EP0087035A1 - Zeolite-containing detergent compositions and process for preparing same - Google Patents
Zeolite-containing detergent compositions and process for preparing same Download PDFInfo
- Publication number
- EP0087035A1 EP0087035A1 EP83101103A EP83101103A EP0087035A1 EP 0087035 A1 EP0087035 A1 EP 0087035A1 EP 83101103 A EP83101103 A EP 83101103A EP 83101103 A EP83101103 A EP 83101103A EP 0087035 A1 EP0087035 A1 EP 0087035A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- aluminosilicate
- weight
- detergent composition
- alkali metal
- cationic surfactant
- 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.)
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003599 detergent Substances 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 239000010457 zeolite Substances 0.000 title claims description 16
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title 1
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 46
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims abstract description 23
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Chemical group 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 claims description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000003856 quaternary ammonium compounds Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 5
- 239000002002 slurry Substances 0.000 abstract description 2
- 230000005764 inhibitory process Effects 0.000 abstract 1
- -1 lithium silicates Chemical class 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical group [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004067 bulking agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- DYBIGIADVHIODH-UHFFFAOYSA-N 2-nonylphenol;oxirane Chemical compound C1CO1.CCCCCCCCCC1=CC=CC=C1O DYBIGIADVHIODH-UHFFFAOYSA-N 0.000 description 1
- 239000001692 EU approved anti-caking agent Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 230000010849 Ion Exchange Activity Effects 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 229910007157 Si(OH)3 Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 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
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000001668 ameliorated effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 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
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- JDVPQXZIJDEHAN-UHFFFAOYSA-N succinamic acid Chemical class NC(=O)CCC(O)=O JDVPQXZIJDEHAN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical class [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
Definitions
- This invention relates in general to granular detergent compositions which comprise as essential .ingredients an alkali metal silicate, a water- insoluble aluminosilicate and a cationic surfactant. More particularly it relates to spray-dried detergent compositions containing the aforesaid essential ingredients wherein the aluminosilicate particles are coated with the cationic surfactant in an amount of at least 50 ppm (wt.) at least prior to being subjected to the elevated temperatures and CO 2 - containing environment of the spray dryer, and preferably prior to being brought into contact with an aqueous solution of the sodium silicate.
- alkali-metal silicate such as sodium silicate.
- a spray-dried detergent composition comprising an alkali metal silicate and an aluminosilicate ion- exchanger prepared by spray drying a precursor composition containing aqueous alkali metal silicate solution and a cationic surfactant-coated aluminosilicate.
- the cationic surfactant is found to inhibit the tendency of the alkali metal silicate or derivatives thereof formed during spray drying to react with the aluminosilicate particle and create non-dispersable floc aggregates.
- the aluminosilicate components used in the present invention are any of synthetic or naturally occurring zeolites heretofore proposed for use in detergent compositions such as (1) crystalline aluminosilicate zeolites having the general formula wherein x and y are integers, preferably having a value of at least 6; the molar ratio of x to y is in the range of 0.1 to 1.1; and z is an integer from about 8 to 264, preferably a value such that in the spray-dried detergent product containing same, the zeolite contains from about 10 to 30 weight-% adsorbed.water, and M is preferably sodium but can also be potassium, ammonium or substituted ammonium; or (2) amorphous hydrated aluminosilicate material of the empirical, formula wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to 2, y is 1 and said material has a magnesium ion exchange capacity of at least about 50 milligrams of CaCO 3 hardness per
- zeolite A and zeolite X wherein either zeolite constitutes at least 30 weight per cent of the overall zeolite mixture and the other zeolite constitutes a complementary amount, are especially preferred as the aluminosilicate constituent.
- the cationic surfactant is preferably any of the quaternary ammonium compounds having the formula wherein at least one, but not more than two, of the R- groups is an organic radical containing a group selected from C 8 - C 22 aliphatic radical, or an alkyl phenyl or alkylbenzyl radical having 10 to 16 carbon atoms in the alkyl chain, the remaining group or groups being selected from C l -C 4 alkyl, C 2 -C 4 hydroxy alkyl, and cyclic structures in which the nitrogen atom forms part of the ring, Y constituting an anionic radical selected from the group consisting of hydroxide, halide, sulfate, methylsulfate, ethylsulfate and phosphate ions.
