EP0534525B1 - Waschmittelpulver und Verfahren zu deren Herstellung - Google Patents
Waschmittelpulver und Verfahren zu deren Herstellung Download PDFInfo
- Publication number
- EP0534525B1 EP0534525B1 EP92202764A EP92202764A EP0534525B1 EP 0534525 B1 EP0534525 B1 EP 0534525B1 EP 92202764 A EP92202764 A EP 92202764A EP 92202764 A EP92202764 A EP 92202764A EP 0534525 B1 EP0534525 B1 EP 0534525B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- citric acid
- weight
- composition according
- detergent
- 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.)
- Expired - Lifetime
Links
- 239000003599 detergent Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000843 powder Substances 0.000 title description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 111
- 239000000203 mixture Substances 0.000 claims description 61
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000007844 bleaching agent Substances 0.000 claims description 7
- 229940071207 sesquicarbonate Drugs 0.000 claims description 7
- 229960001407 sodium bicarbonate Drugs 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000000881 depressing effect Effects 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 235000021317 phosphate Nutrition 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 claims description 2
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical group [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000000429 sodium aluminium silicate Substances 0.000 claims description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229940045872 sodium percarbonate Drugs 0.000 claims description 2
- 239000002585 base Substances 0.000 description 13
- 238000003860 storage Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 9
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- -1 alkyl sulphates Chemical class 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 3
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 3
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 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
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
Definitions
- the present invention relates to detergent powders intended for use in drum-type fabric washing machines.
- the invention is of especial applicability to detergent powders containing no, or reduced levels of, phosphate builders and to powders of high bulk density, which have a tendency to dispense poorly.
- the invention also relates to a process for preparing these detergent powders.
- US-A-4,414,130 discloses detergent compositions comprising an effervescent material which promotes dissolution and dispersion of the detergent particles.
- the detergent particles may comprise sodium carbonate or bicarbonate and that the balance of the composition may include citric acid.
- the present invention provides a granular detergent composition having a bulk density of from 650 to 1100 kg/m 3 and comprising anionic and/or nonionic surfactants, from 5 to 30% by weight of sodium carbonate and/or -bicarbonate and/or sesquicarbonate, other builder material, and from 1 to 15% by weight of particulate citric acid, whereby more than 80% by weight of the citric acid has a particle size which is in the range of from 350 to 1500 ⁇ m.
- the invention also provides a process for preparing this composition, wherein the citric acid is added as a separate granular component to a granular detergent base composition.
- the first aspect of the invention is a granular detergent composition having a bulk density of from 650 to 1100 kg/m 3 , preferably from 700 to 1100 kg/m 3 .
- the composition comprises a base composition to which particulate citric acid, and optionally a foam depressing agent, has been added.
- the base composition may be prepared by spray-drying and dry-mixing/agglomeration. For obtaining high bulk densities, it is preferably prepared by dry-mixing/agglomeration.
- the base composition contains one or more anionic and/or nonionic surfactants, and builder material.
- the base composition preferably also comprises sodium carbonate and/or sodium bicarbonate and/or sodium sesquicarbonate.
- the granular composition of the invention may further contain any of the materials conventionally included in detergent compositions. These are described in more detail below.
- the surfactant component is the surfactant component
- the total amount of surfactant present in the composition of the invention will generally range from 5 to 40 % by weight, more preferably from 10 to 30% by weight, and especially from 12 to 20% by weight. These figures are typical for fully formulated detergent compositions, and as a spray-dried or dry-mixed/agglomerated base forms only part of such a composition the surfactant content of that base, as a percentage, may of course be higher.
- the invention is of especial applicability to compositions containing anionic and nonionic surfactants.
- the amount of anionic surfactant present is desirably at least 3% by weight, and may suitably be in the range of from 3 to 30% by weight, these figures again being based on the fully formulated composition.
