US20090233833A1 - Composition for the protection of glassware in a dishwasher - Google Patents
Composition for the protection of glassware in a dishwasher Download PDFInfo
- Publication number
- US20090233833A1 US20090233833A1 US12/472,804 US47280409A US2009233833A1 US 20090233833 A1 US20090233833 A1 US 20090233833A1 US 47280409 A US47280409 A US 47280409A US 2009233833 A1 US2009233833 A1 US 2009233833A1
- Authority
- US
- United States
- Prior art keywords
- bismuth
- zinc
- composition
- aluminium
- glassware
- 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
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 88
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 70
- 239000004411 aluminium Substances 0.000 claims abstract description 70
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 64
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 63
- 239000011701 zinc Substances 0.000 claims abstract description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000001627 detrimental effect Effects 0.000 claims abstract description 21
- 238000004851 dishwashing Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims description 50
- 238000005260 corrosion Methods 0.000 claims description 50
- 239000003599 detergent Substances 0.000 claims description 35
- 238000009472 formulation Methods 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 22
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 150000002739 metals Chemical class 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 9
- -1 oxide Chemical compound 0.000 claims description 8
- 230000002265 prevention Effects 0.000 claims description 8
- 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 claims description 5
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 2
- 229910001152 Bi alloy Inorganic materials 0.000 claims 1
- 229910001297 Zn alloy Inorganic materials 0.000 claims 1
- 239000011521 glass Substances 0.000 description 89
- 239000008186 active pharmaceutical agent Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 240000002234 Allium sativum Species 0.000 description 7
- 235000004611 garlic Nutrition 0.000 description 7
- 239000003826 tablet Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000005034 decoration Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000007916 tablet composition Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 230000008092 positive effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004382 Amylase Substances 0.000 description 2
- 102000013142 Amylases Human genes 0.000 description 2
- 108010065511 Amylases Proteins 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 2
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 2
- 235000019418 amylase Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 235000013405 beer Nutrition 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 208000001848 dysentery Diseases 0.000 description 2
- 239000005355 lead glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- VQJMAIZOEPPELO-KYGIZGOZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-(2-hydroxy-5-methylhexan-2-yl)-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol hydrochloride Chemical compound Cl.CO[C@]12CC[C@@]3(C[C@@H]1C(C)(O)CCC(C)C)[C@H]1Cc4ccc(O)c5O[C@@H]2[C@]3(CCN1CC1CC1)c45 VQJMAIZOEPPELO-KYGIZGOZSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 244000218514 Opuntia robusta Species 0.000 description 1
- 235000003166 Opuntia robusta Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001777 Tupperware Polymers 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910021527 natrosilite Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 235000015041 whisky Nutrition 0.000 description 1
- 235000020097 white wine Nutrition 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/19—Silica-free oxide glass compositions containing phosphorus containing boron
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
Definitions
- the present invention relates to a composition comprising zinc and bismuth for use in the protection of glassware in an automatic dishwasher process particularly from detrimental phenomena caused by the presence of aluminium.
- the damage may include cloudiness, scratches, streaks and other discoloration/detrimental effects.
- Silicate materials have been suggested to be effective in preventing materials from being released by the glass composition.
- the use of silicate compounds can have detrimental side effects, such as the tendency to increase separation of silicate material at the glass surface.
- a further solution has been to use zinc, either in metallic form (such as described in U.S. Pat. No. 3,677,820) or in the form of compounds.
- zinc in metallic form (such as described in U.S. Pat. No. 3,677,820) or in the form of compounds.
- soluble zinc compounds in the prevention of glassware corrosion in a dishwasher is described in, for example, U.S. Pat. No. 3,255,117.
- WO-A-01/64823 describes the use of a ceramic composition comprising zinc to protect glassware in an automatic dishwashing process.
- GB-A-2 372 500 and WO-A-00/39259 describe the use of a soluble glass composition comprising zinc (present in the form of ions) to protect glassware in an automatic dishwashing process.
- the use of a ceramic/glass zinc containing composition overcomes the problems of poor solubility/precipitation described above whilst offering effective glassware protection.
- Bismuth has been used as an additive to aid the prevention of corrosion of glazed glassware corrosion.
- BE 860180 describes the use of bismuth to avoid damage of decorated, glazed articles.
- the value of bismuth in this purpose has been diminished by the detrimental effects that the use of bismuth compound has on other components of the washing process.
- bismuth has been found to stain plastic materials (such as Tupperware®).
- Bismuth also causes the formation of a brown stain on non-decorated glassware and cutlery.
- the glazed portion of the glassware may receive protection, bismuth has been found to stain the non-glazed portions. For these reasons the use of bismuth as a glaze protector has been avoided.
- a major problem with the use of aluminium is that, with use, the glassware adopts an iridescence. This has the effect of changing the glass from being transparent and colourless to having a coloured hue. Indeed, it has been observed that the detrimental efficacy of aluminium in this regard is so high that even when aluminium is present in a very small amount in the dishwasher liquor this effect is observed. As an example, the use of aluminium based dyes in dishwasher detergents, even in the minuscule quantities that such dyes are required, is avoided so that the iridescence effect does not occur.
- aluminium is known to exacerbate glass clouding corrosion. This is in contrast to the positive effect of aluminium on mass loss and cord lines. Clearly this detrimental effect prevails over any positive effect and is to be avoided.
- a composition comprising zinc and bismuth for the protection of glassware in an automatic dishwashing process from detrimental effects caused by exposure of the glassware to aluminium.
- composition is for use in addressing potential problems which may be caused by exposure of glassware to a source of aluminium in a dishwasher liquor.
- glassware includes items made of glass (such as drinking glasses and plates) which may be decorated (such as with a glaze and/or with etching/glass addition).
- the term glassware is also understood to include other items of houseware, which may comprise a material other than glass (such as a ceramic) but which have a glass/glaze coating or decoration (such as a glazed ceramic plate).
- the ratio of zinc to bismuth in the composition used is preferably in the range from 1:100 to 100:1 (based on mass of the metals). More preferably the ratio of zinc to bismuth in the composition (by mass) is from 1:10 to 10:1, more preferably from 1:5 to 5:1 and most preferably about 1:1.
- the amount of zinc and bismuth provided to a dishwasher cycle is preferably from 1 to 1000 mg, more preferably from 1 to 500 mg, more preferably from 1 to 200 mg and more preferably 5 to 100 mg.
- this weight refers to the combined weight of both metals.
- zinc and bismuth are available as ions in the dishwasher washing liquor.
- the zinc and bismuth may be in any suitable form to provide ions in the dishwasher liquid.
- a suitable form is the use of a metallic form of the metals.
- This form may be as separate forms of each metal disposed within the dishwasher. Such forms have been found to be solubilised over a number of wash cycles, to provide soluble ions of bismuth and zinc.
- the metal form may also comprise an admixture (such as an alloy) of zinc and bismuth.
- the alloy may contain further elements, such as other metal elements necessary to ensure stability/solubility of the alloy.
- Preferred physical forms of the metal/alloy include sheets, perforated sheets, fibres, granules, powders, blocks (e.g. cuboid) or an admixture thereof.
- a suitable form is the use of a salt or compound of one or both of bismuth and zinc.
- the salt/compound is one which has an appreciable solubility in the washing liquor so that the effect of the zinc and bismuth can be observed.
