EP0518576A2 - High bulk density granular detergent compositions - Google Patents
High bulk density granular detergent compositions Download PDFInfo
- Publication number
- EP0518576A2 EP0518576A2 EP92305203A EP92305203A EP0518576A2 EP 0518576 A2 EP0518576 A2 EP 0518576A2 EP 92305203 A EP92305203 A EP 92305203A EP 92305203 A EP92305203 A EP 92305203A EP 0518576 A2 EP0518576 A2 EP 0518576A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent
- composition
- bulk density
- litre
- detergent composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000003599 detergent Substances 0.000 title claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 46
- 239000007844 bleaching agent Substances 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 22
- 239000004615 ingredient Substances 0.000 claims abstract description 19
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims abstract description 16
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 14
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 37
- 229940045872 sodium percarbonate Drugs 0.000 claims description 23
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- -1 alkylbenzene sulphonate Chemical class 0.000 claims description 15
- 239000002736 nonionic surfactant Substances 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 150000004682 monohydrates Chemical group 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- 238000000280 densification Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 50
- 238000003860 storage Methods 0.000 description 21
- 235000017550 sodium carbonate Nutrition 0.000 description 18
- 229940001593 sodium carbonate Drugs 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 229910021532 Calcite Inorganic materials 0.000 description 12
- 238000009472 formulation Methods 0.000 description 12
- 239000000344 soap Substances 0.000 description 9
- 239000008187 granular material Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 235000013305 food Nutrition 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229940076133 sodium carbonate monohydrate Drugs 0.000 description 4
- 229960001922 sodium perborate Drugs 0.000 description 4
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 4
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229940120146 EDTMP Drugs 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 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
- 239000012190 activator Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 2
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate 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
- 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
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000008096 xylene 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
- 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
- C11D17/06—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
- C11D3/02—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/1233—Carbonates, e.g. calcite or dolomite
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Definitions
- the present invention relates to granular detergent compositions built with alkali metal carbonate and finely divided calcium carbonate, and containing a peroxy bleach system.
- Granular detergent compositions built with alkali metal carbonate and finely divided calcium carbonate are disclosed in a series of Unilever patents, the earliest of which is GB 1 437 950.
- Compositions containing peroxy bleaching compounds such as sodium perborate are disclosed, for example, GB 1 437 950 discloses in Example 18 a fully formulated detergent composition comprising a spray-dried base powder containing detergent-active compounds, sodium carbonate, calcite and sodium silicate, and postdosed sodium perborate.
- the moisture content of the powder is about 10 wt%, a value typical of a spray-dried powder.
- GB 1 583 081 discloses granular detergent compositions built with sodium carbonate and finely divided calcite and containing sodium percarbonate.
- the compositions are prepared by contacting the sodium carbonate with liquid or pasty detergent active compound to form granules, and then adhering the finely divided calcite to the granules.
- the sodium carbonate is generally wholly or predominantly in monohydrate form to ensure that all moisture present (generally about 4-5 wt% of the formulation) is bound as water of hydration of sodium carbonate monohydrate; preferably sodium carbonate monohydrate prepared by spray-drying an aqueous solution is used.
- the compositions are not densified; bulk densities ranging from 520 to 740 g/litre are disclosed, but the higher figures are apparently achieved only by the incorporation of very high levels of sodium carbonate (eg 60 wt%).
- the present invention is based on the discovery that stable detergent powders of high bulk density (750 g/litre and above, especially 800 g/litre and above), built with alkali metal carbonate and finely divided calcium carbonate, may be prepared to very low moisture contents indeed (2 wt% or less, or even zero), without the need to use large amounts of sodium carbonate in monohydrate form, and these powders exhibit enhanced peroxy bleach, especially sodium percarbonate, stability.
- the present invention provides a granular detergent composition
- a granular detergent composition comprising
- the subject of the present invention is a bleaching granular detergent composition containing detergent-active compounds, a builder system based on alkali metal carbonate and finely divided calcium carbonate, and a peroxy bleach system.
- Other optional ingredients may also be present as desired or required, provided that the content of water removable at 75°C does not exceed 4 wt%, and preferably does not exceed 2 wt%.
- the detergent compositions of the invention will contain, as essential ingredients, one or more detergent-active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
- surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof.
- suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
- the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
- Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8-C15; primary and secondary alkyl sulphates, particularly C12-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Sodium salts are generally preferred.
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C10 ⁇ C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C12 ⁇ C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol; and alkylpolyglycosides.
- detergent-active compound surfactant
- amount present will depend on the intended use of the detergent composition: different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
- the total amount of surfactant present will also depend on the intended end use, but will generally range from 5 to 60 wt%, preferably from 5 to 40 wt%.
- Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combination of the two in any ratio, optionally together with soap.
- compositions contain the anionic surfactant, linear alkylbenzene sulphonate, optionally in combination with one or more nonionic surfactants.
- content of water removable at 75°C does not exceed 4 wt%.
- compositions contain the anionic surfactant, primary alcohol sulphate, optionally in combination with one or more nonionic surfactants.
- content of water removable at 75°C preferably does not exceed 2 wt%.
- compositions of the invention comprise, as detergency builder, alkali metal (preferably sodium) carbonate. In principle this may be present in amy amount of from 10 to 60 wt%, but preferably the amount present does not exceed 30 wt%, and more preferably does not exceed 20 wt%, in order to avoid excessive alkalinity.