- the alkali metal silicates employed in preparing the present detergent compositions are preferably sodium silicates with about 1.0 to 4.0 moles of SiO 2 per mole of Na 2 o. Equivalent potassium and lithium silicates are also useful.
- the alkali metal silicates are preferably employed in the form of concentrated aqueous solutions containing from 20 to 60% solids, but hydrated and anhydrous silicate powders can be imparted to the overall detergent composition along with an appropriate amount of water if desired.
- the aluminosilicate constituent be coated with the cationic surfactant, or a portion thereof, before there is contact of the aluminosilicate with the alkali metal silicate under conditions which permit significant reaction between these two materials.
- the aluminosilicate is coated with from about 100 ppm to about 2000.ppm of the cationic surfactant before any contact with an aqueous sodium silicate solution is allowed, i.e. the aluminosilicate-cationic surfactant composite is imparted to the crutcher as an already prepared material. In all events the aluminosilicate must contain the cationic surfactant coating before the overall detergent composition is subjected to spray-drying.
- the principal cause of bridging of the aluminosilicate particles to form undesirable aggregates is a condensation reaction between silicic acid an/or terminal silanol groups on polymerized silicic species and ⁇ Si-OH groups of the aluminosilicate.
- silicic acid While relatively small amounts of silicic acid are present in the alkali metal silicate solution employed, there is apparently enough to cause appreciable floc formation even at ambient room temperatures during prolonged periods.
- the detergent feed containing relatively large amounts of water is contacted at elevated temperatures, i.e., 500°F to about 900°F, by a rather high concentration of carbon dioxide. This permit the formation of H 2 C0 3 which then can react with the alkali metal silicate to produce silicic acid in accordance with the following equation:
- the cationic surfactant coating on the aluminosilicate interferes with this or similar bonding reactions without inhibiting appreciably the ion exchange activity of the aluminosilicate when the detergent is added to the washing medium.
- the method of coating the aluminosilicate with the surfactant is not a critical factor. Ordinarily the alumin- osilicate is simply slurried or otherwise washed with a solution of the surfactant in a suitable solvent such as water or a mixture of water and polar organic solvent such as isopropanol.
- a suitable solvent such as water or a mixture of water and polar organic solvent such as isopropanol.
- Anionic surfactants are particularly important in the detergent compositions of our invention.
- Such anionic materials include, among others, alkali metal soaps of fatty acids, alkali metal salts of alkyl sulfuric acid reaction products, sodium alkyl glyceryl ether sulfonates, succinamates and anionic phosphates, one of the most commonly used anionic surfactants is the sodium salt of linear alkyl benzene sulfonate (LAS) wherein the alkyl group contains more than 10 carbon atoms. LAS forms at least a part of many of the surfactant systems used in our detergent compounds and may be the only surfactant used.
- LAS linear alkyl benzene sulfonate
- Nonionic surfactants are also useful and include, among others, polyethylene oxide condensate of alkyl phenols, condensation products of aliphatic alcohols with ethylene oxide, nonyl phenol-ethylene oxide condensates, amine oxides and posphine oxides.
- Ampholytic surfactants such as th ⁇ aliphatic derivatives of heterocyclic secondary and tertiary amines and zevitterionie surfactants such as derivatives of aliphatic quaternary ammonium compounds are also useful.
- auxiliary builder in the detergent compositions of our invention.
- auxiliary builders include salts of phosphates, pryophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, and polyhydroxysulfonates, organic sequestering agents such as polyacetates, carboxylates, polyaminocarboxylates and polyhydroxysulfonates are of use in our detergent compositions.
- useful materials include sodium and potassium salts of tripolyphosphate, pyrophosphate, hexametaphosphate, ethylenediaaminotetraacetic acid, nitrilotriacetic acid, citric acid, citric acid isomers and others.
- the present detergents can also include numerous . . additional detergent ingredients.
- Antirediposition agents such as sodium carboxymethyl cellulose prevent certain types of soils from redipositioning on clean fabric.
- Minor detergent ingredients such as enzymes, optical brighteners and bleaches are included to remove stains and/or improve the appearance of the fabric.
- Other minor detergent ingredients such as perfumes, anti-caking agents, dyes, colored specks and fabric softeners are added to improve the properties or appearance of the detergent or the fabric. Since detergent actives are effective at low concentrations, it is important the bulking agents be added to the formulation so that measurement of the appro- priate dose is facilitated. We have found bulking agents such as sodium sulfates, sodium chloride and other neutral alkali metal salts to be effective.
