CA2380682A1 - Cleaning compositions - Google Patents
Cleaning compositions Download PDFInfo
- Publication number
- CA2380682A1 CA2380682A1 CA002380682A CA2380682A CA2380682A1 CA 2380682 A1 CA2380682 A1 CA 2380682A1 CA 002380682 A CA002380682 A CA 002380682A CA 2380682 A CA2380682 A CA 2380682A CA 2380682 A1 CA2380682 A1 CA 2380682A1
- Authority
- CA
- Canada
- Prior art keywords
- cleaning composition
- water
- inorganic material
- agent
- 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.)
- Abandoned
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000004140 cleaning Methods 0.000 title claims abstract description 61
- 239000008187 granular material Substances 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 36
- 239000011147 inorganic material Substances 0.000 claims abstract description 36
- 239000007884 disintegrant Substances 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 11
- 239000003599 detergent Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910021536 Zeolite Inorganic materials 0.000 claims description 11
- 239000001913 cellulose Substances 0.000 claims description 9
- 229920002678 cellulose Polymers 0.000 claims description 9
- 235000010980 cellulose Nutrition 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 230000008961 swelling Effects 0.000 claims description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 229920002472 Starch Polymers 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 229920000881 Modified starch Polymers 0.000 claims description 3
- 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 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000011164 primary particle Substances 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000001767 crosslinked sodium carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010947 crosslinked sodium carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims 1
- 150000001449 anionic compounds Chemical class 0.000 claims 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims 1
- 229940105329 carboxymethylcellulose Drugs 0.000 claims 1
- 239000000843 powder Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 108010081873 Persil Proteins 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- -1 zeolite P Chemical compound 0.000 description 6
- 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 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000007844 bleaching agent Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004851 dishwashing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 229920005646 polycarboxylate Polymers 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- TXEODFPNVFYFIP-UHFFFAOYSA-N 3-carboxyoxy-2-methoxy-3-oxopropanoic acid Chemical class COC(C(O)=O)C(=O)OC(O)=O TXEODFPNVFYFIP-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229920002785 Croscarmellose sodium Polymers 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000168 Microcrystalline cellulose Polymers 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical class OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 235000019813 microcrystalline cellulose Nutrition 0.000 description 1
- 239000008108 microcrystalline cellulose Substances 0.000 description 1
- 229940016286 microcrystalline cellulose Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000005373 porous glass Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005029 sieve analysis Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000007916 tablet composition Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A cleaning composition formed into moulded bodies for use in for example fabric washing, dishware washing, stain removal and water softening incorporates disintegrant granules comprising a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20 % of the combined weight of said inorganic material.
Description
CLEANING COMPOSITIONS
This invention relates to cleaning compositions and, in particular, particulate cleaning compositions to be formed into moulded bodies for use in, for example, fabric washing, dishware washing, stain removal and water softening.
Detergent compositions in the form of tablets are widely described and are currently enjoying increasing popularity with consumers. They are described, for example, in GB 0 911 204 (Unilever), US 3 953 350 (Kao), DE 19 637 606 (Henkel), EP 0 711 (Unilever) and WO 98/40463 (Henkel). Tablets for machine dishwashing applications are described in, for example, WO 96/28530 (P&G). Tabletted detergents and cleaning compositions have several advantages over powdered or liquid compositions:
they are easier to dispense and handle, do not require measuring to obtain the correct dose and, being compact, are more economical to store and transport.
Tablets of cleaning compositions are generally made by compression or compaction of a quantity of the composition in the form of particles. Production of tablets which are sufficiently hard and strong to withstand storage and handling requires a relatively high pressure to be used in this compaction process. It is then necessary that, despite this compaction, the tablets are able to disperse and dissolve rapidly when added to wash water.
One approach to achieving good dispersion of the tablet is to include in the tablet a particulate insoluble but water-swellable agent. These particles then swell with ingress of water, leading to stresses in the tablet and thence to break-up of the tablet. Thus (Unilever) describes the use of 'water-insoluble, water-swellable polymeric material' which 'promotes disintegration of the tablets in water'. Typical swelling agents which have been disclosed as possible tablet disintegrating agents are starches, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinyl pyrrolidones, gelatines and formaldehyde casein as well as a wide variety of clay minerals and certain ion-exchange resins.
These water swelling agents have no function in fabric washing except to aid tablet disintegration. Furthermore, because they are insoluble and of relatively large particle size, they tend to deposit on clothes during the wash (see, for example, WO 98/55575 (Henkel) and WO
98/55582). As a result, several attempts have been made to minimise the deposition of these disintegrants, for example by combining such a water-swellable, insoluble disintegrant with a second, highly soluble disintegrating aid - see WO 98/55582 (Unilever). Other attempts have included use of a preferred particle size of the disintegrant. Thus, for example, WO 98/55583 (Unilever) claims use of such material at a particle dimension of at least 400 tam to give more efficient disintegration. On the other hand, WO 98/55575 (Henkel) teaches the use of cellulose disintegrating aids with a particle size of less than 100 Vim, in order to minimise deposition. This material is co-granulated with 'microcrystalline cellulose and/or one or several ingredients of detergents and cleaning agents'.
Surprisingly, we have now found that if a water-swellable disintegrating aid is co granulated with an insoluble or sparingly soluble, hydrophilic solid before being incorporated into a tablet, then the disintegrant is much more efficient in disintegrating the tablet in use. Thus, less of the disintegrating aid needs to be added for effective disintegration, lowering the probability of deposition of the disintegrating aid on the substrate being cleaned.
The present invention seeks to provide a particulate cleaning composition in the form of a moulded body and which is relatively inexpensive to manufacture and sufficiently robust to withstand handling during production and packaging processes but readily breaks up and dissolves when contacted with an aqueous medium during the cleaning process for which it is intended without resulting in undue deposition on the substrate being cleaned.
According to the present invention there is provided a cleaning composition, the composition including disintegrant in the form of granules comprising a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular disintegrant, the granules being combined with the active ingredients of the cleaning composition in a compacted moulded body.
According to a particular aspect of the invention, a granular composition suitable for use in a cleaning composition consists essentially of a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular composition.
By "water insoluble", we mean a compound with a water solubility of less than grams, preferably less than 1 gram, per 100 grams water (at a temperature of 25°C).
Preferably, the water-swellable agent comprises, in its anhydrous state, no more than 15%, more preferably no more than 10%, of the combined weight of said inorganic material and said agent of the granular disintegrant. In a typical composition of the invention, the water swellable agent comprises, in its anhydrous state, no more than 8%, e.g. 7.5%
or less, of the combined weight of said inorganic material and said agent. Generally, at least 1 % of the combined weight of the water-swellable agent and the inorganic material in the granules comprises water-swellable agent.
A feature of the invention is the relatively small amount of water-swellable agent that may be employed while securing satisfactory properties for the compacted cleaning composition. Frequently, the amount of water-swellable agent in the cleaning composition is less than 2% by weight. Preferably, the amount is less than 1 % of the cleaning composition but, usually, at least 0.2% of the water-swellable agent is present in the cleaning composition.