- Anionic surfactants are well known to those skilled in the art. Examples of suitable anionic surfactants include alkylbenzene sulphonates,particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; primary and secondary alkyl sulphates, particularly sodium C 12 -C 15 primary alkyl sulphates; sodium salts of fatty acids (i.e. soaps); olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
- Specific nonionic surfactants are alkyl (C 6 -C 22 ) phenols-ethylene oxide condensates, generally with 5 to 25 units of ethylene oxide (i.e.: 5-25 EO) per molecule, and the condensation products of aliphatic ( C 8 -C 18 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 3-40 EO.
- alkyl polyglycosides and glucose ethers and esters may be effectively used as nonionic surfactants.
- the sodium carbonate and/or bicarbonate and/or - sesquicarbonate may be added to the base composition but is preferably present in it.
- the amount of this material present in the composition of the invention is in the range of from 5 to 30% by weight based on a fully formulated detergent composition. In zeolite built detergent powder according to the invention this amount is preferably in the range of from 5 to 15% by weight, whereas in detergent powder including a calcite/sodium carbonate builder system this amount is preferably in the range of from 15 to 30% by weight.
- the citric acid is a separate granular component and needs to be added to the base composition.
- the amount of particulate citric acid needed to obtain the desired good dispensing characteristics and storage stability is in the range of from 1 to 15% by weight, preferably from 2 to 12% by weight, more preferably from 3 to 10% by weight, based on a fully formulated composition.
- more than 80% by weight of the particulate citric acid has a particle size of from 350 to 1500 ⁇ m, preferably from 350 to 1000 ⁇ m, a particle size range of 350-750 ⁇ m being most preferred.
- the composition according to the invention includes at least one further builder material capable of reducing the level of free calcium ions in the wash liquor and preferably providing the composition with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.
- the total level of the detergency builder may be from 10% to 70% by weight, preferably from 25% to 50% by weight of the detergent composition.
- Preferred builders are ion exchange builders such as the crystalline (zeolite) or amorphous alkali metal alumino-silicates.
- organic and inorganic polymers may be present, for example, polycarboxylate polymers such as polyacrylates, acrylic-maleic copolymers such as SOKALAN types of polymers may be present.
- polycarboxylate polymers such as polyacrylates
- acrylic-maleic copolymers such as SOKALAN types of polymers
- Other preferred builder systems are precipitant builders such as those containing calcite and sodium carbonate as described in EP-A-267,042.
- the detergent composition according to the invention is preferably essentially free of phosphates-containing builders such as orthophosphates and alkali metal tripolyphosphates.
- citric acid and sodium (bi)carbonate and/or sodium sesquicarbonate preferably results in a reduction in the residue of at least 10 percentage points, most preferably at least 20 percentage points.
- an improvement of this magnitude can only be observed if the control powder exhibits poor dispensing properties.
- the present invention is therefore especially applicable to powders which, without citric acid and sodium (bi)carbonate and/or -sesquicarbonate, give dispenser residues of at least 20% by weight.
- the powder is a zero-phosphate composition built with amorphous or crystalline (zeolite) sodium alumino-silicate; and/or if it has a bulk density of at least 650, preferably of at least 700 kg/m 3 .
- zeolite amorphous or crystalline sodium alumino-silicate
- the granular detergent composition of the invention preferably also contains one or more foam depressing agents.
- Silicone oil based compositions containing high or low viscosity silicone oil, particularly high viscosity silicone oil, may be effectively used as antifoaming agents.
- bleaches are the oxygen bleaches, for example in the form of an inorganic persalt, preferably with a precursor, or as a peroxy acid compound. From an environmental point of view, the most preferred bleach compound is percarbonate. Effective amounts of these bleach compounds present in the detergent composition of the invention range from 5 to 20% by weight, preferably from 10 to 20% by weight.
- the powder of the invention may contain sodium silicate.
- High levels of silicate can in themselves have a beneficial effect on dispensing, as well as on powder structure and prevention of machine corrosion, but are undesirable in powders containing alumino-silicate because the two components react together to form insoluble siliceous species.