- detergent compositions of this invention thus comprise, prior to spray-drying:
- the aluminosilicate composites contain a coating of from about 100 ppm to 2000 ppm by weight based on the anhydrous weight of the 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)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
- This invention relates in general to granular detergent compositions which comprise as essential .ingredients an alkali metal silicate, a water- insoluble aluminosilicate and a cationic surfactant. More particularly it relates to spray-dried detergent compositions containing the aforesaid essential ingredients wherein the aluminosilicate particles are coated with the cationic surfactant in an amount of at least 50 ppm (wt.) at least prior to being subjected to the elevated temperatures and CO2- containing environment of the spray dryer, and preferably prior to being brought into contact with an aqueous solution of the sodium silicate.
- Because of the suspected entrophication properties attributed to phosphate builders in detergent compositions such as those used for laundering fabrics, it has become conventional in the art to substitute for some or all of the phosphate formerly employed, a water-insoluble aluminosilicate which can be either amorphous or crystalline. Another necessary component of such detergents is an alkali-metal silicate, such as sodium silicate. These compounds are found to minimize the corrosion of washing machine surfaces attributed to the other detergent components. In addition it has been proposed that alkali metal silicates are desirable components in spray-dried detergent granules in that they aid in crutcher mix processing and also aid in maintaining crisp free- following granules.
- It is further known, however, that there are difficulties attendant the use of both aluminosilicates and alkali metal silicates in the same detergent composition. As reported in U.S.P. 4,019,999 issued April 26, 1977 to T. H. Ohren et al these two constituents have a pronounced tendency to aggregate through bridging of the aluminosilicate particles. In aqueous slurry a chemical reaction takes place which can the theorized as involving ESi-OH and/or ESiO- ionized groups of the aluminosilicate and the alkali metal silicate which can condense to form Si-O-Si linkages and result in the aggregation by bridging. The aggregates then fail to disperse in the washing medium and deposit on the fabric as a white floc which is particularly evident on dark fabrics.
- It has been proposed to avoid the deposition problem by limiting the amount of sodium silicate to less than about 3% by weight based on the overall weight of the detergent compositions containing from 5 to 95 weight per cent aluminosilicate. This solution is disclosed in U.S.P. 3,985,669 issued October 12, 1976 to Krummel et al. The sodium silicate is employed in the form of a solid particle. A third essential ingredient is a watersoluble surface-active agent selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic surfactants. It would be desirable, however, to be able to utilize greater concentrations of alkali metal silicates and/or aqueous solutions of alkali metal silicates in preparing detergent compositions.
- It is therefore the general object of the present invention to provide a detergent composition suitable for spray-drying which contains an aqueous solution of alkali metal silicate in conjunction with an aluminosilicate builder, and which is highly dispersible in water even after spray-drying so that floc deposition on fabrics is ameliorated.
- A spray-dried detergent composition comprising an alkali metal silicate and an aluminosilicate ion- exchanger prepared by spray drying a precursor composition containing aqueous alkali metal silicate solution and a cationic surfactant-coated aluminosilicate. The cationic surfactant is found to inhibit the tendency of the alkali metal silicate or derivatives thereof formed during spray drying to react with the aluminosilicate particle and create non-dispersable floc aggregates.
- The aluminosilicate components used in the present invention are any of synthetic or naturally occurring zeolites heretofore proposed for use in detergent compositions such as (1) crystalline aluminosilicate zeolites having the general formula
- The cationic surfactant is preferably any of the quaternary ammonium compounds having the formula
- The alkali metal silicates employed in preparing the present detergent compositions are preferably sodium silicates with about 1.0 to 4.0 moles of SiO2 per mole of Na2o. Equivalent potassium and lithium silicates are also useful. The alkali metal silicates are preferably employed in the form of concentrated aqueous solutions containing from 20 to 60% solids, but hydrated and anhydrous silicate powders can be imparted to the overall detergent composition along with an appropriate amount of water if desired.