In one embodiment of the invention the inorganic material used in the formation of the disintegrant granules comprises a silica.
This invention relates to cleaning compositions and, in particular, particulate cleaning compositions to be formed into moulded bodies for use in, for example, fabric washing, dishware washing, stain removal and water softening.
Detergent compositions in the form of tablets are widely described and are currently enjoying increasing popularity with consumers. They are described, for example, in GB 0 911 204 (Unilever), US 3 953 350 (Kao), DE 19 637 606 (Henkel), EP 0 711 (Unilever) and WO 98/40463 (Henkel). Tablets for machine dishwashing applications are described in, for example, WO 96/28530 (P&G). Tabletted detergents and cleaning compositions have several advantages over powdered or liquid compositions:
they are easier to dispense and handle, do not require measuring to obtain the correct dose and, being compact, are more economical to store and transport.
Tablets of cleaning compositions are generally made by compression or compaction of a quantity of the composition in the form of particles. Production of tablets which are sufficiently hard and strong to withstand storage and handling requires a relatively high pressure to be used in this compaction process. It is then necessary that, despite this compaction, the tablets are able to disperse and dissolve rapidly when added to wash water.
One approach to achieving good dispersion of the tablet is to include in the tablet a particulate insoluble but water-swellable agent. These particles then swell with ingress of water, leading to stresses in the tablet and thence to break-up of the tablet. Thus (Unilever) describes the use of 'water-insoluble, water-swellable polymeric material' which 'promotes disintegration of the tablets in water'. Typical swelling agents which have been disclosed as possible tablet disintegrating agents are starches, cellulose and cellulose derivatives, alginates, dextrans, cross-linked polyvinyl pyrrolidones, gelatines and formaldehyde casein as well as a wide variety of clay minerals and certain ion-exchange resins.
These water swelling agents have no function in fabric washing except to aid tablet disintegration. Furthermore, because they are insoluble and of relatively large particle size, they tend to deposit on clothes during the wash (see, for example, WO 98/55575 (Henkel) and WO
98/55582). As a result, several attempts have been made to minimise the deposition of these disintegrants, for example by combining such a water-swellable, insoluble disintegrant with a second, highly soluble disintegrating aid - see WO 98/55582 (Unilever). Other attempts have included use of a preferred particle size of the disintegrant. Thus, for example, WO 98/55583 (Unilever) claims use of such material at a particle dimension of at least 400 tam to give more efficient disintegration. On the other hand, WO 98/55575 (Henkel) teaches the use of cellulose disintegrating aids with a particle size of less than 100 Vim, in order to minimise deposition. This material is co-granulated with 'microcrystalline cellulose and/or one or several ingredients of detergents and cleaning agents'.
Surprisingly, we have now found that if a water-swellable disintegrating aid is co granulated with an insoluble or sparingly soluble, hydrophilic solid before being incorporated into a tablet, then the disintegrant is much more efficient in disintegrating the tablet in use. Thus, less of the disintegrating aid needs to be added for effective disintegration, lowering the probability of deposition of the disintegrating aid on the substrate being cleaned.
The present invention seeks to provide a particulate cleaning composition in the form of a moulded body and which is relatively inexpensive to manufacture and sufficiently robust to withstand handling during production and packaging processes but readily breaks up and dissolves when contacted with an aqueous medium during the cleaning process for which it is intended without resulting in undue deposition on the substrate being cleaned.
According to the present invention there is provided a cleaning composition, the composition including disintegrant in the form of granules comprising a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular disintegrant, the granules being combined with the active ingredients of the cleaning composition in a compacted moulded body.
According to a particular aspect of the invention, a granular composition suitable for use in a cleaning composition consists essentially of a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular composition.
By "water insoluble", we mean a compound with a water solubility of less than grams, preferably less than 1 gram, per 100 grams water (at a temperature of 25°C).
Preferably, the water-swellable agent comprises, in its anhydrous state, no more than 15%, more preferably no more than 10%, of the combined weight of said inorganic material and said agent of the granular disintegrant. In a typical composition of the invention, the water swellable agent comprises, in its anhydrous state, no more than 8%, e.g. 7.5%
or less, of the combined weight of said inorganic material and said agent. Generally, at least 1 % of the combined weight of the water-swellable agent and the inorganic material in the granules comprises water-swellable agent.
A feature of the invention is the relatively small amount of water-swellable agent that may be employed while securing satisfactory properties for the compacted cleaning composition. Frequently, the amount of water-swellable agent in the cleaning composition is less than 2% by weight. Preferably, the amount is less than 1 % of the cleaning composition but, usually, at least 0.2% of the water-swellable agent is present in the cleaning composition.
In one embodiment of the invention the inorganic material used in the formation of the disintegrant granules comprises a silica.
In a second embodiment of the invention the inorganic material used in the formation of the disintegrant granules conveniently comprises a material which acts as a functional ingredient of the cleaning composition. In this instance, the inorganic material may be an aluminosilicate such as zeolite P, A or X or mixtures thereof, with zeolite P
being preferred.
Alkali metal aluminosilicates, especially zeolites, are commonly used in detergent compositions as a detergency builder. Where a cleaning composition of the invention is one containing an alkali metal aluminosilicate as detergency builder, preferably at least part of the aluminosilicate constituent of the cleaning composition is employed as the inorganic material used in the formation of the disintegrant granules. For instance, the aluminosilicate constituent typically comprises about 10 to about 60% by weight of the cleaning composition and preferably, when zeolite is used in the disintegrant granules and as a detergency builder, then at least 1 % of the detergent composition comprises a zeolite constituent employed in the form of disintegrant granules.
The water-swellable agent preferably has an average primary particle size up to about 600 Vim, but, conveniently, has an average primary particle size of no more than 200 pm, preferably no more than 100 Vim, and a water swelling capacity of at least 5 ml/gram, preferably 10 ml/gram and more preferably 20 ml/gram as determined in the test described hereinafter.
Typically the water-swellable agent comprises polymer, frequently a wholly or partially cross-linked polymer, e.g. natural cellulose, cross-linked cellulose, (sodium) carboxy methyl cellulose, cross-linked sodium carboxymethyl cellulose, pre-gelatinised starch, cross linked starch, or cross linked polyvinyl pyrrolidone. Currently preferred are Aquasorb A500 (ex Hercules) and Ac-Di-Sol (ex FMC Corp).
The moulded body formed using the cleaning composition of the present invention may consist wholly of the cleaning composition or alternatively the moulded body may comprise a number of discrete portions, at least one of which comprises a cleaning composition in accordance with the invention. In this event, the remaining portion or portions of the moulded body may be constituted by at least one other ingredient, usually one suitable for use in detergent and cleaning applications such as fabric washing, dishware washing, stain removal and water softening.
Cleaning compositions of the invention may also contain, as essential ingredients, one or more detergency builders (wholly or partly incorporated in the disintegrant granules), and/or one or more detergent-active compounds which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof and/or other conventional additives.