- a salt of either element which only has a low solubility may also be used. In the latter case (as when a metallic form of one or more of the elements themselves is used) the amount of salt/compound which is used in the dishwasher may be increased accordingly to counter the low solubility of the low solubility salts.
- the salt/compound does not contain a component which is aggressive/detrimental to the dishwasher/dishwasher contents.
- the salt/compound is ionic it is preferred that the salt/compound is free from chloride anions which are recognised to have a detrimental effect on dishwashers (more particularly on stainless steel dishwasher components/cutlery).
- soluble metal salts include compounds with anions such as nitrate, sulphate, halide (especially fluoride), phosphate (where soluble), carbonate and carboxylate (such as the anions from C 1 -C 10 mono or multi carboxy function containing carboxylic acids, especially acetate and citrate).
- Preferred examples of metal compounds having a lower solubility include the oxides of the metals.
- An admixture of more than one compound may be used. Also a different compound of each metal may be used.
- the salt/compound is part of a detergent formulation.
- the detergent formulation may comprise a rinse aid.
- the detergent formulation may be any common detergent formulation of the type which are usually employed with dishwashers.
- the formulation may comprise a liquid, gel, powder or tablet formulation. Where the formulation is a liquid/gel generally the zinc and bismuth will be present in solution within the liquid/gel. However, it is also contemplated to have the zinc and bismuth present in the liquid/gel in the form of an insoluble salt/compound so that the zinc/bismuth may comprise a suspended particle (e.g. such as a “speckle” typically found in these formulations).
- the detergent formulation normally comprises other components which are typically found in dishwasher detergent formulations.
- the detergent formulation typically comprises one or more components selected from the group comprising surfactants (non-ionic, anionic, cationic and zwitterionic), builders, enzymes, foam suppressants, bleaches, bleach activators, thickeners, perfumes and dyes.
- the metals comprise from 0.002 to 6 wt % (based on the weight of both metals) of the detergent formulation. More preferably the metals comprise from 0.01 to 3 wt % and most preferably from 0.02 to 1.3 wt % of the dishwasher detergent formulation (e.g. 0.4 wt % for a 20 g tablet).
- the metals comprise from 0.03 to 30 wt % (based on the weight of both metals) of the rinse aid formulation. More preferably the metals comprise from 0.15 to 15 wt % and most preferably from 0.3 to 7 wt % of the rinse aid formulation.
- the zinc and/or bismuth may also be present in a soluble ceramic/glass formulation.
- the glass/ceramic may contain a glass forming material such as silica (SiO 2 ) or a boron oxide (e.g. B 2 O 3 ), an alkali/alkaline metal oxide (e.g. Na 2 O, K 2 O, CaO) and/or a phosphorus oxide (e.g. P 2 O 5 ).
- the glass/ceramic may comprise a homogenous body or in the alternative may be ground/crushed. Where the glass/ceramic is ground or crushed it preferably has an average particle size of less than 500 ⁇ m.
- one of the metals may be present in an additive whilst the other metal may be present in a detergent/rinse-aid formulation.
- the zinc may be present in the dishwasher detergent/rinse-aid together with one or more other detergent components whilst the bismuth may be added as a separate additive such as a glass composition which is disposed within the dishwasher machine.
- the bismuth may be added as a separate additive such as a glass composition which is disposed within the dishwasher machine.
- composition comprising zinc, bismuth and aluminium for the protection of the glassware in an automatic dishwasher.
- the aluminium may be present in the composition in any form (e.g. metallic form, fully/partially soluble aluminium salt/organic compound).
- the aluminium is present in the formulation such that from 5 to 200 mg of aluminium is released per wash cycle.
- composition comprising zinc, bismuth and silicate for the protection of aluminium items in an automatic dishwasher.
- the amount of silicate is present in a ratio of up to 1000:1 based on the weight of the zinc and bismuth components (with the term weight referring to the weight of the elements per se in any compound/admixture containing same). More preferably the amount of silicate is present in a ratio to zinc and bismuth of up to 500:1 and most preferably up to 100:1.
- the silicate may be present in the composition in any form (e.g. fully/partially soluble salt, organic compound (e.g. silicone), water soluble glass or ceramic).
- the silicate preferably comprises an admixture of a metal oxide (e.g. an alkali metal oxide such as sodium Na 2 O or potassium K 2 O) and silica (SiO 2 ).
- a metal oxide e.g. an alkali metal oxide such as sodium Na 2 O or potassium K 2 O
- silica SiO 2
- the preferred ratio of silica to metal oxide is between 1.0 to 4.0.
- a preferred example of a silicate is a metal (e.g. an alkali metal) disilicate such as Na 2 Si 2 O 5 , (metal oxide to silica ratio of 2.0).
- detergent composition (as shown in Table GL 1a) was used as a detergent formulation base.
- the formulation was used in tablet form.
- the glass formulation used was in the form of a solid body (measuring 4 cm ⁇ 1 cm ⁇ 1 cm).
- the mass loss of the glass block was on average 0.35 g/cycle, equating to 10 mg Bi 3+ per cycle and 40 mg Zn 2+ per cycle.
- test glasses were washed 50 to 100 times in a special endurance test dishwasher (Miele G 541 Special).
- a 20 g tablet of the base detergent described above was used with alternative additives (as specified in the Examples). Automatic dosing of the tablet occurred at the beginning of the cleaning cycle.
- Water Hardness in the machine less than 0.5 dGH, central softening through ion exchangers, internal ion exchangers not in operation.
- the test report comprised the following types of glass:
- the weight loss was determined gravimetrically after 50 to 100 test washes. Visible changes to the glass surface were evaluated in natural light (iridescence) or in a special light box (glass clouding, line corrosion and decoration damage).
- the dimensions of the light box were 70 cm ⁇ 40 cm ⁇ 65 cm (1 ⁇ b ⁇ h) and the inside of the box was painted matt black.
- the box was lit from above with an L 20 w/25 S (60 cm long) Osram lamp, which was covered in front with a screen. Shelves were disposed in the box on which the glasses were placed for evaluation. The box was open at the front.
- the glass corrosion was evaluated using the following criteria; glass clouding (GC), line corrosion (CL), decoration damage (DS) and iridescence (IR). For each parameter a score was given in accordance with the table below.
- Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 35 59 Octime 25 48 Longchamp 58 94 RKG Kölsch 24.5 45.5 RKG Bier 40 72
- Mass Loss 70
- Arcoroc Elegance 17 30
- Decorated Glassware Snoopy 223 502 Teddy 67 145 Kenia Plates 110
- Comparative Examples 1 and 2 show that whilst aluminium is able to provide mass loss/line corrosion protection for both decorated and non-decorated glassware it causes an iridescence effect on both decorated and non-decorated glassware (when present in the dishwasher liquor in metallic form as a garlic press). Aluminium also exacerbates glass clouding corrosion—this is particularly noticeable after 100 wash cycles.
- the aluminium garlic press was also present in the dishwasher.
- Example 1 show that the presence of both bismuth and zinc completely eliminates the detrimental effect of iridescence caused by the presence of the aluminium.
- the aluminium garlic press was also present in the dishwasher (however, please see next paragraph).
- Example 2 surprisingly shows that a formulation containing a combination of zinc and bismuth, when combined with a source of aluminium (the garlic press) provides enhanced glassware corrosion protection (when compared to a combination of zinc and bismuth).
