourth essential component herein is a water-soluble copolymer or derivative thereof as defined above.
- the copolymeric ingredient is used in an amount from about 0.1% to about 3%, preferably from 0.25% to 1.5%.
- the alkyl vinyl ethers constituting coponent (i) of the composition of the invention are preferably methyl vinyl ethers.
- Preferred molecular weights for these copolymers are in the range from 12,000 to 1,500,000, more preferably 50,000 to 300,000.
- Copolymers in anhydride form believed to be of this class are commercially available from GAF Corporation under the trade names Gantrez AN119 (MWt.200,000 in anhydride form)
- Gantrez AN139 MWt.500,000 in anhydride form
- AN149 MWt.750,000 in anhydride form
- AN169 MWT.1,125,000 in anhydride form.
- Ethyl and methyl vinyl ether/maleic anhydride copolymers are also available from BASF under the trade name Sokalan and having molecular weight about 30,000. Higher than methyl alkyl vinyl ethers, especially C to C 4 alkyl, have been found to be most effective in copolymers of much lower molecular weight, preferably in the range from 2,000 to 20,000, especially about 4,000 to 12,000.
- the molecular weight of these copolymers is the viscosity average molecular weight and is determined as follows :
- acryiic-maleic copolymers derived from olefin (ii) above are preferably based upon methyl acrylate or methyl methacrylate, although higher alkyl esters may be employed.
- the manufacture of these polymers, and the control of the molar ratio of the monomers one to other is described by Seymour, Harris and Branum in Industrial and Engineering Chemistry, Volume 41, pages 1509 to 1513, 1949
- Preferably copolymers wherein the molar ratio of acrylate ester to maleic acid is from about 2:1 to 1:1 are employed herein, especially close to 1:1; their molecular weight is preferably in the range from 3,000 to 1,500,000, especially from about 5,000 to 30,000.
- the molecular weight of these copolymers is determined by the method described above.
- the copolymers are preferably of high molecular weight and are preferably based on ethylene.
- the preferred molecular weight range is from 275,000 to 1,500,000.
- Another preferred group of materials within this class are copolymers of maleic anhydride or acid with propylene, isobutylene, alkyl substituted isobutylene and, especially, di-isobutylene, having mols. cular weight in the range from about 500 to 50,000 and molar ratic of olefine to maleic acid in the range from - l:l to 1:2. Suitable materials of this type are available under the trade names "Empicryl" of Albright and Wilson Ltd. and "Orotan” of Rohm and Haas.
- the vinyl pyrrolidone maleic copolymers (using olefin (iv)above) preferably have molecular weignt in the rarge from about 50,000, especially about 20,000 to 30,000.
- the molecular weight is determined by the method described above but employing 1M NaOH as solvent and using the equation II above.
- the styrene-maleic acid copolymers (olefin (v) above) preferably have molecular weight about 300,000. The molecular weight is determined by the same method but employing acetone as solvent and using the equation I above.
- copolymers are those of methyl and ethyl vinyl ether-maleic described above.
- compositions may also be included in the composition other inorganic salts which have some detergency building effect and effect.upon the alkalinity of the compositions, or act as fillers, such as sodium or potassium carbonates, borates, sulphates and silicates.
- an alkali metal especially sodium, silicate be present.
- the alkali metal silicate preferably is used in an amount from 0.5% to 10%, preferably from 3% to 8%.
- Suitable silicate solids have a molar ratio of Si0 2/ alkali metal 2 0 in the range from about 0.5 to about 4.0, but much more preferably from 1.0 to 1.8, especially about 1.6.
- the alkali metal silicates suitable herein can be commercial preparations of the combination of silicone dioxide and alkali metal oxide, fused together in varying proportions.
- Crystalline silicate solids normally possess a high alkalinity content; in addition hydration water is frequently present as, for example, in metasilicates which can exist having 5, 6 or 9 molecules of water.
- the alkalinity is provided through the monovalrnt alkali metal ions such as, for example, sodium, potassium, lithium and mixtures thereof.
- the sodium and potassium silicate solids are generally used. Highly preferred for the compositions herein are the commercially widespread available sodium silicate solids.
- the alkali metal silicate solids are preferably incorporated into the instant detergent compdsitions during the crutchinr operation together with the other major constituents, particularly the surface-active agent and the water-insoluble aluminosilicate ion exchange material.