- alkali metal preferably sodium
- the compositions of the present invention do not need high sodium carbonate contents in order to achieve high bulk densities.
- the sodium carbonate used in the composition need not be in sodium carbonate monohydrate form; there is no need for special processing steps to effect partial hydration of the carbonate, which can simply be used in normal anhydrous form (soda ash). A small amount of partial hydration may fortuitously occur during processing, but that is not essential to the present invention.
- compositions of the invention also comprise finely divided, high-surface-area calcium carbonate, suitably in an amount of from 5 to 40 wt%, preferably from 10 to 30 wt%.
- the calcium carbonate has a surface area of at least 10 m2/g, preferably at least 20 m2/g.
- Particularly preferred forms of calcium carbonate have surface areas in the range of from 30 to 100 m2/g. Surface areas are determined by the standard Brunauer, Emmett and Teller (BET) method.
- BET Brunauer, Emmett and Teller
- the preferred form of calcium carbonate is calcite, but vaterite and aragonite are possible alternatives. Suitable forms of calcium carbonate are commercially available. For more detailed disclosure on possible forms of calcium carbonate the reader is referred to the aforementioned GB 1 437 950 and GB 1 583 081 (Unilever).
- the detergent compositions of the invention also contain a peroxy bleach system, which may comprise a peracid; an inorganic or organic persalt which acts as a source of hydrogen peroxide; or an inorganic or organic persalt together with a peracid precursor (also known as a bleach precursor or bleach activator).
- a peroxy bleach system which may comprise a peracid; an inorganic or organic persalt which acts as a source of hydrogen peroxide; or an inorganic or organic persalt together with a peracid precursor (also known as a bleach precursor or bleach activator).
- the invention is especially concerned with compositions containing bleach systems based on the inorganic persalts, sodium perborate (more especially the monohydrate) and sodium percarbonate. These salts are suitably present in amounts of from 5 to 30 wt%, preferably from 10 to 20 wt%.
- compositions containing sodium percarbonate are of especial interest because of that salt's high sensitivity to moisture.
- the replacement of phosphates by zeolites in detergent powders in recent years has virtually outlawed the use of sodium percarbonate because of the high levels of mobile water inevitably present in zeolite-built powders.
- the alkali metal carbonate/calcium carbonate builder system represents an alternative route to zero-phosphate powders that circumvents this difficulty.
- compositions may advantageously contain a bleach activator (bleach precursor), to improve bleaching performance at lower wash temperatures.
- a bleach activator bleach activator
- Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors.
- TAED tetraacetylethylene diamine
- the molar ratio of percarbonate to precursor may suitably range from 0.5:1 to 20:1, preferably from 1:1 to 10:1.
- a bleach stabiliser for example, a salt of ethylenediaminetetracetic acid (EDTA) or ethylenediamine tetramethylenephosphonic acid (EDTMP or Dequest (Trade Mark)) may be present.
- EDTA ethylenediaminetetracetic acid
- EDTMP ethylenediamine tetramethylenephosphonic acid
- Dequest Trade Mark
- detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; enzymes, such as proteases, amylases, cellulases and lipases; lather control agents or lather boosters as appropriate; pigments; and perfumes. This list is not intended to be exhaustive.
- compositions of the invention have low free or mobile water contents, not greater than 4 wt%, preferably not greater than 2 wt%, and advantageously not greater than 1 wt%.
- These figures refer to water removable at 75°C, which represents relatively mobile water that could adversely effect the stability of water-sensitive ingredients such as sodium percarbonate.
- compositions of the invention have bulk densities of at least 750 g/litre, preferably at least 800 g/litre. Stability of compositions containing moisture-sensitive ingredients is especially problematic at higher bulk densities where ingredients are forced into closer proximity with each other.
- compositions of the invention are produced by processes which include use of a high-speed mixer/granulator.
- This apparatus described in more detail below, can be used both to densify a preformed powder prepared by spray-drying or other conventional technique, and to produce a powder directly from its raw materials by mixing and granulation; intermediate "part-part" processes are of course also possible.
- Preferred high-speed batch mixer/granulators have both a stirring action and a cutting action, as described in EP 340 013A (Unilever).
- the stirrer and the cutter may be operated independently of one another, and at separately variable speeds.
- Such a mixer is capable of combining a high energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation. It is thus a highly versatile and flexible piece of apparatus.
- a preferred type of batch high-speed mixer/granulator is bowl-shaped and preferably has a substantially vertical stirrer axis.
- mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
- the stirrer and cutter may be operated independently of one another, and at separately variable speeds.
- the Fukae mixer requires batch operation.
- continuous processes may be employed, for example, using a continuous high-speed mixer/granulator such as the Lödige (Trade Mark) Recycler, optionally followed by a moderate-speed continuous mixer/granulator such as the Lödige Ploughshare.
- Suitable processes are disclosed in EP 367 339A, EP 390 251A and EP 420 317A (Unilever), and in our copending European Patent Application No. 91 200 740.8.
- a first preferred process for the production of compositions in accordance with the invention includes the steps of:
- a second preferred process for the preparation of compositions in accordance with the invention includes the steps of:
- the calcite used was Socal (Trade Mark) U3 ex Solvay, having a surface area of 70 m2/g.
- the sodium carbonate used was anhydrous (light soda ash).
- the zeolite A used in the Comparative Examples was Wessalith (Trade Mark) P powder ex Degussa.