A further aspect of the invention comprises a process for the preparation of a cleaning composition comprising forming a granular disintegrant composition consisting essentially of a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular composition and mixing said granular composition with one or more detergent-active compounds and, optionally, with one or more detergency builders.
Alkali metal aluminosilicates are favoured as environmentally acceptable water s insoluble builders, e.g. zeolites A, X and P or mixtures thereof. Other inorganic detergency builders include layered sodium silicate as described in US-A-4 664 839 and marketed by Hoechst as SKS-6, and alkali metal (generally sodium) carbonate. Water-soluble phosphorous containing detergency building compounds such as alkali metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates may be used. Also possible are organic detergency builders such as polycarboxylate polymers, e.g. polyacrylates, acrylic/maleic polymers, and acrylic phosphonates, monomeric polycarboxylates, e.g., gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
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 sodium linear alkylbenzene sulphonates having an alkyl chain length of Ce - C,S; primary and secondary alkyl sulphates, particularly sodium Ce - C,5 primary alcohol sulphates; olefin sulphonates;
alkane sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, and ethoxylates of esterified fatty acids, especially the C9 -C,5 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
The choice of surfactant, and the amount present, will depend on the intended use of the detergent composition. For example, for machine dishwashing a relatively low level of a low-foaming nonionic surfactant is generally preferred. In fabric washing compositions, different surfactant systems may be chosen, as is well known by the skilled detergent formulator, for handwashing products and for machine washing products.
The total amount of surfactant present will of course depend on the intended end use and may be as low as 0.5% by weight of the total composition, for example, in a machine dishwashing composition, or as high as 60% by weight of the total composition, for example, in a composition for washing fabrics by hand. For fabric washing compositions in general, an amount of from 5 to 40% by weight of the total composition is generally appropriate.
being preferred.
Alkali metal aluminosilicates, especially zeolites, are commonly used in detergent compositions as a detergency builder. Where a cleaning composition of the invention is one containing an alkali metal aluminosilicate as detergency builder, preferably at least part of the aluminosilicate constituent of the cleaning composition is employed as the inorganic material used in the formation of the disintegrant granules. For instance, the aluminosilicate constituent typically comprises about 10 to about 60% by weight of the cleaning composition and preferably, when zeolite is used in the disintegrant granules and as a detergency builder, then at least 1 % of the detergent composition comprises a zeolite constituent employed in the form of disintegrant granules.
The water-swellable agent preferably has an average primary particle size up to about 600 Vim, but, conveniently, has an average primary particle size of no more than 200 pm, preferably no more than 100 Vim, and a water swelling capacity of at least 5 ml/gram, preferably 10 ml/gram and more preferably 20 ml/gram as determined in the test described hereinafter.
Typically the water-swellable agent comprises polymer, frequently a wholly or partially cross-linked polymer, e.g. natural cellulose, cross-linked cellulose, (sodium) carboxy methyl cellulose, cross-linked sodium carboxymethyl cellulose, pre-gelatinised starch, cross linked starch, or cross linked polyvinyl pyrrolidone. Currently preferred are Aquasorb A500 (ex Hercules) and Ac-Di-Sol (ex FMC Corp).
The moulded body formed using the cleaning composition of the present invention may consist wholly of the cleaning composition or alternatively the moulded body may comprise a number of discrete portions, at least one of which comprises a cleaning composition in accordance with the invention. In this event, the remaining portion or portions of the moulded body may be constituted by at least one other ingredient, usually one suitable for use in detergent and cleaning applications such as fabric washing, dishware washing, stain removal and water softening.
Cleaning compositions of the invention may also contain, as essential ingredients, one or more detergency builders (wholly or partly incorporated in the disintegrant granules), and/or one or more detergent-active compounds which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds, and mixtures thereof and/or other conventional additives.
A further aspect of the invention comprises a process for the preparation of a cleaning composition comprising forming a granular disintegrant composition consisting essentially of a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular composition and mixing said granular composition with one or more detergent-active compounds and, optionally, with one or more detergency builders.
Alkali metal aluminosilicates are favoured as environmentally acceptable water s insoluble builders, e.g. zeolites A, X and P or mixtures thereof. Other inorganic detergency builders include layered sodium silicate as described in US-A-4 664 839 and marketed by Hoechst as SKS-6, and alkali metal (generally sodium) carbonate. Water-soluble phosphorous containing detergency building compounds such as alkali metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates may be used. Also possible are organic detergency builders such as polycarboxylate polymers, e.g. polyacrylates, acrylic/maleic polymers, and acrylic phosphonates, monomeric polycarboxylates, e.g., gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxy-methyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
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 sodium linear alkylbenzene sulphonates having an alkyl chain length of Ce - C,S; primary and secondary alkyl sulphates, particularly sodium Ce - C,5 primary alcohol sulphates; olefin sulphonates;
alkane sulphonates;
dialkyl sulphosuccinates; and fatty acid ester sulphonates.
Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, and ethoxylates of esterified fatty acids, especially the C9 -C,5 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol.
The choice of surfactant, and the amount present, will depend on the intended use of the detergent composition. For example, for machine dishwashing a relatively low level of a low-foaming nonionic surfactant is generally preferred. In fabric washing compositions, different surfactant systems may be chosen, as is well known by the skilled detergent formulator, for handwashing products and for machine washing products.
The total amount of surfactant present will of course depend on the intended end use and may be as low as 0.5% by weight of the total composition, for example, in a machine dishwashing composition, or as high as 60% by weight of the total composition, for example, in a composition for washing fabrics by hand. For fabric washing compositions in general, an amount of from 5 to 40% by weight of the total composition is generally appropriate.
Generally, cleaning compositions of the invention will contain from 1 to 20%
by weight of the disintegrant granules based on total weight of the composition.
Frequently the cleaning compositions will contain from 4 to 10 % by weight of the disintegrant granules.
A suitable type of cleaning composition suitable for use in most automatic fabric washing machines contains both anionic and nonionic surfactants. Cleaning compositions according to the invention may also suitably contain a bleach system. Machine dishwashing compositions may suitably contain a chlorine bleach, while fabric washing compositions may contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. Again, the skilled detergent worker will have no difficulty in applying the normal principles to choose a suitable bleach system.
Other materials that may be present in detergent compositions of the invention include sodium silicate, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents or lather boosters as appropriate, pigments, and perfumes. This list is not intended to be exhaustive.
Procedures and Tests Granule Production The granules of inorganic material and swelling agent may be prepared by any of the methods that will be known to those skilled in the art, e.g. by blending the dry ingredients in a mixer (such as a Pek mixer available from George Tweedy & Co of Preston - 281b S.A.