- the present invention enables the dispensing behaviour of zeolite-built powders to be improved without a corresponding increase in the level of insoluble material. Accordingly, the invention is of especial applicability to powders containing less than 10% by weight, more especially less than 5% by weight, of sodium silicate.
- fluorescers include fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, bleach activators, and bleach stabilizers. These may be included in the spray-dried base powder or postdosed according to their known suitability for undergoing spray-drying processes and their compatibility with other slurry ingredients.
- a phosphate-free detergent base powder was prepared, by slurry-making, spray-drying and subsequently densifying in a Lödige "Recycler/ploughshare", as described in EP-A-367,339, to form the following nominal composition: Parts LAS 8.3 Nonionic EO 6.7 Soap 1.8 Zeolite 4A 28.0 Sokalan CP5 4.5 Carbonate 8.5 Minor ingredients + moisture 14.8 To this base powder, the following components were postdosed: Parts Silicone 0.4 Percarbonate 20.0 TAED 5.0 Carbonate 2.0 The bulk density of the detergent powder obtained was 850 kg/m 3 .
- citric acid of which more than 80% by weight has a particle size in the range of 350-1000 ⁇ m was added at four different levels.
- the dispensing properties of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine using 100 g powder, and 5 litres of water at 20°C flowing in over a period of 1 minute.
- Other samples were stored during 6 weeks in wax-laminated cartons at 28 °C and 70% RH, and thereafter tested in the Philips washing machine.
- Table 1 shows the resulting dispenser residues. TABLE 1 1 2 3 4 Parts citric acid added 0 1 2 3 Dispenser Residue (%) 80 50 0 0 Dispenser Residue after After storage for 6 weeks 80 65 10 0
- the bulk density of the detergent powder obtained was 850 kg/m 3 .
- citric acid of which more than 80% by weight has a particle size in the range of 350-1000 ⁇ m was added at four different levels.
- Samples of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine, as described above. Other samples were stored during 6 weeks in wax-laminated cartons at 28°C and 70% RH, and thereafter tested in the Philips washing machine.
- Table 2 shows the resulting dispenser residues. TABLE 2 5 6 7 8 9 Parts citric acid added 0 2 4 6 8 Dispenser Residue (%) 80 70 40 0 0 Dispenser Residue after Storage for 6 weeks (%) 80 70 40 10 0
- citric acid of which more than 80% by weight has a particle size in the range of 50-100 ⁇ m was added at several levels. Samples of the thus obtained compositions were tested in a Philips (trade mark) AWB 126 washing machine, as described above. Other samples were stored during 4 weeks in wax laminated cartons at 37°C and 70% RH, and thereafter tested in the Philips washing machine. Table 3 shows the resulting dispenser residues. TABLE 3 A B C D E Parts citric acid added 0 0.5 1 2 4 Dispenser Residue (%) 80 15 0 0 0 Dispenser Residue after Storage for 4 weeks (%) 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80
- citric acid of which more than 80% by weight has a particle size in the range of 1500-2000 ⁇ m was added at several levels. Samples of the thus obtained compositions were tested as described above for Comparative Examples A-E. Table 4 shows the resulting dispenser residues. TABLE 4 F G H I Parts citric acid added 0 2 4 8 Dispenser residue (%) 80 70 53 35 Dispenser residue after Storage for 4 weeks (%) 80 80 80 80 80 80
- particulate citric acid of which more than 80% by weight has a larger partical size than according to the present invention is not very effective at improving dispensing, neither immediately after preparation of the detergent powder nor after storage for 4 weeks.
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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)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Claims (10)
- Körnige Reinigungsmittelzusammensetzung einer Schüttdichte von 650 bis 1100 kg/m3, die anionische und/oder nichtionische grenzflächenaktive Mittel, 5 bis 30 Gew.-% Natriumcarbonat und/oder -bicarbonat und/oder -sesquicarbonat, weitere Buildermaterialien sowie 1 bis 15 Gew.-% teilchenförmige Citronensäure umfaßt, wobei mehr als 80 Gew.-% der Citronensäure eine Teilchengröße im Bereich von 350 bis 1500 µm aufweisen.