- nonionic surfactants used were Synperonic (Trade Mark) A7 and A3 ex ICI, which are C12-C15 alcohols ethoxylated respectively with an average of 7 and 3 moles of ethylene oxide.
- Detergent powders of high bulk density were prepared to the following formulations (in wt %):
- Powders 1 and 2 were prepared by granulation in a Magimix (Trade Mark) Cuisine System 5000 food mixer.
- the dry ingredients (linear alkylbenzene sulphonate, sodium carbonate, calcite, SCMC) were mixed, then aqueous sodium silicate solution was added, followed by a mixture of the two nonionic surfactants.
- the powders were then dried at 80°C for 1-10 minutes using a fluid bed dryer (Johnson Mathey), to the desired final moisture content (see below).
- Sodium percarbonate, TAED, and antifoam granules were then admixed.
- Powders A and B were prepared as follows.
- a base powder containing the linear alkylbenzene sulphonate, the nonionic surfactant 7EO, the soap, the sodium carbonate, the zeolite, the polymer and the SCMC was prepared by spray-drying an aqueous slurry; the nonionic surfactant 3EO was sprayed on using a rotating pan.
- the powder was then granulated and densified using the Fukae (Trade Mark) FS-30 high-speed mixer/granulator, some water being added to effect granulation.
- Fukae Trade Mark
- the mixer was operated at a stirrer speed of 200 rpm and a cutter speed of 3000 rpm, the temperature being controlled at 60°C by means of a water jacket; the granulation time was 2 minutes.
- the densified powders were then dried at 80°C in a fluid bed as described above for powders 1 and A; and the sodium percarbonate (commercial) then admixed (1.25 g per 8.75 g of base).
- the powders had the following content of free water, ie water removable at 75°C:
- Example 1 was a calcite/carbonate powder of very low free water content
- Example 2 was an otherwise identical calcite/carbonate powder of slightly higher, but still low, free water content
- Comparative Example A was a zeolite powder of comparable (very low) free water content to that of Example 1
- Comparative Example B was a zeolite powder of comparable free water content to that of Example 2.
- both calcite/carbonate powders showed significantly better storage stability than those if the zeolite powders; and that of the very low water content powder 1 was significantly better than that of the powder 2 of higher water content. Both calcite/carbonate powders were substantially more stable than the zeolite powders, which both showed unacceptable storage characteristics, the very low water content powder A not being significantly better than the higher water content powder B.
- Example C was outside the invention because its free water content was greater than 4 wt%.
- a powder (Comparative Example D) was prepared in accordance with Example 11 of GB 1 583 081, to the following formulation:
- the powder was prepared as follows. Sodium carbonate monohydrate was first prepared by spray-drying an aqueous suspension of sodium carbonate containing the sodium lauryl sulphate to lower the density of the product. The powder was then prepared by a continuous granulation process in which all the dry particulate ingredients, except the sodium percarbonate, were premixed and fed at constant rate to an inclined pan granulator, and the nonionic surfactant and perfume (premixed) were sprayed on at a constant rate according to the relative amounts required in the product. The sodium percarbonate was then postdosed.
- the product had a bulk density of 508 g/l.
- the total water content was found to be 5.5 wt%, and the free water content (content of water removable at 75°C) was 1.8 wt%.
- a sample of the powder was densified, using the Fukae mixer, to a bulk density of 780 g/litre (Comparative Example E). Its total water content was 6.0 wt% and its free water content was 1.6 wt%.
- Example D the powder obtained by following the directions of Example 11 of GB 1 583 081 had a bulk density of 508 g/litre. On densification to a bulk density comparable with that of Example 1, the bleach stability deteriorated still further.
- GB 1 583 081 does not teach a composition of high bulk density having good bleach stability on storage.
- Powders of the composition given for Examples 1 and 2 but containing sodium perborate monohydrate instead of standard sodium percarbonate, were prepared by the process described for Examples 1 and 2.
- High bulk density powders having a formulation similar to that of Examples 1 and 2 but containing a different anionic detergent active compound - primary alcohol sulphate instead of linear alkylbenzene sulphonate - were prepared by the food mixer method described for Examples 1 and 2.
- Bulk density was 878 g/litre.
- the bleach compound was commercial sodium percarbonate.
- High bulk density powders were prepared to the formulation given below.
- the powders were prepared by spray-drying an aqueous slurry of the non-heat sensitive ingredients (primary alcohol sulphate, part of the nonionic surfactant, soap, sodium carbonate, sodium silicate, sodium carboxymethylcellulose); densifying the resulting base powder in the Fukae mixer, then postdosing the remaining nonionic surfactant, calcite, sodium percarbonate, TAED, antifoam granules, enzyme granules and perfume.
- the bulk density was 756 g/litre.
- High bulk density powders of the formulation of Examples 31 to 33 were prepared by a different process: mixing and granulation of the surfactants, soap, sodium carbonate, sodium silicate, calcite and SCMC in the Fukae mixer, then postdosing the bleach ingredients, enzyme granules, antifoam granules and perfume.
- the bulk density was 840 g/litre.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
- The present invention relates to granular detergent compositions built with alkali metal carbonate and finely divided calcium carbonate, and containing a peroxy bleach system.
- Granular detergent compositions built with alkali metal carbonate and finely divided calcium carbonate are disclosed in a series of Unilever patents, the earliest of which is GB 1 437 950. Compositions containing peroxy bleaching compounds such as sodium perborate are disclosed, for example, GB 1 437 950 discloses in Example 18 a fully formulated detergent composition comprising a spray-dried base powder containing detergent-active compounds, sodium carbonate, calcite and sodium silicate, and postdosed sodium perborate. The moisture content of the powder is about 10 wt%, a value typical of a spray-dried powder.