Machine) and compacting on a roller compactor (Alexanderwerk WP50 -manufactured by Alexanderwerk AG, D 5630 Remscheid 1, Germany). A typical preparative method is now described in detail with reference to silica as the inorganic material. Silica and water swelling organic particulate are blended together, in the appropriate proportions, in a Pek mixer for 30 minutes. A minimum of 2 kg of blended material so prepared is compacted by feeding into an Alexanderwerk roller compactor, fitted with a sintered block vacuum deaeration system. The roller pressure setting is selected according to the strength of granule desired, higher pressures leading to stronger granules. Generally, roller pressure is between 8 and 25 MPa and a typical roller pressure is 10 MPa. The compacted material from the compactor is fed into a granulator, which forms part of the machine, and forced through a mesh and the resulting granules are then screened to the desired particle size range, e.g. an average particle size of 250 to 1500 ym, using standard laboratory sieves. Preferably, the particles have a size range of 500 to 1200 Vim.
Tablet Production Tablets used in the Examples that follow were produced using a 45 mm diameter die set (stainless steel) in conjunction with a Universal Testing Machine Type No.
2030 from Zwick GmbH, Ulm, Germany. A known quantity, 40-45 grams, of the cleaning composition which comprised the compositions mentioned in the Examples below was placed in the die, the die plunger was inserted and the assembly was placed between the platens of the Zwick machine which was operated to apply a predetermined pressure to produce a tablet having a defined density and, in particular, a dimensionally stable and fracture resistant tablet. Tablets thus produced were cylindrical in shape, with a diameter of 45 mm and a height of about 20 mm.
Tablets with different densities were produced in order to determine the tablet disintegration and conductivity profiles. Tablets prepared had densities in the range 1250-1450 kg/m3, which are typical values for commercial fabric washing tablets found in the Western European market in 1998-9.
Determination of tablet disintegration profile Method 1 (Dynamic) The tablet disintegration profile provides an indication of the extent to which various tablets (e.g. different compositions, different densities) disintegrate under the defined conditions.
4500 g of demineralised water at 20°C were added to a 5 litre vessel fitted with pH, conductivity and temperature probes and maintained at a constant temperature of 20°C by immersion in a water bath. The tablets to be tested were inserted into a metal cage having the dimensions 9 cm x 4.7 cm x 2.7 cm and having 16 apertures (each about 2 mm square) per cm2. The metal cage was attached to the shaft of an overhead stirrer (Heidolph/Janke and Kunkel stirrer) to allow it and its contents to be rotated while immersed in the demineralised water. Prior to testing, the empty cage was immersed in the demineralised water and rotated at 80 rpm for a short period of time until the temperature of the demineralised water as detected by the temperature probe had stabilised at 20 ~ 0.2°C. At this time, the conductivity, pH and temperature values registered by the respective probes were recorded. The stirrer was then switched oft to allow the cage to be raised out of the water so that a pre-weighed detergent tablet to be investigated could be inserted into the cage. The cage was then re-immersed in the demineralised water together with the inserted tablet and the stirrer was switched on to resume rotation of the container at 80 rpm. Measurements of conductivity and pH, initially at 15 second intervals for one minute and thereafter at one minute intervals, were made over a period of 10 minutes after which time the cage was raised out of the demineralised water to allow the residue of the tablet to be removed. The residue was then dried in an oven at 105°C so that the dry weight of the residue could be calculated as a percentage of the original tablet weight. This procedure was repeated for a number of tablets having different compositions and different densities.
Method 2 (Static) 45008 of tap water at 20° C were added to a 5 litre vessel, which was maintained at 20° C by immersion in a water bath. The tablets to be tested were weighed and inserted into a metal cage 20 cm in diameter with 1 cm2 perforations. The cage was lowered into the 5 litre vessel and left for 60 seconds. The cage was then removed from the water, residue of the tablets was placed on an aluminium tray, dried for 24 hrs at 105° C and weighed to determine the percentage which had not disintegrated.
Determination of Tablet Conductivity Profile The tablet conductivity profile provides an indication of the extent to which various tablets (e.g. different compositions, different densities) dissolve under the defined conditions.
Conductivity measurements were obtained from the conductivity probe mentioned in Method 1 above at the same time as the tablet disintegration was measured.
Measurements of conductivity and pH were taken, initially at 30 second intervals for ten minutes and thereafter at one minute intervals for a further 20 minutes or until the conductivity measurements were observed to have reached a plateau corresponding to substantially total dissolution of the soluble portion of the tablet, i.e.
equilibration of the tablet with water. This procedure was repeated for a number of tablets having different compositions and different densities.
Determination of water swelling capacity of water-swellable agent To demonstrate the water swelling capacity of the water-swellable agent, 19.6 g of the agent was blended with 0.4 g of ultramarine pigment and compressed into a tablet using a laboratory tablet press at about 250 Mpa to give a tablet 32 mm in diameter.
This was crushed and sieved to give granules 500-1000 Nm in size. A glass tube, 33 mm in internal diameter and about 30 cm long with a sintered porous glass disc (porosity 1 ) fitted at one end was immersed upright, with said one end lowermost, in a large beaker of water (at 25° C) so that the water level rose to about 14 cm above the sintered glass. 1 g of granules was added to the tube and allowed to settle onto the sintered glass disc. With this arrangement water has access to the granules from both above and below. The granules immediately began to swell, forming a jelly-like mass. The ultramarine pigment imparted a blue colour to the mass making it easy to see the top and to record its height. The height of the swelling mass was recorded at intervals and showed an initial rapid rise followed by a levelling off after about 20-30 minutes. From the diameter of the tube, the volume of the swollen mass can be calculated. The result was expressed as ml/g water-swellable agent after 20 minutes.
Conductivity and disintegration profiles were investigated for a number of tablet formulations and densities, all based on concentrated Persil (Registered Trade Mark) original non-Biological detergent powder as manufactured by Lever Brothers of Kingston-upon Thames, UK - formulation as sold in the UK. The detergent powder was blended with different amounts of disintegrant granules. In each instance, the disintegrant granules comprised a water insoluble inorganic material, specifically a zeolite or a silica or a combination thereof, and a water-swellable agent. For comparative purposes, granules consisting of Persil powder alone or comprising a water-swellable agent or a mixture of a water soluble material, specifically sodium silicate or sodium carbonate, and a water-swellable material were also prepared and tested. In the Examples given below, Doucil A24 (Trade Mark) is a P-type zeolite sold by Crosfield Limited of Warrington, UK; SD2255 is a silica also obtainable from Crosfield Limited;
Doucil 4A (Trade Mark) is a 4A zeolite obtainable from Crosfield Limited; the sodium disilicate is obtainable from Crosfield Limited under the trade mark Pyramid 95; the sodium carbonate is obtainable from Solvay Chemicals Limited (identified in their product literature as Soda Ash (Sodium Carbonate) Light Rheinberg); and the water-swellable agent was sodium carboxymethylcellulose as sold under the trade mark Aquasorb A500 by Hercules Limited of Salford, UK.