- composition offers protection for both non-decorated and decorated glassware.
- detergent composition (as shown in Table AL1a) was used as a detergent formulation base.
- the formulation was used in tablet form.
- the glasses used were as those used in the Glass Examples.
- the evaluation of the glass corrosion was carried out in the same manner as for the Glass Examples.
- the plates comprised an alloy of magnesium and aluminium as (ALMg4 96% aluminium and 4% magnesium).
- the plates measured 100 mm ⁇ 50 mm ⁇ 1.5 mm and weighed 20 g.
- the weight loss was determined gravimetrically after 50 to 100 test washes.
- the aluminium corrosion was evaluated using the following criteria; discoloration aluminium (DA) and Shine Units (SU).
- DA discoloration aluminium
- SU Shine Units
- Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 7 59 Octime 9 48 Longchamp 15 94 RKG Kölsch 7 45.5 RKG Bier 6 72 Hämann Longdrink 15 124 Arcoroc Elegance 7 30 Sum 66 472.5 Decorated Glassware Snoopy 25 502 Teddy 12 145 Kenia Plates 20 230 Sum 57 877 Al-Plates Plate 2138 4698
- Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 3 6 Octime 0.5 4.5 Longchamp 23 48 RKG Kölsch 14 26.5 Goodmann Longdrink 4 10 Arcoroc Elegance 5 5 Sum 49.5 100 Decorated Glassware Snoopy 5 11 Teddy 0 7 Kenia Plates 0 0 Sum 5 18 Al-Plates Plate 104.5 217
- Comparative Examples 1 to 4 show that aluminium materials without protection dissolve, lose shine and cause iridescence on glassware
- the base detergent formulation was used with 0.67 g of zinc acetate, 0.19 g bismuth citrate and 3.8 g of sodium disilicate.
- Example 1 show that the presence of a combination of zinc, bismuth and disilicate gives good protection to aluminium such that the corrosion is low and the aluminium keeps its shine. Additionally this combination minimises detrimental effects on glassware: iridescence, glass corrosion on plain and decorated glassware is all vastly reduced.
Abstract
The present invention provides a composition. The composition comprises zinc and bismuth. The composition is for use in the protection of glassware in an automatic dishwashing process from detrimental effects caused by exposure to aluminium.
Description
- The present invention relates to a composition comprising zinc and bismuth for use in the protection of glassware in an automatic dishwasher process particularly from detrimental phenomena caused by the presence of aluminium.
- The problem of glassware corrosion in automatic dishwasher processes is well recognised. It has been put forward that the problem of glassware corrosion is the result of two separate phenomena. Firstly, it is suggested that the corrosion is due to leakage of minerals from the glass network, accompanied by hydrolysis of the silicate network. Secondly, silicate material is suggested to be released from the glass.
- These phenomena can cause damage to glassware after a number of separate wash cycles. The damage may include cloudiness, scratches, streaks and other discoloration/detrimental effects.
- Silicate materials have been suggested to be effective in preventing materials from being released by the glass composition. However, the use of silicate compounds can have detrimental side effects, such as the tendency to increase separation of silicate material at the glass surface.
- A further solution has been to use zinc, either in metallic form (such as described in U.S. Pat. No. 3,677,820) or in the form of compounds. The use of soluble zinc compounds in the prevention of glassware corrosion in a dishwasher is described in, for example, U.S. Pat. No. 3,255,117.
- The use of glasses and ceramics containing zinc has been found to address the problem of glassware corrosion in a dishwasher. WO-A-01/64823 describes the use of a ceramic composition comprising zinc to protect glassware in an automatic dishwashing process. GB-A-2 372 500 and WO-A-00/39259 describe the use of a soluble glass composition comprising zinc (present in the form of ions) to protect glassware in an automatic dishwashing process. The use of a ceramic/glass zinc containing composition overcomes the problems of poor solubility/precipitation described above whilst offering effective glassware protection.
- However, there is still a problem associated with the ceramic/glass zinc containing compositions (and also with water soluble/insoluble zinc compounds) in that these compositions do not perform satisfactorily in the prevention of decorated glassware corrosion.
- Bismuth has been used as an additive to aid the prevention of corrosion of glazed glassware corrosion. For example, BE 860180 describes the use of bismuth to avoid damage of decorated, glazed articles. However, the value of bismuth in this purpose has been diminished by the detrimental effects that the use of bismuth compound has on other components of the washing process. In this regard bismuth has been found to stain plastic materials (such as Tupperware®). Bismuth also causes the formation of a brown stain on non-decorated glassware and cutlery. Also although the glazed portion of the glassware may receive protection, bismuth has been found to stain the non-glazed portions. For these reasons the use of bismuth as a glaze protector has been avoided.
- A further problem which may be encountered when washing glassware in a dishwasher, and which has as yet not been addressed by automatic dishwasher detergent manufactures, is that caused by the presence of aluminium ions in the dishwasher.
- In the past aluminium has been put forward as a glass corrosion inhibition agent in, for example, U.S. Pat. No. 3,255,117 and WO-A-96/36687, for fine tableware such as lead crystal.
- However, there is some doubt that aluminium is entirely effective in this aim: whilst a reduction in mass loss and cord lines, when the glass is washed repeatedly in an automatic dishwasher is observed, glass clouding is exacerbated.
- Additionally, a major problem with the use of aluminium is that, with use, the glassware adopts an iridescence. This has the effect of changing the glass from being transparent and colourless to having a coloured hue. Indeed, it has been observed that the detrimental efficacy of aluminium in this regard is so high that even when aluminium is present in a very small amount in the dishwasher liquor this effect is observed. As an example, the use of aluminium based dyes in dishwasher detergents, even in the minuscule quantities that such dyes are required, is avoided so that the iridescence effect does not occur.
- Clearly this detrimental effect on glassware is undesirable. As a result the presence of aluminium in automatic dishwashing detergents has had to be avoided. However, although the aluminium content of a detergent (and also the automatic dishwashing machine) can be controlled and is usually kept as low as possible, the action of a consumer can still lead to exposure of glassware to aluminium. This can happen if, for example, a user washes an aluminium item (such as a common household garlic press) in an automatic dishwasher. In this instance the release of aluminium into the dishwasher liquor is enough to cause the detrimental effects described above. This effect may even be apparent after the single wash cycle the effect has also been observed if the user washes other aluminium items such as some pre-prepared food containers in the dishwasher. The effect may also be caused if the dishwasher contains any exposed aluminium components such as screws or sieves.
- The problem of metallic aluminium dissolution leading to the iridescent issues is particularly pronounced in a dishwashing machine as the dishwasher liquor is normally alkaline and aluminium dissolution enhanced at high pH.
- A further detrimental effect associated with the use of aluminium is that aluminium is known to exacerbate glass clouding corrosion. This is in contrast to the positive effect of aluminium on mass loss and cord lines. Clearly this detrimental effect prevails over any positive effect and is to be avoided.
- It is an object of the present invention to obviate/mitigate the problems outlined above.
- According to a first aspect of the present invention there is provided the use of a composition comprising zinc and bismuth for the protection of glassware in an automatic dishwashing process from detrimental effects caused by exposure of the glassware to aluminium.
- It will be appreciated that the composition is for use in addressing potential problems which may be caused by exposure of glassware to a source of aluminium in a dishwasher liquor.