- GB 1 583 081 (Unilever) discloses granular detergent compositions built with sodium carbonate and finely divided calcite and containing sodium percarbonate. The compositions are prepared by contacting the sodium carbonate with liquid or pasty detergent active compound to form granules, and then adhering the finely divided calcite to the granules. In these compositions, the sodium carbonate is generally wholly or predominantly in monohydrate form to ensure that all moisture present (generally about 4-5 wt% of the formulation) is bound as water of hydration of sodium carbonate monohydrate; preferably sodium carbonate monohydrate prepared by spray-drying an aqueous solution is used. The compositions are not densified; bulk densities ranging from 520 to 740 g/litre are disclosed, but the higher figures are apparently achieved only by the incorporation of very high levels of sodium carbonate (eg 60 wt%).
- The present invention is based on the discovery that stable detergent powders of high bulk density (750 g/litre and above, especially 800 g/litre and above), built with alkali metal carbonate and finely divided calcium carbonate, may be prepared to very low moisture contents indeed (2 wt% or less, or even zero), without the need to use large amounts of sodium carbonate in monohydrate form, and these powders exhibit enhanced peroxy bleach, especially sodium percarbonate, stability.
- The present invention provides a granular detergent composition comprising
- (a) at least one detergent-active compound,
- (b) an alkali metal carbonate detergency builder,
- (c) finely divided calcium carbonate having a surface area of at least 10 m²/g,
- (d) a peroxy bleach system,
- (e) optionally other detergent ingredients,
the composition having a bulk density of at least 750 g/litre and containing not more than 4 wt%, preferably not more than 2 wt%, of water removable at 75°C. - The subject of the present invention is a bleaching granular detergent composition containing detergent-active compounds, a builder system based on alkali metal carbonate and finely divided calcium carbonate, and a peroxy bleach system. Other optional ingredients may also be present as desired or required, provided that the content of water removable at 75°C does not exceed 4 wt%, and preferably does not exceed 2 wt%.
- The detergent compositions of the invention will contain, as essential ingredients, one or more detergent-active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
- The preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.
- Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C₈-C₁₅; primary and secondary alkyl sulphates, particularly C₁₂-C₁₅ primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred.
- Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C₁₀₋C₂₀ aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C₁₂₋ C₁₅ primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol; and alkylpolyglycosides.
- The choice of detergent-active compound (surfactant), and the amount present, will depend on the intended use of the detergent composition: different surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
- The total amount of surfactant present will also depend on the intended end use, but will generally range from 5 to 60 wt%, preferably from 5 to 40 wt%.
- Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or nonionic surfactant, or combination of the two in any ratio, optionally together with soap.
- According to one preferred embodiment of the invention, compositions contain the anionic surfactant, linear alkylbenzene sulphonate, optionally in combination with one or more nonionic surfactants. In this embodiment of the invention the content of water removable at 75°C does not exceed 4 wt%.
- According to another preferred embodiment of the invention, compositions contain the anionic surfactant, primary alcohol sulphate, optionally in combination with one or more nonionic surfactants. In this embodiment of the invention the content of water removable at 75°C preferably does not exceed 2 wt%.
- The compositions of the invention comprise, as detergency builder, alkali metal (preferably sodium) carbonate. In principle this may be present in amy amount of from 10 to 60 wt%, but preferably the amount present does not exceed 30 wt%, and more preferably does not exceed 20 wt%, in order to avoid excessive alkalinity. The compositions of the present invention do not need high sodium carbonate contents in order to achieve high bulk densities.
- Unlike the sodium carbonate used in GB 1 583 081 (Unilever), discussed above, the sodium carbonate used in the composition need not be in sodium carbonate monohydrate form; there is no need for special processing steps to effect partial hydration of the carbonate, which can simply be used in normal anhydrous form (soda ash). A small amount of partial hydration may fortuitously occur during processing, but that is not essential to the present invention.
- The compositions of the invention also comprise finely divided, high-surface-area calcium carbonate, suitably in an amount of from 5 to 40 wt%, preferably from 10 to 30 wt%. The calcium carbonate has a surface area of at least 10 m²/g, preferably at least 20 m²/g. Particularly preferred forms of calcium carbonate have surface areas in the range of from 30 to 100 m²/g. Surface areas are determined by the standard Brunauer, Emmett and Teller (BET) method. The preferred form of calcium carbonate is calcite, but vaterite and aragonite are possible alternatives. Suitable forms of calcium carbonate are commercially available. For more detailed disclosure on possible forms of calcium carbonate the reader is referred to the aforementioned GB 1 437 950 and GB 1 583 081 (Unilever).
- The detergent compositions of the invention also contain a peroxy bleach system, which may comprise a peracid; an inorganic or organic persalt which acts as a source of hydrogen peroxide; or an inorganic or organic persalt together with a peracid precursor (also known as a bleach precursor or bleach activator).
- The invention is especially concerned with compositions containing bleach systems based on the inorganic persalts, sodium perborate (more especially the monohydrate) and sodium percarbonate. These salts are suitably present in amounts of from 5 to 30 wt%, preferably from 10 to 20 wt%.