Sodium Property SD2255 Doucil Doucil DisilicateSoda Aquasorb A24 4A Ash Surface 650 NM NM NM NM NM
Area (m2/9) Pore Volume1.3 NM NM NM NM NM
(ml/g) APS (pm) 5 1.2* 3* 100* See 40*
below Moisture 2 10* 20* 18-20* < 1.5 5*
Content (%
by weight) Oil absorption228 60* 40* NM NM NM
(g/100g) NM = Not measured In Table 1, APS represents average particle size (dso) as measured using a Malvern Mastersizer (Trade Mark) obtainable from Malvern Instruments in the UK and the values marked * are taken from typical data for the product or from specifications supplied by the manufacturer.
The Soda Ash used in the Examples had a bulk density of 0.53 kg/dm3 and was found to have a particle size distribution (by sieve analysis) as follows:
>1000ym=1wt%
500 - 1000 ~m = 0.5 wt 250-500~m=3.5wt%
75 - 250 pm = 74.5wt 0-75~m=20.5wt%
by weight of the disintegrant granules based on total weight of the composition.
Frequently the cleaning compositions will contain from 4 to 10 % by weight of the disintegrant granules.
A suitable type of cleaning composition suitable for use in most automatic fabric washing machines contains both anionic and nonionic surfactants. Cleaning compositions according to the invention may also suitably contain a bleach system. Machine dishwashing compositions may suitably contain a chlorine bleach, while fabric washing compositions may contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. Again, the skilled detergent worker will have no difficulty in applying the normal principles to choose a suitable bleach system.
Other materials that may be present in detergent compositions of the invention include sodium silicate, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, enzymes, lather control agents or lather boosters as appropriate, pigments, and perfumes. This list is not intended to be exhaustive.
Procedures and Tests Granule Production The granules of inorganic material and swelling agent may be prepared by any of the methods that will be known to those skilled in the art, e.g. by blending the dry ingredients in a mixer (such as a Pek mixer available from George Tweedy & Co of Preston - 281b S.A.
Machine) and compacting on a roller compactor (Alexanderwerk WP50 -manufactured by Alexanderwerk AG, D 5630 Remscheid 1, Germany). A typical preparative method is now described in detail with reference to silica as the inorganic material. Silica and water swelling organic particulate are blended together, in the appropriate proportions, in a Pek mixer for 30 minutes. A minimum of 2 kg of blended material so prepared is compacted by feeding into an Alexanderwerk roller compactor, fitted with a sintered block vacuum deaeration system. The roller pressure setting is selected according to the strength of granule desired, higher pressures leading to stronger granules. Generally, roller pressure is between 8 and 25 MPa and a typical roller pressure is 10 MPa. The compacted material from the compactor is fed into a granulator, which forms part of the machine, and forced through a mesh and the resulting granules are then screened to the desired particle size range, e.g. an average particle size of 250 to 1500 ym, using standard laboratory sieves. Preferably, the particles have a size range of 500 to 1200 Vim.
Tablet Production Tablets used in the Examples that follow were produced using a 45 mm diameter die set (stainless steel) in conjunction with a Universal Testing Machine Type No.
2030 from Zwick GmbH, Ulm, Germany. A known quantity, 40-45 grams, of the cleaning composition which comprised the compositions mentioned in the Examples below was placed in the die, the die plunger was inserted and the assembly was placed between the platens of the Zwick machine which was operated to apply a predetermined pressure to produce a tablet having a defined density and, in particular, a dimensionally stable and fracture resistant tablet. Tablets thus produced were cylindrical in shape, with a diameter of 45 mm and a height of about 20 mm.
Tablets with different densities were produced in order to determine the tablet disintegration and conductivity profiles. Tablets prepared had densities in the range 1250-1450 kg/m3, which are typical values for commercial fabric washing tablets found in the Western European market in 1998-9.
Determination of tablet disintegration profile Method 1 (Dynamic) The tablet disintegration profile provides an indication of the extent to which various tablets (e.g. different compositions, different densities) disintegrate under the defined conditions.
4500 g of demineralised water at 20°C were added to a 5 litre vessel fitted with pH, conductivity and temperature probes and maintained at a constant temperature of 20°C by immersion in a water bath. The tablets to be tested were inserted into a metal cage having the dimensions 9 cm x 4.7 cm x 2.7 cm and having 16 apertures (each about 2 mm square) per cm2. The metal cage was attached to the shaft of an overhead stirrer (Heidolph/Janke and Kunkel stirrer) to allow it and its contents to be rotated while immersed in the demineralised water. Prior to testing, the empty cage was immersed in the demineralised water and rotated at 80 rpm for a short period of time until the temperature of the demineralised water as detected by the temperature probe had stabilised at 20 ~ 0.2°C. At this time, the conductivity, pH and temperature values registered by the respective probes were recorded. The stirrer was then switched oft to allow the cage to be raised out of the water so that a pre-weighed detergent tablet to be investigated could be inserted into the cage. The cage was then re-immersed in the demineralised water together with the inserted tablet and the stirrer was switched on to resume rotation of the container at 80 rpm. Measurements of conductivity and pH, initially at 15 second intervals for one minute and thereafter at one minute intervals, were made over a period of 10 minutes after which time the cage was raised out of the demineralised water to allow the residue of the tablet to be removed. The residue was then dried in an oven at 105°C so that the dry weight of the residue could be calculated as a percentage of the original tablet weight. This procedure was repeated for a number of tablets having different compositions and different densities.
Method 2 (Static) 45008 of tap water at 20° C were added to a 5 litre vessel, which was maintained at 20° C by immersion in a water bath. The tablets to be tested were weighed and inserted into a metal cage 20 cm in diameter with 1 cm2 perforations. The cage was lowered into the 5 litre vessel and left for 60 seconds. The cage was then removed from the water, residue of the tablets was placed on an aluminium tray, dried for 24 hrs at 105° C and weighed to determine the percentage which had not disintegrated.
Determination of Tablet Conductivity Profile The tablet conductivity profile provides an indication of the extent to which various tablets (e.g. different compositions, different densities) dissolve under the defined conditions.
Conductivity measurements were obtained from the conductivity probe mentioned in Method 1 above at the same time as the tablet disintegration was measured.
Measurements of conductivity and pH were taken, initially at 30 second intervals for ten minutes and thereafter at one minute intervals for a further 20 minutes or until the conductivity measurements were observed to have reached a plateau corresponding to substantially total dissolution of the soluble portion of the tablet, i.e.
equilibration of the tablet with water. This procedure was repeated for a number of tablets having different compositions and different densities.
Determination of water swelling capacity of water-swellable agent To demonstrate the water swelling capacity of the water-swellable agent, 19.6 g of the agent was blended with 0.4 g of ultramarine pigment and compressed into a tablet using a laboratory tablet press at about 250 Mpa to give a tablet 32 mm in diameter.
This was crushed and sieved to give granules 500-1000 Nm in size. A glass tube, 33 mm in internal diameter and about 30 cm long with a sintered porous glass disc (porosity 1 ) fitted at one end was immersed upright, with said one end lowermost, in a large beaker of water (at 25° C) so that the water level rose to about 14 cm above the sintered glass. 1 g of granules was added to the tube and allowed to settle onto the sintered glass disc. With this arrangement water has access to the granules from both above and below. The granules immediately began to swell, forming a jelly-like mass. The ultramarine pigment imparted a blue colour to the mass making it easy to see the top and to record its height. The height of the swelling mass was recorded at intervals and showed an initial rapid rise followed by a levelling off after about 20-30 minutes. From the diameter of the tube, the volume of the swollen mass can be calculated. The result was expressed as ml/g water-swellable agent after 20 minutes.