- It is an important aspect of this invention that the aluminosilicate constituent be coated with the cationic surfactant, or a portion thereof, before there is contact of the aluminosilicate with the alkali metal silicate under conditions which permit significant reaction between these two materials. Advantageously, and preferably, the aluminosilicate is coated with from about 100 ppm to about 2000.ppm of the cationic surfactant before any contact with an aqueous sodium silicate solution is allowed, i.e. the aluminosilicate-cationic surfactant composite is imparted to the crutcher as an already prepared material. In all events the aluminosilicate must contain the cationic surfactant coating before the overall detergent composition is subjected to spray-drying.
- While not wishing to be bound by any particular theory, it is believed that the principal cause of bridging of the aluminosilicate particles to form undesirable aggregates is a condensation reaction between silicic acid an/or terminal silanol groups on polymerized silicic species and ≡Si-OH groups of the aluminosilicate.' While relatively small amounts of silicic acid are present in the alkali metal silicate solution employed, there is apparently enough to cause appreciable floc formation even at ambient room temperatures during prolonged periods.
- In the spray-dryer, however, the detergent feed containing relatively large amounts of water is contacted at elevated temperatures, i.e., 500°F to about 900°F, by a rather high concentration of carbon dioxide. This permit the formation of H2C03 which then can react with the alkali metal silicate to produce silicic acid in accordance with the following equation:
- 2 Si(OH)3O- Na+ + H2CO3 - 2 Si(OA)4 + Na2CO3 The silicic acid in turn bonds to aluminosilicate (zeolite) surfaces by the following equation:
- The cationic surfactant coating on the aluminosilicate interferes with this or similar bonding reactions without inhibiting appreciably the ion exchange activity of the aluminosilicate when the detergent is added to the washing medium.
- The method of coating the aluminosilicate with the surfactant is not a critical factor. Ordinarily the alumin- osilicate is simply slurried or otherwise washed with a solution of the surfactant in a suitable solvent such as water or a mixture of water and polar organic solvent such as isopropanol.
- There is a considerable attraction between the cationic surfactant and the mimic aluminosilicate, and accordingly other types of surfactants; builders and other traditional detergent ingredients can be included in the present compositions without loss of the benefits obtained using the three essential ingredients alone. The compositions, properties and preparation of other organic surfactants are well represented in the patent literature and a detailed review of such readily available material will not be undertaken here. We hereinafter disclose examples of certain classes of and individual surfactants that can be used in the detergents of our invention. It is not intended that the scope of our invention be limited to these specific materials, but that equivalent materials also be included.
- Anionic surfactants are particularly important in the detergent compositions of our invention. Such anionic materials include, among others, alkali metal soaps of fatty acids, alkali metal salts of alkyl sulfuric acid reaction products, sodium alkyl glyceryl ether sulfonates, succinamates and anionic phosphates, one of the most commonly used anionic surfactants is the sodium salt of linear alkyl benzene sulfonate (LAS) wherein the alkyl group contains more than 10 carbon atoms. LAS forms at least a part of many of the surfactant systems used in our detergent compounds and may be the only surfactant used.
- Nonionic surfactants are also useful and include, among others, polyethylene oxide condensate of alkyl phenols, condensation products of aliphatic alcohols with ethylene oxide, nonyl phenol-ethylene oxide condensates, amine oxides and posphine oxides.
- Ampholytic surfactants such as thë aliphatic derivatives of heterocyclic secondary and tertiary amines and zevitterionie surfactants such as derivatives of aliphatic quaternary ammonium compounds are also useful.
- Although sufficient aluminosilicate-cationic surfactant composite builder and alkali metal silicate can be used to accommodate any laundering environment it may be desired to include an auxiliary builder in the detergent compositions of our invention. Such auxiliary builders include salts of phosphates, pryophosphates, orthophosphates, polyphosphates, phosphonates, carbonates, and polyhydroxysulfonates, organic sequestering agents such as polyacetates, carboxylates, polyaminocarboxylates and polyhydroxysulfonates are of use in our detergent compositions. Specific examples of useful materials include sodium and potassium salts of tripolyphosphate, pyrophosphate, hexametaphosphate, ethylenediaaminotetraacetic acid, nitrilotriacetic acid, citric acid, citric acid isomers and others.