- Compositions containing sodium percarbonate are of especial interest because of that salt's high sensitivity to moisture. The replacement of phosphates by zeolites in detergent powders in recent years has virtually outlawed the use of sodium percarbonate because of the high levels of mobile water inevitably present in zeolite-built powders. The alkali metal carbonate/calcium carbonate builder system represents an alternative route to zero-phosphate powders that circumvents this difficulty.
- As indicated above, the compositions may advantageously contain a bleach activator (bleach precursor), to improve bleaching performance at lower wash temperatures. Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors.
- The molar ratio of percarbonate to precursor may suitably range from 0.5:1 to 20:1, preferably from 1:1 to 10:1.
- If desired, a bleach stabiliser (heavy metal sequestrant), for example, a salt of ethylenediaminetetracetic acid (EDTA) or ethylenediamine tetramethylenephosphonic acid (EDTMP or Dequest (Trade Mark)) may be present.
- Other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; enzymes, such as proteases, amylases, cellulases and lipases; lather control agents or lather boosters as appropriate; pigments; and perfumes. This list is not intended to be exhaustive.
- The compositions of the invention have low free or mobile water contents, not greater than 4 wt%, preferably not greater than 2 wt%, and advantageously not greater than 1 wt%. These figures refer to water removable at 75°C, which represents relatively mobile water that could adversely effect the stability of water-sensitive ingredients such as sodium percarbonate.
- The compositions of the invention have bulk densities of at least 750 g/litre, preferably at least 800 g/litre. Stability of compositions containing moisture-sensitive ingredients is especially problematic at higher bulk densities where ingredients are forced into closer proximity with each other.
- Preferred compositions of the invention are produced by processes which include use of a high-speed mixer/granulator. This apparatus, described in more detail below, can be used both to densify a preformed powder prepared by spray-drying or other conventional technique, and to produce a powder directly from its raw materials by mixing and granulation; intermediate "part-part" processes are of course also possible.
- Preferred high-speed batch mixer/granulators have both a stirring action and a cutting action, as described in EP 340 013A (Unilever). Preferably the stirrer and the cutter may be operated independently of one another, and at separately variable speeds. Such a mixer is capable of combining a high energy stirring input with a cutting action, but can also be used to provide other, gentler stirring regimes with or without the cutter in operation. It is thus a highly versatile and flexible piece of apparatus.
- A preferred type of batch high-speed mixer/granulator is bowl-shaped and preferably has a substantially vertical stirrer axis. Especially preferred are mixers of the Fukae (Trade Mark) FS-G series manufactured by Fukae Powtech Kogyo Co., Japan; this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall. The stirrer and cutter may be operated independently of one another, and at separately variable speeds.
- As indicated previously, the Fukae mixer requires batch operation. Alternatively, continuous processes may be employed, for example, using a continuous high-speed mixer/granulator such as the Lödige (Trade Mark) Recycler, optionally followed by a moderate-speed continuous mixer/granulator such as the Lödige Ploughshare. Suitable processes are disclosed in EP 367 339A, EP 390 251A and EP 420 317A (Unilever), and in our copending European Patent Application No. 91 200 740.8.
- A first preferred process for the production of compositions in accordance with the invention includes the steps of:
- (i) spray-drying an aqueous slurry of ingredients other than the finely divided calcium carbonate and the peroxy bleach system, to form a particulate detergent base composition; and
- (ii) granulating and densifying the spray-dried detergent base composition in a high-speed mixer/granulator to give a particulate product having a bulk density of at least 750 g/litre, preferably at least 800 g/litre, and containing not more than 4 wt%, preferably not more than 2 wt%, of water removable at 75°C;
the finely divided calcium carbonate being admixed either before or after step (ii) and the peroxy bleach system being admixed after step (ii). - A second preferred process for the preparation of compositions in accordance with the invention includes the steps of:
- (i) mixing and granulating detergent-active compound, alkali metal carbonate detergency builder, finely divided calcium carbonate and optionally other detergent ingredients in a high-speed mixer/granulator to give a particulate detergent base composition having a bulk density of at least 750 g/litre, preferably at least 800 g/litre, and containing not more than 4 wt%, preferably not more than 2 wt%, of water removable at 75°C; and
- (ii) admixing the peroxy bleach system.
- The invention is further illustrated by the following non-limiting Examples, in which parts and percentages are by weight unless otherwise stated. Examples identified by numbers are in accordance with the invention, while those identified by letter are comparative.
- The calcite used was Socal (Trade Mark) U3 ex Solvay, having a surface area of 70 m²/g.
- The sodium carbonate used was anhydrous (light soda ash).
- The zeolite A used in the Comparative Examples was Wessalith (Trade Mark) P powder ex Degussa.
- The following inorganic persalts were used:
- (a) commercial sodium percarbonate, having a surface area of 0.5 m²/g: Oxyper (Trade Mark) ex Interox.
- (b) fractionated sodium percarbonate: the 500-710 micrometre sieve fraction of Oxyper.
- (c) sodium percarbonate/sodium carbonate compound (about 65 wt% sodium percarbonate) ex FMC;
- (d) sodium perborate monohydrate, ex EKA, having a surface area of 7.56 m²/g.
- The nonionic surfactants used were Synperonic (Trade Mark) A7 and A3 ex ICI, which are C₁₂-C₁₅ alcohols ethoxylated respectively with an average of 7 and 3 moles of ethylene oxide.