Conductivity and disintegration profiles were investigated for a number of tablet formulations and densities, all based on concentrated Persil (Registered Trade Mark) original non-Biological detergent powder as manufactured by Lever Brothers of Kingston-upon Thames, UK - formulation as sold in the UK. The detergent powder was blended with different amounts of disintegrant granules. In each instance, the disintegrant granules comprised a water insoluble inorganic material, specifically a zeolite or a silica or a combination thereof, and a water-swellable agent. For comparative purposes, granules consisting of Persil powder alone or comprising a water-swellable agent or a mixture of a water soluble material, specifically sodium silicate or sodium carbonate, and a water-swellable material were also prepared and tested. In the Examples given below, Doucil A24 (Trade Mark) is a P-type zeolite sold by Crosfield Limited of Warrington, UK; SD2255 is a silica also obtainable from Crosfield Limited;
Doucil 4A (Trade Mark) is a 4A zeolite obtainable from Crosfield Limited; the sodium disilicate is obtainable from Crosfield Limited under the trade mark Pyramid 95; the sodium carbonate is obtainable from Solvay Chemicals Limited (identified in their product literature as Soda Ash (Sodium Carbonate) Light Rheinberg); and the water-swellable agent was sodium carboxymethylcellulose as sold under the trade mark Aquasorb A500 by Hercules Limited of Salford, UK.
Sodium Property SD2255 Doucil Doucil DisilicateSoda Aquasorb A24 4A Ash Surface 650 NM NM NM NM NM
Area (m2/9) Pore Volume1.3 NM NM NM NM NM
(ml/g) APS (pm) 5 1.2* 3* 100* See 40*
below Moisture 2 10* 20* 18-20* < 1.5 5*
Content (%
by weight) Oil absorption228 60* 40* NM NM NM
(g/100g) NM = Not measured In Table 1, APS represents average particle size (dso) as measured using a Malvern Mastersizer (Trade Mark) obtainable from Malvern Instruments in the UK and the values marked * are taken from typical data for the product or from specifications supplied by the manufacturer.
The Soda Ash used in the Examples had a bulk density of 0.53 kg/dm3 and was found to have a particle size distribution (by sieve analysis) as follows:
>1000ym=1wt%
500 - 1000 ~m = 0.5 wt 250-500~m=3.5wt%
75 - 250 pm = 74.5wt 0-75~m=20.5wt%
The different formulations of the disintegrant granules (on a by weight basis) are given in Table 2.
Granule Code Wt. % of AquasorbRemainder of Granule A500 in granule (Wt.
and Material) A 10 90% SD2255 Silica B 10 45% SD2255 Silica, 45% Doucil A24 C 10 90% Doucil 4A
D 10 90% Doucil A24 E 7.5 92.5% Doucil A24 F 5 95% Doucil A24 G 10 Pyramid 95 H 10 Sodium Carbonate The granules coded G and H contain inorganic materials which are water soluble and '~ as such are not within the scope of the present invention. These particular Examples are included for comparative purposes.
A series of tablets were prepared at a standard density of 1325 ~10kg/m3.
Tablets 1A
to 1 H contain 2% by weight of granules A to H respectively, the other 98%
being formed from concentrated Persil original non-Biological detergent powder. Tablet 1J was fabricated entirely from the same Persil powder. Tablets 1 K and 1 L were prepared from the same Persil powder, but incorporated 0.2% and 2% by weight of Aquasorb A500 powder respectively.
Table 3 shows the level of disintegration and the conductivity obtained after minutes immersion in water for these tablets using the experimental protocol described above in Method 1. The conductivity measurements are representative of the degree of dissolution of the soluble ionic constituents of the Persil detergent powder, the higher the conductivity value the greater the degree of tablet dissolution. The measurement of disintegration shows the level of undisintegrated residue retained in the 'cage'. Thus a high value indicates a poorly disintegrating tablet.
Granule Code Wt. % of AquasorbRemainder of Granule A500 in granule (Wt.
and Material) A 10 90% SD2255 Silica B 10 45% SD2255 Silica, 45% Doucil A24 C 10 90% Doucil 4A
D 10 90% Doucil A24 E 7.5 92.5% Doucil A24 F 5 95% Doucil A24 G 10 Pyramid 95 H 10 Sodium Carbonate The granules coded G and H contain inorganic materials which are water soluble and '~ as such are not within the scope of the present invention. These particular Examples are included for comparative purposes.
A series of tablets were prepared at a standard density of 1325 ~10kg/m3.
Tablets 1A
to 1 H contain 2% by weight of granules A to H respectively, the other 98%
being formed from concentrated Persil original non-Biological detergent powder. Tablet 1J was fabricated entirely from the same Persil powder. Tablets 1 K and 1 L were prepared from the same Persil powder, but incorporated 0.2% and 2% by weight of Aquasorb A500 powder respectively.
Table 3 shows the level of disintegration and the conductivity obtained after minutes immersion in water for these tablets using the experimental protocol described above in Method 1. The conductivity measurements are representative of the degree of dissolution of the soluble ionic constituents of the Persil detergent powder, the higher the conductivity value the greater the degree of tablet dissolution. The measurement of disintegration shows the level of undisintegrated residue retained in the 'cage'. Thus a high value indicates a poorly disintegrating tablet.
Tablet Code Conductivity (microSiemen)Undisintegrated Residue (%) 1 g 4100 0 The data clearly demonstrate the following:
1) The Tablet 1J, composed entirely of concentrated Persil powder, does not disintegrate or dissolve well; after 10 minutes it is only about 50% disintegrated.
2) Addition of 0.2% Aquasorb A500 (Tablet 1 K) has no appreciable effect (this is equivalent to the amount of Aquasorb added via granule incorporation in Tablets 1 A to 1 D, 1 G and 1 H).
3) Addition of more Aquasorb in Tablet 1 L (equivalent to the total weight addition of granules in Tablets 1A-1H) appears to suppress disintegration and dissolution.
4) Tablets 1A-1 D are essentially fully disintegrated/dissolved after 10 minutes.
5) In contrast, when the Aquasorb has been co-granulated with a soluble material (Tablets 1G, 1 H), the disintegration and dissolution is far less effective. In the case of silicate, the granules actually appear to retard disintegration relative to Tablet 1 J.
6) Even when the level of Aquasorb in the granules is reduced to 7.5% or 5%
(Tablets 1 E, 1 F, respectively) disintegration of the tablets is very well advanced after 10 minutes.
Table 4 below shows data for Tablets 2E, 2F equivalent to the data in Table 3.