- the required amount of silicate solids can also be incorporated into the detergent composition in the form of colloidal silicates-called water glass which are frequently sold as a 20-50% aqueous solution.
- Silicate solids are frequently added to heavy-duty granular detergent compositions as corrosion inhibitors to provide protection to the metal parts of the washing machines in which the alkali washing liquor is utilized.
- sodium silicates provide a certain degree of crispness and pourability to detergent granules whicn is very desirable to avoid lumping and caking, particularly during prolonged storage. It is known, nowever, that silicate solids cannot easily be incorporated into detergent compositions, comprising major amounts of water-insoluble aluminosilicate ion exchange materials as they are capable of enhancing-and facilitating the deposition of these water-insoluble particles on the textiles being laundered as well as on the machine.
- alkali metal silicate solids and water-insoluble aluminosilicates apparently adversely affects the capacity.and rate of hardness depletion of the ion exchange material in laundry liquor. It is believed that this can be due to a physical blocking of the ion exchange sites on the synthetic zeolites herein.
- a minor effective amount of alkali metal silicate solids has been found to be compatiblewith a major amount of synthetic aluminosilicate materials in the presence of organic syntnetic detergents, thereby providing effective corrosion inhibition and crispness benefits without concurrently enhancing the deposition of the synthetic aluminosilicate par-_ ticles on the textiles and on the walls of thewashing machine.
- the detergent compositions of the present invention can contain, in addition to the aluminosilicateion exchange builders, small amounts of other non-phosphate builders ⁇
- polyphosphonates specifically include, for example, the sodium and postassiumsalts of ethylene diphosphonic acid, the sodium and potassium saltsof ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid.
- Examples of these and other phosphorous builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021;. 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
- polyacetate and polycarboxylate builder salts include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriaceticacid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, andcitric acid.
- Highly preferred non-phosphorous auxiliary builder materialsherein include sodium carbonate, sodium bicarocnate, sodium citrate, sodiumoxy- disuccinate, sodium mellitate, sodium nitrilotriacetate, and sodium ethylenediaminetetraacetate,and mixtures thereof.
- compositions of this invention can require the presenceof a suds regulating or suppressing agent.
- Suds regulating components are normally used in an amount from about 0.001% to About 5%, preferably fromabout 0.05%toabout 3%and especially from about 0.10%to about 1%
- the suds suppressing (regulating) agents which are known to be suitable as sudssuppressing agents in detergent context canbe used in the compositionsherein. These include the silicone suds suppressing agents, especially the mixtures of silicones and silica described in U.S. Patent No . 3,933,672, the disclosure of which is incorporated herein by reference.
- a particularly preferred suds suppressor is the material knownas "HYFAC", the sodium salt of a long-chain (C 20 -C 24 ) fatty acid.
- the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
- Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the rarge from 400-1 000; and a penetration value of at least 6, measured at 77°C by ASTM-D1321.
- Suitable examples of the above waxes include : microcrystallineand oxidized microcrystalline petrolatum_waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax : beeswax; candelilla; and carnauba wax.
- the detergent compositions herein can contain all manner of other materials commonly found in laundering and cleaning compositions.
- such compositions can contain thickeners and soil suspending agents such as carboxymethylcellulose and the like.
- Enzymes, especially the proteolytic and lipolytic enzymes commonly used in laundry detergent compositions, can also be present herein.
- Various perfumes, optical bleaches, fillers, anti-caking agents, fabric softeners and the like can be present in the compositions to provide the usual benefits occasioned by the use of such materials in detergent compositions. It is to be recognized that all such adjuvant materials are useful herein inasmuch as they are compatible and stable in the presence of the aluminosilicate ion exchange builders.
- the granular detergent compositions herein can also advantageously contain a peroxy bleaching component in an amount from about 3% to about 40% by weight,preferably from about 8% to about 33% by weight.
- suitable peroxy bleach components for use herein include perborates, persulfates, persilicates, perphosphates, percarbonates, and more in general all inorganic and organic peroxy bleaching agents which are known to be adapted for use in the subject compositions.
- the composition can also advantagenusly include a bleach activator which is normally an organic compound containing an N-acyl,or an 0-acyl(preferably acetyl) group. Preferred materials are N,N,N',N' -tetraacetyl ethylene diamine and N,N,N',N' -tetraacetylglycouril.