-
- Powders 1 and 2 were prepared by granulation in a Magimix (Trade Mark) Cuisine System 5000 food mixer. The dry ingredients (linear alkylbenzene sulphonate, sodium carbonate, calcite, SCMC) were mixed, then aqueous sodium silicate solution was added, followed by a mixture of the two nonionic surfactants. The powders were then dried at 80°C for 1-10 minutes using a fluid bed dryer (Johnson Mathey), to the desired final moisture content (see below). Sodium percarbonate, TAED, and antifoam granules were then admixed.
- Powders A and B were prepared as follows. A base powder containing the linear alkylbenzene sulphonate, the nonionic surfactant 7EO, the soap, the sodium carbonate, the zeolite, the polymer and the SCMC was prepared by spray-drying an aqueous slurry; the nonionic surfactant 3EO was sprayed on using a rotating pan. The powder was then granulated and densified using the Fukae (Trade Mark) FS-30 high-speed mixer/granulator, some water being added to effect granulation. The mixer was operated at a stirrer speed of 200 rpm and a cutter speed of 3000 rpm, the temperature being controlled at 60°C by means of a water jacket; the granulation time was 2 minutes. The densified powders were then dried at 80°C in a fluid bed as described above for powders 1 and A; and the sodium percarbonate (commercial) then admixed (1.25 g per 8.75 g of base).
-
- Thus Example 1 was a calcite/carbonate powder of very low free water content; Example 2 was an otherwise identical calcite/carbonate powder of slightly higher, but still low, free water content; Comparative Example A was a zeolite powder of comparable (very low) free water content to that of Example 1; and Comparative Example B was a zeolite powder of comparable free water content to that of Example 2.
- The powders were then stored in sealed bottles at at 37°C. Storage stabilities were assessed by removing samples at different time intervals and measuring their available oxygen content by titration with potassium permanganate. The results, expressed as percentages of the initial value, were as follows:
- Thus both calcite/carbonate powders showed significantly better storage stability than those if the zeolite powders; and that of the very low water content powder 1 was significantly better than that of the powder 2 of higher water content. Both calcite/carbonate powders were substantially more stable than the zeolite powders, which both showed unacceptable storage characteristics, the very low water content powder A not being significantly better than the higher water content powder B.
- In a separate series of experiments, the storage stabilities of the powders used for Examples 1 and 2 above, and three more of the same composition and bulk density but different free water contents, were measured both at 37°C and at 28°C. The free water contents of the powders were as follows:
Example C was outside the invention because its free water content was greater than 4 wt%. -
-
-
- The powder was prepared as follows. Sodium carbonate monohydrate was first prepared by spray-drying an aqueous suspension of sodium carbonate containing the sodium lauryl sulphate to lower the density of the product. The powder was then prepared by a continuous granulation process in which all the dry particulate ingredients, except the sodium percarbonate, were premixed and fed at constant rate to an inclined pan granulator, and the nonionic surfactant and perfume (premixed) were sprayed on at a constant rate according to the relative amounts required in the product. The sodium percarbonate was then postdosed.
- The product had a bulk density of 508 g/l. The total water content was found to be 5.5 wt%, and the free water content (content of water removable at 75°C) was 1.8 wt%.
- A sample of the powder was densified, using the Fukae mixer, to a bulk density of 780 g/litre (Comparative Example E). Its total water content was 6.0 wt% and its free water content was 1.6 wt%.
-
- It will therefore be seen that, although most of the water in Comparative Example D was tied up as water of hydration of sodium carbonate monohydrate, the bleach stability of this prior art composition was markedly inferior to that of Example 1.
- As previously observed, the powder (Comparative Example D) obtained by following the directions of Example 11 of GB 1 583 081 had a bulk density of 508 g/litre. On densification to a bulk density comparable with that of Example 1, the bleach stability deteriorated still further.
- Thus GB 1 583 081 does not teach a composition of high bulk density having good bleach stability on storage.
- Powders of the composition and bulk density given for Examples 1 and 2, but containing fractionated sodium percarbonate instead of standard sodium percarbonate, were prepared by the process described for Examples 1 and 2.
-
-
- Powders of the composition and bulk density given for Examples 1 and 2, but containing FMC sodium percarbonate compound instead of standard sodium percarbonate, were prepared by the process described for Examples 1 and 2.
-
-
- Powders of the composition given for Examples 1 and 2, but containing sodium perborate monohydrate instead of standard sodium percarbonate, were prepared by the process described for Examples 1 and 2.
-
-
- High bulk density powders having a formulation similar to that of Examples 1 and 2 but containing a different anionic detergent active compound - primary alcohol sulphate instead of linear alkylbenzene sulphonate - were prepared by the food mixer method described for Examples 1 and 2. Bulk density was 878 g/litre. The bleach compound was commercial sodium percarbonate.
-
-
-
- These results show a preference for a free water content below 1 wt% for this formulation.
- High bulk density powders having the formulation of Examples 19 to 22 but containing a different bleach compound, FMC sodium percarbonate compound, were prepared by the food mixer method described for Examples 1 and 2.
-
-
- With FMC percarbonate, this formulation gave good storage stability at moisture contents below 2 wt%.
- High bulk density powders having the formulation of Examples 19 to 22 but containing a different bleach compound, sodium perborate monohydrate, were prepared by the food mixer method described in Examples 1 and 2.
-
-
- With sodium perborate monohydrate, this formulation gave good storage stability at moisture contents below 2 wt%.