- In the present invention it is understood that the term glassware includes items made of glass (such as drinking glasses and plates) which may be decorated (such as with a glaze and/or with etching/glass addition). The term glassware is also understood to include other items of houseware, which may comprise a material other than glass (such as a ceramic) but which have a glass/glaze coating or decoration (such as a glazed ceramic plate).
- It has been found that a combination of zinc and bismuth has especially beneficial properties in the prevention of detrimental effects (such as iridescence) caused by the presence of aluminium in the dishwasher liquor in an automatic dishwashing process. Additionally the use of the composition is highly effective at protecting normal glassware and also the composition has been found to be highly effective in protecting glazed glassware/crockery. Thus a single composition may now be used to provide glassware corrosion protection for both decorated glassware/crockery and non-decorated glassware in a dishwasher, as well as tackling the issues raised by the presence of aluminium.
- The ratio of zinc to bismuth in the composition used is preferably in the range from 1:100 to 100:1 (based on mass of the metals). More preferably the ratio of zinc to bismuth in the composition (by mass) is from 1:10 to 10:1, more preferably from 1:5 to 5:1 and most preferably about 1:1.
- Bearing the ratios outlined above in mind, the amount of zinc and bismuth provided to a dishwasher cycle is preferably from 1 to 1000 mg, more preferably from 1 to 500 mg, more preferably from 1 to 200 mg and more preferably 5 to 100 mg. Preferably this weight refers to the combined weight of both metals.
- Most preferably the zinc and bismuth are available as ions in the dishwasher washing liquor.
- The zinc and bismuth may be in any suitable form to provide ions in the dishwasher liquid.
- One example of a suitable form is the use of a metallic form of the metals. This form may be as separate forms of each metal disposed within the dishwasher. Such forms have been found to be solubilised over a number of wash cycles, to provide soluble ions of bismuth and zinc. The metal form may also comprise an admixture (such as an alloy) of zinc and bismuth. The alloy may contain further elements, such as other metal elements necessary to ensure stability/solubility of the alloy.
- Preferred physical forms of the metal/alloy include sheets, perforated sheets, fibres, granules, powders, blocks (e.g. cuboid) or an admixture thereof.
- Another example of a suitable form is the use of a salt or compound of one or both of bismuth and zinc. Most preferably the salt/compound is one which has an appreciable solubility in the washing liquor so that the effect of the zinc and bismuth can be observed. However, a salt of either element which only has a low solubility may also be used. In the latter case (as when a metallic form of one or more of the elements themselves is used) the amount of salt/compound which is used in the dishwasher may be increased accordingly to counter the low solubility of the low solubility salts.
- Most preferably the salt/compound does not contain a component which is aggressive/detrimental to the dishwasher/dishwasher contents. In the case where the salt/compound is ionic it is preferred that the salt/compound is free from chloride anions which are recognised to have a detrimental effect on dishwashers (more particularly on stainless steel dishwasher components/cutlery).
- Preferred examples of soluble metal salts include compounds with anions such as nitrate, sulphate, halide (especially fluoride), phosphate (where soluble), carbonate and carboxylate (such as the anions from C1-C10 mono or multi carboxy function containing carboxylic acids, especially acetate and citrate).
- Preferred examples of metal compounds having a lower solubility include the oxides of the metals.
- An admixture of more than one compound may be used. Also a different compound of each metal may be used.
- Most preferably the salt/compound is part of a detergent formulation. The detergent formulation may comprise a rinse aid.
- The detergent formulation may be any common detergent formulation of the type which are usually employed with dishwashers. The formulation may comprise a liquid, gel, powder or tablet formulation. Where the formulation is a liquid/gel generally the zinc and bismuth will be present in solution within the liquid/gel. However, it is also contemplated to have the zinc and bismuth present in the liquid/gel in the form of an insoluble salt/compound so that the zinc/bismuth may comprise a suspended particle (e.g. such as a “speckle” typically found in these formulations).
- The detergent formulation normally comprises other components which are typically found in dishwasher detergent formulations. In this regard the detergent formulation typically comprises one or more components selected from the group comprising surfactants (non-ionic, anionic, cationic and zwitterionic), builders, enzymes, foam suppressants, bleaches, bleach activators, thickeners, perfumes and dyes.
- It is most preferred that when the bismuth and zinc are present together in a dishwasher detergent formulation, the metals comprise from 0.002 to 6 wt % (based on the weight of both metals) of the detergent formulation. More preferably the metals comprise from 0.01 to 3 wt % and most preferably from 0.02 to 1.3 wt % of the dishwasher detergent formulation (e.g. 0.4 wt % for a 20 g tablet).
- In the case of a rinse aid, especially when the rinse aid is the only source of bismuth and zinc for the dishwasher, it is preferred that the metals comprise from 0.03 to 30 wt % (based on the weight of both metals) of the rinse aid formulation. More preferably the metals comprise from 0.15 to 15 wt % and most preferably from 0.3 to 7 wt % of the rinse aid formulation.
- The zinc and/or bismuth may also be present in a soluble ceramic/glass formulation. The glass/ceramic may contain a glass forming material such as silica (SiO2) or a boron oxide (e.g. B2O3), an alkali/alkaline metal oxide (e.g. Na2O, K2O, CaO) and/or a phosphorus oxide (e.g. P2O5).
- The glass/ceramic may comprise a homogenous body or in the alternative may be ground/crushed. Where the glass/ceramic is ground or crushed it preferably has an average particle size of less than 500 μm.
- It will also be appreciated that for all the forms of the bismuth and zinc mentioned above an admixture of different forms, wherein each metal is present in a different physical format may be used.
- In this regard it is also possible that one of the metals may be present in an additive whilst the other metal may be present in a detergent/rinse-aid formulation. As an example the zinc may be present in the dishwasher detergent/rinse-aid together with one or more other detergent components whilst the bismuth may be added as a separate additive such as a glass composition which is disposed within the dishwasher machine. Clearly other combinations of physical forms which satisfy the requirement that both bismuth and zinc are supplied to the wash liquor in accordance with the present invention.
- Strangely it has also been found that when a combination of bismuth and zinc has been used to address the problems caused by the presence of aluminium in the dishwasher liquor not only have the detrimental effects caused by the aluminium being eliminated but furthermore the positive effects of the bismuth and zinc on the prevention of decorated and non-decorated glassware corrosion have been enhanced.
- Thus in accordance with the second aspect of the invention there is provided a composition comprising zinc, bismuth and aluminium for the protection of the glassware in an automatic dishwasher.
- Surprisingly when this composition is used in an automatic dishwasher over repeated wash cycles the previously observed detrimental effect of glass clouding attributed to the presence of aluminium is vastly reduced.
- It will be appreciated that features of the first aspect of the invention shall apply mutatis mutandis to the second aspect of the invention.
- The aluminium may be present in the composition in any form (e.g. metallic form, fully/partially soluble aluminium salt/organic compound). Preferably the aluminium is present in the formulation such that from 5 to 200 mg of aluminium is released per wash cycle.
- Additionally it has been found that when a combination of zinc and bismuth has been used to address the problems caused by the presence of aluminium ions in the dishwasher, this composition, if used in combination with a source of silicate, is able to achieve the same effects in terms of glass corrosion protection but also corrosion protection for aluminium items placed in the dishwasher (previously a widely observed problem) is greatly improved.