- The present detergents can also include numerous . . additional detergent ingredients. Antirediposition agents such as sodium carboxymethyl cellulose prevent certain types of soils from redipositioning on clean fabric. Minor detergent ingredients such as enzymes, optical brighteners and bleaches are included to remove stains and/or improve the appearance of the fabric. Other minor detergent ingredients such as perfumes, anti-caking agents, dyes, colored specks and fabric softeners are added to improve the properties or appearance of the detergent or the fabric. Since detergent actives are effective at low concentrations, it is important the bulking agents be added to the formulation so that measurement of the appro- priate dose is facilitated. We have found bulking agents such as sodium sulfates, sodium chloride and other neutral alkali metal salts to be effective.
- The detergent compositions of this invention thus comprise, prior to spray-drying:
- (a) 0 to 30% by weight of one or more organic surfactants;
- (b) 10 to 902 by weight of a builder system consisting of
- (1) 1 to 90 parts by weight of an aluminosilicate having as a coating on the particles thereof, at least 50 ppm by weight of a cationic surfactant, said aluminosilicate being
- (i) a crystalline aluminosilicate zeolite having the general formula Mx[(A102)X (SiO2)ylz H 2 0 wherein x and y are integers, the molar ratio of x to y being in the range of 0.1 to 1.1, and z is an integer from about 8 to 264; or
- (ii) an amorphous hydrated aluminosilicate having the empirical formula Mz(zA102· ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to 2, y is 1, said material having a magnesium ion-exchange capacity of at least ; about 50 milligrams of CaCO3 hardness per gram of anhydrous aluminosilicate; or
- (iii) mixtures of (i) and (ii); and (2) 4 to 35 parts by weight of a water soluble alkali metal silicate having a molar composition equivalent to 1.0 to 4.0 moles of SiO2 per mole of Na20, said alkali metal silicate being in the form of an aqueous solution having a solids content of from 20 to 60 weight per cent.
- (1) 1 to 90 parts by weight of an aluminosilicate having as a coating on the particles thereof, at least 50 ppm by weight of a cationic surfactant, said aluminosilicate being
- From presently available test data it appears that significant improvement in the inhibiting aggregation due to aluminosilicate bridging is obtained when as little as about 100 ppm (wt.) of the cationic surfactant is coated on the aluminosilicate particles. It appears that with coatings constituting more than about 2000 ppm (wt), no further improvement is obtained, and in fact some decrease in effectiveness results compared with the effectiveness of lesser amounts. Accordingly it is preferred that the aluminosilicate composites contain a coating of from about 100 ppm to 2000 ppm by weight based on the anhydrous weight of the aluminosilicate.
- In order to demonstrate the effectiveness of cationic surfactant-treated zeolite particles in promoting the dispersability of a spray-dried detergent containing high levels of sodium silicate and zeolite particles, two spray-dried detergents were prepared in which the only significant difference was in the zeolite constituent. In one sample (A) the zeolite particles were coated with about 500 ppm of a cationic quaternary ammonium (alkyltrimethylammonium chloride in which the primary alkyl group contains from 14 to 18 carbon atoms). In sample B, the zeolite was untreated. The composition contained:
-
- (a) The clean sieve series plus sieve bottom and 3½ Buchner funnel (with filter paper) were dried in a 100°C oven, cooled to room temperature, and weighed.
- (b) One liter of a solution of hardness water (150 ppm, Ca++/Mg++ = 3/2) was heated to 50°C in the tergotometer.
- (c) Twenty-five grams of the detergent sample to be tested was added to the hardness water in the tergotometer and the contents agitated for 10 minutes at 100 RPM.
- (d) A "sieve tower" is prepared from the sieve series and set into the 10½" diameter Buchner funnel, which is inserted into the four liter Erlemeyer flask.
- (e) The contents of the tergotometer were emptied , into the sieve tower. Particles clinging to the tergotometer ; tub were rinsed out with distilled water and added to the same tower.
- (f) When it was observed that water was no longer dripping from the sieve tower, the bottom was placed on the tower and the entire apparatus placed in a 100°C drying oven for twenty-two hours.
- (g) The collected liquid fraction was filtered with the aid of vacuum using the weighed 3½" Buchner funnel and Whatman No. 1 filter paper.
- (h) The 3½" Buchner funnel with filtered contents was placed in a 100°C drying oven for twenty-two hours.
- (i) After drying the sieve top was placed on the sieve tower and along with the Buchner funnel was allowed to cool to room temperature.
- (j) The sieve tower was placed in the R.O. Tap Testing Sieve Shaker for three minutes.