- the detergent compositions of this invention can be prepared by any of the several well known procedures for preparing commercial detergent compositions.
- the compositions can be prepared by simply admixing the aluminosilicate ion exchange material with the water-soluble organic detergent compound.
- the adjuvant builder material and optional ingredients can be simply admixed therewith, as desired.
- an aqueous slurry of the aluminosilicate ion exchange builder containing the dissolved, water-soluble organic detergent compound and the optional and auxiliary materials can be spray-dried in a tower to provide a grar.ular composition.
- the granules of such spray-dried detergent compositions contain the aluminosilicate ion exchange builder, the organic detergent compound and the optional and auxiliarymaterials.
- the surfactant ingredients, thealumino- silicate and the polymeric material are slurried in an aqueous medium, together with sodium silicate and sodium sulfate, if present.
- This mixture is then spray-dried and the necessary quantities of the phosphate salt, e.g. sodium tripolyphosphate, is added separately to thespray- dried mixture.
- Other ingredients which are normally added after the spray-drying step are enzyme and bleach.
- the sodium tripolyphosphate be dry-mixed in this fashion because this avoids the possibility of reversicn of the tripolyphosphate to ortho and/or pyrophosphate, it being known that such reverted phosphate materials tend to deposit noticebly on both the laundered fabrics and on washing machine surfaces.
- the compositions of the present invention show very little or ro tendency to deposit soluble phosphate salts on to fabric or machine surfaces and are very advantageous in this regard.
- a specific type of,sodium silicate and specific drying conditions are used to avoid agglomeration of the aluminosilicate material.
- Agglomeration of the aluminosilicate tends to cause a high level of insolubles, an unsightly solution appearance, deposits on fabrics, and blocking of cation exchange sites with resulting reduced calcium depletion capacity.
- the two parameters controlling the tendency for the aluminosilicate to agglomerate are ratio and level of silicate and the level of base powder moisture.
- silicate solutions involve whathas become known as the crystalloid-collo ⁇ dal (amorphous) balance with the break-point at the ratio 2.0 molar or 1.96 weight (based on Si0 2 /Na 2 0).
- the silicate anion consists of either one or two nonionic crystalline species.
- the molecular weight of silicates increases as polymerization occurs, with a step change in intrinsic viscosity : It has been found that the degree of aluminosilicate agglomeration is dramatically reduced by the use of low, e.g. 1.6 ratio si silicate.
- decreasing base powder moisture tends to increase agglomeration of aluminosilicate, especially if the base granules are overdried below the level corresponding to the aluminosilicate bound moisture.
- the process uses 1.6 ratio silicate at a level from 3% to 8% and the base powder is dried to a free moisture level of from 2% to 6%, especially about 4%.
- the detergent compositions herein are employed in aqueous liquros to cleanse surfaces, especially fabric surfaces, using any of the standard laundering and cleansing techniques.
- the compositions herein are particularly suited for use in standard automatic washing machines at concentrations of from about 0.1% to about 1.5% by weight.
- Optimal results are obtained when the compositions herein are employed in an aqueous laundry bath at a level of at least about 0.5% by weight.
- the dry compositions herein are usually added to a conventional aqueous laundry solution at a rate of about 1.0 cup/17 gallons of wash water.
- the detergent compositions containing such materials have a pH in the range of from about 8.0 to about 11, preferably about 9.5 to about 10.2.
- the compositions herein function optimally within the basic pH range to remove soils e.g. triglyceride soils and stains.
- the aluminosilicates herein inherently provide a basic solution
- the detergent compositions comprising the aluminosilicate and the organic detergent compound can additionally contain from about 5% tc about 25% by weight of a pH adjusting agent.
- Such compositions can, of course, contain the auxiliary builder materials and optional ingredients as hereinbefore described.
- the optional pH adjusting agents useful herein include any of the water-soluble, basic materials commonly employed in detergentcompositions.
- typicalexamples of such water-soluble materials include the sodiumphosphates :sodium hydroxide : potassium hydroxide; triethanolamine;diethanolamine hydroxide and the like.
- Preferred pH adjusting agents herein include sodium hydroxide and triethanolamine
- the present invention is illustrated by the following Examples.