- Thus in accordance with a third aspect of the invention there is provided a composition comprising zinc, bismuth and silicate for the protection of aluminium items in an automatic dishwasher.
- Surprisingly when this composition is used in an automatic dishwasher over repeated wash cycles the previously observed detrimental occurrence of aluminium corrosion is vastly reduced.
- It will be appreciated that features of the first aspect of the invention shall apply mutatis mutandis to the third aspect of the invention.
- Preferably the amount of silicate is present in a ratio of up to 1000:1 based on the weight of the zinc and bismuth components (with the term weight referring to the weight of the elements per se in any compound/admixture containing same). More preferably the amount of silicate is present in a ratio to zinc and bismuth of up to 500:1 and most preferably up to 100:1.
- The silicate may be present in the composition in any form (e.g. fully/partially soluble salt, organic compound (e.g. silicone), water soluble glass or ceramic).
- The silicate preferably comprises an admixture of a metal oxide (e.g. an alkali metal oxide such as sodium Na2O or potassium K2O) and silica (SiO2). The preferred ratio of silica to metal oxide is between 1.0 to 4.0. A preferred example of a silicate is a metal (e.g. an alkali metal) disilicate such as Na2Si2O5, (metal oxide to silica ratio of 2.0).
- The invention is now further described with reference to the following non-limiting Examples.
- In the Examples the following detergent composition (as shown in Table GL 1a) was used as a detergent formulation base. The formulation was used in tablet form.
-
TABLE GL 1a Component % Sodium Tripolyphosphate 45.0 Sodium Bicarbonate 2.0 Sodium Carbonate 18.5 Sodium Perborate 10.0 TAED 2.5 Protease 1.5 Amylase 0.5 Non-ionic Surfactant 3.5 Polyethylene-glycol) 7.5 Perfume + Dye 0.3 Auxiliaries Rest - In the Examples the following glass composition was used as a source of zinc and bismuth (as shown in Table GL 1b).
- The glass formulation used was in the form of a solid body (measuring 4 cm×1 cm×1 cm).
-
TABLE GL 1b Component % P2O5 60.0 K2O 20.3 Bi2O3 3.2 (2.86% Bi) B2O3 1.3 Ca0 1.0 ZnO 14.2 (11.4% Zn) - When used in accordance with the method described below the mass loss of the glass block was on average 0.35 g/cycle, equating to 10 mg Bi3+ per cycle and 40 mg Zn2+ per cycle.
- In the Examples test glasses were washed 50 to 100 times in a special endurance test dishwasher (Miele G 541 Special).
- Cleaning Dosage: A 20 g tablet of the base detergent described above was used with alternative additives (as specified in the Examples). Automatic dosing of the tablet occurred at the beginning of the cleaning cycle.
- Water Hardness in the machine: less than 0.5 dGH, central softening through ion exchangers, internal ion exchangers not in operation.
- Cleaning program 65° C. (both the cleaning and the rinse cycle were operated at 65° C.).
- Water consumption per cycle: 23.5 litres.
- There was no soiling of the glassware tested.
- The test report comprised the following types of glass:
- “linea Michelangelo David” C32 Whitewine glass 19 cl.
- “Luminarc Octime Transparent”, Whisky glass 30 cl.
- “Longchamp”, 17 cl, Stemglass, lead crystal glass.
- “Arcoroc Elegance”, Wineglass, 14.5 cl.
- “Kölner Stange”, 24 cl, beer glass.
- “Longdrink-glass”, special edition (dishwasher sensitive), produced especially for Reckitt Benckiser.
- “Snoopy Look In”, Longdrink Nordland 28 cl.
- “Teddy”, Primusbecher 16 cl.
- “Kenia”, dinner plate, 19.5 cm.
- The weight loss was determined gravimetrically after 50 to 100 test washes. Visible changes to the glass surface were evaluated in natural light (iridescence) or in a special light box (glass clouding, line corrosion and decoration damage). The dimensions of the light box were 70 cm×40 cm×65 cm (1×b×h) and the inside of the box was painted matt black. The box was lit from above with an L 20 w/25 S (60 cm long) Osram lamp, which was covered in front with a screen. Shelves were disposed in the box on which the glasses were placed for evaluation. The box was open at the front.
- The glass corrosion was evaluated using the following criteria; glass clouding (GC), line corrosion (CL), decoration damage (DS) and iridescence (IR). For each parameter a score was given in accordance with the table below.
-
Evaluation Damage Impact 0 No glass damage 1 First minor damage/hardly visible 2 Slight damage, visible to expert or in the light box 3 Visible damage 4 Strong damage, clearly visible - In this Comparative Example only the base detergent formulation was used.
- The results of the tests are shown in Table GL 2a (Glass Corrosion) and Table GL 2b (Mass Loss).
-
TABLE GL 2a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 2.5 3.0 0.0 2.5 4.0 0.0 Octime 1.0 3.0 0.0 2.0 4.0 0.0 Longchamp 3.5 3.0 0.0 4.0 4.0 0.0 RKG Kölsch 0.5 3.0 0.0 1.0 4.0 0.0 RKG Bier 2.5 3.5 0.0 3.0 4.0 0.0 Nachtmann Longdrink 3.0 0.0 0.0 4.0 0.0 0.0 Arcoroc Elegance 3.0 3.5 0.0 4.0 4.0 0.0 Average 2.29 2.71 0.0 2.93 3.43 0.0 Decorated Glassware DS IR DS IR Snoopy 3.0 — 3.5 — Teddy 3.5 — 4.0 — Kenia Plates 3.5 0.0 4.0 0.0 Average 3.33 — 3.83 — -
TABLE GL 2b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 35 59 Octime 25 48 Longchamp 58 94 RKG Kölsch 24.5 45.5 RKG Bier 40 72 Nachtmann Longdrink 70 124 Arcoroc Elegance 17 30 Sum 269.5 472.5 Decorated Glassware Snoopy 223 502 Teddy 67 145 Kenia Plates 110 230 Sum 400 877 - In this Comparative Example only the base detergent formulation was used. In addition an aluminium garlic press was present in the dishwasher.
- The results of the tests are shown in Table GL 3a (Glass Corrosion) and Table GL 3b (Mass Loss).
-
TABLE GL 3a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 2.5 1.5 2.5 4.0 4.0 3.0 Octime 2.5 2.0 2.0 3.0 3.5 2.5 Longchamp 1.5 2.0 3.0 4.0 4.0 3.0 RKG Kölsch 1.5 1.0 2.0 3.5 3.0 2.5 RKG Bier 3.0 2.0 2.5 4.0 4.0 3.0 Nachtmann Longdrink 3.5 0.0 3.0 4.0 0.0 3.5 Arcoroc Elegance 2.0 0.5 2.0 4.0 3.0 2.0 Average 2.36 1.29 2.5 3.79 3.07 2.81 Decorated Glassware DS IR DS IR Snoopy 2.5 — 3.5 — Teddy 2.5 — 3.5 — Kenia Plates 3.0 3.0 3.5 3.0 Average 2.67 — 3.5 — -
TABLE GL 3b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 8 25 Octime 5.5 12.5 Longchamp 21 49 RKG Kölsch 6 13 RKG Bier 23 53 Nachtmann Longdrink 24 55 Arcoroc Elegance 7 14 Sum 94.5 221 Decorated Glassware Snoopy 77 181 Teddy 16 46 Kenia Plates 35 93 Sum 128 320 - Comparative Examples 1 and 2 show that whilst aluminium is able to provide mass loss/line corrosion protection for both decorated and non-decorated glassware it causes an iridescence effect on both decorated and non-decorated glassware (when present in the dishwasher liquor in metallic form as a garlic press). Aluminium also exacerbates glass clouding corrosion—this is particularly noticeable after 100 wash cycles.