These tablets which are similar to the tablets used in Example 1 but contain granules E and F
respectively, incorporated into tablets at 4% by weight instead of 2%. The test method for measuring disintegration was Method 1. Again, it is clear that, by increasing the weight of granule in the tablet at these lower levels of Aquasorb inclusion, the excellent disintegrating properties of the granules can be retained without the need to significantly increase the total weight of disintegrating polymer in the tablet (since 4% inclusion of granule F corresponds to 2% of granule D in terms of the total weight of Aquasorb introduced into the granule).
Tablet Code Conductivity (microSiemen)Undisintegrated Residue (%) Table 5 below shows further data for disintegration/conductivity (using disintegration Method 1 ) for tablets containing various of the granules, again incorporated into the tablets at 2% by weight. These tablets are identified as 3X, where the X is the letter corresponding to the granule identity in Table 2. In this case, the tablets have been prepared at a higher density (1350 ~ 10 kg/m3). At this higher density, it is possible to discriminate between the performance of the different granules A to D. From this data, it appears that the zeolite-containing granules are preferred over the silica-containing variant, with the granules prepared from Doucil A24 being the best performing disintegrating agents.
Tablet Code Conductivity (microSiemen)Undisintegrated Residue (%) 3g 3500 9 A number of tablets were prepared using a standard detergent base powder, similar to concentrated Persil powder, but without minor additives, such as perfume.
Tablets containing disintegrant granules as shown in Table 6 below were prepared at a nominal density of 1250 kg/m3 with 5% by weight of granules in the final detergent composition.
The disintegrant granules used were all based on the zeolite P, Doucil A24, which consisted of 90%
aluminosilicate and 10% water by weight.
Granule Water-swellable agent in granule Code (% by weight) 4M Aquasorb A500 (7.5) 4N Ac-Di-Sol' (5.0) 40 Ac-Di-Sol' (7.5) 4P Ac-Di-Sol' (10.0) 4Q Ac-Di-Sol' (15.0) 4R Cellulose powder BFT' Fines (7.5) 4S National 78- 1551' (7.5) 4T Arbocel FT40" (7.5) 'Ac-Di-Sol is a croscarmellulose sodium available from FMC Corporation, Philadelphia USA.
ZCellulose powder BFT is a granulated sulphite cellulose available from Vendico Chemical AB, Malmo, Sweden.
3National 78-1551 is a pre-gelatinised starch available from National Starch &
Chemical, Manchester, UK.
'Arbocel FT40 is a fibrous natural cellulose available from J. Rettenmaier &
Sohne, Rosenberg, Germany.
The disintegration of the tablets was measured using Method 2, described hereinbefore, and the results are given in Table 7 below.
Disintegrant code Undisintegrated residue (%w/w) no disintegrant 87 In general, the amount of residue found using Method 2 is larger than that found using Method 1, but the results still clearly demonstrate that the tablets containing disintegrant granules disintegrate to a much larger extent than tablets containing no granules.
1) The Tablet 1J, composed entirely of concentrated Persil powder, does not disintegrate or dissolve well; after 10 minutes it is only about 50% disintegrated.
2) Addition of 0.2% Aquasorb A500 (Tablet 1 K) has no appreciable effect (this is equivalent to the amount of Aquasorb added via granule incorporation in Tablets 1 A to 1 D, 1 G and 1 H).
3) Addition of more Aquasorb in Tablet 1 L (equivalent to the total weight addition of granules in Tablets 1A-1H) appears to suppress disintegration and dissolution.
4) Tablets 1A-1 D are essentially fully disintegrated/dissolved after 10 minutes.
5) In contrast, when the Aquasorb has been co-granulated with a soluble material (Tablets 1G, 1 H), the disintegration and dissolution is far less effective. In the case of silicate, the granules actually appear to retard disintegration relative to Tablet 1 J.
6) Even when the level of Aquasorb in the granules is reduced to 7.5% or 5%
(Tablets 1 E, 1 F, respectively) disintegration of the tablets is very well advanced after 10 minutes.
Table 4 below shows data for Tablets 2E, 2F equivalent to the data in Table 3.
These tablets which are similar to the tablets used in Example 1 but contain granules E and F
respectively, incorporated into tablets at 4% by weight instead of 2%. The test method for measuring disintegration was Method 1. Again, it is clear that, by increasing the weight of granule in the tablet at these lower levels of Aquasorb inclusion, the excellent disintegrating properties of the granules can be retained without the need to significantly increase the total weight of disintegrating polymer in the tablet (since 4% inclusion of granule F corresponds to 2% of granule D in terms of the total weight of Aquasorb introduced into the granule).
Tablet Code Conductivity (microSiemen)Undisintegrated Residue (%) Table 5 below shows further data for disintegration/conductivity (using disintegration Method 1 ) for tablets containing various of the granules, again incorporated into the tablets at 2% by weight. These tablets are identified as 3X, where the X is the letter corresponding to the granule identity in Table 2. In this case, the tablets have been prepared at a higher density (1350 ~ 10 kg/m3). At this higher density, it is possible to discriminate between the performance of the different granules A to D. From this data, it appears that the zeolite-containing granules are preferred over the silica-containing variant, with the granules prepared from Doucil A24 being the best performing disintegrating agents.
Tablet Code Conductivity (microSiemen)Undisintegrated Residue (%) 3g 3500 9 A number of tablets were prepared using a standard detergent base powder, similar to concentrated Persil powder, but without minor additives, such as perfume.
Tablets containing disintegrant granules as shown in Table 6 below were prepared at a nominal density of 1250 kg/m3 with 5% by weight of granules in the final detergent composition.
The disintegrant granules used were all based on the zeolite P, Doucil A24, which consisted of 90%
aluminosilicate and 10% water by weight.
Granule Water-swellable agent in granule Code (% by weight) 4M Aquasorb A500 (7.5) 4N Ac-Di-Sol' (5.0) 40 Ac-Di-Sol' (7.5) 4P Ac-Di-Sol' (10.0) 4Q Ac-Di-Sol' (15.0) 4R Cellulose powder BFT' Fines (7.5) 4S National 78- 1551' (7.5) 4T Arbocel FT40" (7.5) 'Ac-Di-Sol is a croscarmellulose sodium available from FMC Corporation, Philadelphia USA.
ZCellulose powder BFT is a granulated sulphite cellulose available from Vendico Chemical AB, Malmo, Sweden.
3National 78-1551 is a pre-gelatinised starch available from National Starch &
Chemical, Manchester, UK.
'Arbocel FT40 is a fibrous natural cellulose available from J. Rettenmaier &
Sohne, Rosenberg, Germany.
The disintegration of the tablets was measured using Method 2, described hereinbefore, and the results are given in Table 7 below.
Disintegrant code Undisintegrated residue (%w/w) no disintegrant 87 In general, the amount of residue found using Method 2 is larger than that found using Method 1, but the results still clearly demonstrate that the tablets containing disintegrant granules disintegrate to a much larger extent than tablets containing no granules.
Claims (22)
1. A cleaning composition, the composition including disintegrant in the form of granules comprising a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular disintegrant, the granules being combined with the active ingredients of the cleaning composition in a compacted moulded body.