- Zusammensetzung nach Anspruch 1, wobei mehr als 80 Vol.-% der Citronensäure eine Teilchengröße im Bereich von 350 bis 1000 µm aufweisen.
- Zusammensetzung nach Anspruch 2, wobei mehr als 80 Gew.-% der Citronensäure eine Teilchengröße im Bereich von 350 bis 750 µm aufweisen.
- Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei die Zusammensetzung ein schaumunterdrückendes Mittel umfaßt.
- Zusammensetzung nach Anspruch 4, wobei das schaumunterdrückende Mittel ein hochviskoses Siliconöl ist.
- Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei die Zusammensetzung eine Bleichmittelkomponente umfaßt.
- Zusammensetzung nach Anspruch 6, wobei die Bleichmittelkomponente Natriumpercarbonat ist.
- Zusammensetzung nach einem der Ansprüche 1 bis 7, wobei das weitere Buildermaterial Natriumalumosilicat umfaßt.
- Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei die Zusammensetzung im wesentlichen keine Phosphate enthält.
- Verfahren zur Herstellung der Zusammensetzung nach Anspruch 1, wobei die Citronensäure als getrennte körnige Komponente einer körnigen Reinigungsmittelgrundlagenzusammensetzung zugesetzt wird.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB919120657A GB9120657D0 (en) | 1991-09-27 | 1991-09-27 | Detergent powders and process for preparing them |
GB9120657 | 1991-09-27 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0534525A2 EP0534525A2 (de) | 1993-03-31 |
EP0534525A3 EP0534525A3 (en) | 1993-09-01 |
EP0534525B1 true EP0534525B1 (de) | 1996-12-27 |
EP0534525B2 EP0534525B2 (de) | 2007-10-10 |
Family
ID=10702133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92202764A Expired - Lifetime EP0534525B2 (de) | 1991-09-27 | 1992-09-11 | Waschmittelpulver und Verfahren zu deren Herstellung |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0534525B2 (de) |
JP (1) | JPH05202398A (de) |
AU (1) | AU651732B2 (de) |
BR (1) | BR9203769A (de) |
CA (1) | CA2078718C (de) |
DE (1) | DE69216191T3 (de) |
ES (1) | ES2097860T3 (de) |
GB (1) | GB9120657D0 (de) |
ZA (1) | ZA927383B (de) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994028098A1 (en) † | 1993-05-26 | 1994-12-08 | Unilever Plc | Detergent compositions |
GB9324129D0 (en) * | 1993-11-24 | 1994-01-12 | Unilever Plc | Detergent compositions and process for preparing them |
HU219203B (en) * | 1993-11-24 | 2001-03-28 | Unilever Nv | Particulate detergent composition and process for producing thereof |
WO1997024423A1 (en) * | 1995-12-28 | 1997-07-10 | Rhone-Poulenc Surfactants & Specialties, L.P. | Processes for producing solid surfactant compositions with enhanced dissolution rates |
GB9600547D0 (en) * | 1996-01-11 | 1996-03-13 | Reckitt & Colman Inc | Improved compositions containing organic compounds |
DE19603760A1 (de) * | 1996-02-02 | 1997-08-07 | Henkel Kgaa | Feste Reinigungsmittelzubereitungen |
ID16213A (id) † | 1996-03-11 | 1997-09-11 | Kao Corp | Komposisi deterjen butiran untuk mencuci pakaian |
CA2248994C (en) * | 1996-03-15 | 2001-05-15 | David S. Staley | Free-flowing agglomerated nonionic surfactant detergent composition and process for making same |
HUP9902766A3 (en) * | 1996-05-17 | 2001-10-29 | Procter & Gamble | Detergent composition |