- In this Example the bismuth and zinc containing glass was used in addition to the base detergent tablet.
- The aluminium garlic press was also present in the dishwasher.
- The results are shown in Table GL 4 (Iridescence).
-
TABLE GL 4 Iridescence 50 cycles 100 Cycles IR IR Glasses Michelangelo 0.0 0.0 Octime 0.0 0.0 Longchamp 0.0 0.0 RKG Kölsch 0.0 0.0 RKG Bier 0.0 0.0 Nachtmann Longdrink 0.0 0.0 Arcoroc Elegance 0.0 0.0 Average 0.0 0.0 Decorated Glassware Snoopy — — Teddy — — Kenia Plates 0.0 0.0 Average — — - The results of Example 1 show that the presence of both bismuth and zinc completely eliminates the detrimental effect of iridescence caused by the presence of the aluminium.
- In this Example the bismuth and zinc containing glass was used in addition to the base detergent tablet.
- The aluminium garlic press was also present in the dishwasher (however, please see next paragraph).
- The results of the tests are shown in Table GL 5a (Glass Corrosion) and Table GL 5b (Mass Loss). In these tables the figures shown in parentheses were achieved in the absence of aluminium—namely with only the detergent formulation and the bismuth and zinc water soluble glass block. The remaining figures show the results achieved in the presence of the aluminium garlic press.
-
TABLE GL 5a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL GC CL Michelangelo 0.5 (1.5) 1.0 (1.5) 2.5 (2.0) 1.5 (3.0) Octime 2.0 (2.5) 1.0 (1.0) 2.5 (2.5) 1.5 (2.5) Longchamp 0.0 (1.0) 0.5 (1.0) 0.5 (2.5) 1.0 (3.0) RKG Kölsch 0.0 (0.0) 1.0 (1.0) 0.0 (1.0) 2.0 (2.0) RKG Bier 1.5 (1.5) 1.0 (0.5) 2.0 (2.0) 1.0 (2.0) Nachtmann Longdrink 2.0 (2.5) 0.0 (0.0) 4.0 (4.0) 0.0 (0.0) Arcoroc Elegance 1.5 (2.0) 1.0 (1.5) 2.5 (3.5) 2.0 (2.5) Average 1.07 0.79 2.0 1.29 (1.57) (0.93) (2.50) (2.14) Decorated Glassware DS DS Snoopy 1.0 (1.5) 2.0 (2.5) Teddy 1.5 (2.0) 2.5 (2.5) Kenia Plates 1.0 (2.0) 2.0 (3.0) Average 1.17 (1.83) 2.17 (2.67) -
TABLE GL 5b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 3.0 (11) (25) Octime 0.0 (14.5) (20.5) Longchamp 3.0 (19) (30) RKG Kölsch 2.0 (9.5) (18.5) RKG Bier 5.0 (13) (26) Nachtmann Longdrink 0.0 (26) (34) Arcoroc Elegance 2.0 (9) (14) Sum 15.0 (102) (168) Decorated Glassware Snoopy 7.0 (62) 21.0 (121) Teddy 6.0 (24) 13.0 (46) Kenia Plates 20.0 (33) 31.0 (61) Sum 33.0 (119) 65.0 (228) - Example 2 surprisingly shows that a formulation containing a combination of zinc and bismuth, when combined with a source of aluminium (the garlic press) provides enhanced glassware corrosion protection (when compared to a combination of zinc and bismuth).
- Additionally the enhanced glassware corrosion protection is achieved without observation of any of the detrimental effects that would normally be caused by the presence of aluminium. Namely both iridescence caused by the presence of aluminium and excessive glass clouding are not observed.
- These effects are both unexpected.
- Furthermore the composition offers protection for both non-decorated and decorated glassware.
- In the Examples the following detergent composition (as shown in Table AL1a) was used as a detergent formulation base. The formulation was used in tablet form.
-
TABLE AL1a Component % Sodium Tripolyphosphate 45.0 Sodium Bicarbonate 2.0 Sodium Carbonate 18.5 Sodium Perborate 10.0 TAED 2.5 Protease 1.5 Amylase 0.5 Non-ionic Surfactant 3.5 Polyethylene-glycol) 7.5 Perfume + Dye 0.3 Auxiliaries Rest - In the Aluminium Examples the test methods used were as those used in the Glass Examples.
- The glasses used (decorated and non-decorated) were as those used in the Glass Examples. The evaluation of the glass corrosion was carried out in the same manner as for the Glass Examples.
- Two aluminium plates were added to the dishwasher. The plates comprised an alloy of magnesium and aluminium as (ALMg4 96% aluminium and 4% magnesium). The plates measured 100 mm×50 mm×1.5 mm and weighed 20 g.
- The weight loss was determined gravimetrically after 50 to 100 test washes.
- The aluminium corrosion was evaluated using the following criteria; discoloration aluminium (DA) and Shine Units (SU). For DA a score was given in accordance with the table below.
-
Evaluation Damage Impact 0 No aluminium damage 1 First minor damage/hardly visible 2 Slight damage, visible to expert 3 Visible damage 4 Strong damage, clearly visible - For SU the measurement technique according to the “Colour Guide Gloss” for handhold instruments from the company BYK Gardner GmbH was used. With the D65/10° setting and the measurement aperture set at 11 mm, ten evaluations on the back and ten on the front side of the plate were performed. The measurement from these twenty evaluations was averaged.
- In this Comparative Example only the base detergent formulation was used.
- The results of the tests are shown in Table AL2a (Glass Corrosion) and Table AL2b (Mass Loss).
-
TABLE AL2a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 1.5 1.5 3.0 3.0 4.0 3.5 Octime 2.5 1.5 1.5 2.5 1.5 1.5 Longchamp 1.5 1.5 2.5 3.5 2.5 4.0 RKG Kölsch 0.5 1.5 2.0 2.0 2.0 2.0 RKG Bier 1.0 1.0 1.5 2.0 1.5 3.0 Nachtmann Longdrink 3.0 0.0 2.0 4.0 0.0 3.0 Arcoroc Elegance 1.0 0.5 1.0 3.5 2.0 1.5 Average 1.57 1.07 2.06 2.93 1.93 2.75 Decorated Glassware DS IR DS IR Snoopy 2.0 — 3.0 — Teddy 1.5 — 2.5 — Kenia Plates 2.0 3.0 2.5 3.5 Average 3.33 — 2.67 — Al-Plates DA DA SU Plate 1.0 1.5 4.1 -
TABLE AL2b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 7 59 Octime 9 48 Longchamp 15 94 RKG Kölsch 7 45.5 RKG Bier 6 72 Nachtmann Longdrink 15 124 Arcoroc Elegance 7 30 Sum 66 472.5 Decorated Glassware Snoopy 25 502 Teddy 12 145 Kenia Plates 20 230 Sum 57 877 Al-Plates Plate 2138 4698 - In this Comparative Example only the base detergent formulation was used. In addition 3.67 g of sodium disilicate was added to the tablet formulation.