- (k) Each sieve plus bottom and Buchner funnel was weighed and any increase in weight noted.
- (1) The total solids recovered plus the percentage of solids on each sieve were recorded. The percentage of solids collected on the sieve bottom and the filter were combined to represent the fine fraction. Screen analysis of the starting samples showed that the median particle size of Sample A was about 360 micrometers, and for Sample B the median particle size was about 345 micrometers. The results of the dissolution screen analysis procedure showed that detergent Sample A (containing the surfactant coated zeolite) dispersed to the degree that the median particle size was less than 44 micrometers, whereas the comparison Sample B (containing untreated zeolite particles) the dispersion was such that the median particle size was about 120 micrometers.
Claims (6)
[R, R2 R3 R4 N]+ Y- wherein at least one, but not more than two, of the R-groups is an organic radical containing a group selected from C8-C22 aliphatic radical, or an alkyl phenyl or alkylbenzyl radical having 10 to 16 carbon atoms in the alkyl chain, the remaining group or groups being selected from C1-C4 alkyl, C2-C4 hydroxy alkyl, and cyclic structures in which the nitrogen atom forms part of the ring, Y constituting an anionic radical selected from the group consisting of hydroxide, halide, sulfate, methylsulfate, ethylsulfate and phosphate ions.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83101103T ATE15500T1 (en) | 1982-02-08 | 1983-02-05 | DETERGENT COMPOSITIONS CONTAINING ZEOLITE AND PROCESS FOR THEIR PREPARATION. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US34665382A | 1982-02-08 | 1982-02-08 | |
US346653 | 1982-02-08 |
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EP0087035A1 true EP0087035A1 (en) | 1983-08-31 |
EP0087035B1 EP0087035B1 (en) | 1985-09-11 |
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ID=23360419
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EP83101103A Expired EP0087035B1 (en) | 1982-02-08 | 1983-02-05 | Zeolite-containing detergent compositions and process for preparing same |
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EP (1) | EP0087035B1 (en) |
JP (1) | JPS6049680B2 (en) |
AT (1) | ATE15500T1 (en) |
DE (1) | DE3360741D1 (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4534880A (en) * | 1984-03-27 | 1985-08-13 | Dow Corning Corporation | Detergent composition with siliconate-zeolite and silicate builder |
EP0260971A2 (en) * | 1986-09-19 | 1988-03-23 | Unilever Plc | Detergent composition and process for its production |
EP0318219A2 (en) * | 1987-11-24 | 1989-05-31 | Unilever Plc | Aluminosilicates |
EP0364184A2 (en) * | 1988-10-10 | 1990-04-18 | Unilever Plc | Liquid cleaning compositions and process for their preparation |
WO1997034980A1 (en) * | 1996-03-15 | 1997-09-25 | Crosfield Limited | Modified aluminosilicate |
US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
WO2007017070A1 (en) * | 2005-08-10 | 2007-02-15 | Henkel Kommanditgesellschaft Auf Aktien | Washing and cleaning agents comprising readily soluble capsules |
WO2010070088A1 (en) | 2008-12-18 | 2010-06-24 | Basf Se | Surfactant mixture comprising branched short-chained and branched long-chained components |
WO2011003904A1 (en) | 2009-07-10 | 2011-01-13 | Basf Se | Surfactant mixture having short- and long-chained components |
WO2011117350A1 (en) | 2010-03-25 | 2011-09-29 | Basf Se | Electrochemical textile-washing method |
US9435073B2 (en) | 2010-03-25 | 2016-09-06 | Basf Se | Electrochemical textile-washing process |
US11441105B2 (en) | 2017-12-15 | 2022-09-13 | Rhodia Operations | Composition containing lanthanide metal complex |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4704221A (en) * | 1986-10-22 | 1987-11-03 | The Procter & Gamble Company | Granular detergents which contain high levels of anionic surfactant that forms a middle-phase, surface treated with a water soluble cationic surfactant |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3985669A (en) * | 1974-06-17 | 1976-10-12 | The Procter & Gamble Company | Detergent compositions |