GB2315761A (en) * | 1996-07-31 | 1998-02-11 | Procter & Gamble | Detergent composition comprising a particulate acid source and an alkaline source |
GB2315763A (en) * | 1996-07-31 | 1998-02-11 | Procter & Gamble | Preparation of an agglomerated detergent composition comprising a surfactant a an acid source |
US6162784A (en) * | 1996-07-31 | 2000-12-19 | The Procter & Gamble Company | Process and composition for detergents |
DE19704229A1 (de) * | 1997-02-06 | 1998-08-13 | Henkel Kgaa | Cobuilderhaltiges Additiv für Wasch- oder Reinigungsmittel |
GB2323384A (en) * | 1997-03-20 | 1998-09-23 | Procter & Gamble | A detergent composition |
EP0872544A1 (de) † | 1997-04-14 | 1998-10-21 | The Procter & Gamble Company | Trockene Brausegranulate und dessen Verwendung in granulierten Zusammensetzungen |
GB9711350D0 (en) * | 1997-05-30 | 1997-07-30 | Unilever Plc | Granular detergent compositions and their production |
ID29296A (id) | 1997-05-30 | 2001-08-16 | Unilever Nv | Komposisi deterjen butiran lembut yang bebas mengalir |
GB9711356D0 (en) | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
GB9711359D0 (en) | 1997-05-30 | 1997-07-30 | Unilever Plc | Detergent powder composition |
DE19723616A1 (de) * | 1997-06-05 | 1998-12-10 | Henkel Kgaa | Granulares Waschmittel |
US6534474B1 (en) | 1998-06-04 | 2003-03-18 | Kao Corporation | Surfactant composition |
DE19847281A1 (de) * | 1998-10-14 | 2000-04-20 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit organischen Oligocarbonsäuren |
DE19854083A1 (de) * | 1998-11-24 | 2000-05-25 | Henkel Kgaa | Citronensäurehaltiges Waschmittel |
US6683043B1 (en) | 1998-12-08 | 2004-01-27 | The Procter & Gamble Company | Process for manufacturing effervescence components |
GB2344597A (en) * | 1998-12-08 | 2000-06-14 | Procter & Gamble | Effervescence components |
WO2001064035A2 (en) * | 2000-02-28 | 2001-09-07 | The Procter & Gamble Company | Acidic antimicrobial compositions for treating food and food contact surfaces and methods of use thereof |
GB0006037D0 (en) | 2000-03-13 | 2000-05-03 | Unilever Plc | Detergent composition |
GB0115552D0 (en) | 2001-05-16 | 2001-08-15 | Unilever Plc | Particulate laundry detergent composition containing zeolite |
GB0125212D0 (en) * | 2001-10-19 | 2001-12-12 | Unilever Plc | Detergent compositions |
DE10163603B4 (de) * | 2001-12-21 | 2006-05-04 | Henkel Kgaa | Verfahren zur Herstellung builderhaltiger Tensidgranulate |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1374105A (en) * | 1970-12-03 | 1974-11-13 | Scherico Ltd | Effervescent compositions |
GB1515299A (en) * | 1974-08-28 | 1978-06-21 | Unilever Ltd | Stabilisation of sodium percarbonate |
US4231887A (en) * | 1979-06-26 | 1980-11-04 | Union Carbide Corporation | Zeolite agglomerates for detergent formulations |
US4414130A (en) * | 1976-08-17 | 1983-11-08 | Colgate Palmolive Company | Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them |
EP0367339A2 (de) * | 1988-11-02 | 1990-05-09 | Unilever N.V. | Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3653914A (en) * | 1970-03-20 | 1972-04-04 | Alberto Culver Co | Production of tablets |
JPS5438122B1 (de) * | 1971-04-27 | 1979-11-19 | ||
US3920586A (en) * | 1972-10-16 | 1975-11-18 | Procter & Gamble | Detergent compositions |