-
- The powders were prepared by spray-drying an aqueous slurry of the non-heat sensitive ingredients (primary alcohol sulphate, part of the nonionic surfactant, soap, sodium carbonate, sodium silicate, sodium carboxymethylcellulose); densifying the resulting base powder in the Fukae mixer, then postdosing the remaining nonionic surfactant, calcite, sodium percarbonate, TAED, antifoam granules, enzyme granules and perfume. The bulk density was 756 g/litre.
-
-
-
- High bulk density powders of the formulation of Examples 31 to 33 were prepared by a different process: mixing and granulation of the surfactants, soap, sodium carbonate, sodium silicate, calcite and SCMC in the Fukae mixer, then postdosing the bleach ingredients, enzyme granules, antifoam granules and perfume. The bulk density was 840 g/litre.
-
-
-
- These results demonstrate a preference for a free water content below 1 wt% for this formulation.
Claims (15)
the finely divided calcium carbonate being admixed either before or after step (ii) and the peroxy bleach system being admixed after step (ii).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9112384 | 1991-06-10 | ||
GB919112384A GB9112384D0 (en) | 1991-06-10 | 1991-06-10 | Detergent compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0518576A2 true EP0518576A2 (en) | 1992-12-16 |
EP0518576A3 EP0518576A3 (en) | 1993-08-04 |
EP0518576B1 EP0518576B1 (en) | 1998-01-28 |
Family
ID=10696356
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92305203A Expired - Lifetime EP0518576B1 (en) | 1991-06-10 | 1992-06-05 | High bulk density granular detergent compositions |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0518576B1 (en) |
CA (1) | CA2070471C (en) |
DE (1) | DE69224233T2 (en) |
ES (1) | ES2112299T3 (en) |
GB (1) | GB9112384D0 (en) |
IN (1) | IN174518B (en) |
TW (1) | TW229228B (en) |
ZA (1) | ZA924231B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995016019A1 (en) * | 1993-12-10 | 1995-06-15 | The Procter & Gamble Company | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
US5658867A (en) * | 1995-05-31 | 1997-08-19 | The Procter & Gamble Company | Cleaning compositions containing a crystalline builder material in selected particle size ranges for improved performance |
US5707959A (en) * | 1995-05-31 | 1998-01-13 | The Procter & Gamble Company | Processes for making a granular detergent composition containing a crystalline builder |
US5731279A (en) * | 1995-05-31 | 1998-03-24 | The Procter & Gamble Company | Cleaning compositions containing a crystalline builder material having improved performance |
US5733865A (en) * | 1995-05-31 | 1998-03-31 | The Procter & Gamble Company | Processes for making a crystalline builder having improved performance |
US5773399A (en) * | 1993-12-10 | 1998-06-30 | The Procter & Gamble Comapny | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
US6100232A (en) * | 1998-03-02 | 2000-08-08 | The Procter & Gamble Company | Process for making a granular detergent composition containing a selected crystalline calcium carbonate builder |
US6114289A (en) * | 1997-03-11 | 2000-09-05 | The Procter & Gamble Company | Encapsulated crystalline calcium carbonate builder for use in detergent compositions |
US6130194A (en) * | 1997-03-11 | 2000-10-10 | The Procter & Gamble Company | Crystalline calcium carbonate builder enrobed with a hydrotrope for use in detergent compositions |
US6610645B2 (en) | 1998-03-06 | 2003-08-26 | Eugene Joseph Pancheri | Selected crystalline calcium carbonate builder for use in detergent compositions |
AU2021204239B2 (en) * | 2016-03-02 | 2023-04-20 | Chem-Dry, Inc. | Stain and odor treatment |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2391274A1 (en) * | 1977-05-18 | 1978-12-15 | Unilever Nv | PRODUCTION OF PULVERULENT DETERGENT COMPOSITIONS BASED ON ALKALINE METAL CARBONATE AND CALCIUM CARBONATE |
GB2003913A (en) * | 1977-09-12 | 1979-03-21 | Colgate Palmolive Co | Particulate detergent compositions containing alkali metal carbonate and bicarbonate |
EP0150613A2 (en) * | 1983-12-21 | 1985-08-07 | Unilever Plc | Detergent compositions |
US4738793A (en) * | 1985-11-01 | 1988-04-19 | Lever Brothers Company | Process for producing detergent powder of high bulk density |
EP0390251A2 (en) * | 1989-03-30 | 1990-10-03 | Unilever N.V. | Detergent compositions and process for preparing them |
-
1991
- 1991-06-10 GB GB919112384A patent/GB9112384D0/en active Pending
-
1992
- 1992-06-04 CA CA002070471A patent/CA2070471C/en not_active Expired - Fee Related
- 1992-06-05 DE DE69224233T patent/DE69224233T2/en not_active Expired - Fee Related
- 1992-06-05 EP EP92305203A patent/EP0518576B1/en not_active Expired - Lifetime
- 1992-06-05 ES ES92305203T patent/ES2112299T3/en not_active Expired - Lifetime
- 1992-06-10 ZA ZA924231A patent/ZA924231B/en unknown
- 1992-06-10 IN IN187BO1992 patent/IN174518B/en unknown
- 1992-06-10 TW TW081104522A patent/TW229228B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2391274A1 (en) * | 1977-05-18 | 1978-12-15 | Unilever Nv | PRODUCTION OF PULVERULENT DETERGENT COMPOSITIONS BASED ON ALKALINE METAL CARBONATE AND CALCIUM CARBONATE |
GB2003913A (en) * | 1977-09-12 | 1979-03-21 | Colgate Palmolive Co | Particulate detergent compositions containing alkali metal carbonate and bicarbonate |
EP0150613A2 (en) * | 1983-12-21 | 1985-08-07 | Unilever Plc | Detergent compositions |
US4738793A (en) * | 1985-11-01 | 1988-04-19 | Lever Brothers Company | Process for producing detergent powder of high bulk density |
EP0390251A2 (en) * | 1989-03-30 | 1990-10-03 | Unilever N.V. | Detergent compositions and process for preparing them |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1995016019A1 (en) * | 1993-12-10 | 1995-06-15 | The Procter & Gamble Company | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