- The results of the tests are shown in Table AL3a (Glass Corrosion) and Table AL3b (Mass Loss).
-
TABLE AL3a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 2.0 3.5 3.5 2.5 4.0 4.0 Octime 2.5 3.0 3.0 3.5 4.0 3.5 Longchamp 4.0 3.5 3.5 4.0 4.0 4.0 RKG Kölsch 4.0 3.0 4.0 4.5 4.0 4.0 Nachtmann Longdrink 4.0 0.0 3.5 4.0 0.0 4.0 Arcoroc Elegance 4.0 4.0 3.5 4.0 4.0 4.0 Average 3.42 2.83 3.42 3.67 3.33 3.92 Decorated Glassware DS IR DS IR Snoopy 3.0 — 3.5 — Teddy 3.0 — 3.5 — Kenia Plates 1.5 4.0 2.0 4.0 Average 2.5 — 3.0 — Al-Plates DA DA SU Plate 3.5 4.0 34.9 -
TABLE AL3b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 29 52 Octime 15 22 Longchamp 76 109 RKG Kölsch 15 27 Nachtmann Longdrink 46 90 Arcoroc Elegance 10 23 Sum 192 323 Decorated Glassware Snoopy 130 256 Teddy 48 99 Kenia Plates 45 76 Sum 223 431 Al-Plates Plate 0.0 0.0 - In this Comparative Example only the base detergent formulation was used. In addition 0.67 g of zinc acetate was added to the tablet formulation
- The results of the tests are shown in Table AL4a (Glass Corrosion) and Table AL4b (Mass Loss).
-
TABLE AL4a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 0.5 1.5 0.5 0.5 1.5 0.5 Octime 1.5 1.0 0.5 2.5 1.5 0.5 Longchamp 0.0 1.0 0.0 0.0 1.5 0.0 RKG Kölsch 0.5 2.0 0.5 1.5 2.5 1.0 Nachtmann Longdrink 0.5 0.0 1.0 0.5 0.0 0.5 Arcoroc Elegance 1.0 0.5 1.0 1.5 1.0 1.0 Average 0.67 1.00 0.58 1.08 1.33 0.58 Decorated Glassware DS DS Snoopy 1.0 2.0 Teddy 1.0 1.5 Kenia Plates 1.0 2.5 Average 1.00 2.00 Al-Plates DA DA SU Plate 2.0 3.0 73.2 -
TABLE AL4b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 15 16 Octime 2 0 Longchamp 7 17 RKG Kölsch 0 0 Nachtmann Longdrink 1 8 Arcoroc Elegance 1 7 Sum 26 48 Decorated Glassware Snoopy 14 32 Teddy 5 16 Kenia Plates 17 41 Sum 36 89 Al-Plates Plate 118 233 - In this Comparative Example only the base detergent formulation was used. In addition 0.19 g of bismuth citrate was added to the tablet formulation.
- The results of the tests are shown in Table AL5a (Glass Corrosion) and Table AL5b (Mass Loss).
-
TABLE AL5a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 0.5 1.5 1.0 2.0 1.5 1.0 Octime 2.0 1.5 0.5 2.0 2.0 0.5 Longchamp 1.0 1.0 0.5 2.5 1.5 0.5 RKG Kölsch 0.5 1.5 0.5 2.0 2.5 0.5 Nachtmann Longdrink 1.5 0.0 0.0 2.0 0.0 0.0 Arcoroc Elegance 1.0 1.0 0.5 1.5 2.0 0.5 Average 1.08 1.08 0.50 2.00 1.58 0.50 Decorated Glassware DS DS Snoopy 1.0 1.0 Teddy 0.5 1.0 Kenia Plates 0.5 0.5 Average 0.67 0.83 Al-Plates DA DA SU Plate 3.0 4.0 28.0 -
TABLE AL5b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 3 6 Octime 0.5 4.5 Longchamp 23 48 RKG Kölsch 14 26.5 Nachtmann Longdrink 4 10 Arcoroc Elegance 5 5 Sum 49.5 100 Decorated Glassware Snoopy 5 11 Teddy 0 7 Kenia Plates 0 0 Sum 5 18 Al-Plates Plate 104.5 217 - Comparative Examples 1 to 4 show that aluminium materials without protection dissolve, lose shine and cause iridescence on glassware
- Addition of sodium disilicate eliminates the dissolution of aluminium materials. However, the aluminium is discoloured, turning an unpleasant brownish-black colour also the shine of the aluminium material is gone. Moreover, sodium disilicate has a negative effect on glassware: glass clouding, line corrosion and even iridescence (due to silicate rather than aluminium) occur. Furthermore the mass loss of clear and decorated glassware is increase and the decoration protection (given by the dissolving aluminium) is no longer present.
- Addition of zinc acetate reduces the mass loss of the aluminium plate (to a level 1/20th that as in the absence of zinc). Iridescence and glass corrosion is also improved. However, the performance on decoration protection is still poor.
- Addition of bismuth citrate reduces the mass loss of the aluminium plate in a similar level to that observed with the use of zinc. However, discoloration of the aluminium increases. With bismuth the performance on decorated glass protection care is good, but the performance on glass corrosion care is weak.
- In this Example the base detergent formulation was used with 0.67 g of zinc acetate, 0.19 g bismuth citrate and 3.8 g of sodium disilicate.
- The results of the tests are shown in Table AL6a (Glass Corrosion) and Table AL6b (Mass Loss).
-
TABLE AL6a Glass Corrosion 50 cycles 100 Cycles Glasses GC CL IR GC CL IR Michelangelo 0.0 1.0 0.5 0.5 1.5 0.5 Octime 1.0 0.5 0.0 2.5 1.5 0.5 Longchamp 0.0 1.0 0.5 0.0 1.5 0.0 RKG Kölsch 0.0 1.0 0.5 1.5 2.5 1.0 Nachtmann Longdrink 1.0 0.0 0.5 0.5 0.0 0.5 Arcoroc Elegance 0.5 1.0 0.5 1.5 1.0 1.0 Average 0.42 0.75 0.42 1.08 1.33 0.58 Decorated Glassware DS IR DS IR Snoopy 0.0 0.5 Teddy 0.5 0.5 Kenia Plates 0.0 0.0 1.0 0.0 Average 0.17 0.67 Al-Plates DA DA SU Plate 0.5 1.0 124.83 -
TABLE AL6b Mass Loss 50 cycles 100 cycles Mass Loss (mg) Mass Loss (mg) Glasses Michelangelo 2 4 Octime 0 0 Longchamp 1 0 RKG Kölsch 5 5 Nachtmann Longdrink 3 2 Arcoroc Elegance 1 2 Sum 12 13 Decorated Glassware Snoopy 2 2 Teddy 0 0 Kenia Plates 0 0 Sum 2 2 Al-Plates Plate 16 16 - The results of Example 1 show that the presence of a combination of zinc, bismuth and disilicate gives good protection to aluminium such that the corrosion is low and the aluminium keeps its shine. Additionally this combination minimises detrimental effects on glassware: iridescence, glass corrosion on plain and decorated glassware is all vastly reduced.