2. A cleaning composition in which the water-swellable agent comprises, in its anhydrous state, no more than 15% of the combined weight of said inorganic material and said agent of the granular disintegrant.
3. A cleaning composition in which the water-swellable agent comprises, in its anhydrous state, no more than 10% of the combined weight of said inorganic material and said agent of the granular disintegrant.
4. A cleaning composition in which the water-swellable agent comprises, in its anhydrous state, no more than 8% of the combined weight of said inorganic material and said agent of the granular disintegrant.
5. A cleaning composition in which the water-swellable agent comprises, in its anhydrous state, at least 1% of the combined weight of said inorganic material and said agent of the granular disintegrant.
6. A cleaning composition as claimed in any one of the preceding claims in which the inorganic material comprises a silica.
7. A cleaning composition as claimed in any one of the preceding claims in which the inorganic material acts as functional ingredient of the cleaning composition.
8. A cleaning composition as claimed in any one of the preceding claims in which the inorganic material comprises an aluminosilicate.
9. A cleaning composition as claimed in Claim 8 in which the inorganic material comprises a zeolite.
10. A cleaning composition as claimed in Claim 9 in which the inorganic material comprises a zeolite P.
11. A cleaning composition as claimed in any one of Claims 7 to 10 in which the inorganic material comprises from about 10% to about 60% by weight of the cleaning composition.
12. A cleaning composition as claimed in Claim 11 in which the cleaning composition contains at least 1% by weight of the inorganic material embodied in the form of disintegrant granules.
13. A cleaning composition as claimed in any of the preceding claims in which the water-swellable agent has an average primary particle size of no more than 200 µm.
14. A cleaning composition as claimed in any one of the preceding claims in which the water-swellable agent has a water swelling capacity of at least 5 ml/gram.
15. A cleaning composition as claimed in any one of the preceding claims in which the water-swellable agent is selected from the group consisting of cellulose, cross-linked cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cross-linked sodium carboxy-methyl cellulose, pre-gelatinised starch, cross-linked starch and cross-linked polyvinyl pyrrolidone.
16. A cleaning composition as claimed in any one of the preceding claims in which the moulded body consists entirely of said cleaning composition.
17. A cleaning composition as claimed in any one of Claims 1 to 15 in which only part of the moulded body is constituted by said cleaning composition, the remainder of the moulded body being constituted by at least one other ingredient for use in detergent and cleaning applications such as fabric washing, dishware washing, stain removal and water softening.
18. A cleaning composition as claimed in any one of the preceding claims in which the amount of water-swellable agent is less than 2% by weight of the cleaning composition.
19. A cleaning composition as claimed in any one of the preceding claims in which the granular disintegrant is present in an amount in the range 1 to 20% by weight of the total cleaning composition.
20. A granular composition suitable for use in a cleaning composition consisting essentially of a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular composition.
21. A process for the preparation of a cleaning composition comprising forming a granular disintegrant composition consisting essentially of a water insoluble inorganic material and a water-swellable agent which, in its anhydrous state, comprises no more than 20% of the combined weight of said inorganic material and said agent of the granular composition and mixing said granular composition with one or more detergent-active compounds and, optionally, with one or more detergency builders.
22. A process as claimed in claim 21 in which the detergent-active compound is a soap, a synthetic non-soap anionic compound or a synthetic non-soap nonionic compound.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB9918782.5A GB9918782D0 (en) | 1999-08-10 | 1999-08-10 | Cleaning compositions |
GB9918782.5 | 1999-08-10 | ||
PCT/GB2000/002785 WO2001011000A1 (en) | 1999-08-10 | 2000-07-24 | Cleaning compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2380682A1 true CA2380682A1 (en) | 2001-02-15 |
Family
ID=10858865
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002380682A Abandoned CA2380682A1 (en) | 1999-08-10 | 2000-07-24 | Cleaning compositions |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1203069A1 (en) |
AR (1) | AR024984A1 (en) |
AU (1) | AU6003800A (en) |
BR (1) | BR0013037A (en) |
CA (1) | CA2380682A1 (en) |
CZ (1) | CZ2002484A3 (en) |
GB (1) | GB9918782D0 (en) |
MX (1) | MXPA02001371A (en) |
NO (1) | NO20020642L (en) |
PL (1) | PL353233A1 (en) |
WO (1) | WO2001011000A1 (en) |
ZA (1) | ZA200200627B (en) |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4414130A (en) * | 1976-08-17 | 1983-11-08 | Colgate Palmolive Company | Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them |
JPS53122679A (en) * | 1977-03-31 | 1978-10-26 | Sankyo Co Ltd | Process for preparing forming tablets |
GB9422924D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
WO1998003064A1 (en) * | 1996-07-23 | 1998-01-29 | Fmc Corporation | Disintegrant composition for dispersible solids |
GB9711831D0 (en) * | 1997-06-06 | 1997-08-06 | Unilever Plc | Cleaning compositions |
DE19901063A1 (en) * | 1999-01-14 | 2000-07-20 | Henkel Kgaa | Aid granules for washing and cleaning active moldings |
-
1999
- 1999-08-10 GB GBGB9918782.5A patent/GB9918782D0/en not_active Ceased
-
2000
- 2000-07-24 AU AU60038/00A patent/AU6003800A/en not_active Abandoned
- 2000-07-24 CA CA002380682A patent/CA2380682A1/en not_active Abandoned
- 2000-07-24 WO PCT/GB2000/002785 patent/WO2001011000A1/en not_active Application Discontinuation
- 2000-07-24 EP EP00946163A patent/EP1203069A1/en not_active Withdrawn
- 2000-07-24 PL PL00353233A patent/PL353233A1/en unknown
- 2000-07-24 MX MXPA02001371A patent/MXPA02001371A/en not_active Application Discontinuation
- 2000-07-24 BR BR0013037-0A patent/BR0013037A/en not_active Application Discontinuation
- 2000-07-24 CZ CZ2002484A patent/CZ2002484A3/en unknown
- 2000-07-28 AR ARP000103921A patent/AR024984A1/en unknown
-
2002
- 2002-01-23 ZA ZA200200627A patent/ZA200200627B/en unknown
- 2002-02-08 NO NO20020642A patent/NO20020642L/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP1203069A1 (en) | 2002-05-08 |
AU6003800A (en) | 2001-03-05 |
BR0013037A (en) | 2002-04-16 |
WO2001011000A1 (en) | 2001-02-15 |
GB9918782D0 (en) | 1999-10-13 |
AR024984A1 (en) | 2002-11-06 |
NO20020642D0 (en) | 2002-02-08 |
ZA200200627B (en) | 2003-06-25 |
NO20020642L (en) | 2002-04-03 |
PL353233A1 (en) | 2003-11-03 |
MXPA02001371A (en) | 2004-07-16 |
CZ2002484A3 (en) | 2002-09-11 |
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Legal Events
Date | Code | Title | Description |
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FZDE | Discontinued |