US4028262A (en) * | 1972-10-16 | 1977-06-07 | Colgate-Palmolive Company | Citrate-carbonate built detergent |
US4129526A (en) * | 1977-07-14 | 1978-12-12 | The Lion Fat & Oil Co., Ltd. | Granular detergent compositions and a process for producing same |
CA1275019A (en) * | 1985-10-09 | 1990-10-09 | The Procter & Gamble Company | Granular detergent compositions having improved solubility |
GB8918984D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Detergent compositions |
EP0456315B1 (de) * | 1990-05-08 | 1996-08-21 | The Procter & Gamble Company | Niedrig-pH-Waschmittelgranulate enthaltend Aluminiumsilikat, Zitronensäure und Carbonatbuilder |
-
1991
- 1991-09-27 GB GB919120657A patent/GB9120657D0/en active Pending
-
1992
- 1992-09-11 EP EP92202764A patent/EP0534525B2/de not_active Expired - Lifetime
- 1992-09-11 DE DE69216191T patent/DE69216191T3/de not_active Expired - Fee Related
- 1992-09-11 ES ES92202764T patent/ES2097860T3/es not_active Expired - Lifetime
- 1992-09-21 CA CA002078718A patent/CA2078718C/en not_active Expired - Lifetime
- 1992-09-21 JP JP4251218A patent/JPH05202398A/ja active Pending
- 1992-09-25 BR BR929203769A patent/BR9203769A/pt not_active IP Right Cessation
- 1992-09-25 AU AU25355/92A patent/AU651732B2/en not_active Ceased
- 1992-09-25 ZA ZA927383A patent/ZA927383B/xx unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1374105A (en) * | 1970-12-03 | 1974-11-13 | Scherico Ltd | Effervescent compositions |
GB1515299A (en) * | 1974-08-28 | 1978-06-21 | Unilever Ltd | Stabilisation of sodium percarbonate |
US4414130A (en) * | 1976-08-17 | 1983-11-08 | Colgate Palmolive Company | Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them |
US4231887A (en) * | 1979-06-26 | 1980-11-04 | Union Carbide Corporation | Zeolite agglomerates for detergent formulations |
EP0367339A2 (de) * | 1988-11-02 | 1990-05-09 | Unilever N.V. | Verfahren zur Herstellung einer körnigen Reinigungsmittelzusammensetzung mit hoher Schüttdichte |
Non-Patent Citations (6)
Title |
---|
"Proceedings of the second World Conference on Detergents, American Oil Chemists'Society,1987,p.177-180 * |
Hoffman la Roche sales brochure on citric acid on the market in 1988; Jungbunzlauer sales brochure on citric acid on the market before 1991 ADM sales brochure on citric acid, confirmed by ADM to be of essentially the same specification as the citric acid on the market before 1991; and CEH market research report on citric acid,of 1996, * |
Ind.Enp.Chem.Process Des-Der,Vol.9,n°3,pp363-367(1970) * |
JP-62-62889(published 19 March 1987), and translation into English. * |
prior use evidence of Ariel Ultra D product * |
prior use evidence of Cheer ZM product * |
Also Published As
Publication number | Publication date |
---|---|
EP0534525B2 (de) | 2007-10-10 |
ZA927383B (en) | 1994-03-25 |
DE69216191T3 (de) | 2008-03-13 |
CA2078718C (en) | 2003-12-09 |
AU651732B2 (en) | 1994-07-28 |
EP0534525A2 (de) | 1993-03-31 |
BR9203769A (pt) | 1993-04-20 |
EP0534525A3 (en) | 1993-09-01 |
DE69216191T2 (de) | 1997-06-05 |
ES2097860T3 (es) | 1997-04-16 |
DE69216191D1 (de) | 1997-02-06 |
GB9120657D0 (en) | 1991-11-06 |
CA2078718A1 (en) | 1993-03-28 |
JPH05202398A (ja) | 1993-08-10 |
AU2535592A (en) | 1993-04-01 |
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