Claims (23)
1. A composition for use in the protection of glassware exposed to aluminum in an automatic dishwashing process, said composition comprising zinc and bismuth, wherein the composition comprises a detergent composition, a rinse aid composition or a soluble glass or ceramic composition and wherein the ration of zinc to bismuth in the composition is from 1:100 to 100:1 based on mass of the metals.
2. (canceled)
3. A composition according to claim 1 , wherein the mass ratio of zinc to bismuth in the composition is from 1:10 to 10:1.
4. A composition according to claim 1 , wherein the zinc or bismuth are in metallic form.
5. A composition according to claim 4 , wherein the metallic form is an alloy of zinc and bismuth.
6. A composition according to claim 1 , wherein the zinc and/or bismuth are present as a salt or compound.
7. A composition according to claim 6 , wherein the salt or compound is a nitrate, oxide, sulphate, phosphate, halide, carbonate or carboxylate salt.
8. (canceled)
9. A composition according to claim 1 , wherein the bismuth and zinc comprise from 0.002 wt % to 6 wt % based on the weight of both metals of the detergent formulation.
10. A composition according to claim 9 , wherein the bismuth and zinc comprise from 0.01 to 3 wt % and most preferably from 0.02 to 1.3 wt % (e.g. 0.4 wt %) of the detergent formulation.
11. (canceled)
12. A composition according to claim 1 , wherein the bismuth and zinc comprise from 0.03 wt % to 30 wt % based on the weight of both metals of the rinse aid formulation
13. (canceled)
14. The use of a composition comprising zinc and bismuth for the protection of glassware in an automatic dishwashing process from detrimental effects caused by exposure of the glassware to aluminium.
15. The use according to claim 14 , wherein the amount of zinc and bismuth provided to a dishwasher cycle is from 1 to 1000 mg.
16. The use according to claim 15 , wherein the amount of zinc and bismuth provided to a dishwasher cycle is from 5 to 500 mg.
17. The use according to claim 16 , wherein 5 to 100 mg zinc and 5 to 100 mg bismuth is provided to a dishwasher cycle.
18. An automatic dishwashing process additive composition comprising zinc, bismuth and aluminium for prevention of glassware corrosion in an automatic dishwasher.
19. An automatic dishwashing process additive composition containing zinc, bismuth and silicate for prevention of aluminium corrosion in an automatic dishwasher.
20. An automatic dishwashing process additive composition containing zinc, bismuth and silicate for prevention of aluminium corrosion and glassware corrosion in an automatic dishwasher.
21. The automatic dishwashing process additive composition of claim 20 , wherein the zinc is present as zinc acetate, the bismuth is present as bismuth citrate and the silicate is present as sodium disilicate.
22. The automatic dishwashing process additive composition of claim 20 , wherein the amount of silicate is present in a ratio to zinc and bismuth of up to 500:1.
23. The automatic dishwashing process additive composition of claim 22 , wherein the amount of silicate is present in a ratio to zinc and bismuth of up to 500:1.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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US12/472,804 US20090233833A1 (en) | 2003-10-17 | 2009-05-27 | Composition for the protection of glassware in a dishwasher |
US13/012,373 US8216990B2 (en) | 2003-10-17 | 2011-01-24 | Composition for protection of glassware in dishwasher |
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
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GB0324295.9 | 2003-10-17 | ||
GB0324295A GB0324295D0 (en) | 2003-10-17 | 2003-10-17 | Composition |
GB0404469A GB0404469D0 (en) | 2004-02-28 | 2004-02-28 | Composition |
GB0404469.9 | 2004-02-28 | ||
US10/575,201 US20070054825A1 (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
PCT/GB2004/004410 WO2005037975A1 (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
US12/472,804 US20090233833A1 (en) | 2003-10-17 | 2009-05-27 | Composition for the protection of glassware in a dishwasher |
Related Parent Applications (3)
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PCT/GB2004/004410 Continuation WO2005037975A1 (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
US10/575,201 Continuation US20070054825A1 (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
US11/575,201 Continuation US8345089B2 (en) | 2005-09-09 | 2006-09-08 | Receiving apparatus and intra-subject information acquiring system |
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US13/012,373 Continuation US8216990B2 (en) | 2003-10-17 | 2011-01-24 | Composition for protection of glassware in dishwasher |
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US20090233833A1 true US20090233833A1 (en) | 2009-09-17 |
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US10/575,201 Abandoned US20070054825A1 (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
US12/472,804 Abandoned US20090233833A1 (en) | 2003-10-17 | 2009-05-27 | Composition for the protection of glassware in a dishwasher |
US12/474,521 Expired - Fee Related US7741236B2 (en) | 2003-10-17 | 2009-05-29 | Water-soluble glass composition |
US13/012,373 Expired - Fee Related US8216990B2 (en) | 2003-10-17 | 2011-01-24 | Composition for protection of glassware in dishwasher |
Family Applications Before (1)
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US10/575,201 Abandoned US20070054825A1 (en) | 2003-10-17 | 2004-10-18 | Composition for protection of glassware in dishwashers |
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US12/474,521 Expired - Fee Related US7741236B2 (en) | 2003-10-17 | 2009-05-29 | Water-soluble glass composition |
US13/012,373 Expired - Fee Related US8216990B2 (en) | 2003-10-17 | 2011-01-24 | Composition for protection of glassware in dishwasher |
Country Status (10)
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US (4) | US20070054825A1 (en) |
EP (1) | EP1673426B1 (en) |
AT (1) | ATE394462T1 (en) |
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DE (1) | DE602004013615D1 (en) |
ES (1) | ES2302030T3 (en) |
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GB2402132B (en) * | 2003-05-28 | 2005-10-19 | Reckitt Benckiser Nv | Dishwasher anti-corrosion composition |
WO2005037975A1 (en) * | 2003-10-17 | 2005-04-28 | Reckitt Benckiser N.V. | Composition for protection of glassware in dishwashers |
US8067321B2 (en) * | 2008-05-21 | 2011-11-29 | Icl Performance Products, Lp | Sodium-potassium hexametaphosphate and potassium metaphosphate with a low insolubles content |
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US20070181224A1 (en) * | 2006-02-09 | 2007-08-09 | Schlumberger Technology Corporation | Degradable Compositions, Apparatus Comprising Same, and Method of Use |
Also Published As
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US7741236B2 (en) | 2010-06-22 |
US20110118167A1 (en) | 2011-05-19 |
AU2004281311A1 (en) | 2005-04-28 |
BRPI0415349A (en) | 2006-12-05 |
ES2302030T3 (en) | 2008-07-01 |
US8216990B2 (en) | 2012-07-10 |
BRPI0415349B1 (en) | 2016-11-16 |
WO2005037975A1 (en) | 2005-04-28 |
EP1673426A1 (en) | 2006-06-28 |
ATE394462T1 (en) | 2008-05-15 |
AU2004281311B2 (en) | 2010-05-13 |
US20070054825A1 (en) | 2007-03-08 |
DE602004013615D1 (en) | 2008-06-19 |
PL1673426T3 (en) | 2008-07-31 |
CA2542596C (en) | 2014-01-21 |
CA2542596A1 (en) | 2005-04-28 |
US20090239731A1 (en) | 2009-09-24 |
EP1673426B1 (en) | 2008-05-07 |
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