US5773399A (en) * | 1993-12-10 | 1998-06-30 | The Procter & Gamble Comapny | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
CN1080297C (en) * | 1993-12-10 | 2002-03-06 | 普罗格特-甘布尔公司 | Stabilization of oxidation-sensitive ingredients in percarbonate detergent compositions |
US5658867A (en) * | 1995-05-31 | 1997-08-19 | The Procter & Gamble Company | Cleaning compositions containing a crystalline builder material in selected particle size ranges for improved performance |
US5707959A (en) * | 1995-05-31 | 1998-01-13 | The Procter & Gamble Company | Processes for making a granular detergent composition containing a crystalline builder |
US5731279A (en) * | 1995-05-31 | 1998-03-24 | The Procter & Gamble Company | Cleaning compositions containing a crystalline builder material having improved performance |
US5733865A (en) * | 1995-05-31 | 1998-03-31 | The Procter & Gamble Company | Processes for making a crystalline builder having improved performance |
US6114289A (en) * | 1997-03-11 | 2000-09-05 | The Procter & Gamble Company | Encapsulated crystalline calcium carbonate builder for use in detergent compositions |
US6130194A (en) * | 1997-03-11 | 2000-10-10 | The Procter & Gamble Company | Crystalline calcium carbonate builder enrobed with a hydrotrope for use in detergent compositions |
US6100232A (en) * | 1998-03-02 | 2000-08-08 | The Procter & Gamble Company | Process for making a granular detergent composition containing a selected crystalline calcium carbonate builder |
US6610645B2 (en) | 1998-03-06 | 2003-08-26 | Eugene Joseph Pancheri | Selected crystalline calcium carbonate builder for use in detergent compositions |
AU2021204239B2 (en) * | 2016-03-02 | 2023-04-20 | Chem-Dry, Inc. | Stain and odor treatment |
Also Published As
Publication number | Publication date |
---|---|
GB9112384D0 (en) | 1991-07-31 |
EP0518576B1 (en) | 1998-01-28 |
CA2070471A1 (en) | 1992-12-11 |
ES2112299T3 (en) | 1998-04-01 |
TW229228B (en) | 1994-09-01 |
ZA924231B (en) | 1993-12-10 |
DE69224233D1 (en) | 1998-03-05 |
EP0518576A3 (en) | 1993-08-04 |
IN174518B (en) | 1994-12-31 |
DE69224233T2 (en) | 1998-05-20 |
CA2070471C (en) | 1997-05-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1236368A (en) | Process for the preparation of a powder detergent composition of high bulk density | |
EP0552054B1 (en) | Detergent compositions | |
RU2143998C1 (en) | Sodium silicates as structure-forming agent, compound and washing agents or detergents comprising them | |
EP0242138B1 (en) | Process for the preparation of detergent powders | |
US5409627A (en) | Particulate bleaching detergent compositions containing zeolite map and a stable bleach catalyst | |
EP0522726B1 (en) | Detergent compositions | |
AU662586B2 (en) | Detergent compositions | |
MXPA05004773A (en) | Laundry detergent composition. | |
CA2028204A1 (en) | Detergent compositions | |
EP0714432B1 (en) | Granular detergent compositions containing zeolite and process for their preparation | |
EP0518576B1 (en) | High bulk density granular detergent compositions | |
GB2221695A (en) | Granular detergents | |
US5668100A (en) | Detergent mixtures and detergents or cleaning formulations with improved dissolving properties | |
KR960001019B1 (en) | Detergent composition | |
US5536432A (en) | Process for the production of a detergent composition | |
EP0430328B1 (en) | Process for preparing high bulk density detergent powders containing clay | |
EP0502675A2 (en) | Detergent compositions | |
CA2248635C (en) | Particulate aluminosilicate-built detergent compositions comprising cogranules of zeolite map and alkali metal silicate | |
JPH08504864A (en) | Granular cleaning agent and / or cleaning agent | |
CA2463234C (en) | Detergent compositions comprising an alkali metal carbonate salt and a water soluble-organic acid | |
AU725258B2 (en) | Modified aluminosilicate | |
EP0828817B1 (en) | Detergent composition and process for its production | |
CA1182026A (en) | Detergent compositions | |
EA000238B1 (en) | Process for the production of a detergent composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19930809 |
|
17Q | First examination report despatched |
Effective date: 19960924 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): CH DE ES FR GB IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980128 Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980128 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980128 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 69224233 Country of ref document: DE Date of ref document: 19980305 |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2112299 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19980428 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20080626 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20080731 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20080627 Year of fee payment: 17 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20090617 Year of fee payment: 18 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100101 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20090606 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090606 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20100401 Year of fee payment: 19 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20110228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090605 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100630 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20110605 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110605 |