US4019999A (en) * | 1975-07-23 | 1977-04-26 | The Procter & Gamble Co. | Spray-dried granular detergent containing aluminosilicate, silicate, and pyrophosphate |
GB2013707A (en) * | 1978-02-01 | 1979-08-15 | Unilever Ltd | Preparation of Spray-Dryed Detergent Compositions |
EP0063399A1 (en) * | 1981-04-22 | 1982-10-27 | THE PROCTER & GAMBLE COMPANY | Granular detergent compositions containing film-forming polymers |
-
1983
- 1983-02-05 DE DE8383101103T patent/DE3360741D1/en not_active Expired
- 1983-02-05 EP EP83101103A patent/EP0087035B1/en not_active Expired
- 1983-02-05 AT AT83101103T patent/ATE15500T1/en not_active IP Right Cessation
- 1983-02-07 JP JP58017594A patent/JPS6049680B2/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3985669A (en) * | 1974-06-17 | 1976-10-12 | The Procter & Gamble Company | Detergent compositions |
US4019999A (en) * | 1975-07-23 | 1977-04-26 | The Procter & Gamble Co. | Spray-dried granular detergent containing aluminosilicate, silicate, and pyrophosphate |
GB2013707A (en) * | 1978-02-01 | 1979-08-15 | Unilever Ltd | Preparation of Spray-Dryed Detergent Compositions |
EP0063399A1 (en) * | 1981-04-22 | 1982-10-27 | THE PROCTER & GAMBLE COMPANY | Granular detergent compositions containing film-forming polymers |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4534880A (en) * | 1984-03-27 | 1985-08-13 | Dow Corning Corporation | Detergent composition with siliconate-zeolite and silicate builder |
EP0260971A2 (en) * | 1986-09-19 | 1988-03-23 | Unilever Plc | Detergent composition and process for its production |
EP0260971A3 (en) * | 1986-09-19 | 1989-10-11 | Unilever Plc | Detergent composition and process for its production |
US4965015A (en) * | 1986-09-19 | 1990-10-23 | Lever Brothers Company | Detergent composition and process for its production |
EP0318219A2 (en) * | 1987-11-24 | 1989-05-31 | Unilever Plc | Aluminosilicates |
EP0318219A3 (en) * | 1987-11-24 | 1990-06-06 | Unilever Plc | Aluminosilicates |
EP0364184A2 (en) * | 1988-10-10 | 1990-04-18 | Unilever Plc | Liquid cleaning compositions and process for their preparation |
EP0364184A3 (en) * | 1988-10-10 | 1991-07-24 | Unilever Plc | Liquid cleaning compositions and process for their preparation |
WO1997034980A1 (en) * | 1996-03-15 | 1997-09-25 | Crosfield Limited | Modified aluminosilicate |
US6448218B2 (en) | 1996-03-15 | 2002-09-10 | Crosfield Limited | Modified aluminosilicate |
KR100464891B1 (en) * | 1996-03-15 | 2005-02-28 | 크로스필드 리미티드 | Modified Aluminosilicate |
US6235704B1 (en) | 1997-07-30 | 2001-05-22 | Basf Aktiengesellschaft | Solid textile detergent formulation based on glycin-N and N-Diacetic acid derivatives |
WO2007017070A1 (en) * | 2005-08-10 | 2007-02-15 | Henkel Kommanditgesellschaft Auf Aktien | Washing and cleaning agents comprising readily soluble capsules |
US7638476B2 (en) | 2005-08-10 | 2009-12-29 | Henkel Ag & Co. Kgaa | Washing and cleaning agents comprising readily soluble capsules |
WO2010070088A1 (en) | 2008-12-18 | 2010-06-24 | Basf Se | Surfactant mixture comprising branched short-chained and branched long-chained components |
WO2011003904A1 (en) | 2009-07-10 | 2011-01-13 | Basf Se | Surfactant mixture having short- and long-chained components |
WO2011117350A1 (en) | 2010-03-25 | 2011-09-29 | Basf Se | Electrochemical textile-washing method |
US9435073B2 (en) | 2010-03-25 | 2016-09-06 | Basf Se | Electrochemical textile-washing process |
US11441105B2 (en) | 2017-12-15 | 2022-09-13 | Rhodia Operations | Composition containing lanthanide metal complex |
Also Published As
Publication number | Publication date |
---|---|
JPS6049680B2 (en) | 1985-11-02 |
JPS58145796A (en) | 1983-08-30 |
EP0087035B1 (en) | 1985-09-11 |
ATE15500T1 (en) | 1985-09-15 |
DE3360741D1 (en) | 1985-10-17 |
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