- compositions were prepared by spray-drying an aqueous slurry of the ingredients except for sodium perborate which was dry-mixed to the spray-dried granular composition.
- compositions of the above examples provided excellent detergency on a wide range of fabrics and soils, and were equivalent in performance to conventional fully phosphate-built detergents.
- compositions of theabove Examples all provide good detergency performance, comparable to conventional high-phosphate compositions and superior to compositions built with Zeolite A but without the minor content of phosphate and polymeric material.
- Examples 4-6 Similar results are achieved when the tripolyphosphate in Examples 4-6 is replaced by a P 12 glassy phosphate.
- the anionic.nonionic active systems of Examples 6-9 can be replaced by all nonionic systems, for example, with Dobanol 45-E-7 alone or with 8:1 mixtures of, for example, Dobanol 45-E-7 and Dobanol 45-E-3.
- the Zeolite A in Examples 4-6 and 9 can be replaced in whole or in part by an amorphous sodium aluminosilicate.
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- 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)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB2597377 | 1977-06-21 | ||
GB2597377 | 1977-06-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0000215A1 true EP0000215A1 (en) | 1979-01-10 |
Family
ID=10236297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78200034A Withdrawn EP0000215A1 (en) | 1977-06-21 | 1978-06-09 | Low-phosphate detergent composition for fabric washing |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0000215A1 (enrdf_load_html_response) |
BE (1) | BE5T2 (enrdf_load_html_response) |
DE (1) | DE2857154A1 (enrdf_load_html_response) |
FR (1) | FR2416945A1 (enrdf_load_html_response) |
GB (1) | GB2040981B (enrdf_load_html_response) |
IT (1) | IT1096592B (enrdf_load_html_response) |
NL (1) | NL7815009A (enrdf_load_html_response) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0025551A1 (de) * | 1979-09-13 | 1981-03-25 | BASF Aktiengesellschaft | Verwendung von (Meth)acrylsäure-Maleinsäure-Copolymerisaten als Inkrustierungsinhibitoren in Waschmitteln |
EP0063399A1 (en) * | 1981-04-22 | 1982-10-27 | THE PROCTER & GAMBLE COMPANY | Granular detergent compositions containing film-forming polymers |
EP0098187A1 (fr) * | 1982-06-18 | 1984-01-11 | Rhone-Poulenc Chimie | Zeolite comme auxiliaire de détergence |
EP0082564A3 (en) * | 1981-12-23 | 1985-01-23 | Unilever N.V. | Dishwashing composition |
JPS60106895A (ja) * | 1983-08-27 | 1985-06-12 | ザ、プロクタ−、エンド、ギヤンブル、カンパニ− | 洗剤組成物 |
US4545919A (en) * | 1982-08-31 | 1985-10-08 | Ciba-Geigy Corporation | Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof |
EP0193360A3 (en) * | 1985-02-23 | 1987-07-01 | The Procter & Gamble Company | Detergent compositions |
FR2609065A1 (fr) * | 1986-12-24 | 1988-07-01 | Rhone Poulenc Chimie | Nouveaux agents de lavage et compositions les contenant |
EP0279134A1 (fr) * | 1986-12-24 | 1988-08-24 | Rhone-Poulenc Chimie | Latex antiredéposant pour le lavage d'articles textiles |
WO1991009932A1 (en) * | 1989-12-12 | 1991-07-11 | Unilever N.V. | Detergent compositions |
EP0423487A3 (en) * | 1989-10-18 | 1991-11-21 | Joh. A. Benckiser Gmbh | Rinse aid for dishwashing machines |
US5441672A (en) * | 1991-05-23 | 1995-08-15 | Henkel Kommanditgesellschaft Auf Aktien | Concentrated water-containing liquid detergent |
EP0612842A3 (en) * | 1993-02-24 | 1995-10-04 | Enichem Spa | Compositions for textile material washing. |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4265777A (en) * | 1980-04-17 | 1981-05-05 | The Procter & Gamble Company | Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap |
US4343713A (en) * | 1980-10-29 | 1982-08-10 | The Procter & Gamble Company | Particulate composition |
DE3261394D1 (en) * | 1981-01-21 | 1985-01-17 | Unilever Plc | Detergent compositions |
NZ201212A (en) * | 1981-07-15 | 1985-08-16 | Unilever Plc | Detergent additives and compositions |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2291268A1 (fr) * | 1974-11-13 | 1976-06-11 | Procter & Gamble | Compositions detergentes comportant des matallo-silicates insolubles et un copolymere vinyliques soluble dans l'eau |
DE2547389A1 (de) * | 1975-10-23 | 1977-05-05 | Henkel & Cie Gmbh | Phosphatfreies waschmittel |
-
1978
- 1978-06-09 EP EP78200034A patent/EP0000215A1/en not_active Withdrawn
- 1978-06-09 DE DE19782857154 patent/DE2857154A1/de active Granted
- 1978-06-09 NL NL7815009A patent/NL7815009A/xx unknown
- 1978-06-09 GB GB7922535A patent/GB2040981B/en not_active Expired
- 1978-06-09 BE BEBTR5A patent/BE5T2/xx not_active IP Right Cessation
- 1978-06-20 IT IT24739/78A patent/IT1096592B/it active
-
1979
- 1979-05-02 FR FR7911107A patent/FR2416945A1/fr active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2291268A1 (fr) * | 1974-11-13 | 1976-06-11 | Procter & Gamble | Compositions detergentes comportant des matallo-silicates insolubles et un copolymere vinyliques soluble dans l'eau |
DE2547389A1 (de) * | 1975-10-23 | 1977-05-05 | Henkel & Cie Gmbh | Phosphatfreies waschmittel |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0025551A1 (de) * | 1979-09-13 | 1981-03-25 | BASF Aktiengesellschaft | Verwendung von (Meth)acrylsäure-Maleinsäure-Copolymerisaten als Inkrustierungsinhibitoren in Waschmitteln |
EP0063399A1 (en) * | 1981-04-22 | 1982-10-27 | THE PROCTER & GAMBLE COMPANY | Granular detergent compositions containing film-forming polymers |
EP0082564A3 (en) * | 1981-12-23 | 1985-01-23 | Unilever N.V. | Dishwashing composition |
EP0098187A1 (fr) * | 1982-06-18 | 1984-01-11 | Rhone-Poulenc Chimie | Zeolite comme auxiliaire de détergence |
US4545919A (en) * | 1982-08-31 | 1985-10-08 | Ciba-Geigy Corporation | Detergent composition for washing off dyeings obtained with fibre-reactive dyes and washing process comprising the use thereof |
JPS60106895A (ja) * | 1983-08-27 | 1985-06-12 | ザ、プロクタ−、エンド、ギヤンブル、カンパニ− | 洗剤組成物 |
EP0193360A3 (en) * | 1985-02-23 | 1987-07-01 | The Procter & Gamble Company | Detergent compositions |
FR2609065A1 (fr) * | 1986-12-24 | 1988-07-01 | Rhone Poulenc Chimie | Nouveaux agents de lavage et compositions les contenant |
EP0279134A1 (fr) * | 1986-12-24 | 1988-08-24 | Rhone-Poulenc Chimie | Latex antiredéposant pour le lavage d'articles textiles |
EP0423487A3 (en) * | 1989-10-18 | 1991-11-21 | Joh. A. Benckiser Gmbh | Rinse aid for dishwashing machines |
WO1991009932A1 (en) * | 1989-12-12 | 1991-07-11 | Unilever N.V. | Detergent compositions |
US5441672A (en) * | 1991-05-23 | 1995-08-15 | Henkel Kommanditgesellschaft Auf Aktien | Concentrated water-containing liquid detergent |
EP0612842A3 (en) * | 1993-02-24 | 1995-10-04 | Enichem Spa | Compositions for textile material washing. |
Also Published As
Publication number | Publication date |
---|---|
NL7815009A (nl) | 1979-07-31 |
GB2040981A (en) | 1980-09-03 |
FR2416945B1 (enrdf_load_html_response) | 1981-07-31 |
IT1096592B (it) | 1985-08-26 |
GB2040981B (en) | 1982-08-25 |
FR2416945A1 (fr) | 1979-09-07 |
DE2857154C2 (enrdf_load_html_response) | 1988-09-15 |
BE5T2 (fr) | 1980-02-08 |
DE2857154A1 (de) | 1980-01-24 |
IT7824739A0 (it) | 1978-06-20 |
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